title: honey creek twg revision number: revision …€¦ · · 2017-06-29title: honey creek twg...

Title: Honey Creek TWG Revision Number: <#1> Revision Date: <6/12/2009> of 238


Acronyms

BMP = Best management practice, sets of land management techniques that, for a given land use, minimize the environmental damages associated with that land use.

DRP = Dissolved reactive phosphorus

EPA = Environmental Protection Agency

GLPF = Great Lakes Protection Fund

HC-TWG = Honey Creek Targeted Watershed Grant (this grant)

MDL = minimum detection limit

NCWQR = National Center for Water Quality Research, Heidelberg College

OEPA = Ohio Environmental Protection Agency

QA-SOP = Quality Assurance Standard Operating Procedure, an NCWQR document describing many of the quality assurance procedures common to each Standard Operating Procedure and included as Appendix B-2 of the this QAPP.

QAC = Quality Assurance Coordinator (a position in the NCWQR, Dr. Aaron Roerdink)

QAP = Quality Assurance Plan of the NCWQR, presented as Appendix B-1

QAPP = Quality Assurance Project Plan (This document)

SOP = Standard Operating Procedure describes the NCWQR’s implementation of the standard analytical methods for the analysis of various water pollutants or constituents.

SRWC = Sandusky River Watershed Coalition

STORET = EPA’s environmental data storage and retrieval system.

SWCD = Soil and Water Conservation District

TMDL = Total Maximum Daily Load, a procedure used to integrate management of point and nonpoint sources of water quality impairment in order to meet quality criteria.

TP = Total phosphorus

USGS = United States Geological Survey


WAP = Watershed Action Plan, a plan approved by state agencies that, as implemented, will address water quality impairments within the watershed.


Table of Contents NOTE: Because of the substantial differences between components of the quality control programs for the chemical loading studies and biological studies, major portions of the QAPP are divided into two sections, the first dealing with the nutrient and sediment loading studies and the second dealing with the stream biota and habitat studies. Those portions of the QAPP common to both areas (Sections 1.1 – 1.6.0) are not repeated. Section Page 1.0 PROJECT MANAGEMENT 9

1.1 Title and Approval Page (EPA QA/R-5 A1)............................................................................... 9 1.2 Table of Contents (EPA QA/R-5 A2) .......................................................................................... 9 1.3 Distribution List (EPA QA/R-5 A3) ............................................................................................ 9 1.4 Project Organization (EPA QA/R-5 A4)................................................................................... 10 1.5 Problem Definition/Background (EPA QA/R-5 A5)................................................................ 14 1.6 Project/Task Description and Schedule (EPA QA/R-5 A6) .................................................... 16

1.6.1(Chem). Schedule of tasks for the Chemical and Hydrological Monitoring Program ..........17 1.6.2 (Chem) Summary of Work Tasks .........................................................................................17

1.7 (Chem) Quality Objectives and Criteria for Measurement Data (EPA QA/R-5 A7)........... 191.7.1 (Chem) Objectives and Project Decisions ............................................................................19 1.7.2 (Chem) Action Limits/Levels ...............................................................................................20 1.7.3 (Chem) Measurement Performance Criteria/Acceptance Criteria........................................21

1.8 (Chem) Special Training Requirements/Certification (EPA QA/R-5 A8) ............................ 211.9 (Chem) Documents and Records (EPA QA/R-5 A9) ............................................................... 24

1.9.1 (Chem) QA Project Plan Distribution...................................................................................24 1.9.2 (Chem) Field Documentation and Records...........................................................................24 1.9.3 (Chem) Laboratory Documentation and Records .................................................................24 1.9.4 (Chem) Quarterly and/or Final Reports ................................................................................29

2.0 (Chem) DATA GENERATION AND ACQUISITION ..................................................................29 2.1 (Chem) Sampling Design (Experimental Design) (EPA QA/R-5 B1)..................................... 292.2 (Chem) Sampling Methods (EPA QA/R-5 B2)......................................................................... 32 2.3 (Chem) Sample Handling and Custody (EPA QA/R-5 B3)..................................................... 33 2.4 (Chem) Analytical Methods (EPA QA/R-5 B4) ....................................................................... 33

2.4.1 (Chem) Field Measurements Methods..................................................................................33 2.4.2 (Chem) Field Analyses Methods ..........................................................................................33 2.4.3 (Chem) Laboratory Analyses Methods (Off-Site) ................................................................33

2.5 (Chem)Quality Control Requirements (EPA QA/R-5 B5)...................................................... 35 2.5.1 Field Sampling Quality Control............................................................................................36 2.5.2 (Chem)Field Measurement/Analysis Quality Control ..........................................................36 (not applicable) ..............................................................................................................................36 2.5.3 (Chem) Laboratory Analysis Quality Control ......................................................................36

2.6 (Chem) Instrument/Equipment Testing, Inspection, and Maintenance (EPA QA/R-5 B6) 38 2.6.1 (Chem) Field Measurement Instruments/Equipment............................................................38


2.6.2 (Chem) Field Instruments/Equipment (Screening and Definitive).......................................38 2.6.3 (Chem) Laboratory Analysis Instruments/Equipment (Off-Site) .........................................38

2.7 (Chem) Instrument/Equipment Calibration and Frequency (EPA QA/R-5 B7).................. 382.7.1 (Chem) Field Measurement Instruments/Equipment............................................................38 2.7.2 (Chem) Field Instruments/Equipment (Screening and Definitive).......................................40 2.7.3 (Chem) Laboratory Analysis Instruments/Equipment

(Off-Site)..................................................................................................................................40 2.8 (Chem) Inspection/Acceptance Requirements for Supplies and Consumables

(EPA QA/R-5 B8)........................................................................................................................ 40 2.8.1 (Chem) Field Sampling Supplies and Consumables.............................................................40 2.8.2 (Chem) Field Measurement/Analyses (Screening and Definitive) Supplies and

Consumables ............................................................................................................................40 2.8.3 (Chem) Laboratory Analyses (Off-Site) Supplies and Consumables ...................................40

2.9 (Chem) Data Acquisition Requirements (Non-Direct Measurements) (EPA QA/R-5 B9) .. 40 2.10 (Chem) Data Management (EPA QA/R-5 B10) ..................................................................... 41

3.0 (Chem) ASSESSMENT AND OVERSIGHT ..................................................................................42 3.1 (Chem) Assessments/Oversight and Response Actions (EPA QA/R-5 C1) ........................... 42 3.2 (Chem) Reports to Management (EPA QA/R-5 C2) ............................................................... 42

4.0 (Chem) DATA REVIEW AND USABILITY ..................................................................................42 4.1 (Chem) Data Review, Verification, and Validation Requirements ( EPA QA/R-5 D1) ...... 42 4.2 (Chem) Verification and Validation Methods (EPA QA/R-5 D2).......................................... 43 4.3 (Chem) Reconciliation with User Requirements (EPA QA/R-5 D3)...................................... 43

5.0 (Chem) REFERENCES.....................................................................................................................45 Biological Section of QAPP 1.6.1 (Bio) Project/Task Description and Schedule.......................................................................46

1.7 (Bio) Quality Objectives and Criteria for Measurement Data............................................... 46 1.7.1 Objectives and Project Decisions. ........................................................................................47

1.8 (Bio) Special Training Requirements/Certification................................................................. 47 1.9 (Bio) Documents and Records ................................................................................................... 48

1.9.1 QA Project Plan Distribution. ...............................................................................................48 1.9.2 Field Documentation and Records........................................................................................48 1.9.3 Laboratory Documentation and Records ..............................................................................48 1.9.4 Quarterly and/or Final Reports .............................................................................................49

2.0 (Bio) DATA GENERATION AND ACQUISITION ......................................................................49 2.1 (Bio) Sampling Design (Experimental Design)......................................................................... 49

2.1.1 Selection of Ditch Segments.................................................................................................49 2.1.2 Habitat Assessments. ............................................................................................................50 2.1.3 Field Physical-chemical Measurements...............................................................................51 2.1.4 Macroinvertebrate Assessments. ..........................................................................................51

2.2 (Bio) Sampling Methods............................................................................................................. 52 2.2.1 Qualitative Habitat Evaluation Index. ..................................................................................52


2.2.2 Macroinvertebrate Assessments. ..........................................................................................53 2.2.3 Fish Assessments. .................................................................................................................54 2.2.4 Data Analysis. .......................................................................................................................54

2.3 (Bio) Sample Handling and Custody......................................................................................... 542.3.1 Macroinvertebrates. ..............................................................................................................54 2.3.2 Fish........................................................................................................................................55

2.4 (Bio) Analytical Methods............................................................................................................ 55 2.4.1 Field Measurements Methods. Refer to Section 2.1. ..........................................................55 2.4.2 Field Analyses Methods. Refer to Section 2.1....................................................................55 2.4.3 Laboratory Analyses Methods (Off-Site). Not applicable...................................................55

2.5 (Bio)Quality Control Requirements.......................................................................................... 552.5.1 Field Sampling Quality Control............................................................................................55 2.5.2 Field Measurement/Analysis Quality Control. .....................................................................55 2.5.3 Laboratory Analysis Quality Control ...................................................................................55

2.6 (Bio) Instrument/Equipment Testing, Inspection, and Maintenance .................................... 56 2.6.1 Field Measurement Instruments/Equipment. ........................................................................57 2.6.2 Field Instruments/Equipment (Screening and Definitive). ...................................................57 2.6.3 Laboratory Analysis Instruments/Equipment (Off-Site). .....................................................57

2.7 (Bio) Instrument/Equipment Calibration and Frequency ...................................................... 57 2.7.1 Field Measurement Instruments/Equipment .........................................................................57 2.7.2 Field Instruments/Equipment (Screening and Definitive). ...................................................58 2.7.3 Laboratory Analysis Instruments/Equipment (Off-Site). .....................................................58

2.8 (Bio) Inspection/Acceptance Requirements for Supplies and Consumables......................... 58 2.8.1 (Bio) Field Sampling Supplies and Consumables. ...............................................................58 2.8.2 (Bio) Field Measurement/Analyses (Screening and Definitive) Supplies and

Consumables. ...........................................................................................................................58 2.8.3 (Bio) Laboratory Analyses (Off-Site) Supplies and Consumables.......................................59

2.9 (Bio) Data Acquisition Requirements (Non-Direct Measurements) ...................................... 59 2.10 (BIO) Data Management.......................................................................................................... 59

3.0 (BIO) ASSESSMENT AND OVERSIGHT .....................................................................................593.1 (BIO Assessments/Oversight and Response Actions ............................................................... 59 3.2 (Bio) Reports to Management.................................................................................................... 60

4.0 (Bio) DATA REVIEW AND USABILITY.......................................................................................60 4.1 (Bio) Data Review, Verification, and Validation Requirements ............................................ 60 4.2 (Bio) Verification and Validation Methods .............................................................................. 60 4.3 (Bio)Reconciliation with User Requirements ........................................................................... 60

5.0 (Bio) REFERENCES ........................................................................................................................60


Table of Contents for Appendices Appendix A. Biological Section Appendices ...........................................................................................63

A-1. Fact Sheet on Ditch Monitoring Component of this Project .......................................................64

A-2. QHEI (Qualitative Habitat Evaluation Index) form ....................................................................65 A-3. Field Data Sheet for Physical and Miscellaneous Habitat Parameters........................................67 A-4. Protocol for Picking and Sorting Benthic Invertebrate Samples Collected for the Targeted

Watershed Project ..........................................................................................................................68

Appendix B. Chemical Section Appendices..............................................................................................74

B-1. Quality Assurance Plan, NCWQR...............................................................................................75 B-2. Quality Assurance Standard Operating Procedure, NCWQR .....................................................98 B-3. Method Standard Operating Procedures ....................................................................................105

B-3.1 SOP for Total Suspended Solids (Gravimetric)................................................................105 B-3.2 SOP for Total Phosphorus ................................................................................................111 B-3.3 SOP for Soluble Reactive Phosphorus (Dissolved Reactive Phosphorus) .......................124 B-3.4 SOP for Total Kjeldahl Nitrogen .....................................................................................137 B-3.5 SOP for Fluoride, Chloride, Nitrite, Nitrate, and Sulfate Anions.....................................150 B-3.6 SOP for Ammonia N.........................................................................................................163 B.3.7 SOP for Silica...................................................................................................................176

B-4 Water Quality in Ohio Rivers and Streams, Project Study Plan.................................................188

Appendix C. Work Plan for the Honey Creek Targeted Watershed Project ..........................................211

Appendix D. Fact Sheet for the Honey Creek Targeted Watershed Project.............................................xx Appendix E. Miscellaneous studies of storage effects on dissolved reactive phosphorus and nitrate

nitrogen ................................................................................................................................................xx


List of Tables

Chemical Monitoring QAPP Table 1.1 Timeline for Outcome Monitoring – Chemical and Hydrological Monitoring

Programs .............................................................................................................................................18 Table 1.2 Analytical Parameters and Target Limits for Chemical Transport Studies...............................23 Table 1.3 Portion of the data base for Honey Creek as it appears in Excel files on the tributary

loading website ....................................................................................................................................27 Table 1.4 Sample weekly printout for the Hoeny Creek Station showing both sample concentrations

and associated quality control samples................................................................................................28 Table 2.1 Sampling Design and Rationale.................................................................................................33 Table 2.2 Summary of Field and QC Samples to be collected ..................................................................34 Table 2.3 Analytical Methods, Containers, Preservations and Holding Times.........................................35 Table 2.4 Quality Control Requirements for Analyses..............................................................................37 Table 2.6 Field Equiopment/Instrument Calibration, Maintenance, Testing and Inspection...................39 Biological Monitoring QAPP Table 1. General schedule of activities related to habitat and aquatic biota..............................................46 Table 2.1 Physical-Chemical measurements and methods ........................................................................52 Additional Tables and Figures are contained within the Appendices.

List of Figures

Chemical Monitoring QAPP Figure 1.1 Organizational Chart for the Honey Creek Targeted Watershed Project.................................13 Figure 1.2 Illustration of trends in dissolved reactive phosphours yilds and concentrations for

northwestern Ohio Watersheds ............................................................................................................15 Figure 1.3 Distributions of nutrient and sediment concentrations in ten Ohio rivers during the 2007

water year (~5,000 samples). ...............................................................................................................22 Figure 1.4 Sample Chain of Custody Form/Collections Sheet used for the Honey Creek Stations..........25 Figure 2.1 Map of the Honey Creek Tributary Loading Station in relation to the other tributary

loading stations operated by the NCWQR...........................................................................................30 Figure 2.2 The Honey Creek watershed, showing the location of the Honey Creek Melmore

sampling station and general land use .................................................................................................31

Biological Monitoring QAPP Figure 2.1 Locations of the fifteen ditch segments selected for assessment in 2008 ................................51


1.0 PROJECT MANAGEMENT

1.1 Title and Approval Page (EPA QA/R-5 A1) See page 1.

1.2 Table of Contents (EPA QA/R-5 A2) See pages 4 - 8.

1.3 Distribution List (EPA QA/R-5 A3)

Name: Gary W. Winston Title: Director Organization: National Center for Water Quality Research Contact Information: Heidelberg College, 310 East Market Street, Tiffin, OH 44883; 419 448-2201; [email protected] Name: David B. Baker Title: Research Professor Organization: National Center for Water Quality Research Contact Information: Heidelberg College, 310 East Market Street, Tiffin, OH 44883; 419 448-2941; [email protected] Name: Aaron Roerdink Title: Quality Assurance Coordinator Organization: National Center for Water Quality Research Contact Information: Heidelberg College, 310 East Market Street, Tiffin, OH 44883; 419 448-2250; [email protected] Name: Jack W. Kramer Title: Laboratory Manager Organization: National Center for Water Quality Research Contact Information: Heidelberg College, 310 East Market Street, Tiffin, OH 44883; 419 448-2373; [email protected] Name: Kenneth L. Krieger Title: Senior Research Scientist Organization: National Center for Water Quality Research Contact Information: Heidelberg College, 310 East Market Street, Tiffin, OH 44883; 419 448-2226; [email protected]


Name: Tia Rice Title: Administrator Organization: Seneca Soil and Water Conservation District Contact Information: 3140 S. SR 100, Suite D. Tiffin, OH 44883; 419 447-7073 [email protected]

Name: Johan Gottgens Title: Professor Organization: University of Toledo, Department of Environmental Sciences Contact Information: 419-530-8451; [email protected] Name: Cynthia Brookes Title: Watershed Coordinator, Sandusky River Watershed Coalition Organization: WSOS Community Action Commission, Inc. Contact Information: 219 S. Front St., P.O. Box 590, Fremont, OH 43420; 419 334-5016; [email protected] Name: Rachel Nailer Title: Project Officer Organization: EPA Region 5 Contact Information: (312) 886-0234, [email protected] Name: Paul Thomas Title: Senior Research Scientist Organization: EPA Region 5 Contact Information: (312) 886-7742, [email protected] Name: Simon Manoyan Title: EPA Watersheds and Wetlands, Branch QA Coordinator Organization: EPA Region 5 Contact Information: (312 353-2681), [email protected]

Name: Kevin Pierard Title: Watersheds and Wetlands Branch Chief Organization: EPA Region 5 Contact Information: Name: Tinka G. Hyde Title: Acting Water Division Director Organization: EPA Region 5 Contact Information:

1.4 Project Organization (EPA QA/R-5 A4)


The organization chart for this project is shown in Figure 1.1. Brief descriptions of the

responsibility of each person or group listed in Figure 1.1 are provided below.

Project Manager: Dr. David Baker, NCWQR, will be responsible for overall project coordination, implementation, reporting and fiscal management. He will also be in charge of maintaining the official QA Project Plan (this QAPP).

Laboratory Manager: Jack Kramer, NCWQR, is responsible for the field and laboratory operations

associated with the NCWQR’s tributary loading program (http://wql-data.heidelberg.edu) , which includes operation of the Honey Creek monitoring station at Melmore, OH.

Laboratory QC Officer: Dr. Aaron Roerdink, NCWQR and Heidelberg Chemistry Department, is

responsible for the overall quality control and quality assurance programs associated with the tributary loading and private well testing program of the NCWQR. The Honey Creek monitoring station at Melmore operates within the general quality control program of the Heidelberg College tributary loading program. The nutrient and sediment analyses program of the NCWQR chemistry laboratory operates at Level 3 (the highest level) in the Ohio EPA’s Credible Data Program.

Stream Biota and Macroinvertebrates: Dr. Ken Krieger, NCWQR, is responsible for the overall studies

of stream biota. In addition to his overall responsibilities for the stream biota studies, he directs the field collection and laboratory identification and quantification of macroinvertebrate communities. As such he directly supervises staff and students aiding him in the field collection and laboratory analyses. He has Level 3 certification (highest level) for macroinvertebrate studies in Ohio EPA’s credible data program.

Stream Biota/Fish: Dr. Hans Gottgens, U. of Toledo, is responsible for the fish studies associated with

this project. He is aided by doctoral candidate, Todd Crail, and undergraduate students from the U. of Toledo. Dr. Gottgens has developed the methods and associated quality control operations being applied in the fish component of this study.

BMP Implementation Oversight: Tia Rice, Seneca Soil and Water Conservation District (SWCD), is

taking the lead in the BMP implementation programs included in the Honey Creek TWG. As such, she coordinates programs with the two other SWCDs (Crawford County and Huron County) that operate within the Honey Creek Watershed. She also is the direct supervisor of the Honey Cr. TWG full time technician, Bret Margraf.

BMP Implementation/Farmer Interaction: Bret Margraf, Seneca SWCD, will work directly with

farmers within the Honey Creek Watershed to aid them in the adoption of BMPs. These BMPs have been selected by the grant developers to achieve the environmental outcomes set as goals for the Honey Cr. TWG.

HC-TWG Advisory Group: This advisory board is comprised of farmers within the Honey Creek

Watershed, agrichemical dealers active in the watershed, Ohio State University Extension personnel,


Sandusky River Watershed Coalition representatives, Natural Resource Conservation Service (USDA), and individual supervisors of the SWCDs in the three counties. In addition, Baker, Brookes, Margraf, Rice, and the administrators of the Crawford SWCD (Mike Hall) and Huron SWCD (Cary Brickner) will also meet with the advisory group. This group will serve as the interface between the HC-TWG and farmers within the Honey Creek Watershed. They will also adapt and update, as necessary, the BMP implementation programs included in the HC-TWG in response to changing agricultural production patterns in the watershed (e.g., increasing corn production to supply ethanol production facilities).

Outreach and Education Coordinator: Cindy Brookes is the Watershed Coordinator of the Sandusky

River Watershed Coalition (SRWC). She will coordinate the programs of the HC-TWG with programs implementing other components of the Honey Creek Watershed Action Plan, such as the nutrient reduction programs at the Attica, OH sewage treatment facility (Wick, 2006). She will also coordinate the HC-TWG with other programs in the Sandusky River Watershed and utilize the resources of the coalition for outreach and education activities related to the HC-TWG.

NCWQR Coordintation: Gary Winston is the Director of NCWQR. He will work with Dave Baker to

integrate the work associated within the this project into the overall programs of the NCWQR. Project Officer: Rachel Nailer, EPA Region 5, will ensure that all contractual issues are addressed as

work is performed on this task. Technical Officer: Paul Thomas, EPA Region 5, will provide overall project/program oversight for this

study for EPA Region 5. He will ensure technical quality throughout the project. He will also ensure that contract objectives are adhered to. He will review and approve the final project report.

EPA Watersheds and Wetlands QA Coordinator: Simon Manoyan, EPA Region 5, will be responsible

for reviewing and approving this QAPP. His responsibilities also include conducting external performance and system audits and participating in Agency QA reviews of this study.

EPA Administration Representatives: Kevin Pierard, EPA Region 5 Water Division Director, and Tinka G. Hyde, acting EPA Region 5 Water Division Director, will provide oversight for this contract. They will review and approve the QAPP and ensure that all contractual issues are addressed as the work is performed. The communication linkages between the above groups and individuals is shown in Figure 1.1, the organizational chart for the Honey Creek Targeted Watershed Grant.


David B. Baker Project Manager

NCWQR

Environmental Monitoring Tributary Loading Laboratory Manager – Jack Kramer Lab QC Officer – Aaron Roerdink Stream Biota Macroinvertebrates – Ken Krieger Fish - Johan Gottgens

BMP Implementation Tri-county Coordinator – Tia Rice Honey Cr. TWG Technician – Bret Margraf Honey Creek Advisory Group

Outreach and Education Sandusky River Watershed Coalition – Cynthia Brooks - Coodinator

U.S. Environmental Protection Agency Grants Officer – Rachel Nail

Technical Officer – Paul Thomas QC Officer – Simon Manoyan EPA Administration Representatives – Kevin Pierard & Tinka G. Hyde

NCWQR Coordination NCWQR Director – Gary Winston

Figure 1.1 Organizational Chart for the Honey Creek Targeted Watershed Project


1.5 Problem Definition/Background (EPA QA/R-5 A5)

Honey Creek, a tributary to the Sandusky River, drains a 179.9 square mile watershed in North Central Ohio. Row crop agriculture occupies 80.9% of the land area, with grassland/pasture covering 2.0%, forests covering 9.8% and urban/residential covering 6.7%. Land use in Honey Creek is typical of the agricultural watersheds in the Sandusky Watershed and Northwestern Ohio (Baker and Ostrand, 2001). Because of their high clay content soils, flashy hydrological responses to rainfall events and extensive tile drainage, these watersheds have high export rates of total phosphorus, suspended sediments, and nitrate nitrogen (Baker and Richards, 2002; Baker, 1985). In addition, because of the impacts of intensive row crop agriculture on stream habitat and hydrology, stream biota generally fail to meet Ohio EPA standards, particularly in headwater streams (OEPA, 2003).

The above problems that are general to Northwestern Ohio and the Eastern Corn Belt are particularly well documented for the Honey Creek Watershed. Detailed nutrient and sediment export studies were launched at the U.S. Geological Survey stream gage at Melmore (149 square mile drainage area) by Heidelberg College researchers in 1976, as part of the U.S. Army Corps of Engineers’ Lake Erie Wastewater Management Study (Army Corps of Engineers, 1979). Those studies, which utilize automatic samples to collect 3-4 storm event samples per day as well as daily non-storm samples, have continued to the present time. Through the 2008 water year nutrient, sediment and flow data are available for more than 16,800 samples at this station. These data have been used in numerous studies and publications (see Richards et al, 2002). They document long-term average export rates for suspended sediment, total phosphorus and nitrate-N of 503 kg/ha, 1.28 kg/ha and 17.3 kg/ha, respectively.

In 2001 and 2002, the OEPA conducted detailed studies of the stream biota within the upper portions of the Sandusky River Watershed, including Honey Creek. The resulting technical support document (Ohio EPA, 2003), together with the Heidelberg College tributary loading data for Honey Creek, Rock Creek and the Sandusky River near Fremont, OH, provided the basis for the Upper Sandusky TMDL, which was published in 2004 (OEPA 2004). That document contained information on the extent, causes and sources of impairments to stream biota within the Honey Creek Watershed. The TMDL also called for programs to reduce total phosphorus export from the Honey Creek Watershed by 25% and for programs to reduce nitrate concentrations at the public water supplies that withdraw water from streams in the Honey Creek Watershed.

Upon completion of the TMDL, staff from NCWQR and the Sandusky River Watershed Coalition developed the Honey Creek Watershed Action Plan (Loftus et al, 2006). It is a comprehensive plan to address both point and nonpoint source pollution problems in the Honey Creek Watershed. This action plan received full endorsement by the Ohio EPA and the Ohio Department of Natural Resources in April 2006 and is available on the Coalitions web site (http://www.sanduskyriver.org/watershed/index.php?page=Home/Watershed+Planning/Honey+Creek+WAP/). The proposal for the Honey Creek Targeted Watershed grant was developed to begin implementation of key portions of the Honey Creek Watershed Action Plan.

While the Sandusky TMDL was being conducted, and the Honey Creek Watershed Action plan formulated, another pollution problem in Northwestern Ohio tributaries to Lake Erie has come to the forefront of concern. This problem is the very large increase in the loading of dissolved reactive phosphorus (DRP) to Lake Erie from agricultural watersheds of this region. The increases in DRP are


Figure 1.2. Illustration of trends in dissolved reactive phosphorus yields and concentrations for Northwestern Ohio Watersheds.

Dissolved Reactive Phosphorus, Unit Area Loads

0.00

0.20

0.40

0.60

0.80

1975 1980 1985 1990 1995 2000 2005Water Year

DR

P, u

nit a

rea

load

s, k

g/ha

Sandusky Honey Rock Maumee

Dissolved Reactive Phos., Flow Weighted Mean Conc.

0.000

0.040

0.080

0.120

0.160

1975 1980 1985 1990 1995 2000 2005Water Year

DR

P, F

WM

C, m

g/L


Dissolved Reactive Phos. Time Weighted Mean Conc.

0.000

0.020

0.040

0.060

0.080

0.100

0.120

0.140

1975 1980 1985 1990 1995 2000 2005Water Year

DR

P.TW

MC

, mg/

L


Dissolved phosphorus (start to 1994), unit area yields, kg/ha

Statistic Maumee Sandusky Honey RockMean 0.200 0.197 0.183 0.087Median 0.189 0.185 0.168 0.085Max 0.405 0.481 0.339 0.210Min 0.060 0.034 0.041 0.025Relative Std dev. 51.6% 63.3% 50.8% 63.1%De-trended RSD 43.1% 54.5% 40.0% 62.7%Percent change -59.8% -68.2% -66.6% -20.8%p-value 0.022 0.022 0.006 0.709r2 0.301 0.259 0.381 0.015

Dissolved phos., flow weighted mean concentrations, mg/L Statistic Maumee Sandusky Honey Rock

Mean 0.065 0.058 0.059 0.028Median 0.060 0.055 0.057 0.025Max 0.109 0.101 0.094 0.046Min 0.027 0.015 0.017 0.011Relative Std. Dev. 42.3% 46.0% 37.6% 43.2%De-trended RSD 27.6% 28.9% 24.2% 42.9%Percent change -64.8% -73.0% -62.9% -13.4%p-value 0.0004 0.0001 0.0002 0.735r2 0.572 0.061 0.587 0.012

Dissolved phos., time weighted mean concentration, mg/L Statistic Maumee Sandusky Honey Rock

Mean 0.063 0.041 0.051 0.023Median 0.051 0.036 0.053 0.021Max 0.128 0.077 0.079 0.038Min 0.023 0.010 0.021 0.008Relative Std. Dev. 53.3% 53.6% 37.4% 43.3%De-trended RSD 26.4% 22.8% 16.5% 33.8%Percent change -81.2% -87.5% -69.6% -58.3%p-value 0.00001 <0.0001 <0.0001 0.030r2 0.755 0.819 0.804 0.388

Dissolved phosphorus (1994-2007), unit area yields, kg/ha

Statistic Maumee Sandusky Honey RockMean 0.244 0.243 0.281 0.197Median 0.265 0.168 0.238 0.18Max 0.543 0.784 0.772 0.569Min 0.0628 0.037 0.041 0.026Relative Std dev. 56.3% 83.7% 76.0% 73.4%De-trended RSD 31.9% 49.0% 43.4% 40.1%Percent change 518.0% 1787.5% 6356.0% 4167.0%p-value 0.0003 0.0004 0.0003 0.0002r2 0.680 0.656 0.674 0.701

Dissolved phos., flow weighted mean concentrations, mg/L Statistic Maumee Sandusky Honey Rock

Mean 0.072 0.064 0.079 0.061Median 0.072 0.056 0.079 0.065Max 0.109 0.128 0.150 0.114Min 0.029 0.015 0.017 0.011Relative Std. Dev. 36.3% 52.7% 49.3% 50.8%De-trended RSD 13.1% 21.9% 14.0% 16.3%Percent change 224.0% 372.3% 554.8% 592.3%p-value 0.00001 <0.0001 <0.0001 <0.0001r2 0.870 0.827 0.919 0.897

Dissolved phos., time weighted mean concentration, mg/L Statistic Maumee Sandusky Honey Rock

Mean 0.049 0.037 0.049 0.029Median 0.051 0.031 0.049 0.032Max 0.075 0.066 0.085 0.054Min 0.023 0.010 0.021 0.008Relative Std. Dev. 37.5% 53.0% 40.0% 46.0%De-trended RSD 22.3% 24.9% 15.7% 18.8%Percent change 175.2% 348.0% 266.9% 373.8%p-value 0.00055 <0.0001 <0.0001 <0.0001r2 0 644 0 779 0 846 0 832

Table 5. Statistical summary of unit area loads, f low weighted mean concentrations and time weighted mean concentrations of dissolved reactive phosphorus during the start through 1994, and 1994-2007 periods.

Figure 1.2 Annual unit area loads (A), flow weighted mean concentrations (B) and time weighted mean concentrations (C) of dissolved reactive phosphorus during the study period.


illustrated in Figure 1.2, which shows the annual values of unit area loads and flow-weighted and time- weighted mean concentrations for the period of record of Heidelberg monitoring at four northwestern Ohio streams -- the Maumee River, the Sandusky River, Honey Creek and Rock Creek. Since DRP is highly bioavailable to algae, these increases in DRP loading to Lake Erie are of concern as a contributing factor to the recent increases in harmful algal blooms in the Lake. The causes of the increases in DRP loading appear to be linked the changes in agricultural practices associated with erosion control and particulate phosphorus loading control programs. In response to these observations, the Ohio EPA formed the Ohio Lake Erie Phosphorus Task Force to evaluate the extent of the problem, and to examine DRP sources and remedies (http://www.epa.state.oh.us/dsw/lakeerie/ptaskforce/index.html). Because of these developments, special efforts to reduce the export of DRP have been incorporated into the Honey Creel TWG. Specifically, BMP targeting will be based on a simplified phosphorus index utilizing stratified soil testing (See HC-TWG Work Plan, Appendix C).

In summary, the environmental outcomes of this project, as set forth in the proposal and detailed work plan, are:

� a 25% reduction in total phosphorus export. � a 35% reduction in dissolved reactive phosphorus export. � a 50% reduction in the percentage of time nitrate exceeds the drinking water standard of 10

mg/L nitrate nitrogen. � a reduction in the flashy hydrology of Honey Creek, as measured by the Richards-Baker

Flashiness Index (Baker et al, 2004) � an assessment of the effects of decreasing frequency of ditch dredging on stream habitat

and biota in “maintained ditches. (The decreased frequency of dredging is associated with the success of upland erosion control measures.)

1.6 Project/Task Description and Schedule (EPA QA/R-5 A6)

The project tasks for this grant are discussed and outlined in detail in the Work Plan and Detailed

Budget (Revision of December 21, 2007) for the Honey Creek Targeted Watershed Project (Appendix C, page 211). Within that work plan, project tasks were separated into four areas including:

1. Project Administration 2. Project Outreach and Education 3. Project BMP Implementation 4. Project Outcome Monitoring

a. Chemical and Hydrological Monitoring b. Biological and Habitat Studies.

For each of the above areas, individual tasks were identified, described and scheduled in the work

plan. We interpret this QAPP to be specifically applicable to Area 4, Project Outcome Monitoring. Consequently, the remainder of this document will focus on Area 4.

Furthermore, since the content of the QAPP for the chemical and hydrological monitoring differs significantly from that of the biological and habitat studies, separate sections of the QAPP will be presented for each of these components. Thus sections 1.6.1 through 4.3, as applicable, will be presented first for the chemical and hydrological monitoring, with the section numbers followed by


(Chem), as for example, 1.6 (Chem) or 2.4 (Chem). These sections will then be repeated, as appropriate, for the biological and habitat monitoring, with the section numbers followed by (Bio), as for example 1.6 (Bio) or 2.4 (Bio). This organization of the QAPP is evident in the Table of Contents (pages 4 – 8).

Details of the chemical portion of this QAPP will make frequent reference to the quality control documents and standard operating procedures that are already in place for our analytical and tributary loading programs. The relevant NCWQR quality assurance and quality control documents are included in the Appendix to this QAPP. These consist of four basic parts:

Appendix B-1. Quality Assurance Plan (QAP): The QAP outlines the structure of the NCWQR, basic operation of the Quality Program and Quality Control (QC), and requirements for data to be produced within the Quality Program. It is the intention of the QAP to be the first document utilized for questions of quality or how the laboratory operates to maintain a control environment.

Appendix B-2. Quality Assurance Standard Operating Procedure (QA-SOP):

The QA-SOP outlines the quality assurance testing and parameters for all analytical Standard Operating Procedures (SOPs) covered by the QAP. Areas covered by this document include, but are not limited to, demonstration of initial instrumental performance, generation of control charts for QC, and generation of Method Detection Limits (MDLs).

Appendix B-3. Standard Operating Procedure (SOP) for each analysis:

The SOP outlines the procedure an analyst must follow when performing a particular analysis. All analytical methods must have a corresponding SOP to be covered by the QAP. Each analytical method maintains its own SOP. Samples of quality control charts associated with the analyses included in each SOP are attached to that SOP.

Appendix B-4. Study Plan for Tributary Loading Studies:

A Study Plan outlines specific aspects for a given study, as, for example, the tributary loading program. These aspects include, but are not limited to, study duration, sampling methods, sample collection location, types of sample analysis, etc. In addition, the Study Plan will reference the necessary portions of the QAP, QA-SOP or SOPs.

Appendix E. Dissolved Phosphorus and Nitrate Storage Test Data

1.6.1(Chem). Schedule of tasks for the Chemical and Hydrological Monitoring Program

The schedule of tasks for the chemical and hydrological monitoring program, as presented in the final work plan for this grant, is shown in Table 1.1. These individual work tasks are described in the Work Plan (Appendix C, beginning on page 211) and summarized below.

1.6.2 (Chem) Summary of Work Tasks

a. Prepare QAPP – This task reflects the preparation and approval process for this document. It


was scheduled for completion during the 6-month period beginning in July 2008. Table 1.1. Timeline for Outcome Monitoring – Chemical and Hydrological Monitoring Program

Outcome Monitoring, Chemistry and Hydrology

Project Year, beginning January 2008 (estimate).

Task Jan. 2008

July 2008

Jan. 2009

July 2009

Jan. 2010

July 2010

Jan. 2011

July 2011

Jan. 2012

July 2012

a. Prepare QAPP x x b. Continue sample collection

at Melmore Stream Gage x x x x x x x x x x

c. Continue analytical program for Melmore station on Honey Creek

x x x x x x x x x x

d. Transfer chemical data to STORET and NCWQR tributary loading website

x x x x x

e. Interpret and present data x x x x x x f. Calculate stream flashiness

and interpret data x x x x x

g. Produce quarterly progress reports

x x x x x x x x x x

h. Produce Final Reports and publications

x x x

b. Continue the sampling program at the Melmore Station on Honey Creek. This chemical transport station on Honey Creek has been in operation since October 1976. Its operation is currently funded by a grant from the Great Lakes Protection Fund (GLPF). It provides a major avenue for evaluating the outcomes of the HC-TWG. The operation of this station is being used as part of the local match for this grant and, as such, requires production of this QAPP relative to chemical and hydrological monitoring.

c. Continue the nutrient and sediment analysis program. The chemical analysis program for samples collected at the Honey Creek-Melmore station will continue in its current format. As such, it operates under a quality control/quality assurance program designed to support the multiple goals associated with the Heidelberg College long-term, multi-station tributary loading program. This quality control program has received evaluation by both the Ohio EPA and the U.S. Geological Survey and has met the requirements of both groups. Thus our laboratory is Level 3 certifiable by the Ohio EPA and the USGS has published data from our tributary monitoring program and used our laboratory for contract analyses. It should be noted that we are not currently certified because we do not adhere to the sample holding requirements for dissolved reactive phosphorus and nitrate specified by the U.S. EPA in their analytical methods manuals.

d. Transfer chemical data to STORET and to the NCWQR’s tributary loading website (http://wql-


data.heidelberg.edu. Upon data screening by NCWQR QAC (Aarron Roerdink) and the Project Director (David Baker), the data from this program will be transferred annually to publically available web sites, including STORET.

e. Data Interpretation and Presentation. Information gained from the Melmore station will be presented to multiple organizations and constituencies on an ongoing basis throughout the grant. These data feed into the Outreach and Education Program of this project, as described in the work plan.

f. Calculate stream flashiness. As final daily stream flow data from the Melmore stream gage station become available from the USGS, the annual flashiness index will be calculated. Specifically, the Richards-Baker flashiness index (Baker et al, 2004) will be utilized to examine trends in flashiness in response to changing crop production and agricultural water management practices.

g. Quarterly progress reports. Quarterly progress reports will be produced relative to the status of the chemical and hydrological monitoring program. These reports will be integrated with quarterly progress reports from the other project areas.

h. Final Reports and Publications. Final reports on the results of the chemical transport and hydrological monitoring program will be produced as scheduled in Table 1.1. These reports will be integrated with other areas of this project, including the biological monitoring section and the tracking of BMPs adopted as part of this project.

1.7 (Chem) Quality Objectives and Criteria for Measurement Data (EPA QA/R-5 A7)

Author’s note. A confusing part of utilizing the outline provided by Region 5 for this QAPP is that it is often unclear whether the term “general objectives of the project” applies to the overall project or to the environmental outcome monitoring associated with the project. For example, the subtitle in 1.7.1 can easily be interpreted to refer to the project as a whole. The general objectives of the project are to foster adoption of appropriate best management practices in appropriate locations within the Honey Creek Watershed so as to achieve reductions of the export and concentrations of nutrients identified in the project goals (Section 1.5). The extent of BMP adoption reflects project output, which will be tracked within the BMP implementation portions of the project. The general objectives of the chemical monitoring portion of the project are to conduct a monitoring program capable of recognizing load and concentration reductions of the magnitude projected, in the face of the annual, weather-induced variability in nutrient export and concentrations. In general, we will limit our detailed responses in this QAPP to the chemical, hydrological, biological and habitat monitoring programs, although overall programs will be presented as appropriate. (David Baker, October 2008)

1.7.1 (Chem) Objectives and Project Decisions The general objectives of this project, in terms of load and concentration reductions of agricultural

pollutants, were listed in Section 1.5. The project involves implementing programs that will result in farmer adoption of specific sets of BMPs in critical pollutant source areas within the Honey Creek Watershed. Furthermore, it is anticipated that adoption of those BMPs will lead to the reductions in agricultural nonpoint source pollution previously mentioned. An additional objective of this project is to operate a tributary monitoring program that is not only capable of recognizing the occurrence of the


load and concentration reductions of the sizes projected, but also of causally linking any such reductions to the BMP adoption programs that occurred within the watershed.

If the project results in targeted adoptions of the sets of BMPs currently available to address the problems, and if the pollutant reductions can be both documented and causally linked to the BMP adoption program, then those responsible for area-wide nutrient control programs can proceed with confidence to support similar BMP adoption programs in neighboring watersheds, without undertaking the level of chemical monitoring program accompanying this project. If the monitoring program fails to document the anticipated nutrient reductions, and if that failure cannot be attributed to either weather conditions or contravening changes within the watershed (e.g., a major shift to corn production for ethanol and a resulting decrease in no-till agriculture that would accompany such a shift given the soils of this region), then alternative or more aggressive BMP programs aimed at achieving necessary nutrient load reductions would have to be considered.

1.7.2 (Chem) Action Limits/Levels

This project has two types of goals. One type of goal takes of form of load reductions. Specifically,

the project calls for a 25% reduction in total phosphorus export and a 35% reduction in dissolved phosphorus export, relative to current export rates for the time period of 1994-2001 (OEPA, 2004). To formulate a goal in this format, it is essential to have baseline loading data of high precision. This is particularly important because of the extensive weather-induced annual variability of pollutant loading from agricultural sources (See the detrended relative standard deviation for annual loads and concentrations of DRP shown in Figure 1.2, page 15). The second type of goal takes the form of reducing by 50% the duration of time that nitrate concentrations exceed the drinking water standard at the Honey Creek monitoring station. To formulate a goal in this format also requires extensive baseline data.

The sample collection and the analytical programs of the NCWQR are specifically designed to provide this type of data. Furthermore, this same data collection program is applied to a network of Ohio and Michigan watersheds (currently 13 stations) so that the effects of land use/land management, watershed size, and watershed hydrology can be evaluated. The analytical parameters included in our tributary monitoring program, along with the detection limits for each parameter, are shown in Table 1.2. To aid in data interpretation, additional parameters are routinely measured in every sample that is analyzed. These additional analyses include suspended solids, total Kjeldahl nitrogen, chloride and sulfate.

The term “action limit” is not particularly applicable to this study. While loading goals can be, and are set for watersheds and/or stream segments, the term “action limit” is seldom used because of the major impacts of weather conditions on pollutant loading from agriculture in any particular year. Furthermore, action limits for loading can’t be set in terms of pollutant concentrations because loading is a product of concentration times flow. This reality greatly complicates any simplified application of the “total maximum daily load” concept in the context of either pollutant loading issues or ambient water quality issues. Nutrient concentration standards, relative to ambient water quality in streams, have yet to be adopted in most states, including Ohio. Such standards are also very difficult to establish because of the multiple habitat, hydrological, and nutrient concentration factors that interact to determine algal growth in streams.


In practice, our detection limits represent the most sensitive analytical system we can achieve, consistent with the need for analyzing large numbers of samples at reasonable analytical costs. Where specific chemicals have drinking water or environmental standards, we attempt to achieve detection limits at concentrations no greater that 10% of the standard.

It is essential for pollutant loading studies that accuracy and precision be maintained over the full range of environmental concentrations observed in rivers. This is particularly true for nonpoint source pollution studies where high concentrations and high flows co-occur. Figure 1.3 illustrates the range of sample concentrations observed from the approximately 5,000 samples analyzed from 10 monitored rivers during the 2007 Water Year. The detection limits are also plotted on the graphs. Note that the concentrations observed often range over three orders of magnitude. Thus our SOPs include measures to assure that reported concentrations fall within calibration standards, either through dilution or provision of two ranges of calibration standards.

The analytical parameters included in the study, along with the detection limits currently achieved by our analytical instrumentation and procedures, are shown in Table 1.2.

1.7.3 (Chem) Measurement Performance Criteria/Acceptance Criteria Method performance criteria and acceptance criteria are listed in the SOP for each analytical method

(See Appendix B-3). Within each SOP, relevant information is provided in section 4.0 (Method Performance Validation and Working Linear Range), section 12.0 (Quality Control Requirements) and section 16.0 (Tables, Diagrams, Flowcharts and Validation Data).

The quality control SOPs applicable to each of the analytical SOPs are summarized in Appendix B-2 (Quality Assurance Standard Operating Procedure). This includes descriptions of performance demonstrations as implemented at daily, monthly, quarterly, semiannual and annual frequencies. Several aspects of the quality control requirements for analyses are summarized in Table 2-4 (page 37).

1.8 (Chem) Special Training Requirements/Certification (EPA QA/R-5 A8)

Section 2 of the NCWQR QAP (Appendix B-1, page 75), outlines laboratory personnel training procedures. Form 1 of QAP-Appendix A illustrates the record used to track the training status of new employees. In section 2.0 of each NCWQR SOP (see Appendix B-3), the safety and training appropriate to each analytical method is also described.

Laboratory Certification is described in section 12 (Audits, Accreditations, and Certification) of the NCWQR QAP (Appendix B-1,beginning on page 75). The NCWQR analytical laboratory meets the requirements for level three (highest level) credible data by the Ohio EPA. It is also certified for analyses of suspended sediments by the U.S. Geological Survey.

All employees associated with the tributary loading program have certification by the Ohio EPA as Qualified Data Collectors (QDCs) (Appendix B-4, Section 9, page 193).


Figure 1.3. Distributions of nutrient and sediment concentrations in ten Ohio rivers during the 2007 water year (~5,000 samples)

The above graphs illustrate the ranges of nutrient and sediment concentration observed during the 2007 Water Year in ten Ohio rivers. The concentration data are presented as concentration exceedency curves showing the percentage of samples with concentrations exceeding the Y-axis values.

Suspended solids concentrations in 4982 samples

0

1

10

100

1,000

10,000

0 10 20 30 40 50 60 70 80 90 100Percent of samples with concentrations higher than value on

y-axis

Susp

ende

d so

lids

conc

. mg/

L

Detection Limit

Total phosphorus concentrations in 5002 samples

0.001

0.010

0.100

1.000

10.000

0 10 20 30 40 50 60 70 80 90 100Percent of samples with concentrations exceeding valus on

Y-axisTo

tal P

hosp

horu

s co

nc.,

mg/

L

Detection Limit

Dissolved Reactive Phosphorus concentrations in 4933 samples

0.0001

0.0010

0.0100

0.1000

1.0000

10.0000

0 10 20 30 40 50 60 70 80 90 100Percent of samples with concentrations exceeding values on

Y-axis

Dis

solv

ed R

eact

ive

Phos

, mg/

L

Detection Limit

Nitrate-nitrogen concentrations in 4881 samples

0.01

0.10

1.00

10.00

100.00

0 10 20 30 40 50 60 70 80 90 100Percent of samples with concentrations exceeding those of Y-

axis

Nitr

ate-

nitr

ogen

, mg/

L

Detection Limit

Total Kjeldahl Nitrogen concentrations in 5008 samples

0.01

0.10

1.00

10.00

100.00

0 10 20 30 40 50 60 70 80 90 100Percent of samples with concentrations exceeding those on Y-axis

Tota

l Kje

ldah

l Nitr

ogen

con

cent

ratio

ns

in 5

008

sam

pels

Detection Limit

Chloride concentrations in 5006 samples

0.1

1.0

10.0

100.0

1000.0

0 10 20 30 40 50 60 70 80 90 100Percent of samples with concentrations exceeding value on Y-

axis

Chl

orid

e, m

g/L

Detection Limit


Table 1-2. Analytical Parameters and Target Limits for Chemical Transport Studies

Matrix/Media:

Laboratory Limits2

(applicable units)

Analytical Parameter1

Project Action

Limit/Level (applicable units)

Quantitation Limits

Detection

Limits (mg/L)

Suspended Sediments

NA

10

2.9

Total Phosphorus

NA

0.05

0.0023

Dissolved reactive phosphorus

NA

0.015

0.0008

Nitrate-nitrogen

NA

0.12

0.079

Total Kjeldahl Nitrogen

NA

0.20

0.068

Chloride

NA

2.5

0.457

Sulfate

NA

2.0

0.331

Ammonia

NA

0.01

0.0257

Silica

NA

0.1

0.0610

1 Analytical parameters include both field and laboratory analyses. 2 Laboratory quantitation limits and detection limits are those that an individual laboratory or organization is able to achieve

for a given analysis on a routine basis. C Quantitation limits are the minimum concentrations that can be identified and quantified above the detection limit within some known limits of precision and accuracy/bias. It is recommended that the quantitation limit is supported by the analysis of a standard of equivalent concentration (typically, the lowest calibration standard). C Detection limits are the minimum concentration that can be detected above background or baseline/signal noise of an instrument.


1.9 (Chem) Documents and Records (EPA QA/R-5 A9)

1.9.1 (Chem) QA Project Plan Distribution

Upon approval of this Honey Creek QAPP, electronic copies will be distributed those persons whose

name appears on the distribution list contained in Section 1.3, page 9. A paper copy of the document, including signatures where appropriate, will be delivered to the Project Officer.

1.9.2 (Chem) Field Documentation and Records The field collection records and chain of custody forms associated with the tributary loading

program are described in Section 5 of the NCWQR QAP (Appendix B-1, page 82). Form 1, contained in Appendix C of NCWQR QAP, contains the chain of custody records applicable to samples collected at the Honey Creek Melmore station. At this station, staff from the NCWQR chemical laboratory visit the station every Monday morning, change the sample base, return the previous week’s samples to the analytical laboratory, log the samples into the labs data base management system, and begin the sample preparation (filtering) and analysis the same day. These chain of custody documents are retained by the NCWQR for at least two years (NCWQR QAP, Section 5.4, page 82). Figure 1.4 illustrates the chain of custody form as it is applied for stations visited by NCWQR staff.

1.9.3 (Chem) Laboratory Documentation and Records

See Section 10 of the NCWQR QAP (Data Reduction, Review and Reporting, page 87). This

section includes a diagram of the electronic data flow within the laboratory, as well as data back-up on the college computer. Data for the tributary loading program undergo a final screening by the project director and NCWQR QA Coordinator (QAC) at the end of each water year (September 30) when the USGS instantaneous discharge data are transferred to the NCWQR. The completed data for the just completed water year are then transferred to the NCWQR tributary loading website (http://wql-data.heidelberg.edu) and added to the files already available for each station. A sample of the data from the tributary loading website for the Honey Creek station is shown in Table 1.3.

Paper copies of weekly results for each station are retained within the laboratory for at least three years. These sheets include data for both the environmental samples and the quality control samples (replicates, spikes, stored and fresh) for each station each week. An example of these weekly sheets are shown in Table 1.4.


Figure 1.4 Sample of Chain of Custody Form/Collection Sheet used for the Honey Creek Station.


The coding for the quality control samples as illustrated in Table 1.4 is as follows: RC -- A specific two letter label on each of the 24 bottles in a particular set of bottles for

the ISCO Sampler. The laboratory maintains at least two sets of bottles for each sampling station it operates. For each set of sample bottles, the first 21 bottles (eg. RC-1 to RC-21) are reserved for the sequential collection of three samples per day for seven days.

RC-24 -- This bottle is filled by the sample collection team at the time they visit the sampling station to change the bottle sets in the automatic sampler.

RC-24R – After filtration of a portion of sample RC-24 in the laboratory, two samples are poured from the filtrate for analysis – RC-24 and RC-24R. These represent in lab replicates. For whole water analyses replicates, (TP, TKN and SS) the 24R samples are poured directly from the RC-24 ISCO bottle.

RC-24S – This is a spike of the filtered RC-24 sample. Also for TP, TKN and SS. QC –DW19 – is a distilled water blank QC – DWS19 is a spike of the distilled water used the same spiking material and volume

as used for RC-24S RC1-RC21 are the particular samples selected for analysis from the Honey Creek

Melmore station that week. Depending on flow conditions, the number of samples can vary from 7 to 21.

SX-6 (20080512) is the sample collected the previous week at the same time as bottle 24 of that week. It has been stored in the ISCO sampler and is analyzed with the current sample set (RC) for evaluation of any changes on storage.

SC-14 – This is a bottle blank in which distilled water has been stored in an ISCO bottle set for one week to evaluate effects of sample bottle contamination.

QC xck19 – this is a check standard for total phosphorus and TKN analyses.

In addition to the weekly printouts for the samples from each station, as illustrated in Table 1.4, the software from the analytical system contains a report that summarizes the analytical system performance for each set or tray of samples. These reports include data for the calibration standards that are used for each set or tray. These reports are stored in the laboratories computer files for 4 or more years and can be accessed to verify the analytical system performance for any environmental sample.


Table 1.3. Portion of the data base for Honey Creek as it appears in Excel files on the tributary

loading website.

Row Number

Datetime (date and time of sample

collection)

Days since 741001

Sample Time Window, days

Flow, CFS SS, mg/L (suspended solids)

TP, mg/L as P

SRP, mg/L, as P

NO23, mg/L as N

TKN, mg/L (Total Kjeldahl

Chloride, mg/L

Month

2 01/28/1976 00:00 484.00 1.00 350.0 38.5 0.238 0.080 3.00 -9.00 19.0 1

16137 8/19/2007 12:00 0.83 8.4 12.2 0.113 0.067 1.39 0.67 24.3 816138 8/20/2007 04:00 0.40 8.4 18.4 0.121 0.060 1.41 0.72 29.1 816139 8/20/2007 07:25 0.17 8.0 21.0 0.132 0.071 1.69 0.76 26.3 816140 8/20/2007 12:00 0.26 20.1 47.5 0.439 0.304 3.25 1.40 31.8 816141 8/20/2007 20:00 0.33 463.2 279.4 0.629 0.193 2.05 1.83 14.3 816142 8/21/2007 04:00 0.33 738.9 195.7 0.579 0.246 2.92 1.85 11.6 816143 8/21/2007 12:00 0.33 1294.6 125.2 0.421 0.205 3.28 1.72 9.3 816144 8/21/2007 20:00 0.33 1555.0 92.5 0.387 0.176 3.13 1.44 8.2 816145 8/22/2007 04:00 0.33 1653.8 65.9 0.370 0.174 3.40 1.43 7.3 816146 8/22/2007 12:00 0.33 1665.0 63.4 0.336 0.152 3.25 1.42 7.1 816147 8/22/2007 20:00 0.33 1790.6 67.4 0.320 0.145 2.74 1.18 5.9 816148 8/23/2007 04:00 0.33 1738.6 48.5 0.293 0.149 2.73 1.10 5.4 816149 8/23/2007 12:00 0.33 1506.8 38.9 0.277 0.140 2.86 1.07 6.3 816150 8/23/2007 20:00 0.33 1209.1 35.5 0.274 0.148 2.83 1.00 7.0 816151 8/24/2007 04:00 0.33 946.4 29.6 0.269 0.148 2.67 1.12 8.2 816152 8/24/2007 12:00 0.33 753.6 35.9 0.266 0.161 2.44 1.17 8.3 816153 8/24/2007 20:00 0.33 594.1 36.1 0.267 0.166 2.27 1.24 9.0 816154 8/25/2007 04:00 0.33 460.4 33.5 0.261 0.151 2.07 1.15 8.7 816155 8/25/2007 12:00 0.33 349.7 31.7 0.257 0.145 1.94 1.13 10.5 816156 8/25/2007 20:00 0.33 259.3 35.2 0.244 0.133 1.62 1.20 10.8 816157 8/26/2007 04:00 0.33 190.3 26.6 0.231 0.127 1.55 1.19 11.1 816158 8/26/2007 12:00 0.33 146.1 31.6 0.223 0.115 1.35 1.08 11.2 816159 8/26/2007 20:00 0.33 116.4 28.9 0.204 0.097 1.31 1.14 11.9 816160 8/27/2007 04:00 0.33 89.4 23.2 0.197 0.095 1.31 1.15 11.8 8

16207 9/30/2007 12:00 1.00 11.6 6.7 0.084 0.032 0.81 0.79 31.4 9


Table 1.4 Sample weekly printout for the Honey Creek Station showing both sample concentrations and associated quality control samples that accompanied samples from Honey Creek.


1.9.4 (Chem) Quarterly and/or Final Reports The NCWQR Quality Assurance Standard Operating Procedure (Appendix B-2) describes the

procedures for the demonstration of performance, monthly performance reviews, quarterly demonstration of performance, semi-annual demonstration of performance and annual demonstration of performance. These are applicable to each of the analyses. In addition, the SOPs for the individual analyses (Appendix B-3, beginning on page xx) contain information on reporting requirements.

Relative to the project as a whole, quarterly progress reports will be completed by the project director (Baker), according to Table 1.1. (page 18) the Timeline for Outcome Monitoring. The detailed work plan for this proposal also includes timelines for Project Administration, Project Outreach and Education and Project BMP Implementation. These timelines include quarterly and final reports on the same schedule as those shown in Table 1.1 of this QAPP. In addition to copies of these reports sent to the project officer, the Project Director will keep electronic copies of these reports on his own computer as well as in the Staff Folder of the WQL server.

In the final report documents, annual loads of nutrients and sediments will be calculated from data of the type shown in Table 1.3. These same data sets will be used to evaluate progress in reducing the duration of time nitrate concentrations exceed drinking water standards. All of these data will be interpreted in light of annual precipitation patterns and stream flow patterns during the project period.

2.0 (Chem) DATA GENERATION AND ACQUISITION

2.1 (Chem) Sampling Design (Experimental Design) (EPA QA/R-5 B1) A fundamental aspect of pollutant export and/or loading studies is that they must be conducted at a

watershed scale. The scale (size) of watersheds for which export and loading studies are conducted ranges from laboratory “watersheds” less than 1 m2 to major river basins such as the Mississippi River. At whichever scale one chooses, measurements are generally confined to points at or near the outlet of the watershed. Generally speaking, such outlet points are on a stream or river. Since loading measurements require flow data, it is also essential that such studies be done at a location where stream flow data are available on a continuous basis. Thus, such studies are generally done at locations where stream gaging stations are located. In the United States, such studies are most often done at U.S. Geological Survey stream gages.

Figure 2.1 shows the locations of the tributary loading stations included in the NCWQR’s Tributary Loading Program. Additional information for each of these stations is provided in the NCWQR’s Tributary Loading website (http://wql-data.heidelberg.edu). Of particular relevance to this study is the tributary loading station on Honey Creek at Melmore, Ohio. A map of the Honey Creek watershed showing the location of our collection station at the USGS stream gage at Melmore is shown in Figure 2.2. The USGS stream gaging station at Melmore was established in 1976 for the specific purpose of supporting nutrient and sediment export studies from the Honey Creek Watershed as part of the U.S. Army Corps of Engineer’s Lake Erie Wastewater Management Study (Army Corps of Engineers, 1979). The USGS follows a set of selection criteria for the establishment of new gaging stations. These criteria include selection of a site with a stable cross section, with natural flow control structures in the


Figure 2.1 The Honey Creek Tributary Loading Station in relation to the other tributary loading

stations operated by the NCWQR.

Maumee

GrandVermilion

Muskingum

Scioto

SanduskyCuyahoga

Great Miami

Raisin

N

EW

S0 4 0 8 0 K ilo me te rs1 20

Lake Erie

IN

MI Sampling Station

Honey Creek


Melmore Sampling Station

Figure 2.2. The Honey Creek watershed, showing the location of the Honey Creek Melmore sampling station on the background of land use. streambed, with safe and ready access and with a location suitable for project objectives (in this case inclusion of a large proportion of the Honey Creek watershed, but not under the flow influence of the receiving stream (Sandusky River).

The standard procedure for sample collection in the NCWQR tributary loading program involves the use of refrigerated automatic samplers to collect three discrete samples per day at fixed times—4:00 hrs, 12:00 hours and 20:00 hrs. With these sampling times, each sample represents an 8 hour time period, and the three eight hour periods can be used to characterize a single calendar day. The automatic samplers do not pump water directly from the stream. Instead, a submersible pump is used to deliver a continuous flow of stream water into a “sampling sink” in the sampling shed. The automatic samplers pump water from the sampling sink into the sample bottles. Each automatic sampler contains 24 bottles with 21 bottles used for a single week of sample collection (seven days with three samples per day), and the remaining three bottles available for quality control samples. At weekly intervals, year round, the sampler bases containing the 24 bottles are retuned to the NCWQR’s analytical laboratory and a new base is placed in the automatic sampler for the next week’s collection. The above procedure has proven


to be reliable for sample collections during both high and low stream flow, during all seasons of the year.

This sampling frequency (three samples per day) is utilized for the following reasons: 1. The largest portion of pollutant export from watersheds occurs during storm runoff or snow melt

events. 2. During such events, both pollutant concentrations and stream flow change very rapidly. This

requires frequent sampling across the storm hydrograph to accurate characterize pollutant loads. 3. It is impractical to attempt to use manual grab sampling for storm event sampling programs even

for a single station, let alone a network of stations over a large geographical area. Local observers can’t be expected to collect samples at night and during storm events whenever such storms occur.

4. Since the concentrations of various pollutants peak during different portions of the hydrograph, further optimization of the sampling program for one pollutant (e.g., suspended sediments) would results in suboptimal collections for other pollutants (e.g., nitrate-nitrogen). Thus, samples collected at equal time intervals over the runoff event are needed to detect peak or “near peak” concentrations of chemicals having different pathways of delivery from the land to streams (overland flow versus interflow or tile drainage).

5. Although low return frequency storms (large storms) do have very large pollutant loads, the much more frequent, smaller storms export the largest total amount of pollutants from a watershed. Consequently, accurate loading data from small storms is essential for accurate watershed export studies.

6. Every storm event represents a unique combination of watershed factors interacting with hydrological factors. Consequently, even event mean concentrations of storms are highly variable.

7. Because the general objectives of the NCWQR’s Tributary Loading Program includes research level analyses of pollutant transport in rivers, all analyses are conducted on discrete samples. Thus storm event chemograph signals are used to infer transport pathways from source areas (fields or other land surfaces) to watershed output. This utilization of the data precludes use of flow-weighted composite samples for watershed export estimation.

Thus the sampling design for the Honey Creek TWG includes a single monitoring station (Table 2.1)

equipped with a refrigerated ISCO sampler. Additional details of the sampling program are presented in Appendix B-4 (page 188), the Tributary Loading Study Plan. This study plan includes vicinity maps for each of the stations, including Honey Creek

2.2 (Chem) Sampling Methods (EPA QA/R-5 B2)

The general sampling methods have been described in Section Chem. 2.1. Sample bases from the ISCO samplers are exchanged on Mondays each week, with sampler base containing the sample bottles from the previous weeks collections returned to the analytical laboratory and a new base, with cleaned sample bottles placed in the ISCO sampler. At the sampling station additional bottles are collected for


Table 2-1. Sampling Design and Rationale

Sampling

Location/ID Number

Matrix/ Media

Depth

(Appropriate Units)


Rationale for Sampling Design2

USGS 04197100

Water

NA

All (See Table 1.2)

See Text Section 2.1

use in the quality control program. These include a bottle for use as replicates and matrix spikes and another used for storage stability testing. The latter is placed in the ISCO Sampler and returned to the laboratory one week later to characterize any changes that may occur in the samples during one week of refrigerated storage. A summary of field and QC sample that are collected is shown in Table 2.2.

Upon receipt in the analytical laboratory, samples are logged into the NCWQR’s laboratory data management system. All of the analyses shown in Table 1.2 are performed on water from a single 800 ml HDPE bottle.

2.3 (Chem) Sample Handling and Custody (EPA QA/R-5 B3) The sample collection procedures are described in detail in Section 2.1 of this document. The

general procedures for sample collection are also described in the Tributary Loading Study Plan (Appendix B-4, page 188). The staff who collect the samples (i.e., change the sample bases at weekly intervals), are also the same staff who deliver the samples to our analytical laboratory, log the samples into the laboratory’s data management system, and conduct the analyses. The field collection sheets (Section 5 of the NCWQR QAP Appendix B-1, page 82) constitute the formal record for the performance of the ISCO automatic sampler for the previous week. An example of a completed collection sheet is shown as Figure 1.4. Since 80% of the sample load analyzed in the laboratory is associated with the tributary loading program, laboratory staff members are fully aware of the program procedures, the analytical equipment and the quality control programs.

2.4 (Chem) Analytical Methods (EPA QA/R-5 B4)

2.4.1 (Chem) Field Measurements Methods

At the time that the automatic sampler bases are changed (Mondays), a gage height reading is taken

at the USGS gaging station. If the stage is readable from the continuous recording instrument in the gage house, that value is recorded. A gage height is also taken using the wire weight gage that is usually mounted on a bridge near the station. These readings are used as back-up values in case the automatic gage reading instruments have failed.

2.4.2 (Chem) Field Analyses Methods

Not applicable, no field analyses are done for tributary loading studies. 2.4.3 (Chem) Laboratory Analyses Methods (Off-Site)


Every sample is analyzed for the chemicals shown in Table 2.1 using the methods shown in Table 2.3. The SOP for each method is shown in Appendix B-3 of this QAPP. All of the analytical instruments are equipped with autosamplers. After sample login, the laboratory’s data base system generates a tray set up for each analysis, showing the position of each sample in the tray. Calibration standards are included with each set or tray of samples. The software used by the analytical equipment develops a calibration curve for each tray, and implements screening procedures to be sure that the calibration curve meets acceptance criteria. The curve fit data and related statistics for each tray are stored in the laboratory’s computer files and can be retrieved if subsequent questions regarding analytical system performance arise.

All analyses are completed within four days of sample arrival in the laboratory.

Table 2-2. Summary of Field and QC Samples To Be Collected

Number of

storage tests

Inorganic Analyses3

No. of:

Matrix/ Media


No. of

Sampling Locations

Depth2

(surface,

mid, or deep)

No. of Field

Duplicates

Dup

MS

No. of Trip

Blanks

No. of

Equipment Blanks

No. of

PE Samples4

Total No.

of Samples

LABORATORY ANALYSES:

water

SS

1

Stream-near bottom

1/wk/station

1/wk

(4 sta-tions)

1/wk

1/wk

1/20 s

ext. 4/yr 500-600/yr

4 years

water

TP

1 Stream-

near bottom

1/wk 1/wk

1/wk

1/wk

1/wk

Inter. 4/yr

Exter. 4/yr

500-600/yr 4 years

water

DRP

1

Stream-near bottom

1/wk

1/wk

1/wk

1/wk

1/wk

Inter. 4/yr

Exter. 4/yr

500-600/yr 4 years

water

TKN

1

Stream-near bottom

1/wk

1/wk

1/wk

1/wk

1/wk

Inter. 4/yr

Exter. 4/yr

500-600/yr 4 years

water

Nitrate

1

Stream-near bottom

1/wk

1/wk

1/wk

1/wk

1/wk

Inter. 4/yr

Exter. 4/yr

500-600/yr 4 years

water

Chloride

1

Stream-near bottom

1/wk

1/wk

1/wk

1/wk

1/wk

Inter. 4/yr

Exter. 4/yr

500-600/yr

4 years

water

Sulfate

1 Stream-

near bottom

1/wk 1/wk

1/wk

1/wk

1/wk

Inter. 4/yr

Exter. 4/yr

500-600/yr

4 years

1 Analytical parameters include all laboratory analyses, field analyses (e.g., nutrients by various field test kits, PCBs by immunoassay test kit, select metals by XRF, etc.), and field measurements (e.g., dissolved oxygen, turbidity, pH, etc.). 2 When samples are collected at different depths at the same location, information for each depth category (e.g., surface, mid, or deep/bottom) is provided on a separate line.

3 Information includes the number of associated analytical QC samples, if collection of additional sample volume and/or bottles is necessary. If the QC samples listed are part of the analysis and don’t require the collection of additional sample volume and/or bottles, ANAS@ (for Ano additional sample@) is included in the column. (Note: MS=matrix spike, MSD=matrix spike duplicate, Dup=laboratory duplicate/replicate.)

4 PE or Performance will be submitted for laboratory analysis along with the associated field sampled where noted.


Table 2-3. Analytical Method, Containers, Preservation, and Holding Times Requirements

Matrix/Media:


and/or Field

Measurements2

Analytical

Method Number

Containers (number,

size/volume, type)

Preservation

Requirements (chemical,

temperature, light protection)

Maximum

Holding Times3

ANALYTICAL PARAMETER:

Suspended sediments 160.2 Total phosphorus 365.1

Dissolved React. Phosphorus

365.2

Nitrate-nitrogen

300.1

Chloride 300.1 Sulfate 300.1 Ammonia 350 Silica 370.1

All analyses for a single sample are performed from a

single 800 ml HDPE bottle from

the refrigerated automatic sample.

Up to three samples per day

are analyzed from each station.

No preservatives are used in the sample

bottles. The samples are refrigerated at xx-xx degrees F. in the ISCO sampler. The

samples are delivered to the laboratory and filtered within 2-15 hours after receipt.

The minimum holding

time between collection (pumped from stream) and

laboratory filtration is about 5 hours. The maximum holding

time between collection (pumped from stream) and

filtration is about 8 days. All analyses are

completed within 3 days of arrival at the

lab. Extensive storage testing is done to

evaluate the effect of sample storage on analytical results.

While these sample’s holding times exceed

EPA limits for dissolved reactive phosphorus and

nitrate, the changes we observe during storage

are small in comparison with

sample changes during storm events and trends we have

observed during these studies. See Appendix

B-5. 1 Analytical parameter includes both field and laboratory analyses. 2 Field measurement parameters include those parameters measured directly in the field (e.g., dissolved oxygen, turbidity, pH,

etc.). 3 Maximum holding times include all pertinent holding times for each analytical parameter (e.g., from sample collection to sample preparation, from sample preparation to analysis, from sample collection to analysis, etc.) and field measurement (e.g., from sample collection to measurement).

2.5 (Chem)Quality Control Requirements (EPA QA/R-5 B5)


2.5.1 Field Sampling Quality Control

At four stations, including the Honey Creek at Melmore station, two replicate samples are collected each week for evaluation of the effects of one week of storage on analytical values for each parameter. One of the samples is returned to the laboratory that same day and filtered within four hours of receipt in the laboratory. The second bottle is left in the refrigerated sampler and returned for analyses the following week. The results of these storage tests are shown in the Appendix E beginning on page xx.

At the time of installation of the new stations and/or pumping systems, comparisons between grab samples from the bridge adjacent to the sampling house and pumped samples are completed.

2.5.2 (Chem)Field Measurement/Analysis Quality Control (not applicable)

2.5.3 (Chem) Laboratory Analysis Quality Control The quality control procedures of the NCWQR water analysis laboratory are presented in Sections

9.0 and 10.0 of the QAP (Appendix B-1). In addition, the quality control procedures for each parameter are described in detail in the SOP for each method (Appendix B-3). Method performance evaluation criteria and working linear ranges are also shown in the SOPs. Replicates, blanks and spikes are included in every sample batch, with a batch containing no more than 21 environmental samples. For each quality control parameter, operational control charts are maintained by the QAC from data generated for replicates, check standards, blanks and matrix spikes. The derivation of the control limits for each control chart is shown in the NCWQR’s QA-SOP (Appendix B-2), Section 3.0 (page 101).

Table 2.4 summarizes some of the quality control requirements for nutrient analyses. Table 2-4. Quality Control Requirements for Analyses

(Stream water for Analyses of nutrients and sediments)


Analytical Method/SOP:

QC Sample: Data Quality Indicator

(DQI)

Frequency/ Number

Method/SOP QC Acceptance

Limits

Acceptance Criteria/

Measurement Performance

Criteria1

Corrective Action

LABORATORY ANALYSIS:

Precision 13/week DW Blanks 13/week

Matrix spikes 13/Week

DW spikes 13/week

Check standards

13/wk

See QA-SOP section 3.0 forcalculation ofupper and lower control limits.

Bottle Blanks 13/week Internalevaluation

See SOPs for individualparameters

See SOPs for individualparameters

Storage Test 4/week Internalevaluation, see Appendix B-4.

All chemical parameters

Independent QC standards

Two samples uarterlyq

85-115%ecoveryr

85-115%ecoveryr

QAP section 3.3

Performanceamples (Blind) s

Two Samples, emiannuallyS

1 Information supports the acceptance criteria/measurement performance criteria introduced in Section 1.7.3.


2.6 (Chem) Instrument/Equipment Testing, Inspection, and Maintenance (EPA QA/R-5 B6)

2.6.1 (Chem) Field Measurement Instruments/Equipment Not applicable

2.6.2 (Chem) Field Instruments/Equipment (Screening and Definitive)

Not applicable

2.6.3 (Chem) Laboratory Analysis Instruments/Equipment (Off-Site) The analytical equipment available in the NCWQR water analysis laboratory is listed in Section 4

(page 81) of the NCWQR QAP (Appendix B-1). The analytical equipment used for each analytical method is also shown in Section 6 of its SOP (Appendix B-3). Preventative maintenance procedures, including that for analytical balances, are described in Section 8 (page 85) of the QAP. This section also describes policy with regard to spare parts. In addition, the preventative maintenance procedures for equipment used in each analysis are described in Section 14.0 of each SOP (Appendix B-3).

2.7 (Chem) Instrument/Equipment Calibration and Frequency (EPA QA/R-5 B7)

2.7.1 (Chem) Field Measurement Instruments/Equipment Not applicable – no field measurements are done in the transport studies.

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Not applicable.

2.7.3 (Chem) Laboratory Analysis Instruments/Equipment (Off-Site) The analytical equipment is calibrated for each tray of samples analyzed, using the analytical

software accompanying the instruments. Depending on the number of storm samples analyzed, from 4-10 trays may be analyzed each week. For each parameter, the calibration procedures and frequency are listed in Sections 8 and 10 of its SOP. The method SOPs also contain a listing of Equipment and Supplies (Section 6) needed for each analysis. As noted in Section QAPP Section 2.10, the performance of standards is included in the data stored for each week for each station.

Laboratory balances are checked each day with check weights, as noted in Section 7 (page 108) of the SOP for suspended solids analysis.

2.8 (Chem) Inspection/Acceptance Requirements for Supplies and Consumables (EPA QA/R-5 B8)

2.8.1 (Chem) Field Sampling Supplies and Consumables

Not applicable

2.8.2 (Chem) Field Measurement/Analyses (Screening and Definitive) Supplies and Consumables

Not applicable

2.8.3 (Chem) Laboratory Analyses (Off-Site) Supplies and Consumables The general requirements for chemical reagents used in the analytical laboratory are listed NCWQR

QAP, Section 4.0. Procurement procedures are described in NCWQR QAP, Section 15.0. This section includes information on the labeling of bottles used in the laboratory for either standards or analytical reagents. The specific reagents required for each parameter are included in that parameter’s SOP (Appendix B-3).

2.9 (Chem) Data Acquisition Requirements (Non-Direct Measurements) (EPA QA/R-5 B9) This project will rely on the historical baseline river transport data sets that our laboratory has

generated for the Honey Creek watershed. These river transport studies serve multiple purposes within our long-term adaptive management strategy to advance agricultural pollution abatement in this region. Thus the data sets serve to quantify sediment and nutrient runoff, to support the planning and implementation of agricultural pollution abatement programs, and to assess the effectiveness of those programs. All of our tributary loading studies have operated under the general quality assurance/quality control programs described in this QAPP. We are thus intimately aware of the quality of these data sets.


2.10 (Chem) Data Management (EPA QA/R-5 B10) The data management system of the laboratory is described in Section 10.0 (page 87) of the

NCWQR QAP (Appendix B-1). In general, data flow from the analytical instruments and their associated PCs, to the NCWQR VAX 4000 computer and related servers as illustrated in Figure 10.1 (page 87). Weekly paper copies of the analytical results for each station, along with the quality control samples accompanying that station’s samples, are printed from the VAX and placed into permanent storage, From the VAX the data go to the NCWQR researchers and to the server that supports our tributary loading website. The data on the VAX are backed up at least biweekly on a Heidelberg College server in a separate building. Redundancy in data storage, as illustrated in Figure 10.1 of Section 10 (page 87), addresses the problems of possible data losses.

A sample of the weekly backup file for the Honey Creek Watershed is shown as Table 1.4. A copy of the data files, as downloaded from the tributary loading website, is shown in Table 1.3, page 27.

Our plan for detecting and correcting errors in the chemical data files is also outlined in Section 10 (page 87) of the NCWQR QAP (Appendix B-1). The initial data screening is done by the analyst as described in the SOPs for each parameter. The NCWQR QAC reviews both the QC data and the environmental data as outlined in the Section 10, and reports results to both the laboratory manager and the project director..

Final screening of the environmental data is accomplished by the NCWQR research staff (Baker, Richards) as they utilize the data for their intended purposes. Researchers can trace any questionable data, as evidenced by “outlier” status, back through the entire analytical system to be sure the analytical system was in control when particular numbers were generated. If problems are discovered during those analyses, values can either be corrected or dropped from the data sets, with corresponding changes in the permanent electronic records.

Data analyses primarily consist of the calculation of annual loads for the parameters of interest. Our “official” loads are calculated using the Beale Ratio Estimator Technique. This technique has historically been used by the International Joint Commission in the calculation of tributary loading data for rivers that discharge into the Great Lakes. The technique is described in detail by Richards (1998). In that publication, he describes the automated technique used to optimize flow strata in the calculation. The program we use to implement the Beale Ratio Estimator has been tested by manual calculations.

Additional data analyses will utilize the Analytical Template, a macro-driven Excel workbook that provides rapid graphical analyses of the river data files that are made available on our tributary loading website. The Analytical Template is downloadable from this website. All of the data selection procedures, calculations and graphical presentations produced by the Analytical Template have been checked by against manual procedures with Excel. We developed the Analytical Template to assure that data users were appropriately accounting for the stratified sampling (variable time windows) program used in our tributary loading studies. In these studies, the automated concentrations exceedency plotting procedures will be used to determine the percentage of time that nitrate concentrations exceed drinking water standards.


3.0 (Chem) ASSESSMENT AND OVERSIGHT

3.1 (Chem) Assessments/Oversight and Response Actions (EPA QA/R-5 C1)

The QAC (Roerdink) is responsible for assessing the implementation of the QAP, the QA-SOP and the individual SOPs. He will report to the project director according to the schedules shown in the QAP Section 13.0 (page XX). His report will cover the topics included in Section 9.0 and Section 10.0 of the QAP (Appendix B).

The project director (Baker) is responsible for assessment of progress in the various activities outlined in the work plan of this project (Appendix C). These reviews will include evaluation of the activities of subcontractors including the Seneca Soil and Water Conservation District, the Sandusky River Watershed Coalition and the University of Toledo. Contracts with each of these organizations contain clauses allowing Heidelberg College to terminate the contracts should the specified work be unsatisfactory. The project director will include this information in the quarterly reports submitted to Region V.

Staff of the US EPA, including Project Director (Nailer) and Technical Officer (Thomas) and QC Officer (Manyoyan) will be tracking the progress of this project and may initiate actions they deem appropriate to assure that the project is advancing as outlined in the work plan (Appendix C).

3.2 (Chem) Reports to Management (EPA QA/R-5 C2) The schedule of reports to management relative to the river transport studies are outlined in Section

13.0 (page 93) of the NCWQR QAP (Appendix B-1). The reports as described in that section will be made to the Project Director (Baker) by the QAC (Roerdink). These reports can be forwarded to the EPA Region 5 staff (see Figure 1.1, page 13) upon request.

The status of the project as a whole, including the implementation programs, outreach and education, project administration, and monitoring, will be assessed at quarterly intervals by the project director and reported to the EPA Project Officer (Nailer). The time schedules set forth in the detailed work plan (Appendix C). will serve as the benchmarks for evaluation.

4.0 (Chem) DATA REVIEW AND USABILITY 4.1 (Chem) Data Review, Verification, and Validation Requirements ( EPA QA/R-5 D1)

The review, verification and validation requirements for nutrient and sediment loading measurements have already been described in Chem Section 2.10 (page 41) in connection with our data management procedures. The project manager, who is a primary “end-user” of the data, along with the QAC, review the data for each year prior to its posting on the Tributary Loading Web-site and to the calculation of the annual loads for the year. These reviews start with the data as produced by the analytical laboratory under the procedures outlined in the NCWQR QAP, QA-SOP, and method SOPs. The additional verification and validation methods implemented by the project director, the QAC, and the other researches utilizing the data are described in the next section.


4.2 (Chem) Verification and Validation Methods (EPA QA/R-5 D2)

The verification and validation methods used in the final reviews of the data make use of two aspects of the study design – the near continuous nature of the sampling and analysis program and the expected relationships among parameters having high correlations. Since the sampling and analysis programs provide from one to three samples per day on a continuous basis, plots of concentration versus time (chemographs) follow expected patterns related to seasons and flow conditions in the stream. Thus, during storm runoff events characteristic patterns of concentration changes occur for each parameter. On occasions, individual samples appear as “outliers” to these normal chemograph patterns. Evaluation of the “outliers” includes comparison with parameters that would be expected to correlate with sample in questions. For example, does a sample with a high dissolved phosphorus sample also have a high total phosphorus concentration? Do other parameters, such as conductivity, chloride or suspended solids, also show departures from their chemograph patterns for that sample? If so, a sample identification mix-up may have occurred in the laboratory’s sample handling procedures. If the ammonia concentration is high, it should also show up in a high total Kjeldahl Nitrogen value. Does a slight change in flow provide a possible explanation for what otherwise appears as an outlier? Thus outliers may be real, and reflect some aspect of pollutant loading into the stream; they may reflect a correctable error in laboratory procedures, such as failure to account for sample dilution; or they may reflect some unknown and untraceable source of laboratory error. In addition to considering the above factors, the project director and QAC consider the significance of the sample relative to the overall project objectives. Thus, relative to loading calculations, concentration “errors” may be very significant during high flow conditions in a stream but be insignificant during low flows. In contrast, “outliers” of potentially toxic compounds could be very important, if concentrations are above standards and are an accurate reflection of conditions in the stream. Given the number of samples collected and used for annual load determinations in this study (500-560), individual outliers may have little impact on conclusions.

One rule of thumb used in sample screening is to evaluate very carefully any single sample that, through some combination of concentration, associated stream flow, and time window, represents more than 3% of the total annual load. Such samples undergo careful scrutiny.

At some point is this final screening process, best professional judgment comes into play. Any changes deemed appropriate by the project officer or other NCWQR research users go back through the QAC for changes to the official tributary loading data files as they reside in the VAX computer and its backups. The QAC keeps a record of changes in these files.

4.3 (Chem) Reconciliation with User Requirements (EPA QA/R-5 D3) In the NCWQR laboratory setting, the data users (project directors and researchers) are directly

involved in data screening and work closely with the laboratory’s QAC, laboratory manager and analytical and field collection team. The analytical and field collection team, lab manager and QAC are also quite sensitive to the data needs related to project objectives. The Honey Creek pollutant transport station has now been in operation for 32 years. Issues of reconciliation with user requirements have largely been addresses years ago. Likewise, the methods of data analysis and interpretation, relative to judging whether project objectives have been met, are also well developed and in place. The major


challenge to data interpretation will be to distinguish between watershed responses to BMP adoption and responses associated with variable annual weather and related stream discharge conditions.

This closely integrated program consisting of researchers, project directors, laboratory manager, laboratory and field technicians all working in close proximity with daily contacts, renders some normal components of a QAPP to be non-applicable. Thus reviewing the chain of custody documents, while possible, is unnecessary.

The approaches and procedures used in the Heidelberg tributary loading program have previously been approved by the Great Lakes National Program Office of the U.S. EPA in the early 1980s when they were providing support for this program. Copies of the QAPP submitted at that time, along with responses to issues raised in the EPA’s review of that QAPP are being submitted as pdf files accompanying this document.


5.0 (Chem) REFERENCES Army Corps of Engineers. 1979. Lake Erie Wastewater Management Study: Methodology Report. U.S. Army Corps of Engineers, Buffalo District, Buffalo, NY. Baker, David B. and R. Peter Richards. 2002. Phosphorus Budgets and Riverine Phosphorus Export in Northwestern Ohio Watersheds. Journal of Environmental Quality: 31:96-108. Baker, David B. and Monica Ostrand. 2001. The Sandusky River Watershed: Resource Inventory and Management Plan. The Sandusky River Watershed Coalition. Fremont, OH 43420 ( Web address) Baker, David B., R. Peter Richards, Timothy T. Loftus and Jack W. Kramer. 2004. A New Flashiness Index: Characteristics and Applications to Midwestern Rivers and Streams. Journal of the American Water Resources Association:40(2):503-522. Baker, David B. 1985. Regional Water Quality Impacts of intensive Row-Crop Agriculture: A Lake Erie Basin Case Study. Journal of Soil and Water Conservation 40:125-132. Loftus, Timothy T, David B. Baker, Josephene V. Setzler, and John Crumrine. 2006. Honey Creek Watershed Action Plan. The Sandusky River Watershed Coalition., Fremont, OH 43420 OEPA. 2003. Biological and Water Quality Study of the Sandusky River and Selected Tributaries, 2001. OEPA Technical Report EAS/2003-4-6. Division of Surface Water, Ecological Assessment Section, Columbus, Ohio. OEPA. 2004. Total Maximum Daily Loads for the Upper Sandusky River – Final Report. Ohio Environmental Protection Agency, Division of Surface Water, Columbus, OH. Richards, R. Peter. 1998. Estimation of pollutant loads in rivers and streams: A guidance document for NPS programs. Project report prepared under Grant X998397-01-0, U.S. Environmental Protection Agency, Region VIII, Denver. 108 pages. Richards, R. Peter, Frank G. Calhoun, and Gerald Matisoff. 2002. The Lake Erie Agricultural Systems for Environmental Quality Project: An Introduction. Journal of Environmental Quality: 31:6-16. Wick, Elizabeth. 2006. Municipal Point Source Pollution Controls in the Sandusky Watershed: History and Directions. In Proceedings, The Sandusky River Watershed Symposium, June 27-28, 2006 at Heidelberg College, Tiffin, OH 44883.


Biological Section of QAPP begins here.

1.6.1 (Bio) Project/Task Description and Schedule.

We will investigate the ability of engineered primary headwater streams and agricultural ditches to develop aquatic invertebrate and fish communities in the years following ditch maintenance. To do this, we will compare the habitats, water chemistry, and aquatic invertebrate and fish communities in agricultural ditches across a gradient of landscape conditions (topography, land-use, geology, etc.) and lengths of time since the last maintenance activities took place. We will survey habitats once each spring or summer and will survey invertebrate and fish communities in late spring or early summer and again in late summer. These surveys will be performed on the same ditches in multiple years (to observe the extent of inter-annual variation) and on several additional ditches each of the first four years of this five-year project. In the fifth year, we will apply multivariate analyses of the habitats, landscape conditions, and the compositions of the biotic communities to discern relationships between the environmental factors, time since ditch maintenance, and biotic responses. A timeline of activities is shown in Table 1.

Table 1. General schedule of activities related to habitat and aquatic biota.

Year Activities Products 1 Development of QAPP. Interim report on habitat

characterization (Qualitative Habitat Evaluation Index), qualitative and quantitative macroinvertebrate samples, and quantitative fish surveys on each ditch segment

Ditch selection in coordination with county personnel. Habitat surveys, water chemistry measurement, aquatic macroinvertebrate sampling and analysis, and fish surveys.

2 Selection of additional ditches with help of county personnel.

Same as Year One

New habitat surveys, water chemistry measurements, aquatic macroinvertebrate sampling and analysis, and fish surveys on same ditches as Year 1 and on newly selected ditches

3, 4 Potential selection of additional ditches. Same as Year One New habitat surveys, water chemistry measurements, aquatic macroinvertebrate sampling and analysis, and fish surveys on selected ditches.

5 Complete macroinvertebrate sample analyses. Final report on associations of habitat and water chemistry characteristics with invertebrate and fish community characteristics

Conduct multivariate analyses of data.

1.7 (Bio) Quality Objectives and Criteria for Measurement Data


1.7.1 Objectives and Project Decisions.

Total Maximum Daily Load (TMDL) studies have revealed the need to address impaired biological communities, especially in the headwater streams of Ohio’s agricultural watersheds. The goals of the habitat and biological monitoring component of this project are to provide information on (1) the rate and extent of stream habitat “recovery” of maintained agricultural ditches following dip-out (defined as removal of sediment and vegetation from the ditch channel by means of a back-hoe or similar machine); that is, the natural progressive change in the ditch channel and banks toward conditions similar to those of natural streams that have not been modified by ditch maintenance practices; and (2) the extent to which biological (fish and invertebrate) community integrity is associated with the changes in stream/ditch habitat over time following dip-out. “Dip-out” is defined here as the mechanical removal of sediment and vegetation from the stream or ditch channel, thereby returning the stream or ditch segment to its engineered dimensions and capacity. Of particular interest is the potential facilitation of these “natural channel recovery processes” that results from implementation of best management practices (BMPs) such as upland erosion control, buffer strips, and water management. It is to be expected that large-scale implementation of BMPs in a watershed will result in the restoration of habitat and biological communities in agricultural headwater streams.

Following disruption of the stream habitat and biological communities by ditch “clean-out” or “dip-out”, headwater streams and ditches tend to respond over time, going through a successional process toward more natural conditions. However, repeated excavations of ditches starts the successional process over in those ditches and results in continued impairment of biological communities and lower habitat use designations. It appears that a variety of BMPs implemented over the past thirty years together have reduced the transport of sediment into and through ditch and stream channels, resulting in longer intervals between excavations and, therefore, longer times for successional changes in the habitat and biological communities to take place. If sufficient development of the habitat and biological communities appears to be occurring, management efforts could continue to focus on additional upland erosion control and water management efforts, rather than carrying out major construction projects on the ditches themselves.

The work tasks for the biological monitoring component of this project include: (1) Develop a QAPP for the habitat, field chemical, and biological assessments. (2) Develop criteria for selection of stream/ditch channel segments to be monitored. We proposed

to conduct habitat and biological assessments on 15 segments during each of the first four years of the project.

(3) Conduct a habitat assessment in each selected ditch segment. (4) Conduct a fish community assessment in each selected ditch segment. (5) Conduct an aquatic macroinvertebrate community assessment in each selected ditch segment. (6) Perform multivariate analyses that will relate habitat variables (habitat quality) to the biological

communities (biological integrity) with the intent of discovering those habitat characteristics that most strongly influence biological integrity.

(7) Compare the rates of improvement in habitat quality and biological integrity following channel dip-out in morainal versus lacustrine topographies.

(8) Compile a comprehensive and integrative final report on the findings of the above efforts. 1.8 (Bio) Special Training Requirements/Certification


The lead biological investigators have extensive experience in collecting and analyzing biological samples. As lead biologist on the project, Krieger is certified by Ohio EPA as a Level 3 Qualified Data Collector (QDC) for macroinvertebrate sampling and identification (Certification No. 041) and is also certified at Level 3 to conduct assessments using Ohio’s Qualitative Habitat Evaluation Index (Certification No. 041). He will lead the field effort and will be assisted by two undergraduate technicians at every ditch segment. One of the students assisting in 2008 (Chris Boehler) is already trained in the field work and sample processing methods in the laboratory, having assisted in the previous survey in Marion County. Chris will leave the project in August 2008 as he departs for graduate school. The second student assisting in 2008 (Jakob Boehler) will be trained and closely supervised as he learns the methods, and he will assist in the summer surveys in at least 2008 and 2009. One or two additional student technicians will assist the first two technicians in processing the samples collected in the field. Although we prefer continuity of student technicians during our projects, training of one or more new technicians will be necessary from year to year. Each student will receive training in the field from the lead invertebrate biologist (Krieger) regarding proper sampling of the ditches/streams. Each student will also be closely supervised by Krieger or by experienced lab technician Tamara Keller as the new student learns to follow the detailed written protocol for sample processing shown in Appendix D.

The lead biologist for the fish surveys will be Dr. Hans Gottgens of the University of Toledo, who

is subcontracted for this work. He will direct the field work at each ditch segment and will be accompanied by a graduate assistant (T. Crail) and two undergraduate technicians. Both Gottgens and Crail have considerable experience in conducting fish surveys in agricultural ditches in Ohio and possess the necessary taxonomic skills for accurate identification of fishes.

1.9 (Bio) Documents and Records

1.9.1 QA Project Plan Distribution.

A copy of this QAPP will be placed in the biological laboratory for ready reference by all lab technicians.

1.9.2 Field Documentation and Records.

QHEI forms and scores will be submitted to Ohio EPA for their information. The original QHEI and physical-chemical data forms filled out in the field will be kept in Krieger’s files at the NCWQR. Field notes for biological specimens as well as laboratory forms will also be maintained on file at the NCWQR. All data will be computerized within a few months following field collection or laboratory analysis, as applicable. To the extent feasible, all data on habitat, physical-chemical parameters, invertebrates, and fishes will be entered into STORET. We will designate and train a laboratory technician (perhaps Tamara Keller) to upload and proofread the STORET data. The data will include the physical-chemical parameters (pH, conductivity, turbidity, temperature, dissolved oxygen) and biological information (kind and number of each taxon) for each kind of sample (Ekman grab or qualitative).

1.9.3 Laboratory Documentation and Records


1.9.3.1 Invertebrate bench sheets –We have developed several laboratory bench sheets for recording data from invertebrate samples

like the ones to be collected for this project. We have adapted the bench sheet that was used in a recent study of invertebrates in agricultural ditches in the Olentangy River watershed (Krieger and Stearns 2008). The technician recording information on the bench sheets will be required to double-check that all specimens in the sample have been recorded.

1.9.3.2 Computer input of dataData will be manually input from the bench sheets into an Excel spreadsheet similar in format to

the form included by OEPA in its reports on biological and water quality in Ohio streams.

1.9.3.3 Proofreading data –The laboratory technician will calculate by hand the total number of individuals of each taxon in

those cases where subsampling was done prior to data entry. Once the data are input to the computer, the data on the form for that sample will be visually proofread by one technician reading the number of each taxon to a second technician who will be confirming the number on the bench sheet. Corrections will be made on the spreadsheet the same day.

1.9.4 Quarterly and/or Final Reports

1.9.4.1 Interim Performance and Financial Reports.Performance and financial reports will be submitted according to the procedures and schedule to be

received from the project director.

1.9.4.2 Narrative report.A detailed written report of the project results and interpretation of the biological communities and

quality of the aquatic habitats of agricultural ditches examined in this project will be submitted to the project director. In the report we will attempt to relate our findings to those of OEPA and other organizations who have conducted previous studies on streams and agricultural ditches within the region.

2.0 (Bio) DATA GENERATION AND ACQUISITION

2.1 (Bio) Sampling Design (Experimental Design) 2.1.1 Selection of Ditch Segments.

Because the primary objective of the habitat and biological monitoring component of this project is to measure the rate of development of the water conveyances toward a natural state, one primary criterion for selection was years since the last excavation (dip-out). Secondarily, topography may play a strong role in determining drainage rates and may also affect the rates of change in ditch habitat conditions. The topographic character of the project area consists of two distinct types: a very flat topography found in Lake Plain and former wetland areas, and a rolling topography associated with glacial moraine accompanied by naturally better drainage. Thirdly, the size of the watershed drainage area may impact hydrology within the ditches and influence habitat development. Thus, we will select


ditches on the basis of (1) years since dip-out, (2) glacial moraine or lacustrine (lake-plain) topography, and (3) watershed drainage area at the ditch segment. In order to reduce the number of environmental variables, we will avoid ditches with canopy (tree/shrub) cover and those whose watersheds have substantial suburban/urban influence.

During the winter and spring of 2008, we worked closely with county ditch maintenance personnel

in the Sandusky and Seneca county Soil and Water Conservation Districts to select ditch segments for assessment. Only streams/ditches under county maintenance are included because of the need to have a detailed history of the ditch maintenance, which is often not available for privately maintained ditches. Fifteen ditch segments were selected for assessment in 2008. Their locations are shown in Figure 2-1.

The county SWCD staffs also will help us obtain landowner permission to access each property.

Early in 2008, we developed a fact sheet about the project and distributed it to landowners adjacent to the selected ditch segments (Appendix A). In our proposal, we planned to select and survey 15 streams in each of Years 1 through 4 of the project and to repeat our surveys on a subset of ditch segments two years in succession in order to estimate the extent of inter-annual variation in community composition and habitat metrics. However, it proved difficult to locate a sufficient number of candidate ditch segments beyond the number needed in Year 1, and it appears unlikely that a substantial number of additional ditch segments could be found in the later years of the project to add 15 new ones each year. Furthermore, we are cognizant of the very large variation in stream-flow in agricultural ditches from one year to the next as a result of climatic variations. We believe the dataset would be considerably improved by sampling the same segments at least two consecutive years to obtain a clear picture of the amount of inter-annual variation in habitat features and biological diversity and abundance. We plan to add several additional segments during each of the four years.

2.1.2 Habitat Assessments.

The lead biologist (Krieger) will perform a Qualitative Habitat Evaluation Index (QHEI)

assessment at each ditch segment prior to conducting biological assessments. The QHEI will be conducted on the same 100-meter ditch segment that will be used for the habitat and biological assessments (see 2.1.4). As a certified Level 3 (highest level) Qualified Data Collector (QDC) for the QHEI, Krieger will perform all QHEI assessments with the assistance of the student technicians. The QHEI form is reproduced in Appendix B. We will record additional characteristics on-site. These will include the extent of development of a “bench” or sill within the channel, thickness of sediment bed in channel, bank-full width, and thalweg depth (deepest point in the channel cross-section) below bank-full width. Our field data sheet for recording most of this information is shown in Appendix C. The fish biologists will measure bench development and sediment thickness, and the invertebrate biologists will measure the other characteristics. The lead biologist (Krieger) will also document each site with a set of digital photographs.


Figure 2-1. Locations of the fifteen ditch segments selected for assessment in 2008.

2.1.3 Field Physical-chemical Measurements.

Prior to entering the water upon each visit to a given channel segment when collecting invertebrates or seining for fish, we will measure the parameters listed in Table 1. We will calibrate each instrument according to the manufacturer’s instructions immediately prior to departing for the field each day. In addition, we will carry necessary calibration standards and supplies into the field in the event recalibration becomes necessary (e.g., because of need to replace membrane on oxygen probe).

2.1.4 Macroinvertebrate Assessments. To account for seasonal variations resulting from life cycles and for anticipated substantial

differences in stream flow in the channels between early summer and fall, we will sample macroinvertebrates two times each year in each channel segment, once in May or June and again in August or September. This will be accomplished on each segment during each of years 1 through 4 of


this project (2008-2011). We will select ditches larger than one square mile, which should ensure that they continue to flow during dry weather. However, even large streams can cease flowing during

Table 2-1. Physical-chemical measurements and methods. Parameter Unit Instrument Calibration Method Air temperature °C YSI Model 58 dissolved oxygen meter Factory Water temperature °C YSI Model 58 dissolved oxygen meter Factory Dissolved Oxygen mg/L YSI Model 58 dissolved oxygen meter Saturated air Dissolved Oxygen YSI Model 58 dissolved oxygen meter Saturated air %

saturation Hydrogen ions pH Cole-Parmer Digi-Sense field pH meter pH 7 & 10 buffers

�S/cm 447 �S/cm standard soln. Specific conductance

Oakton Con 100 Series field conductivity meter

Turbidity NTU Hach 2100 P field turbidity meter Set of turbidity standards severe droughts. Therefore, if there is no water above the channel bottom (i.e., no flow in the thalweg and no pools), we will collect any remaining aquatic invertebrates that may have survived in vegetation or below the surface of sediments. This will permit us to characterize the survival abilities of aquatic invertebrates in the segment during periods of no standing water.

Each stream segment will be marked with flags at 0 meters (upstream end), 50 meters, and 100 meters (downstream end), and the coordinates of each point will be recorded from a hand-held GPS receiver. The segment thus will be divided into an upstream 50-meter reach and a downstream 50-meter reach. We will collect one qualitative invertebrate sample from all aquatic habitats in each 50-meter reach to provide two replicate samples for each ditch segment, thereby providing evidence of the extent of homogeneity of the invertebrate community in the overall segment. In addition, the lead biologist (Krieger) or a trained student technician will collect three quantitative samples of bottom sediment with an Ekman grab sampler (early summer only) in the upstream reach at approximately the 50 m, 25 m, and 0 m points. We will not collect Ekman samples in the downstream 50-meter reach because the bottom sediments in that reach will be substantially disturbed by the fish survey crew a few days prior to our invertebrate survey. Thus, for each ditch segment we will collect two replicate qualitative samples both in early summer and in late summer or fall and three replicate quantitative samples in early summer, for a total of 7 samples per ditch segment each year.

2.2 (Bio) Sampling Methods

2.2.1 Qualitative Habitat Evaluation Index.

We will follow the methods and scoring criteria for the QHEI that are spelled out in detail in the QHEI manual (OEPA 2006). The method can be applied to a variety of segment lengths, and we (Krieger plus assistant) will perform the QHEI on 100-meter lengths of ditch in order that they will be the same as the 100-meter ditch segments that we include in our macroinvertebrate surveys (see below). We will conduct the QHEI assessment on each ditch (e.g., see Figure 2-1 for those selected for 2008) a few days prior to the fish and invertebrate surveys.


The method is summarized as follows. Only one individual is required to assess the stream or ditch segment, although an assistant will save time. The upstream and downstream limits of the stream segment are flagged and the GPS coordinates are recorded. The QHEI evaluator begins at the downstream limit and sketches a map on the back side of the QHEI form as he/she zigzags up the stream channel to the upper limit of the segment. Habitat attributes are marked on the sketch such as water depth, type and extent of bottom substrates, channel and streambank vegetation, discharges from pipes, root wads, width of riparian corridor, surrounding land use, and so on. The many characteristics that are recorded are shown on the completed QHEI form that is included in Appendix B. Two characteristics that are measured from topographic maps are drainage area at the stream/ditch segment and stream gradient. Separate scores are tallied for these categories: (1) Substrate, (2) In-stream Cover, (3) Channel Morphology, (4) Bank Erosion and Riparian Zone, (5) Pool/Glide and Riffle/Run Quality, and (6) Gradient/Drainage Area. These six scores are summed for a total QHEI score (maximum of 100 points).

2.2.2 Macroinvertebrate Assessments. As noted in Section 2.1.4, two types of macroinvertebrate samples will be collected in each ditch

segment. One sample per 50-meter reach (two replicate 50-meter samples per ditch segment) will be a qualitative sample, in which we will collect as many different taxa (kinds) of aquatic macroinvertebrates from as many microhabitats within the channel segment as we can. These two samples will permit us to compare the taxonomic richness and overlap of taxa within individual channel segments as well as among channel segments. For these samples, invertebrates will be hand-picked, grabbed with forceps, and collected with dip-nets from every kind of submerged surface and within beds of aquatic vegetation. Two technicians, one on each side of the ditch, will conduct the qualitative sampling. They will move from downstream to upstream to maintain the water clarity where they are collecting. Sampling of invertebrates will be careful and deliberate so as to collect representatives of as many different kinds of invertebrates as possible. When a dip-net is used, materials in the net will be emptied into a shallow white plastic pan with water to aid in seeing the invertebrates. Specimens collected by each technician will be placed in a 500-mL wide-mouth HDPE jar containing >60% ethanol. At the conclusion of sampling the 50-meter reach, all specimens will be combined in a single wide-mouth jar. A label containing the following information will be placed inside the jar and another with the same information will be affixed to the outside: project name, county, ditch name, segment and reach designation, type of sample (qualitative), and date of collection.

The three Ekman samples taken from the upstream reach will be quantitative and will provide an

estimate of the number per unit area of each kind of macroinvertebrate in the bottom sediments. The Ekman samples will be collected by the lead biologist while the qualitative samples are being collected. Each sample will be acquired with a small (6” x 6”) Ekman grab. At three locations within each 50-meter reach (downstream, middle, upstream), the Ekman will be pushed approximately 3 centimeters into the sediment (shallower if an underlying hard substrate is encountered) to obtain all the invertebrates within the 0.023 square meter area. While in the field, the fine sediments will be rinsed from the sample through a screen with 0.50 mm mesh openings (No. 35 mesh). Each Ekman sample will be maintained as a separate sample. The sample residues will be placed in a one-gallon Zip-Loc bag and will be preserved in >60% ethanol. Labels containing the same information as the qualitative samples (except indicating Ekman #1, 2 or 3) will be placed both inside and affixed to the outside of the bag.


Following sample collection, the quantitative (Ekman) samples will be processed in the laboratory

by removing the invertebrates from the sample debris under low magnification using a dissecting microscope. Specimens will be sorted into separate vials containing AGW (85% ethanol, 5% glycerin, 10% water) to separate the major taxonomic groups (e.g., oligochaetes, midges, snails, clams, miscellaneous). Specimens will be identified to the lowest practical taxonomic level, which will be to genus for most insects and molluscs. Chironomid midges will only be identified to family unless sufficient funding is available to identify them to genus, and oligochaete worms will also only be identified to family. We maintain a detailed written protocol for all sample processing procedures in our laboratory that we require all technicians to follow. In addition, we have developed standard bench sheets that are used for recording when and how samples are processed as well as how many of each kind of invertebrate are identified.

2.2.3 Fish Assessments.

To obtain a measure of seasonal variation in the composition of the fish community and to account

for the possibility that some channels may not have surface water during droughts, we will quantify the fish community two times between May and September in each channel segment (e.g., see Figure 2-1 for 2008), once in May or June and again in August or September. We will employ the same methods used in recently completed projects of a similar nature (Arceo 2005, Crail 2007).

The fish community will be assessed at each site using two 3.7 meter seines with 6-millimeter mesh

openings. The first seine will be placed stationary as a blockade at the downstream end of the 100-meter channel segment. A second seine will be moved from 10 meters upstream toward the stationary seine with a 90-degree pivot turn with the downstream brail through the stationary seine to the stream bank. The stationary seine will then be turned on a 90-degree pivot rotation back through the sample stretch to capture any fish missed by the sweep seine. All fish will be identified to species in the field in accordance with identification characteristics in Fishes of Ohio (Trautman 1981), aged into common size-age classes (adult, sub-adult, juvenile), assessed for spawning condition and parasites, and released downstream of a newly placed blockade upstream in the same sample site. The procedure will be replicated in an upstream portion of the channel segment to promote accurate sampling of the entire segment.

2.2.4 Data Analysis.

We will investigate the relationship of characteristics of the macroinvertebrate and fish communities to features of the habitat and water chemistry. To do this, the lead biologists (Krieger and Gottgens) and perhaps one or more graduate students under their direct supervision will apply multivariate statistical techniques that may include principal components analysis, cluster analysis, and/or correspondence analysis. We will also compare the fish and invertebrate communities among the channel segments (and between years for channel segments sampled more than one year) using repeated-measures ANOVA and a variety of similarity and diversity indices.

2.3 (Bio) Sample Handling and Custody

2.3.1 Macroinvertebrates.


During the collection process, the invertebrates collected for each qualitative sample will be placed

in a wide-mouth 500-mL HDPE jar; Ekman samples will be placed in a 1-gallon Zip-Loc bag. Each jar/bag will be labeled with the following information: project name, county, ditch name, segment and reach designation, type of sample (qualitative/Ekman), and date of collection. Another label containing the same information will be placed inside the container. If more than one jar or bag is needed for a sample, each one will additionally be labeled “1 of 2”, 2 of 2”, etc. All invertebrate specimens collected for this study will be preserved in the field and returned to the NCWQR on the day of collection. Because the personnel collecting the samples will be NCWQR staff members who will also process the samples in the laboratory, no transfer of custody will be required. All samples will be processed and archived in the NCWQR. We will record all samples brought to the laboratory in a computerized sample log that will contain information identical to that on the jars/bags except that it will show the total number of containers for each sample rather than listing each container separately.

2.3.2 Fish.

Most fish specimens will be released unharmed back to the ditch within minutes after capture. Rare specimens that cannot be readily identified because of hybridization or other characteristics will be carefully photographed (dorsal, lateral, ventral and close-up view of the head) for later identification and, subsequently, released. Digital images will be labeled, printed and stored in the wetlands laboratory of the Department of Environmental Sciences, University of Toledo. No vouchers will be collected.

2.4 (Bio) Analytical Methods

2.4.1 Field Measurements Methods. Refer to Section 2.1.

2.4.2 Field Analyses Methods. Refer to Section 2.1. 2.4.3 Laboratory Analyses Methods (Off-Site). Not applicable.

2.5 (Bio) Quality Control Requirements

2.5.1 Field Sampling Quality Control.

The lead biologists (Krieger and Gottgens) will be on site during all field sampling and will ensure that the appropriate field sampling protocols are followed.

2.5.2 Field Measurement/Analysis Quality Control.

As noted in Section 2.1.3, all field instruments will be calibrated prior to use in the field, and the lead biologists (Krieger and Gottgens) will be on site during all field measurements to ensure that the appropriate methods are employed.

2.5.3 Laboratory Analysis Quality Control


2.5.3.1 Picking and Sorting of Invertebrates.

We will follow the quality control checks on thoroughness of picking that are prescribed by Section 7.3.1 of Barbour et al. (1999). These checks include: (1) Ten percent of the sorted samples will be examined by a co-worker to look for any organisms that might have been missed by the sorter. If more than 10% more organisms are found than are already sorted from a given sample, the sample will be picked again. If the first 10% of the samples checked fail the QC check, another 10% will be checked. If necessary, additional 10% proportions of the sample set will be checked. Additional attention will be given to the sorting efficiency of new workers at the beginning of their training in order to avoid unacceptable picking efficiency. (2) Upon completion of picking and sorting a sample, all labware that came in contact with the sample will be examined for missed organisms and will be rinsed thoroughly prior to beginning work on the next sample. Any missed organisms will be added to the appropriate sample vial for their group.

Any specimen that is not sorted correctly, that is, it is placed in the wrong vial during picking, will

be found during the identification process and subsequently will be placed in the correct vial for its taxonomic group. If that group has already been processed, the specimen will be placed in a completely labeled new vial containing AGW (aqueous 85% ethanol, 5% glycerin solution, v:v) and will be provided to the appropriate technician for identification and addition to the bench sheet for that sample.

2.5.3.2 Taxonomic Identifications of Invertebrates.

Taxonomic identifications by student technicians will be confirmed by the lead biologist (Krieger) by means of his examination of voucher (reference) specimens that will be maintained separately from other specimens in the samples. One or more voucher specimens will be set aside for every taxon encountered. The voucher vials will contain a paper label with the same information as the sample vials plus the name of the taxon. A computer spreadsheet containing all of the voucher information will be maintained on a daily basis. If the technician who is identifying a particular taxonomic group is replaced by another technician, new voucher specimens will be set aside by the new technician for confirmation. Damaged or immature specimens in any samples that cannot be identified at the prescribed taxonomic level will be assigned within their taxonomic groups according to standard OEPA procedures (Jeff DeShon, OEPA, personal communication, 2005). We will confer with OEPA or other invertebrate specialists to determine or confirm the identification of troublesome specimens.

2.5.3.3 Taxonomic References.

We will identify the invertebrates using the references designated in the most recently updated version of OEPA’s reference list (Table V-1 of OEPA 1989), which we will obtain from OEPA. We will supplement those references as needed if additional references are available for specific taxonomic groups. All fish will be identified to species in the field in accordance with identification characteristics in Fishes of Ohio (Trautman 1981).

2.6 (Bio) Instrument/Equipment Testing, Inspection, and Maintenance


2.6.1 Field Measurement Instruments/Equipment.

All field equipment will be examined prior to departing for field sites each day to ensure functionality. Any malfunction of water testing instruments will be detected during the calibration process.

2.6.2 Field Instruments/Equipment (Screening and Definitive).

Not applicable. 2.6.3 Laboratory Analysis Instruments/Equipment (Off-Site).

Laboratory analytical equipment consists of dissecting and compound microscopes. These not require testing, inspection, or maintenance other than occasional replacement of illuminator bulbs. Proper care includes ensuring that illuminators are turned off and dust covers are replaced at the end of each period of use.

2.7 (Bio) Instrument/Equipment Calibration and Frequency

2.7.1 Field Measurement Instruments/Equipment

2.7.1.1 Sampling gear.We will use dip nets with 500 �m mesh openings. Prior to sampling each site, we will inspect each

net for tears and repair or replace it as necessary. We also will inspect each net prior to sampling each site to be sure no invertebrates from previously sampled sites are attached to it; if so, they will be removed and discarded.

2.7.1.2 Dissolved oxygen.We will record both mg/L and percent saturation of dissolved oxygen (DO) using a YSI Model 58

or YSI Model XX dissolved oxygen meter. The meter and oxygen probe will be at equilibrium with ambient air temperature at the time of calibration. The meter will be calibrated in water-saturated air out of direct sunlight within two hours prior to use, and it will be maintained between uses according to the instrument instructions. The probe will be examined carefully immediately prior to each use to ensure that the membrane is intact and does not have an air bubble beneath it. If necessary, the membrane and electrolyte will be replaced in the field and the instrument will be recalibrated and allowed to equilibrate before use.

2.7.1.3 Temperature.We will record air temperature and water temperature with the thermistor of the DO meter,

ensuring that the thermistor is shaded (out of direct sunlight). The thermistor is factory calibrated and cannot be adjusted by the user; however, in the laboratory we will compare a range of temperature readings with readings from a certified thermometer. We will correct field readings if the comparison shows differences greater than +/- 0.2 degrees Celsius.


2.7.1.4 pH.A Cole-Parmer Digi-Sense Model 5938-00 field pH/mV/ORP meter will be calibrated in the

laboratory daily prior to field sampling using pH 7.00 and pH 10.00 buffers. The pH electrode will be rinsed with reverse-osmosis or deionized water prior to and after use of each buffer. The calibration has been found to be stable for periods longer than a day; therefore, the meter should not need recalibration in the field. However, the buffers and water will be taken into the field for recalibration use if necessary.

2.7.1.5 Conductivity.Prior to each visit to the sites, an Oakton CON 100 Series field conductivity meter will be

calibrated in the laboratory using a standard conductivity solution with a concentration of 447 �S/cm at 25°C. The calibration has been found to be stable for periods longer than a day; therefore, the meter should not need recalibration in the field. However, standard calibration solution will be taken into the field for recalibration if necessary.

2.7.1.6 Turbidity.The Hach Model 2100P Portable Turbidimeter will be calibrated prior to the first sampling event in

the spring and again prior to late summer sampling using 20, 100 and 800 NTU turbidity standards as per the manufacturer’s instructions. Immediately prior to use in the field, the meter will be checked for accuracy using a blank and a 100 NTU standard. The calibration has been found to be stable for periods longer than a year; therefore, the meter should not need recalibration in the field. However, additional standards will be taken into the field should recalibration be necessary.

2.7.2 Field Instruments/Equipment (Screening and Definitive).

Not applicable.

2.7.3 Laboratory Analysis Instruments/Equipment (Off-Site).

Not applicable.

2.8 (Bio) Inspection/Acceptance Requirements for Supplies and Consumables

2.8.1 (Bio) Field Sampling Supplies and Consumables.

These items include HDPE wide-mouth jars with lids, plastic (e.g., Zip-Loc) storage bags, and 95%

or 100% ethanol for storage and preservation of invertebrate samples. Ten percent formalin will be required for preservation of any fish retained for identification in the laboratory. All of these items will be ordered from reputable laboratory supply companies and thus their quality will not need to be ascertained. We will inspect all shipments for damage immediately upon their arrival.

2.8.2 (Bio) Field Measurement/Analyses (Screening and Definitive) Supplies and Consumables.

Not applicable.


2.8.3 (Bio) Laboratory Analyses (Off-Site) Supplies and Consumables.

Invertebrate analyses in the laboratory will require ethanol from the same containers as used for field collections. See Section 2.8.1. Glass vials for specimens will be ordered from a reputable laboratory supply company and will be inspected for damage upon arrival.

2.9 (Bio) Data Acquisition Requirements (Non-Direct Measurements)

Among the environmental factors that may influence the biological communities in the ditches are the watershed area and stream gradient. We will measure watershed area by outlining it on a 7.5’ topographic map, cutting it out, and comparing the cut weight against the weight of a piece representing a known area. We will measure stream gradient by comparing stream length between contour lines on the map by the elevational difference between the contour lines.

2.10 (BIO) Data Management

Field data will be recorded on the QHEI (habitat) form shown in Appendix B and on the form included in Appendix C. The forms will be filed in the lead investigator’s office until the appropriate time to input data from the forms into a computer. The invertebrate data sheets for all samples will be maintained in a three-ring binder in the biological laboratory in alphabetical order by sample type and sample location. All data for the habitat and invertebrates will be entered into Microsoft Excel spreadsheets on a personal computer (presently an IBM ThinkCentre) located in the same laboratory in which the samples will be analyzed. The user directory will be located on a server that is backed up daily, so the only data that could be lost after data entry would be data entered in the past 24 hours, and those data could be readily input again. All data will be proofread by two people against the field sheets or lab bench sheets following data entry in order to correct any input errors. Data will be analyzed by several multivariate statistical techniques using SigmaPlot 11 software. The lead invertebrate biologist (Krieger) will be responsible for managing all data input, verification, and analysis.

3.0 (BIO) ASSESSMENT AND OVERSIGHT

3.1 (BIO Assessments/Oversight and Response Actions The lead biologists (Krieger and Gottgens) will oversee all activities involving the invertebrate and

fish sampling, analysis and reporting. Both will be in direct contact with project personnel on a daily basis to ensure that the project activities are being conducted as planned. No special assessments beyond the QA/QC procedures detailed in other sections of this QAPP will be performed. If we find that proper procedures are not being or have not been performed correctly, we will initiate corrective action. Such corrective action should not be necessary because of our careful training and regular oversight of the analytical staff.


3.2 (Bio) Reports to Management Reports will be provided to the project manager (D. Baker) as requested and as scheduled.

4.0 (Bio) DATA REVIEW AND USABILITY

4.1 (Bio) Data Review, Verification, and Validation Requirements

It will be necessary to review all field data sheets upon return to the office to be sure that all data have been recorded. Likewise, a protocol will be followed (see below) to ensure the completeness and accuracy of data produced in the laboratory following invertebrate sample collection.

4.2 Verification and Validation Methods The forms completed in the field for habitat and water chemistry (see appendices B and C) will be

reviewed for accuracy and completeness upon return to the office. Missing data will be recorded at that time, or if necessary the information will be obtained by making a return trip to the site. The same procedure will be followed for the fish data, all of which will be collected in the field except for occasional laboratory identifications of hybrid specimens.

The invertebrate data will initially be recorded on laboratory bench sheets by the technicians

identifying and counting the specimens in each sample. Invertebrate identifications will be verified by the lead invertebrate biologist (Krieger); to do this, he will confirm the identifications of voucher specimens, which consist of the first specimen(s) of each taxon encountered in the samples. Should it be necessary to replace a technician working on a particular group of invertebrates (such as, if the technician identifying mayflies stops working for the laboratory), the new technician will be required to generate a new set of voucher specimens for that group to ascertain his/her ability to identify specimens correctly. Data entry from each bench sheet into the computer will be accomplished by a technician who is different from the one who produced the data, and that person will look for inconsistencies in the data that might need correction or corroboration. As a final validation step, the lead biologists will randomly check computerized data files against field sheets (fish) and bench sheets (invertebrates). No special forms or checklists will be used in that process.

4.3 Reconciliation with User Requirements The sample results, which will have been reviewed, verified, and validated, will be reconciled with

the project objectives presented in Section 1.7. This will be accomplished both by descriptive and statistical means as described in sections 2.1 and 2.2.

5.0 (Bio) REFERENCES Arceo, A. I. 2005. The impact of a small dam on fish community composition and structure in the

Ottawa River, Ohio. Graduate thesis, Department of Environmental Sciences, The University of


Toledo, Ohio. Barbour, M. T., J. Gerritsen, B. D. Snyder, and J. B. Stribling. 1999. Rapid bioassessment protocols

for use in streams and wadeable rivers: periphyton, benthic macroinvertebrates and fish. Second edition. EPA 841-B-99-002. U.S. Environmental Protection Agency, Office of Water. Washington, DC.

Crail, T. D. 2007. Testing the impact of plant colonization on fish communities in agricultural ditches

of the Ottawa River, Northwest Ohio. Graduate thesis, Department of Environmental Sciences, The University of Toledo, Ohio.

Krieger, K. A., and A. M. Stearns. 2008. A baseline study of macroinvertebrate communities of

McKibben Ditch and Riffle Creek (Olentangy River Watershed) prior to over-wide ditch construction. Final report. Ohio Department of Natural Resources, Division of Soil and Water Conservation, Findlay, Ohio.

Ohio EPA. 1987. Biological criteria for the protection of aquatic life: Vol. II: Users manual for

biological field assessment of Ohio surface waters. (Updated Jan. 1, 1988). Division of Water Quality Monitoring and Assessment, Surface Water Section, Columbus, Ohio.

Ohio EPA. 1989. Biological criteria for the protection of aquatic life: Vol. III: Standardized

biological field sampling and laboratory methods for assessing fish and macroinvertebrate communities. (Updated Sept. 30, 1989). Division of Water Quality Monitoring and Assessment, Surface Water Section, Columbus, Ohio.

Ohio EPA. 2006. Methods for assessing habitat in flowing waters: using the Qualitative Habitat

Evaluation Index (QHEI). Ohio EPA Technical Bulletin EAS/2006-06-1. Ohio Environmental Protection Agency, Groveport, Ohio.

Trautman, M. B. 1981. The fishes of Ohio. Ohio State University Press. Columbus, Ohio.


Appendix A.

Appendices for Biological Section of QAPP

Appendix A.1. Fact Sheet on Ditch Monitoring Component of this Project xx

Appendix A.2. QHEI (Qualitative Habitat Evaluation Index) form xx

Appendix A.3. Field Data Sheet for Physical-Chemical and Miscellaneous Habitat Parameters xx

Appendix A.4.Protocol for Picking and Sorting Benthic Invertebrate Samples Collected for the Targeted Watershed Project...........................................................................................................xx


Appendix A.1. Fact Sheet on Ditch Monitoring Component of this Project


Appendix A.2. QHEI (Qualitative Habitat Evaluation Index) form

Front of QHEI form


Back of QHEI form


Appendix A.3. Field Data Sheet for Physical-Chemical and Miscellaneous Habitat

Parameters


Appendix A.4.

Protocol for Picking and Sorting Benthic Invertebrate Samples Collected for the Targeted Watershed Project


Water Quality Laboratory, Heidelberg College

Protocol for Picking and Sorting Benthic Invertebrate Samples Collected for the Targeted Watershed Project

July 2008

This standard operating procedure (SOP) establishes uniform, consistent methods for this project to be used by all technicians without exception unless changes are approved in advance by the project director (Dr. Krieger). It is necessary that everyone who performs the same steps in a study perform them in exactly the same manner to ensure that differences observed in the resulting sample data reflect real differences in the samples and not simply differences in the way the samples were handled.

Preparations

Each technician will make sure these materials are on hand before starting to process each sample: Sheets of white paper (a recycled sheet, or paper towel, as a working surface on the lab table) Archival (alcohol-resistant) pen Scissors Gridded petri dish (grids 1.2 cm X 1.2 cm) with lid Vials with screw caps, 1-dram, 2-dram, or 4-dram as required (or jar with lid from assorted larger vials and jars for larger samples as needed) Wood block for holding vials – labeled as needed Fine-pointed forceps Fine-diameter dissecting needle Glass or clear plastic pipet with small opening Squeeze bottle containing AGW (aqueous 85% ethanol, 5% glycerin solution, v:v) Sieve with mesh opening size of 0.425 mm (No. 40). White plastic tub Various petri dishes, finger bowls, beakers White enamel pan marked in quarters for subsampling Straight-edge (ruler) to aid subsample separation in pan Plastic jars to contain subsamples 1. Prepare your work station as follows.

a. Remove the cover from the dissecting scope. (Replace it when finished.) b. Place a sheet of clean white scrap paper beside the dissecting scope. c. Place several sample vials in the holes in the wood block. d. Fill each vial 1/2 to 2/3 full with AGW using the squeeze bottle.

2. Locate the sample processing bench sheet. Retrieve a sample that has not been processed. Enter your

initials beside that sample and enter the “started picking” date on the list. (Note: We maintained a bench sheet on the computer for this information in our previous project; not this one.)


3. Prepare a set of labels for the sample – either by using strips of white paper and an archival ink pen, or by printing a standard set of labels (available in the lab’s computer files) - with the correct date (date sample was collected), sample number, proportion to be sorted and other pertinent information. (Note: Examine the sample bag or jar in order to determine the sample date.)

Rinsing the Ekman (Quantitative) Sample 4. Take the sample bag to the sink inside the fume hood, and turn on the light inside the fume hood.

Raise the sash to a height which will allow for adequate access to the sink and sprayer – this will turn the fume hood exhaust on automatically.

IF ENTIRE SAMPLE WILL BE PICKED AND SORTED:

5. Open the bag. Pour a portion or the entire sample into the No. 40 sieve. Save the sample label that was inside the bag. After putting the final portion of sample into the sieve, use the sink spray attachment to rinse remnants from the bag into the sieve. Discard the empty bag.

6. Remove larger pieces of grass, leaves, twigs etc. for closer examination, placing them in a beaker or finger bowl and covering them with water. Set the spray attachment on a gentle flow and spray the sample gently in order to wash smaller particles through the mesh.

7. Using the spray attachment, wash the residue in the #40 sieve. Continue washing sample to

concentrate the residue within a small area of the sieve mesh. Rinse the material from the sieve, spraying water from the underside of the sieve with the spray attachment or a spray bottle while accumulating as little water as possible, into a finger bowl or petri dish (containing a complete label) and set the container aside.

IF ONLY A SUB-SAMPLE WILL BE PICKED AND SORTED:

8. Pre-picking – Do this only if the Ekman sample is to be sub-sampled – not necessary if you will be picking the entire sample. Be sure to record on the sorting bench sheet that there is a pre-picked set of vials as well as the sub-sample set of vials.

9. Place entire rinsed sample into the white enamel pan that has been marked off in quarters. By eye,

carefully scan the entire pan for rare specimens (such as Hexagenia nymphs or large snails). Remove large or rare specimens and sort those pre-picked specimens into separate vials containing ethanol and complete labels showing a Proportion of 1 (or 1:1). Move debris and sediment around in the pan in order to find all the large or rare specimens.

10. Sub-Sampling –Do this after the Pre-Picking is completed. We have decided to do all subsampling in a white pan that has been carefully subdivided into fourths. (In the previous study, we used a plankton splitter.) Be sure that all substrate types & sizes are equally distributed throughout the pan prior to subsampling.

11. Use a random number table to select two fourths or one fourth, depending on whether you have

decided you should pick one-half or only one-fourth of the sample. (You can also subdivide one-fourth


of a sample further into eighths or sixteenths.) Remember to drain the water from the unpicked portions of the sample and replace it with ethanol prior to storage. Put a complete sample label in each jar and be sure to show the sample proportion.

12. Do not re-combine a left-over smaller proportion with a larger proportion. For example, if one-fourth

of a sample has been selected for picking and sorting, preserve the remaining unpicked one-fourth in a separate container from the remaining unpicked one-half. Use the preserved one-fourth sample if you need to pick another one-fourth of the sample to reach the minimum of 200 organisms picked.

13. If need be in order to get rid of turbidity, place the #40 sieve into the white plastic tub, and pour

contents of the final subsample (to be picked) into the sieve. Rinse the subsample gently to eliminate the cloudy water.

14. Decant the water from white plastic tub into the sink and discard the sediment in the trash.

Rinsing the Hand-Picked (Qualitative) Sample 15. Gently pour the contents of the qualitative sample jar into the No. 40 sieve in the sink in the fume

hood; rinse any remaining residue from the container into the sieve with the spray attachment. 16. Sieve fine sediment from the sample by dipping the bottom of the sieve in water in the white plastic

pan. Avoid using the spray attachment if it is not necessary, in order to avoid damage to fragile specimens.

17. Place all of the rinsed material into a finger bowl for observation under a dissecting scope.

Sorting the Sample 18. Next, the material in each beaker (or finger bowl) will be picked and sorted. It is important to note the

following: Both the Ekman (quantitative) and the hand-picked (qualitative) samples should be separated by types of organisms present (oligochaetes, midges, etc.) into as many vials as needed.

19. Place a label (prepared in step 3) in each of several sample vials and in the beaker or bowl of sieved

material. If needed, add vials with appropriate labels as new invertebrates are picked. (Note: If the sample appears to contain a very large number of organisms, subsample as in steps 10 - 14. Otherwise, continue with step 20.)

20. Use a spoon, spatula, or pipet to put an amount of sample approximately equivalent to a tablespoonful

in the gridded petri dish. Spread the material (invertebrates, shells, sand, etc.) fairly evenly across the bottom of the petri dish with the dissecting needle or pipet. The maximum amount of material in the dish should look similar to the drawing below (Figure 1). That is, you should see lots of clear patches on the bottom of the dish with no material obscuring them.

21. Begin at the end of a row at one edge of the grid (your choice). Refer to Figure 2. View the

first grid under the dissecting microscope using the lowest magnification (approximately 6X). (Different scopes vary with regard to the lowest magnification. The goal is to be sure that one row of


the grid nearly fills the entire field of view, i.e., that all corners of one grid nearly touch the edges of the field of view.)

22. Using a small-diameter dissecting needle, gently move material aside within the field of view

sufficiently to be able to discern whether animals are present in the grid. If an animal is present, identify the general group to which it belongs (see below). After some brief experience, the type of invertebrate will be easily recognizable to you.

23. Remove the animal from the gridded dish and place it into the appropriate vial for its group. 24. Animals may be removed from the dish with any of three methods. Your choice of method will

depend on the particular animal. Whenever practical, use a dissecting needle that has a sharp bend about halfway down its length, position the needle beneath the animal, and lift it out with the needle. Dip the needle with the animal adhering to it into the AGW in the sample vial. With some practice, most animals can be moved to the vial in this manner.

start

Figure 1 Figure 2

25. If the animal cannot be lifted out with the dissecting needle, or needle loop ( ), it can

be removed using fine-pointed forceps with minimal pressure so that the animal is not mashed or damaged. Animals that have fragile shells or are too small for the forceps or needle should be sucked into a pipet and expelled into the vial with as little water as possible so as not to dilute the AGW too much.

26. If you cannot be sure whether an object is an animal or not, remove it and put it in a “miscellaneous” vial. It is permissible to increase the magnification in order to take a more detailed look at the object. Return to the lowest magnification before you continue picking. If an animal is discarded, it can never be recovered. Remember our picking motto:

“When in doubt, save it.”


27. Once all the material has been moved about in the grid square and all the animals have been put in vials, move to the next complete or partial grid square in the first row and repeat steps 17 through 22. Once that row is completed, move to the first grid square in the next row and continue the process, following a zigzag pattern until the entire dish has been processed (Figure 2).

28. When the entire dish has been picked, reposition it at a right angle so that rows that were

horizontal are now vertical. Pick through the contents of the dish a second time, exactly as before. 29. Once the dish has been completely picked twice, empty and rinse its remaining contents into a

storage jar which contains a paper label to identify the sample. Place a corresponding tape label on the outside of the jar.

30. Add additional portions of the sample to the gridded dish and process each portion (as in steps

17-25 above). Rinse the beaker or bowl that received material from the sieve thoroughly and include any material in the rinsate in the final portion.

31. When all of the material has been sorted, cover leftover substrate with alcohol. Cover all vials

with screw caps and group together with one or more rubber bands.

Completing the Sorting Procedure 32. On the computer sample processing log, enter the information in the remaining categories and

the fraction of the sample sorted. Be sure to enter the date completed and your initials.

33. Store all vials and jars for the sample in the location specified by the project director.

34. Continue to the next sample. When you have finished for the day, be sure to clean up the work

area, putting away utensils and wiping up any liquids from the stage of the dissecting scope and the lab table. Put the cover on the dissecting scope and be sure all scope lights are off.


Appendix B. Appendices to Chemical Section of QAPP

Appendix B. Chemical Section Appendices..............................................................................................xx

B-1. Quality Assurance Plan, NCWQR...............................................................................................xx B-2. Quality Assurance Standard Operating Procedure, NCWQR .....................................................xx B-3. Method Standard Operating Procedures ......................................................................................xx

B-3.1 SOP for Total Suspended Solids (Gravimetric)..................................................................xx B-3.2 SOP for Total Phosphorus ..................................................................................................xx B-3.3 SOP for Soluble Reactive Phosphorus (Dissolved Reactive Phosphorus) .........................xx B-3.4 SOP for Total Kjeldahl Nitrogen .......................................................................................xx B-3.5 SOP for Fluoride, Chloride, Nitrite, Nitrate, and Sulfate Anions.......................................xx B-3.6 SOP for Ammonia N...........................................................................................................xx B.3.7 SOP for Silica.....................................................................................................................xx

B-4 Water Quality in Ohio Rivers and Streams, Project Study Plan...................................................xx


TABLE OF CONTENTS SECTION 1.0: STATEMENT OF QUALITY ASSURANCE POLICYSECTION 2.0: LABORATORY ORGANIZATION AND TRAININGSECTION 3.0 DATA QUALITY OBJECTIVES SECTION 4.0: LABORATORY EQUIPMENT, INSTUMENTS, AND REAGENTS SECTION 5.0: SAMPLE RECEIPT AND CHAIN OF CUSTODY SECTION 6.0: STANDARD OPERATING PROCEDURES SECTION 7.0: CALIBRATION PROCEDURES SECTION 8.0: PREVENTATIVE MAINTENANCE AND DOCUMENTATION SECTION 10.0: DATA REDUCTION, REVIEW, AND REPORTING SECTION 11.0: CORRECTIVE ACTION PROCEDURES AND CONTINGENCY PLAN SECTION 12.0: AUDITS, ACCREDITATIONS, AND CERTIFICATION SECTION 13.0: REPORTS TO MANAGEMENT SECTION 14.0: DOCUMENT RETENTION AND CONTROL SECTION 15.0: PROCUREMENT SECTION 16.0: CHANGE HISTORY


SECTION 1.0: STATEMENT OF QUALITY ASSURANCE POLICY 1.1. The objective of the National Center for Water Quality Research (NCWQR) is to accurately

characterize the concentrations of sediments, nutrients, and pesticides in natural waters, particularly in relation to non-point pollution from agricultural, urban and forested land use activities; to accurately characterize nutrient, sediment, and pesticide loading into lakes and/or export from watersheds of varying sizes; and to assess changes in concentrations and loading of non-point pollutants in response to changing management practices and/or climate.

1.2. To ensure the highest quality of data, all methods and procedures when specified by a study plan

will adhere to the current Quality Assurance Plan (QAP).

SECTION 2.0: LABORATORY ORGANIZATION AND TRAINING 2.1. The NCWQR consists of 9 employees classified as either research scientists or analytical

laboratory personnel. In addition, as the NCWQR is located at Heidelberg College, Tiffin, Ohio, student interns and student employees (hereafter called Interns) are utilized during the academic year and summer session. The organizational structure for this project is shown in Figure 2.1. For the purposes of specific study plans, members of the NCWQR may be given alternative designations that are independent of their position within the NCWQR. These designations are indicated within the organizational chart found in the study plan.

2.1.1. The Director of the NCWQR and any other member of the NCWQR specified in a Study

Plan will hereafter be known as the Management Team.

2.1.2. At least one member of the NCWQR must hold the designation of Quality Assurance Coordinator (QAC). It is the responsibility QAC to ensure the implementation of this QAP and its various aspects stated herein. Additional members may be designated as a QAC to assist in QAP implementation and Quality Control (QC) Data review; however, a Lead QAC must be distinguished. The Lead QAC is represented by a * on the organizational chart.

2.2.


Figure 2.1

Organizational Chart 2.2.1. One member of the NCWQR must hold the designation of Laboratory Manager. It is the

responsibility of the Laboratory Manager to oversee testing in the Analytical Laboratory. 2.3. Training, education, experience, and a position description are maintained by a QAC for each

employee in a personnel file. These files (hereby called Personnel Files) are stored in Gillmor Science Building Room 327 (hereafter referred to as Gillmor 327) and will be maintained for a minimum two years after the individual is no longer employed by the NCWQR. Any additions or changes to a Personnel File may be completed by using the form in Appendix A or annotating the CV.

2.3.1. Curriculum vitae (CV) and a position description for each member of the NCWQR will

be stored in the individual’s Personnel File. The CVs will be updated yearly with a notation by the QAC if no changes are made. Additions by members to their CV may


include, but are not limited to, completion of degree, completion of short course, published papers, presentations, etc.

2.3.2. Personnel File Forms will be stored in the individual’s Personnel File. Personnel File

Forms document the date, data, certificates, etc., from successful completion of training. (See Appendix A, Form 1)

2.4. Training procedures for new employees are outlined within each method’s SOP or the QA-SOP.

2.4.1. An analyst who has demonstrated competency for a specific method by successfully completing the Demonstration of Performance outlined in the QA-SOP is considered “trained”. Any analyst who has yet to complete the performance assessment must work under the supervision of a trained analyst.

2.4.2. Individuals working within the NCWQR who have not completed training for a specific

method (e.g., Interns) must work under the supervision of a trained NCWQR member when executing part of an analysis that is covered by the QAP, SOP, or QA-SOP. All work requiring a signature or initials will be signed by both the Intern and trained NCWQR member.


SECTION 3.0: DATA QUALITY OBJECTIVES 3.1. Data quality objectives such as, but not limited to, accuracy, precision, and reporting limits are

listed in each method’s Standard Operating Procedure (SOP). Evidence that data quality objectives are met must be produced at least once a year for each SOP and are outlined in the QA-SOP.

3.2. Specific data quality objectives may be set by a study plan, but the objectives must be within the

ranges stated in the SOP or QA-SOP.


SECTION 4.0: LABORATORY EQUIPMENT, INSTUMENTS, AND REAGENTS 4.1. All instrumentation covered by the QAP must be listed within the QAP (See Table 4.1).

Instrument Name Description Manufacturer Model Number(s)

Balance Balance MettlerAB204, AE163, P163,

PB303, PE3000, PG,3001, PJ6000

AAII Segmented Flow Injection Analyzer Seal AutoAnalyzer II

TRAACS Segmented Flow Injection Analyzer Seal Traacs 800

IC Ion Chromatograph Dionex DX320, ICS2000

ICP-MSInductively Coupled

Plasma-Mass Spectrometer

Varian Liberty 810

GC-MS Gas Chromatograph-Mass Spectrometer Varian Varian 3400-Saturn II

Table 4.1 NCWQR Instrumentation

4.2. Reagents are analytical reagent grade or equivalent unless otherwise specified in the method

SOP. 4.3. Laboratory oven, muffle furnace, autoclave and refrigerators temperatures are verified semi-

annually with a NIST-certified thermometer. Daily refrigerator temperatures and all verifications are recorded in a laboratory log.

4.4. Verification of analytical balance calibration is performed using a set of check weights each day

before sample measurement. Each check weight is compared to a certified weight on an annual basis. Results of all verifications are recorded in a laboratory log.

4.5. A schematic of the Laboratory Floor Plan is exhibited in Appendix B.


SECTION 5.0: SAMPLE RECEIPT AND CHAIN OF CUSTODY 5.1. Sample collection requirements are specified in the individual Study Plans. 5.2. Sample storage requirements and holding times are specified in each method’s SOP. 5.3. Chain of Custody requirements can be determined using the following criteria:

5.3.1. Samples collected by NCWQR personnel to comply with the Tributary Loading Study Plan will be accompanied by Form 1, Appendix C.

5.3.2. Samples collected by persons other than NCWQR personnel to comply with the

Tributary Loading Study Plan will be accompanied by Form 2, Appendix C.

5.3.3. Samples received for surface water analysis, other than those covered by the Tributary Loading Study Plan, must be accompanied by Form 3, Appendix C.

5.3.4. Samples received or collected for well water analysis must be accompanied by Form 4,

Appendix C. 5.4. Chain of Custody documents will be retained in the appropriate file in Gillmor 327 for a

minimum of 2 years. 5.5. Samples will be rejected if the sample container has been damaged so that a representative

sample cannot be obtained or if the handling of the sample does not meet the requirements of the appropriate Study Plan. Clients will be notified of any sample rejection and may provide a resample if desired.

5.6. The NCWQR reserves the right to reject any sample deemed inappropriate for analysis.


SECTION 6.0: STANDARD OPERATING PROCEDURES 6.1. All analyses covered by this Quality Assurance Plan (QAP) will follow the method’s Standard

Operating Procedure (SOP). The SOP will contain at a minimum the requirements for equipment preparation, sample preparation, sample cleanup, sample analysis, and routine performance verification procedures. For all current SOPs see the Master File in Gillmor 327 or controlled copies in Gillmor Science Building Rooms 304 and 319 (hereafter referred to as Gillmor 304 and Gillmor 319).

6.2. SOPs for each analytical method are based on published procedures from regulatory agencies

(e.g., US EPA). The published procedure will be referenced in the appropriate section of the SOP. There are no variances from the published procedure for any analytical method with an SOP. Note: See project study plans for additional information.

6.3. Additional performance verification of a method that is not a part of daily routine testing

outlined in the SOP (e.g., Method Detection Limit (MDL), Demonstration of Performance, precision, accuracy, etc.) will be covered in the Quality Assurance Standard Operating Procedure (QA-SOP). For all current SOPs see the Master File in Gillmor 327 or controlled copies in Gillmor 304 and Gillmor 319.


SECTION 7.0: CALIBRATION PROCEDURES 7.1. Calibration type and frequency are specified within each method’s Standard Operating

Procedure (SOP). 7.2. All calculations for calibration are performed electronically by the software of the

instrumentation (see Section 10) and verified by the analyst in accordance with the SOP.


SECTION 8.0: PREVENTATIVE MAINTENANCE AND DOCUMENTATION 8.1. All instrument manuals are located in a designated area near the specific instrument or in

Gillmor 327. 8.2. Preventative maintenance and documentation procedures are specified within each method’s

Standard Operating Procedure (SOP). 8.3. If possible, at least one spare or “back-up” part for routinely replaced components will be kept in

the laboratory. It is the responsibility of the analyst to inform the Laboratory Manager when the “back-up” has been used.

8.4. Any maintenance contracts for equipment covered by the QAP will be stored in the designated

file in Gillmor 327. 8.5. Any new equipment warranty documents covered by the QAP will be stored in the designated

file in Gillmor 327. 8.6. All balances are serviced once a year by an approved service agency (Table 8.1). Balance test

confirmation paperwork is stored in Gillmor 327.

Approved Agencies Address Telephone No.

Mettler Toledo 1900 Polaris Parkway Columbus, OH 43240 1-800-638-8537

Table 8.1 Balance Service Agency


SECTION 9.0: INTERNAL QUALITY CONTROL 9.1. Internal quality control checks, their frequency, and the criteria for acceptability are specified

within the Quality Assurance Standard Operating Procedure (QA-SOP). 9.2. Proficiency Testing (PT) for each method will be completed at least semi-annually. Samples

containing required analytes are provided by an externally accredited source (see Section 15.0). Analytical results are submitted and accuracy is determined. Results of the PT studies are stored in the appropriate file in Gillmor 327.

9.3. Independent quality control standards will be prepared under the supervision of a Quality

Assurance Coordinator (QAC) or purchased from an external supplier and analyzed on at least a quarterly basis. Results will be stored in the appropriate file in Gillmor 327 and reported to the Laboratory Manager and/or electronically by the QAC.

9.4. Quality control performance parameters (e.g., Method Detection Limits (MDLs)) must be

performed at least once a year and are specified in the QA-SOP (hereafter called the Demonstration of Performance). When completed, the SOP and any other documentation specified by the SOP will be updated with the most recent data (hereafter called Validation Data).


SECTION 10.0: DATA REDUCTION, REVIEW, AND REPORTING10.1. Details regarding data calculation and reduction are listed within the method’s Standard

Operating Procedure (SOP). All calculations are performed electronically by the software of the instrument. The organization of the major analytical equipment, corresponding computers, laboratory mainframe computer and output devices is shown in Figure 10.1.

PC Ion Chromatographs

PC TRAACS Autoanalyzer

PC TRAACS Autoanalyzer

PC Technicon Autoanalyzer II

PC ICP-MS Spectrometer

PCGC/MS Pesticides

PCGC/MS VOCs

VAX 4000

Eth

erne

t

Multiple PCs and Macs for GIS, data analysis, etc. Laser, Ink Jet and

wide bed printers

sample barcode reader

balances

Connections to Heidelberg Collegevia Ethernet

and to the outside world via Internet

storage

organics inorganics

WQL server

Figure 10.1, NCWQR Electronic Data Flow


10.2. Data is retained by the laboratory in the form of a paper copy and an electronic version stored on the VAX system. The paper copy of the data is the primary method of data retention and stored in the designated file in Gillmor 327. The electronic data stored in the VAX system is backed-up at least bi-weekly to a disk format and stored in Campus Center 125.

10.3. Quality Control Data for each method is reviewed by a Quality Assurance Coordinator (QAC)

on a monthly basis. For the Quality Control Data generated for each method, refer to the method SOP.

10.3.1. Primary responsibility for quality data resides with the analyst. Quality Control Data is

collected by an analyst on a weekly basis. Data are added to the Quality Control Charts and examined to determine if the given system is out of control.

10.3.1.1. Using plotting software (e.g., Excel or Datadesk), individual and/or

multiple parameters for each location are visually displayed so that disparate data points or “outliers” can be identified.

10.3.1.2. Questionable data are investigated by researching original data input to

discover the possible source of the error or omission. Some accurate data that do not conform to expected patterns may appear to be “outliers”.

10.3.1.3. If the error can be readily explained and documentation is available with

the correct entry, the correction (if necessary) is made in the VAX database and the corrective action is documented.

10.3.1.4. If the error cannot be readily explained and/or documentation is

unavailable, the questionable data are brought to the attention of the Laboratory Manager. A meeting between the laboratory manager and QAC will be conducted to determine the course of action. In most cases, the data will be retained in the VAX, but may be replaced with “-9” in any working databases to indicate missing data, and the corrective action will be documented electronically as “comments” in the data file.

10.3.1.5. Copies of corrected VAX data sets are added to existing working database

servers for use by research scientists and educators. Working databases are updated at least quarterly by the QAC.

10.3.2. Review of the Quality Control Data by a QAC for the previous month’s data must be

completed by the 15th of the current month. The QAC will report the findings of the review, including any deficiencies, to the Laboratory Manager by the 20th of the current month (See Section 13.0). A copy of the Quality Control Data review report will be stored in the appropriate file in Gillmor 327 or on separate electronic server known as


“server-six” that is maintained by the Heidelberg College Computer Network Information Technologies department.

10.3.3. If any deficiencies are found by the QAC in the Quality Control Data (i.e., a system that

is out of statistical control, etc.), the deficiencies will be brought to the attention of the Laboratory Manager and any applicable analyst. Corrective action measures will be taken until the deficiencies are corrected (see Section 11.0).

10.3.4. It is the responsibility of a QAC to update the appropriate files with the new Quality

Control Data (see Section 9.0). 10.4. It is the responsibility of the designee in the appropriate Study Plan to report data generated

within the specifications of the QAP to the appropriate agency (e.g., QDC to the Ohio EPA). 10.5. Data are extracted from the VAX monthly by QAC, reviewed for completeness and errors, and

corrected as needed. All corrections are documented in a correction log.


SECTION 11.0: CORRECTIVE ACTION PROCEDURES AND CONTINGENCY PLAN 11.1. Corrective action procedures for quality control failures can be found within each method’s

Standard Operating Procedure (SOP). 11.2. If the NCWQR laboratory is unable to perform quality analyses for any reason, samples will be

forwarded to an appropriate contract laboratory for analysis.


SECTION 12.0: AUDITS, ACCREDITATIONS, AND CERTIFICATION 12.1 All current accreditations and certifications and their durations are represented in Table 12.1.

SummaryOhio Evironmental Protection Agency --

Department of Environmental Services Audit and Successful Completion December 2007

Table 12.1 NCWQR Accreditations and Certifications

12.2 Internal auditing of the Quality Assurance Plan (QAP) is undertaken during the yearly review of

the QAP, SOPs, and QA-SOP (See Section 14.5) by at least one Quality Assurance Coordinator (QAC) and any other assigned members of the NCWQR.

12.3 A QAC may audit the NCWQR at any time to ensure the proper implementation of the QAP. If

any deficiencies are found, they will be corrected in a timely fashion and noted in the monthly report from the QAC to the Management (see Section 13.0).

12.4 As indicated in Section 9.0, PT samples are purchased from approved vendors (see Section 15.3)

and tested as samples according to the appropriate SOP.

12.4.1 Samples may be diluted given the possible concentrations to ensure they are within the routine working range of the instrument.

12.4.2 After completion of the analysis, results are reported to the PT agency by a QAC.

12.4.3 Acceptable performance is determined by comparing the NCWQR laboratory result to

the Acceptance Range for the analyte.

12.4.3.1 For PT samples from the Water Supply Program (WS), the acceptance range is calculated based upon the United States Environmental Protection Agency Nation Standards for Water Proficiency Testing Program Criteria Document (NERL-Ci-0045). The acceptance limits are defined as ± two standard deviations from the estimated mean. See Table 12.2 for an example.

Analyte Reported Value EPA MeanEPA Standard

Deviation Acceptance Range EvaluationChloride 94 92.6 4.14 83.2-102 Acceptable

Table 12.2 WS PT Sample Acceptance Example


12.4.3.2 For PT samples from the Water Pollution Program (WP), the acceptance range is calculated based upon the United States Environmental Protection Agency Nation Standards for Water Proficiency Testing Program Criteria Document (NERL-Ci-0045). The acceptance limits are defined as ± three standard deviations from the estimated mean. See Table 12.3 for an example.

Analyte Reported Value EPA MeanEPA Standard

Deviation Acceptance Range EvaluationTotal Phosphorus (TP) 6.42 6.09 0.367 4.99-7.19 Acceptable

Table 12.3 WP PT Sample Acceptance Example

12.4.4 Any PT results determined to be outside the acceptance range will result in an

investigation by the QAC. The investigation will involve, but is not limited to the following action items. The findings of the investigation will be noted in the appropriate file in Gillmor 327.

12.4.4.1 The QAC will request a re-test of the remaining PT sample. Should the

PT sample return results within the acceptance range, a note will be placed in the PT file and analysis of the analyte will resume. Should the PT Sample still return results outside of the acceptance range, analysis will halt until a reason for failure can be identified.

12.4.4.2 The QAC will investigate the raw data produced by the instrument.

12.4.5 PT samples can be maintained and used as QC samples as outlined in Section 9.3. The acceptance criteria will be the same as Section 12.4.3.


SECTION 13.0: REPORTS TO MANAGEMENT 13.1. Monthly Reports will be generated to summarize QC data. These reports may include, but are

not limited to, QC Data such as statistical process control chart results for blanks, sample duplicates, “spike” recovery and check standard analysis from each relevant SOP. The original print copy will be stored in the designated file in Gillmor 327. Additional copies will be made available to the members of the NCWQR Management Team upon request.

13.1.1. Quarterly results from the Performance Evaluation will be incorporated into the Monthly

Reports as they become available.

13.1.2. Validation Study data will be incorporated into the Monthly Reports as they are completed.

13.2. Staff meetings will be held with the following frequency:

13.2.1. A Quarterly meeting will be held with the Laboratory Manager and designated analytical staff members to review QC Data, Performance Evaluations, Control Charts, etc.

13.2.2. An annual meeting will be held with all NCWQR employees to review summaries of

quality control data and to discuss other quality concerns. This meeting may be used as training for any revisions to the QAP. An annual report will be prepared by a QAC and stored in the designated file in Gillmor 327.


SECTION 14.0: DOCUMENT RETENTION AND CONTROL 14.1. Original signed documents (e.g, QAP, SOPs, etc.) will be stored in the designated file cabinet in

Gillmor 327 (hereafter referred to as the Master File). The signature with the most recent date will be considered the effective date of the document. A signed document with a greater version number will void any signed document with a lesser version number.

14.1.1. All Standard Operating Procedures (SOPs) and Quality Assurance Standard Operating

Procedures (QA-SOPs) must be signed by the individual who prepared the document (Prepared by), a second member for the NCWQR (Reviewed by) and a QAC or the Director (Approved by).

14.1.2. The QAP must be signed by the individual who prepared the document (Prepared by), a

QAC if not the preparer (Reviewed by) and the Director (Approved by).

14.1.3. It is the responsibility of a QAC to update the Master File and all controlled copies with the most recent copy of the document. In addition, a QAC will inform all members of the NCWQR that an updated version has gone into effect. This communication may be in the form of an e-mail.

14.1.4. All previous versions of original signed documents will be stored in the Master File for a

minimum of three years after being voided. The date which the document is voided will be marked on the original signed document by a QAC.

14.1.5. Current copies of electronic documents will be stored in the WQL folder on “server-six”

that is maintained by the Heidelberg College Computer Network Information Technologies department. Electronic copies and any printouts made from them are considered uncontrolled; however, they may be used as long as the document is effective.

14.2. Controlled copies of all effective SOPs and the QA-SOP can be found within designated binders

in Gillmor 319 & 304. Any duplicates made from these copies are considered uncontrolled. 14.3. Revisions to the QAP may be initiated by any member of the NCWQR; however, all changes

must be approved by the Director (see Section 14.1.2). 14.4. SOPs may be written or revised by any member of the NCWQR; however, all changes must be

approved by a QAC (see Section 14.1.1). 14.5. The QAP and all SOPs must be reviewed at least once a year. A year is defined as the Water

Year which runs from October 1st to September 30th.


14.5.1. If no changes are needed for the QAP, the QA-SOP or an SOP after the yearly review, the original copy in the Master File will be marked as reviewed by a QAC.

14.5.2. SOPs that have been updated with the most current Validation Data (see Section 9.0) will

be considered reviewed for the year in which the Validation Study took place.

14.6. Logbooks will be used to document the performance of assigned equipment and preparation of solutions.

14.6.1. Logbooks will be in the form of a bound laboratory notebook. 14.6.2. Completed logbooks will be stored in the designated area in Gillmor 327 for at least 3

years. 14.7. Material Safety Data Sheets (MSDSs) for all chemicals used within the NCWQR will be stored

in Gillmor 327. The MSDSs will be continually updated by a QAC.


SECTION 15.0: PROCUREMENT 15.1. The minimum grade of reagents or supplies required for analyses are listed in each method’s

SOP. A reagent or supply may only be substituted with an equivalent or higher grade. 15.2. Any vendor may be used to provide a chemical, reagent, or supply on the condition that the

grade received is sufficient for the analysis. If a particular vendor’s product does not give a suitable performance, a note will be placed in the method’s SOP.

15.3. Proficiency Testing (PT) samples may be obtained from one of the following sources, Table

15.1. It is the responsibility of the Lead QAC, or designee, to order the PT samples and log them in as samples.

Approved Agencies Address Telephone No.

Analytical Products Group, Inc. (APG)

2730 Washington Blvd Belpre, OH 45714

740-423-4200 800-272-4442

Table 15.1

Proficiency Testing Sample Approved Supplier

15.4. All reagents used in testing covered by the QAP must be labeled with the received date, opened date, and an orange or yellow sticker (see Figure 15.1 and 15.2).

Figure 15.1 Orange Sticker

Figure 15.2 Yellow Sticker


SECTION 16.0: CHANGE HISTORY 16.1 Version 1 -- Initial issuing of Quality Assurance Plan; Version Author, Aaron Roerdink 16.2 Version 2 – Update organizational chart, new director; Update Qualified Data Collector (QDC)

Certifications; ; Version Author, Aaron Roerdink 16.3 Version 3 – Update organizational chart; remove Appendix A form 1; Add statement for

analytical method variances, Section 6.2; Update instrument chart, new ion chromatograph; Add statement of electronic storage, Section 9.3; Update QC data handling, Section 10.3; Add statement of successful OEPA audit, Section 12.1; Add criteria for acceptance of inter/intra laboratory studies, Section 12.4; Add yellow sticker for approved reagents, Section 15.4; Version Author, Aaron Roerdink


TABLE OF CONTENTS 1.0 SCOPE AND APPLICATION 992.0 DEMONSTRATION OF PERFORMANCE 993.0 MONTHLY PERFORMANCE REVIEW 1004.0 QUARTERLY DEMONSTRATION OF PERFORMANCE 1015.0 SEMI-ANNUAL DEMONSTRATION OF PERFORMANCE 1026.0 ANNUAL DEMONSTRATION OF PERFORMANCE 1027.0 CHANGE HISTORY 102Appendix A 103


1.0 SCOPE AND APPLICATION 1.1 This procedure outlines the quality assurance testing and parameters for all analytical Standard

Operating Procedures (SOPs). See each SOP for the required testing and occurrence. 1.2 An analyst performing studies (hereafter called the Validation Study) with this procedure must

also follow the SOP for which the Validation Study is being completed. For safety, specific training requirements, sample collection, sample receipt, interferences, equipment, supplies, reagents, standards, calibration procedures, sample preparation, and the analytical procedure relevant to this method, see the corresponding SOP.

2.0 DEMONSTRATION OF PERFORMANCE 2.1 The demonstration of performance is used to characterize the instrument’s performance

(determination of accuracy through the analysis of the Quality Control Standard (QCS)) and laboratory performance (determination of Method Detection Limits (MDLs) prior to performing analyses on samples by the SOP.

2.1.1 Prepare and analyze calibration standards for all analytes according to the SOP.

2.1.2 Verify the calibration standards and acceptable instrument performance with the

preparation and analyses of the stated Quality Control Standard (QCS), see Quality Assurance Plan (QAP) Section 9.3. The determined concentration must be within the stated tolerance (see Section 4.1) for the performance to be acceptable. The source of any problem that gives an unacceptable value according to stated criteria must be corrected before any further studies are completed.

2.1.3 The Method Detection Limit (MDL) must be established for all analytes, using reagent

water fortified at a concentration of three to ten times the estimated Instrument Detection Limit (IDL). To determine the MDL value, take at least seven replicate aliquots of the fortified reagent water and process them through the entire analytical method if applicable. Perform all calculations defined in the method and report the concentration values in the appropriate units. Calculate the MDL as follows:

� �� st�MDL

t = Student’s t value for the 99% confidence level (one tailed) with n-1 degrees of

freedom, see Appendix A for t value

s = the standard deviation of the replicate analyses.


2.2 The analyst will forward results (here after called Validation Results, see QAP Section 9.0)) of the Demonstration of Performance to a Quality Assurance Coordinator (QAC). Results will be filed in the appropriate location(s) in Gillmor 327, and the QAC will update the relevant Standard Operating Procedures (SOPs) with the given data.

3.0 MONTHLY PERFORMANCE REVIEW 3.1 Operational control charts for each method will be maintained by a QAC from data generated for

Replicates, Check Standards, Blanks, and Matrix Spikes. Data is retrieved and reviewed according to the stated procedure in (QAP) Section 10.0.

3.2 Precision is evaluated using replicate samples. A replicate is a second portion that is expected to

contain the same quantity of analyte(s) as the original. Replicates must be handled and analyzed using the same procedures as the original sample. One replicated sample will be included with each batch of 20 samples as stated in the method’s SOP.

3.2.1. The percent difference between the original and the replicate is calculated by the

following equation:

e%Differenc100MeanRange

��

3.2.2. Operational control limits of the percent difference are determined based on the average

range ( R ) and standard deviation (s) of values determined from Section 3.2.1. The Upper Control Limit and Lower Control Limit will be established as follows:

+ 3 s RUpper Control Limit (UCL) =

3.2.3. New operational control limits will be determined and maintained by a QAC as defined in the QAP (Section 10.0).

3.3 Check Standards will be prepared at concentrations relevant to the calibration range.

3.3.1. The percent recovery is determined by dividing the found value by the true value of the check standard and multiplying by 100.

x3.3.2. Operational control limits will be determined based on the average ( ) and standard

deviation (s) of values determined from the Check Standards. The Upper Control Limit and Lower Control Limit will be established as follows:

+ 3 s xUpper Control Limit (UCL) = - 3 s xLower Control Limit (LCL) =


3.3.3. New operational control limits will be determined and maintained by a QAC as defined

in the QAP (Section 10.0). 3.4 Blanks will be prepared using reagent grade water.

3.4.1. The blank value (mg/L or ppm) is plotted on the control chart.

x3.4.2. Operational control limits will be determined based on the average ( ) and standard deviation (s) of values determined from the Blanks. The Upper Control Limit and Lower Control Limit will be established as follows:



in the QAP (Section 10.0).

3.5 Matrix spikes will be prepared at concentrations approximate to the sample concentrations and relevant to the calibration range.

3.5.1. The percent recovery is determined by the following equation:

%Recovery100Spike of Value True

Result Sample -Result Spike��

x3.5.2. Operational control limits will be determined based on the average ( ) and standard

deviation (s) of values determined from the Spikes. The Upper Control Limit and Lower Control Limit will be established as follows:



in the QAP (Section 10.0)

4.0 QUARTERLY DEMONSTRATION OF PERFORMANCE 4.1 Independent quality control standards will be prepared at concentrations relevant to the

calibration range and analyzed by the appropriate method on a quarterly basis, See QAP Section 9.3. This demonstration is to ensure the accuracy of the given method.


4.1.1. The percent recovery is determined by dividing the found value by the true value of the

check standard and multiplying by 100. 4.1.2. Calculated recoveries must fall between 85-115% of the expected concentration. If

recoveries fall outside of this range, deficiencies will be addressed as specified in Section 10.3.3 of the QAP.

5.0 SEMI-ANNUAL DEMONSTRATION OF PERFORMANCE 5.1 All methods will undergo a semi-annual demonstration of performance, hereafter called

Proficiency Testing (see QAP Section 15.0). This demonstration is to ensure the accuracy of the given method.

5.2 It is the responsibility of a QAC to file the results of the Proficiency Testing in Gillmor 327. In

addition, a QAC will report the results of the Proficiency Testing to the Laboratory Manager according to the Quality Assurance Plan (QAP).

6.0 ANNUAL DEMONSTRATION OF PERFORMANCE 6.1 MDLs will be determined for each method annually according to Section 2.1 6.2 The analyst will forward results of the MDL Study to a Quality Assurance Coordinator (QAC).

The QAC will update the SOP with the relevant data.

7.0 CHANGE HISTORY7.1 Version 1 – Initial issuing of Quality Assurance Standard Operating Procedure; Version Author,

Aaron Roerdink. 7.2 Version 2 – Add Appendix A, Student’s t table for MDL calculations; define concentration of

sample used for MDL study; remove watermark; Version Author, Aaron Roerdink.


Appendix A Table 1 Student’s t table for 99% confidence interval (one tailed).

Degrees of Freedom

99% Confidence Limit

6 3.1437 2.9988 2.8969 2.82110 2.76415 2.60220 2.52825 2.48530 2.45740 2.42360 2.39120 2.358� 2.326


Table of Contents

1.0 SCOPE AND APPLICATION 1062.0 SAFETY AND TRAINING 1063.0 SAMPLE COLLECTION AND RECEIPT 1064.0 METHOD PERFORMANCE AND WORKING LINEAR RANGE 1075.0 INTERFERENCES AND CORRECTIVE MEASURMENTS 1076.0 EQUIPMENT AND SUPPLIES 1077.0 CHECK WEIGHTS AND CALIBRATION 1078.0 SAMPLE PREPARATION 1079.0 ANALYTICAL PROCEDURE 10710.0 CALCULATIONS 10811.0 QUALITY CONTROL REQUIREMENTS 10812.0 DATA REPORTING REQUIREMENTS 10813.0 PREVENTATIVE MAINTENANCE 10914.0 REFERENCES 10915.0 CHANGE HISTORY 109


1.0 SCOPE AND APPLICATION

1.1 This method can be used to determine non-filterable residue in aqueous environmental samples.

2.0 SAFETY AND TRAINING

2.1 The drying oven used to dry samples is hot and presents a potential serious burn hazard.

2.2 The toxicity or carcinogenicity of environmental samples must be considered unknown. Samples should be regarded as potential health hazards and exposure to them should be as low as reasonably achievable. Use these methods in a fume hood if necessary. Always wear safety glasses or a shield for eye protection and wear protective clothing.

2.3 All personnel handling environmental samples known to contain or to have been in contact with human waste should be immunized against known disease causative agents.

2.4 A new analyst who will perform analyses of residues using this method must be first trained by an experienced analyst who is proficient in this analysis. The new analyst must demonstrate proficiency in this analysis by performing a satisfactory QC test batch (see QA SOP). Upon successful completion of the test batch, the analyst will be permitted to perform the entire residue analysis.

3.0 SAMPLE COLLECTION AND RECEIPT

3.1 Appropriate sample quantities and collection techniques (grab, composite, etc.) are designated by the project leader and depend on the goals of the project. Care must be taken to assure that the sample is representative of the body of water under study. Refer to the appropriate Study Plan for details of sampling requirements.

3.2 Sample containers are HDPE plastic and are cleaned with tap water, then rinsed with Type II reagent (processed through a reverse osmosis system) water before use. For grab samples, rinse sample containers with sample water before filling container for analysis. Autosampler is equipped with a line purge cycle after each sample is drawn. Label sample containers to identify location, date, collector’s initials and time of sample.

3.3 Any required preservation of sample is specified in the project’s Study Plan. If no specific requirements are stated, preservation of samples is not necessary.

3.4 Upon arrival at the laboratory, samples are stored at 4° C prior to analysis. Maximum refrigerated holding times are as follows: refrigerated – 7 days.

3.5 Minimum sample to be collected for any one analysis – 100 mL.


3.6 Sample collector must initial and date chain of custody form for samples delivered. Samples received by parcel delivery must be accompanied by chain of custody paperwork. Analyst must sign and date chain of custody upon receipt.

4.0 METHOD PERFORMANCE AND WORKING LINEAR RANGE

4.1 The method detection limit (MDL) based on a low-level standard (10.0 mg/L) is 2.86 mg/L. See Section 16.0.

5.0 INTERFERENCES AND CORRECTIVE MEASURMENTS

5.1 There are no interferences or corrective measures.

6.0 EQUIPMENT AND SUPPLIES

6.1 Analytical balance, 0.1 mg

6.2 Top-loading balance, 0.1 g

6.3 Drying oven, temperature maintainable at 105 +/- 2°C

6.4 Drying dishes and assorted glassware. Minimum cleaning required is rinsing with tap water and distilled water.

6.5 Check weights for balances

7.0 CHECK WEIGHTS AND CALIBRATION

7.1 Verify the accuracy of the balance by weighing at least two check weights that bracket the expected value of the sample(s).

7.2 Balances are serviced once a year according to the Quality Assurance Plan (QAP), Section 8.0.

8.0 SAMPLE PREPARATION

8.1 Be sure to mix the sample thoroughly immediately before analysis. The principal source of error in the determination is failure to obtain a representative sample.

9.0 ANALYTICAL PROCEDURE

9.1 Total Suspended Solids (TSS, Non-filterable Residue) in Water

9.1.1 Weigh a 47 mm Whatman 934AH, or equivalent, on an 0.1 mg analytical balance; this is the initial weight (WF0). Record this weight to 4 places after the decimal point.


9.1.2 Place sample bottle on a top-loading balance (0.1 g minimum) and tare the balance. Mix sample thoroughly and pour approximately 100 mL (100 g) of sample into filter apparatus, and place the bottle back on the top-loading balance. Record the reading from the balance, without the negative sign, to the nearest 0.1 gram.

9.1.2.1 If the sample contains < 10 g/L of residue, this weight can be assumed to be equal to the volume in mL, Vs.

9.1.2.2 If sample contains > 10g/L of residue, this method is not appropriate for determination of total suspended sediment (residue, solids) (TSS).

9.1.3 Place filter in an oven set to 105°C to evaporate the sample to dryness, then hold temperature at 105°C for four hours.

9.1.4 Cool filter. If filter is to be weighed longer than one hour after drying, store in a desiccator until it can be weighed.

9.1.5 Reweigh filter on 0.1 mg analytical balance; this is the weight after drying (WFd).

9.1.6 Calculate the Non-filterable Residue using the formula in Section 10.0.

10.0 CALCULATIONS

10.1 Symbols WF0: initial weight of filter, mg Ws: eight of sample, g WFd: weight of filter after drying, mg

10.2 For water samples, residue values are calculated as:

s

0d

WWFWF � Total suspended sediment (residue, solids) =

11.0 QUALITY CONTROL REQUIREMENTS

11.1 Balances must be checked daily using known check weights to be certain they are giving the expected values. These readings are recorded in the laboratory computer with the date and time.

11.2 Blanks and duplicates are run with every 20 samples to allow assessment of precision and low-concentration bias.

12.0 DATA REPORTING REQUIREMENTS

12.1 For water samples, residue measurements are reported to 0.1 mg/L.


13.0 PREVENTATIVE MAINTENANCE

13.1 Balances are under maintenance contract, which supplies annual maintenance and NIST traceable calibration weights.

14.0 REFERENCES

14.1 Standard Methods for the Examination of Water and Wastewater, Method 2540, 19th Edition of Standard Methods. 1995.

14.2 Method 160.x. Edited by J. O’Dell. Determination of residues. EPA 600/R-79/020: Environmental Monitoring Systems Laboratory, Office of Research and Development, US EPA. Cincinnati, Ohio. 1993.

15.0 TABLES, DIAGRAMS, FLOW CHARTS, AND VALIDATION DATATable 15.1 Method Detection Limit. The method detection limit quoted in Section 4.1 was calculated from the standard deviation of 8 standards (10.00 mg/L) analyzed in a single run on December 13, 2007, as MDL = t.01,n-1 * s

Trial No. TSS mg/L1 7.40002 8.55003 9.40005 9.60004 9.30006 10.20007 9.60008 10.4000

Average 9.3063Std Dev 0.9549

MDL 2.8626

16.0 CHANGE HISTORY16.1 Version 1 – Initial issuing of Standard Operating Procedure; Version Author, Aaron Roerdink 16.2 Version 2 – Correct numbering within Section 6.0; Define the use of check weights; remove

interference statement; correct calculation; Version Author, Aaron Roerdink 16.3 Version 3 – Move Section 15.0 Change History to Section 16.0; insert Section 15.0 Tables,

Diagrams, etc.; insert MDL Data into Sections 4.0 and 15.0.


Table of Contents

1.0 SCOPE AND APPLICATION 1122.0 SAFETY AND TRAINING 1123.0 SAMPLE COLLECTION AND RECEIPT 1134.0 METHOD PERFORMANCE VALIDATION AND WORKING LINEAR RANGE 113 5.0 INTERFERENCES AND CORRECTIVE MEASRUEMENTS 1136.0 EQUIPMENT AND SUPPLIES 1147.0 REAGENTS AND STANDARDS 1148.0 CALIBRATION PROCEDURES 1159.0 SAMPLE PREPARATION 11610.0 ANALYTICAL PROCEDURE 11611.0 CALCULATIONS 11712.0 QUALITY CONTROL REQUIREMENTS 11713.0 DATA REPORTING REQUIREMENTS 11814.0 PREVENTATIVE MAINTENANCE 11815.0 REFERENCES 11916.0 TABLES, DIAGRAMS, FLOW CHARTS, AND VALIDATION DATA 12017.0 CHANGE HISTORY 122



1.1 This method covers the determination of total phosphorus (TP) in water samples. The term total phosphorus (TP) refers to the analysis of whole-water samples, digested to convert all forms of phosphorus to orthophosphate.

1.2 INSTRUMENTATION: Technicon Autoanalyzer II


2.1 The toxicity or carcinogenicity of each reagent used in this method has not been fully established. Each chemical should be regarded as a potential health hazard and exposure to these compounds should be as low as reasonably achievable.

2.2 The laboratory has a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data safety sheets (MSDS) is available in Gillmor 327 to all personnel involved in the chemical analysis.

2.3 Specifically, concentrated nitric and hydrochloric acids present various hazards and are moderately toxic and extremely irritating to skin and mucus membranes. Use these reagents in a fume hood whenever possible and if eye or skin contact occurs, flush with large volumes of water. Always wear safety glasses or a shield for eye protection, wear protective clothing and observe proper mixing when working with these reagents.

2.4 The acidification of samples containing reactive materials may result in the release of toxic gases, such as cyanides or sulfides. Acidification of samples should be done with appropriate fume evacuation.

2.5 Appropriate disposal of wastes from these analyses is the responsibility of the analyst. See section 7.4 for disposal methods.


2.7 A new analyst who will perform analyses of total phosphorus and/or total soluble phosphorus using this method must be first trained by an experienced analyst who is proficient in this analysis. The new analyst must demonstrate proficiency in this analysis by performing a satisfactory QC test batch (see QA SOP). Upon successful completion of the test batch, the analyst will be permitted to perform the entire total phosphorus and/or total soluble phosphorus analysis.




3.2 HDPE sample containers, sample glassware, and reagent glassware are cleaned with tap water, and then rinsed with Type II reagent (processed through a reverse osmosis system) water before use. If contamination is observed in the Reagent blank, sample containers and glassware is cleaned with detergent. For grab samples, rinse sample containers with sample water before filling container for analysis. Autosampler is equipped with a line purge cycle after each sample is drawn. Label sample containers to identify location, date, collector’s initials and time of sample.

3.3 Minimum sample volume to be collected for autoanalyzer analysis: 250 mL.

3.4 If preservation is required in the Study Plan, pack the sample container containing the collected sample in ice or refrigerate for travel to laboratory.

3.5 Upon arrival at the laboratory, samples are stored at 4° C prior to analysis. Maximum refrigerated holding times are as follow: unpreserved – 48 hours.


4.0 METHOD PERFORMANCE VALIDATION AND WORKING LINEAR RANGE

4.1 The method detection limit (MDL) based on low-level standards (2% of maximum working range) is 0.002 mg/L (Section 16).

4.2 The Working Linear Range is 0.1 to 1.0 mg/L or 0.001 to 0.1 mg/L in the sample as analyzed for Total Phosphorus depending upon the calibration standards used.

4.3 The method reporting limit (MRL) is 0.05 mg/L.

5.0 INTERFERENCES AND CORRECTIVE MEASRUEMENTS

5.1 Arsenic creates a positive interference with this method because, like phosphorus, it also reacts to form a blue color. Correction may be necessary by detection of arsenic content by another method (see Method 200.8 - Metals by ICP/MS) and calculation of difference between method results.


5.2 Mercuric chloride leads to a background absorbance. For samples known to be preserved with mercuric chloride, interference can be avoided by adding KCl to the mixed phosphorus reagent to provide a 0.1N KCl concentration. However, it is preferrable to avoid the use of mercuric chloride as a preservative.


6.1 Technicon Autoanalyzer II

6.2 NCWQR Manifold for Phosphorus (see Figure 17.1)

6.3 Mettler AE-163 Analytical Balance. Capable of weighing to .01 mg.

6.4 Membrane filters for total soluble phosphorus -0.45 �m

6.5 Glass volumetric pipets, volumetric flasks and plastic containers for standard preparation. Minimum cleaning required is rinsing once with tap water and three times with distilled water.

6.6 Autoanalyzer tubes. Soaked in acetic acid, scrubbed with a brush and rinsed at least three times with distilled water before use. Any discolored or otherwise damaged tubes are replaced as needed.

7.0 REAGENTS AND STANDARDS

7.1 Stock solutions – assign six-month expiry to these reagents

7.1.1 Sulfuric acid solution (5 N H2SO4): Add 70 mL of conc. sulfuric acid to 800 mL of distilled water, mix, cool and dilute to 1 L.

7.1.2 Sulfuric acid solution (13 N H2SO4): Add 310 mL of conc. sulfuric acid to about 600 mL of distilled water, cool and dilute to 1 L.

7.1.3 Ammonium molybdate solution: Dissolve 40 grams (NH4)6M7O24•4H2O in 800 mL of distilled water and dilute to 1 Liter.

7.1.4 Antimony Potassium Tartrate solution: Dissolve 2.6 g of antimony potassium tartrate in about 800 mL of distilled water and dilute to 1 Liter.

7.1.5 Sodium Laural Sulfate solution (15% SLS): Dissolve 150 grams sodium laural sulfate in 900 mL distilled water and dilute to 1 Liter.

7.1.6 Phosphorus standard stock solution: Dissolve 0.439 g KH2PO4 in 800 mL of water and dilute to 1 L. 1 mL of this stock solution in 1 L of distilled water provides a concentration of 0.1 mg/L.


7.1.7 Ammonium persulfate [(NH4)2S2O8], granular

7.2 Autoanalyzer solutions – prepared as needed.

7.2.1 Ascorbic acid solution: Dissolve 58.9 g of ascorbic acid in 500 mL of distilled water and mix well. Add 50 mL of acetone and dilute to 1 L. Add 5 mL 15% SLS. Assign a one month expiry.

7.2.2 Mixed reagent: combine in the order listed: 250 mL 5 N H2SO4; 150 mL ammonium molybdate solution; 50 mL antimony potassium tartrate. Dilute to 1 Liter with distilled water, and then add 5 mL SLS solution. Assign a one month expiry.

7.2.3 Wash receptacle solution: 20 mL of 13 N sulfuric acid (Section 7.1.2) added to 1 L of distilled water. Assign a six month expiry.

7.3 Standards are prepared in two different concentration ranges. Assign a one week expiry to all solutions.

7.3.1 Normal Level standards: 0.1, 0.2, 0.5 and 1.0 mg/L. Prepared by addition of 1, 2, 5 or 10 mL of phosphorus stock (see 7.1.6) up to 1 L with distilled water.

7.3.2 Low Level standards: 0.01, 0.02, 0.05 and 0.10 mg/L. Prepared by addition of 1.0 mL of phosphorus stock (see 7.1.6) up to 1 L with distilled water to prepare an intermediate standard solution (0.1 mg/L), then using 10, 20, or 50 mL of the intermediate solution and dilute to 100 mL with distilled water.

7.4 Disposal of samples and reagents is done in compliance with US EPA waste management practices.

8.0 CALIBRATION PROCEDURES

8.1 The autoanalyzer system is interfaced with the laboratory computer, and software provided by the manufacturer is used to produce a calibration curve. The software is NAP version 4.3. For specific software parameters see Section 16.0.

8.2 Place standards at the end of the run of samples, with a blank followed by standards in order of increasing concentration, and analyze as if they were samples. Sample analysis is done under computer control, and the measured absorbances are transferred electronically to a computer file.

8.3 After the run is complete, a least squares fit is applied to the absorbances for the standards to create a calibration for the run. The regression relationship, its correlation coefficient value, and the calculated concentrations in the standards are reported on a printout at the end of the run, along with the concentrations in the samples.



9.1 Obtain newly received, refrigerated or iced sample from storage; sign and date chain of custody form.

9.2 Using chain of custody information, analyst enters sample ID into computer database manually by keyboard.

9.3 If total soluble phosphorus is desired, filter sample with a 0.45�m membrane filter. For total phosphorus, do NOT filter at this point.

9.4 Sample digestion: place a 50 mL well-mixed aliquot of sample in a 125 mL Erlenmeyer flask. To the flask add 1 mL 13N sulfuric acid and 0.4 g ammonium persulfate. Cover the flask with a 100 mL disposable beaker and autoclave the flasks for the sample set at 115° C for 45 minutes. Cool to a comfortable handling temperature and examine the samples.

9.4.1 If a sample contains sediment, the sediment should be a light grey color. If the sediment is brown, digestion is incomplete: add 0.8 g of additional ammonium persulfate and re-digest. If digestion remains incomplete after this step, the analysis should begin again with a new aliquot of sample, diluted two- to four-fold. The appropriate dilution is selected by the analyst based on prior experience with the method.

9.4.2 If a sample contains sediment, it must be filtered through a glass fiber filter after digestion while warm.

9.5 Pre-rinse autoanalyzer tube with the sample, then pour sample into tube and place in the autosampler tray.

9.6 Calibration standard tubes are pre-rinsed with standard solution prior to filling.


10.1 Close platens. Connect tubing using the configuration shown in Figure 16.1.

10.2 Check the level of all reagent containers to assure an adequate supply.

10.3 Heater coil and lamp are left on continuously during normal laboratory operation. If autoanalyzer is shut off completely, allow a minimum of 60 minutes for warm up.

10.4 Turn on the autoanalyzer and allow it to warm up for 30-60 minutes.

10.5 Call up the sample list from the VAX into the autoanalyzer computer.

10.6 Arrange sample tray beginning with a high-range standard as a “primer”, followed by the samples, a reagent blank and the calibration standards.


10.7 Examine the electronic trace. After a stable baseline has been obtained, start the sample run by starting the computer program which runs the autoanalyzer.

10.8 Absorbance values are transferred electronically and, together with the concentration values in the standards chosen by the analyst, are used to produce a calibration curve by least squares linear fit. The correlation coefficient on the calibration absorbances must be at least 0.99 for an acceptable calibration curve. Less than 0.99 results require the analyst to re-run the calibration curve procedure (see steps 10.6 and 10.7).

10.9 Analysis results

10.9.1 All sample concentrations must be within the range covered by standards. For any sample with a concentration exceeding this range, dilute the remaining undigested sample with a known volume of distilled water sufficiently that the concentration will fit within the range, and re-analyze. If diluting digested sample, use dilute H2SO4 (see 7.2.3) to dilute sample, then re-analyze.

10.9.2 The NCWQR computer programs will allow the analyst to enter any dilutions involved, and applies these in its calculations, reporting the concentration in the undiluted sample.

10.10 Daily shut-down procedures: Remove all reagent and sample lines, place in distilled water, pump for 10 minutes, remove from distilled water, pump air for 10 minutes. Return reagents to storage. Leave in stand-by mode.

11.0 CALCULATIONS11.1 Calculated concentrations are provided by the computer at the end of the sample run.

Concentrations are corrected for any dilutions which have been applied. The program code for these calculations is available on request.


12.1 Standards are run at the end of each tray: a blank followed by standards in order of increasing concentration. Quality control data must pass the Instrument Performance Verification parameters in Table 16.8.

12.1.1 If the calibration is unacceptable, routine operation is suspended until the source of the poor calibration is determined and corrected.

12.1.2 An unacceptable calibration may indicate contaminated or poorly prepared standards. Inspect bench sheets - analyst or QC coordinator - for evidence of calculation or other error.


12.1.3 Once the problem is identified, calibration and check standards are run and evaluated for acceptability. If acceptable calibration is achieved, the routine analysis of samples is resumed.

12.2 Digested samples are analyzed before the remainder of the sample is discarded, allowing for re-analysis if necessary.

12.3 Following the analytical run, the computer calculates a calibration curve from the standards and applies it to the samples to determine their concentrations. A report of concentrations is produced for approval by the analyst. For any samples which fall above the calibration range, the extract from the sample is diluted and re-analyzed with the next tray of samples.

12.4 Replicates, blanks and spikes are included in every sample batch.

12.4.1 Field replicates are analyzed and used to reflect the precision of the overall method including the sample collection.

12.4.2 Laboratory replicates also address the precision of the method, but only represent laboratory methods.

12.4.3 Field blanks address possible sources of contamination of sample containers prior to sample collection.

12.4.4 Laboratory blanks address possible sources of contamination in laboratory glassware and/or autoanalyzer tubing.

12.4.5 Spikes reflect the presence of matrix interference.

12.4.6 Replicates, blanks, and spike vials must be analyzed a minimum of one each for every 20 samples.


13.1 Results are reported in mg/L (i.e., parts-per-million or ppm) to the thousandth of a milligram.


14.1 Pump lines should be flushed with distilled water for 10 minutes at the end of the period of operation, and then flushed with air for 10 minutes.

14.2 Autoanalyzer tubing is replaced when it reaches 200 hours of use, to avoid atypical system operation, which can range from irregular peak shape and non-reproducible peak times to outright rupture of the tubing.


14.3 All spills should be cleaned up immediately: reagents and prepared samples can be highly corrosive.

14.4 Periodically, as needed: clean rollers with isopropyl alcohol and oil them; clean platens with distilled water; change lamps; and replace flow cells. Refer to schedules in the Traacs Maintenance Manual.

15.0 REFERENCES

15.1 Method 365.1- Edited by J. O’Dell. Determination of phosphorus by semi-automated colorimetry. EPA 600/R-93/100: Environmental Monitoring Systems Laboratory, Office of Research and Development, US EPA. Cincinnati, Ohio. 1993.

15.2 Technicon AA II system operation manual. Technical publication # TA1-0170-20. Technicon Instruments Corporation, Tarrytown, NY. 1970.

15.3 Standard Methods for the Examination of Water and Wastewater, Method 4500-P F. "Phosphorus – automated ascorbic acid reduction method", 19th Edition of Standard Methods. 1995.


16.0 TABLES, DIAGRAMS, FLOW CHARTS, AND VALIDATION DATA

Sam

ple

Asc

orbi

c re

agen

t

Mix

ed p

hosp

horu

s re

agen

t

Air

1 2 3 4 5

was

te

Flow

Cel

l

was

te

pull

thro

ugh

4.7

mL

45°C

Tubi

ng s

izes

:

m

L/m

in

colo

r cod

e

1. 0

.80

r

ed/re

d 2.

0.4

2

ora

nge/

oran

ge

3. 0

.42

o

rang

e/or

ange

4.

0.3

2

bla

ck/b

lack

5.

1.0

0

gre

y/gr

ey

Flow

Cel

l: 3

0mm

x 1

.0

Filte

r: 8

80 n

m

10 tu

rns

10 tu

rns

Figu

re 1

7.1.

Aut

oana

lyze

r Con

figur

atio

n: T

P in

Wat

er S

ampl

es

Pul

l thr

ough


Table 16.1 Method Detection Limit. The method detection limit quoted in Section 4.2 was calculated from the standard deviation of 11 standards (0.02 mg/L) analyzed in a single run on December 12, 2007, as MDL = t.01,n-1 * s

Total P Tray No.0.0213 63340.0212 63340.0211 63340.0205 63340.0206 63340.0201 63340.0199 63340.0195 63340.0193 63340.0191 63340.0191 6334


MDL 0.0023 Table 16.2 NAP Version 4.3 Parameters for tphigh

Peaks per Screen 40 Theshold 1Decimal Places 4 Ascending Slope 0.3Chart Speed 60 Descending Slope(-) 0.2Start Ignore Time 200 Apex Points 6Initial Baseline 70 Plateau Points 5Final Baseline 180 Integration Points 2Filter Level 10 Order of Fit FirstInverse Chemistry No R^2 Lower Limit 0

Table 16.3 NAP Version 4.3 tphigh Standard SettingsStandard 1 0Standard 2 0.1Standard 3 0.2Standard 4 0.5Standard 5 1

Table 16.4 NAP Version 4.3 tphigh Sampler TimesAspirate Time 50Cycle Time 60

Table 16.5 NAP Version 4.3 Parameters for tplow


Peaks per Screen 40 Theshold 1Decimal Places 4 Ascending Slope 0.7Chart Speed 60 Descending Slope(-) 0.3Start Ignore Time 200 Apex Points 6Initial Baseline 70 Plateau Points 5Final Baseline 120 Integration Points 2Filter Level 10 Order of Fit FirstInverse Chemistry No R^2 Lower Limit 0

Table 16.6 NAP Version 4.3 tplow Standard SettingsStandard 1 0Standard 2 0.01Standard 3 0.02Standard 4 0.05Standard 5 0.10

Table 16.7 NAP Version 4.3 tplow Sampler TimesAspirate Time 80Cycle Time 90

Table 16.8 Instrument Performance Verification

R2 � 0.995Duplicate ± 20%

Check Standard 0.68 - 0.92 mg/L

Instrument Performance Verification

17.0 CHANGE HISTORY17.1 Version 1 – Initial issuing of SOP; version author, Anne Stearns. 17.2 Version 2 – Update cleaning procedure; remove all references to Total Soluble Phosphorus

(TSP); include MRL value in Section 4.3; include Instrument Performance Verification in Section 12.1; insert Instrument Performance Verification parameters table 16.8; version author, Aaron Roerdink.


Table of Contents

1.0 SCOPE AND APPLICATION 1252.0 SAFETY AND TRAINING 1253.0 SAMPLE COLLECTION AND RECEIPT 1264.0 METHOD PERFORMANCE VALIDATION AND WORKING LINEAR RANGE 126 5.0 INTERFERENCES AND CORRECTIVE MEASUREMENTS 1266.0 EQUIPMENT AND SUPPLIES 1277.0 REAGENTS AND STANDARDS 1278.0 CALIBRATION PROCEDURES 1289.0 SAMPLE PREPARATION 12910.0 ANALYTICAL PROCEDURE 12911.0 CALCULATIONS 13012.0 QUALITY CONTROL REQUIREMENTS 13013.0 DATA REPORTING REQUIREMENTS 13114.0 PREVENTATIVE MAINTENANCE 13115.0 REFERENCES 13116.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA 13217.0 CHANGE HISTORY 134



1.1 This method covers the determination of soluble reactive phosphorus in filtered water samples. The term soluble reactive phosphorus refers to the analysis water samples filtered with a 0.45μm filter without digestion. This method quantifies orthophosphate and some low-molecular-weight polyphosphates.

1.2 INSTRUMENTATION: Traacs 800




2.10 Concentrated sulfuric and hydrochloric acids present various hazards and are moderately toxic and extremely irritating to skin and mucus membranes. Use these reagents in a fume hood whenever possible and if eye or skin contact occurs, flush with large volumes of water. Always wear safety glasses or a shield for eye protection, protective clothing and observe proper mixing when working with these reagents.

2.11 The acidification of samples containing reactive materials may result in the release of toxic gases, such as cyanides or sulfides. Acidification of samples should be done in a fume hood.



2.14 A new analyst who will perform analyses of soluble reactive phosphorus using this method must be first trained by an experienced analyst who is proficient in this analysis. The new analyst must demonstrate proficiency in this analysis by performing a satisfactory QC test batch (see QA SOP). Upon successful completion of the test batch, the analyst will be permitted to perform the entire soluble reactive phosphorus analysis.





3.3 Minimum sample volume to be collected for Traacs analysis: 250 mL.

3.4 If preservation is required in the Study Plan, pack the sample container containing the collected sample in ice or refrigerate for travel to laboratory. Samples collected for soluble reactive phosphorus analysis CANNOT be preserved with H2SO4 or other acid. Samples for soluble reactive phosphorus analysis must be filtered prior to analysis – field filtering is preferable.

3.5 Upon arrival at the laboratory, samples are stored at 4° C prior to analysis. Maximum refrigerated holding times are as follows: unpreserved – 48 hours.



4.1 The method detection limit based on low-level standards (2% of maximum working range) is 0.001 mg/L (Section 16).

4.2 The Working Linear Range is 0.01 to 0.1 mg/L or 0.1 to 1.0 mg/L.

4.3 The Method Reporting Limit (MRL) is 0.015 mg/L

5.0 INTERFERENCES AND CORRECTIVE MEASUREMENTS

5.1 Arsenic can interfere with this method because, like phosphorus, it also reacts to form a blue color. Arsenic has a positive interference. Correction may be necessary by detection of arsenic content by another method (see NCWQR Method 200.8 - Metals by ICP/MS) and calculation of difference.


5.2 Mercuric chloride leads to a background absorbance which increases over time. For samples known to be preserved with mercuric chloride, interference can be avoided by adding KCl to the mixed phosphorus reagent to provide a 0.1N KCl concentration. However, it is preferable to avoid the use of mercuric chloride as a preservative.


6.1 Traacs 800

6.2 NCWQR Manifold for phosphorus (see Figure 17.1)


6.4 Glass volumetric pipets, volumetric flasks and plastic containers for standard preparation

6.5 Plastic Traacs tubes. Soaked in acetic acid, scrubbed with a brush and rinsed at least three times with distilled water before use. Any discolored or otherwise damaged tubes are disposed and replaced with new as needed.


7.1 All reagents and stock solutions are prepared from analytical reagent grade or equivalent chemicals unless otherwise noted – assign six-month expiry to these reagents.

7.1.1 Sulfuric acid solution (5N H2SO4): Add 70 mL of conc. sulfuric acid to 800 mL of distilled water, mix and dilute to 1 Liter.

7.1.2 Ammonium molybdate solution: Dissolve 40 grams (NH4)6M7O24•4H2O in 800 mL of distilled water and dilute to 1 Liter.

7.1.3 Antimony Potassium Tartrate solution: Dissolve 2.6 g of antimony potassium tartrate in about 800 mL of distilled water and dilute to 1 Liter.

7.1.4 Sodium Laural Sulfate solution (15% SLS): Dissolve 150 grams sodium laural sulfate in 900 mL distilled water and dilute to 1 Liter.

7.1.5 Phosphorus standard stock solution: Dissolve 0.439 g KH2PO4 in 800 mL of water and dilute to 1 L. 1 mL of this stock solution in 1 L of distilled water provides a concentration of 0.1 mg/L.

7.2 Traacs solutions - Prepare as needed.


7.2.1 Ascorbic acid solution: Dissolve 58.9 g of ascorbic acid in 500 mL of distilled water and mix well. Add 50 mL of acetone and dilute to 1 L. Add 5 mL 15% SLS. Assign a one month expiry

7.2.2 Mixed reagent: combine the following reagents in the order listed: 500 mL 5 N H2SO4; 150 mL ammonium molybdate solution; and 50 mL antimony potassium tartrate. Dilute to 1 L with distilled water, and then add 5 mL SLS solution. Assign a one month expiry

7.2.3 Wash receptacle solution: distilled water.

7.3 Standards are prepared in two different concentration ranges. Assign a one week expiry to all solutions.

7.3.1 Intermediate Stock solution: 1.0 mg/L P. Prepared by addition of 5 mL of phosphorus stock (see 7.1.6) to a 500 mL volumetric flask. Dilute to volume with distilled water. (If desired, this standard can be combined with a silica standard for reactive silica analysis. See SOP NCWQR Method 370.1, Section 7.4)

7.3.2 High (Off-scale) Standard: 0.5 mg/L P. Prepared by addition of 5 mL of phosphorus stock (see 7.1.6) to a 1 L volumetric flask. Dilute to volume with distilled water.

7.3.3 Low (On-scale) Standards: 0.01, 0.02, 0.05 and 0.10 mg/L. The 0.10 mg/L Standard is prepared by pipetting 50 mL of Intermediate Stock solution (see 7.3.1) into a 500 mL volumetric flask and diluting with distilled water. The 0.05 mg/L is prepared by pipetting 50 mL of 0.10 mg/L Standard into a 100 mL volumetric flask and diluting with distilled water. The 0.02 mg/L is prepared by pipetting 20 mL of 0.10 mg/L Standard into a 100 mL volumetric flask and diluting with distilled water. Finally, the 0.01 mg/L is prepared by pipetting 10 mL of 0.10 mg/L Standard into a 100 mL volumetric flask and diluting with distilled water.

7.3.4 Blanks are distilled water.



8.1 The Traacs system is interfaced with the laboratory computer, and software provided by the manufacturer is used to produce a calibration curve. The software is NAP version 3.1.

8.2 Place standards at the beginning of the run of samples, with a blank followed by standards in order of increasing concentration, and analyze as if they were samples. Sample analysis is done under computer control, and the measured absorbance values are transferred electronically to a computer file.


8.3 After the run is complete, a least squares fit is applied to the absorbance values for the standards to create a calibration for the run. The regression relationship, its correlation coefficient value, and the calculated concentrations in the standards are reported on a printout at the end of the run, along with the concentrations in the samples.


9.1 Obtain sample; sign and date chain of custody form.


9.3 Filter sample with a 0.45�m membrane filter. Filter must be pre-washed with at least 200 mL of distilled water prior to sample filtration.

9.4 Rinse the autosampler vial with sample, then fill completely with sample. Place vial in the autosampler tray.

9.5 Calibration standard vials are rinsed with distilled water prior to filling with standard solutions.

10.0 ANALYTICAL PROCEDURE10.1 Close platens. Connect tubing using the configuration shown in Figure 16.1. 10.2 Check the level of all reagent containers to assure an adequate supply. Fill distilled water

reservoir. 10.3 Heater coil and lamp are left on continuously during normal laboratory operation. If Traacs is

shut off completely, allow a minimum of 60 minutes for warm up. 10.4 Turn on the Traacs and allow it to warm up for 5-10 minutes. 10.5 Flush the sampler wash receptacle with about 25 mL of distilled water. 10.6 Call up the sample list from the VAX into the Traacs computer. 10.7 Arrange sample tray beginning with a high-range standard as a “primer”, followed by a distilled

water blank. The autosampler is random-access and sampling order is dictated by a computer program.

10.8 Examine the chart recorder trace. After a stable baseline has been obtained start the sample run by starting the computer program which runs the Traacs.

10.9 Begin with 7 calibration standards. After calibration curve is created, the Traacs will run 2 washes.

10.10 Absorbance values are transferred electronically and, together with the concentration values in the standards chosen by the analyst, are used to produce a calibration curve by least squares linear fit. The correlation coefficient (R2) for the calibration absorbances past the requirement state in Table 16.8.

10.11 Next run samples, including duplicates, check standards and spikes. Finally, two “I-cup” check standards (5% and 95% of mid-range calibration standard) are run for every 20 samples, 10.11.1 All sample concentrations must be within the range covered by standards. For any

sample with a concentration exceeding this range, dilute the remaining sample with a known volume of distilled water sufficiently that the concentration will fit within the


range, and re-analyze. 10.11.2 The NCWQR computer programs will allow the analyst to enter any dilutions

involved, and applies these in its calculations, reporting the concentration in the undiluted sample.

10.12 Daily shut-down procedures: Remove all reagent and sample lines, place in distilled water and pump for 10 minutes. Next, remove all lines from distilled water and pump air for 10 minutes. Open platens after pumping air. Return reagents to storage and leave instrument in stand-by mode

11.0 CALCULATIONS11.1 Calculated concentrations are provided by the computer at the end of the sample run.



12.1 Standards are run at the beginning of each tray: a blank followed by standards in order of increasing concentration. Quality control data must pass the Instrument Performance Verification parameters in Table 16.8.


12.1.2 An unacceptable calibration may indicate contaminated or poorly prepared standards. Inspect bench sheets - analyst or QC coordinator for evidence of calculation or other error.


12.2 Samples are analyzed before the remainder of the sample is discarded, allowing for re-analysis if necessary.







12.4.4 Laboratory blanks address possible sources of contamination in laboratory glassware and/or Traacs tubing.




13.1 Results are reported in mg/L (i.e., parts-per-million or ppm) to three significant digits.



14.2 Traacs tubing is replaced when it reaches 200 hours of use, to avoid atypical system operation, which can range from irregular peak shape and non-reproducible peak times to outright rupture of the tubing.



15.0 REFERENCES

15.1 Method 365.1- Edited by J. O’Dell. Determination of phosphorus by semi-automated colorimetry. EPA 600/R-93/100: Environmental Monitoring Systems Laboratory, Office of Research and Development, US EPA. Cincinnati, Ohio. 1993.

15.2 Traacs 800 Continuous Flow Analytical System Operation Manual Version 3.03. Bran + Luebbe Analyzing Technologies, Inc. Elmsford, N.Y. 1988.

15.3 Standard Methods for the Examination of Water and Wastewater, Method 4500-P F."Phosphorus – automated ascorbic acid reduction method", 19th Edition of Standard Methods. 1995.


16.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA

High High range

Sampl

Ascorbic

Mixed phosphorus reagent

Ai

1

2

3

4

5

wast

4.7 mL

45°

Flow

wast

Tubing sizes:

mL/mi color

1. 1.00 grey/gre

2. 1.00 grey/ y

y

range

4. 0.42 orange/orange

5. 0.32 black/black

6. 1.00

Flow 0 (low range) 50mm x 1.0 (high range)

Filtegre

3. 0.42 orange/o

Cells: 10mm x 1.

r: 880 nm

10 10

Figure 17.1 Autoanalyzer Configuration: SRP in Water Samples, low range and high range

Pull 6

1 2

3 4

5 6 Pull through

Low

Air

Mixed phosphorus reagent

Ascorbic reagent

Sample

wast

10 10

4.7 45°

Low

Flow

wast

Tubing sizes: Flow Cells: 10mm x 1.0 (low range)

50mm x 1.0 (high range)

mL/min

color code

1. 1.00 grey/grey

2. 1.00 grey/grey Filter: 880 nm



5. 0.32 black/black

Note: Phasing is important! 6. 1.00 grey/grey

Note: Phasing is important!

Figure 16.1 Autoanalyzer Configuration: SRP in Water Samples, low range and high range


Table 16.1 Method Detection Limit. The method detection limit quoted in Section 1.5 was calculated from the standard deviation of 10 low-level standards (0.005 mg/L) analyzed in a single run on December 12, 2007, as MDL = t.01,n-1 * s

SRP Tray No.0.0028 90580.0030 90580.0031 90580.0032 90580.0036 90580.0035 90580.0031 90580.0035 90580.0031 90580.0028 9058


MDL 0.0008Table 16.2 NAP Version 4.3 Parameters for SRP.MTH

Peaks per Screen 20 Theshold 1Decimal Places 4 Ascending Slope 0.2Percent Full Scale 100 Descending Slope(-) 8Chart Speed 60 Apex Points 5Start Ignore Time 340 Plateau Points 10Initial Baseline 60 Integration Points 5Final Baseline 120 Corrections ONFilter Level 5 Order of Fit First

Units mg/L soluble P

Force Through Origin No

Rpt Neg Conc. Yes R^2 Lower Limit 0.0000Rpt Neg Peak Hts. Yes Inverse Chemistry NoDraw Baseline Yes

Table 16.3 NAP Version 4.3 SRP.MTH Standard Settings Standard 1 0.1Standard 2 0.05Standard 3 0.02Standard 4 0.01Standard 5 0.00

Table 16.4 NAP Version 4.3 SRP.MTH and SRP2.MTH Dilution Concentrations

Cycle 1 0.50Cycle 2 0.00

Table 16.5 NAP Version 4.3 SRP.MTH and SRP2.MTH Sampler Times


Aspirate Time 50Cycle Time 60

Table 16.6 NAP Version 4.3 Parameters for SRP2.MTHPeaks per Screen 20 Theshold 1Decimal Places 4 Ascending Slope 0.2Percent Full Scale 100 Descending Slope(-) 8Chart Speed 60 Apex Points 5Start Ignore Time 340 Plateau Points 1Initial Baseline 60 Integration Points 3Final Baseline 120 Corrections ONFilter Level 3 Order of Fit First

Units mg/L soluble P


Rpt Neg Conc. Yes R^2 Lower Limit 3Rpt Neg Peak Hts. Yes Inverse Chemistry NoDraw Baseline Yes

Table 16.7 NAP Version 4.3 SRP2.MTH Standard Settings Standard 1 0.1Standard 2 0.05Standard 3 0.02Standard 4 0.01Standard 5 0.00Standard 11 0.5

Table 16.8 Instrument Performance Verification Parameters


Check Standard Icup 1 0.00425 - 0.00575 mg/LCheck Standard Icup 2 0.08075 - 0.10925 mg/L


17.0 CHANGE HISTORY17.1 Version 1 – Initial issuing of SOP; version author, Anne Stearns. 17.2 Version 2 – Update cleaning procedure; include MRL value in Section 4.3; include Instrument

Performance Verification in Section 12.1; insert Instrument Performance Verification parameters table 16.8; version author, Aaron Roerdink.

17.3 Version 3 – Correct the concentration limits for IPV; version author, Aaron Roerdink


Table of Contents

1.0 SCOPE AND APPLICATION 1372.0 SAFETY AND TRAINING 1373.0 SAMPLE COLLECTION AND RECEIPT 1384.0 METHOD PERFORMANCE VALIDATION AND WORKING LINEAR RANGE 138 5.0 INTERFERENCES AND CORRECTIVE MEASUREMENTS 1386.0 EQUIPMENT AND SUPPLIES 1397.0 REAGENTS AND STANDARDS 1398.0 CALIBRATION PROCEDURES 1409.0 SAMPLE PREPARATION 14110.0 ANALYTICAL PROCEDURE 14111.0 CALCULATIONS 14212.0 QUALITY CONTROL REQUIREMENTS 14213.0 DATA REPORTING REQUIREMENTS 14314.0 PREVENTATIVE MAINTENANCE 14315.0 REFERENCES 14416.0 TABLES, DIAGRAMS, FLOW CHARTS, AND VALIDATION DATA 14517.0 CHANGE HISTORY 147



1.1 This method covers the determination of total Kjeldahl nitrogen (TKN) in drinking and surface waters, and domestic and industrial wastes. The procedure converts nitrogen components such as amino acids, proteins and peptides to ammonia, but may not convert the nitrogenous compounds of some industrial wastes such as amines, nitro compounds, hydrazones, oximes, semicarbazones and some refractory tertiary amines. The applicable range of this method is 0.1 to 20 mg/L TKN. The normal operating range at the National Center for Water Quality Research (NCWQR) is 0.5 to 2 mg/L.

1.2 INSTRUMENTATION: Autoanalyzer II




2.17 Sodium hydroxide presents various hazards and are moderately toxic and extremely irritating to skin and mucus membranes. The following chemicals have the potential to be highly toxic or hazardous: mercury, sulfuric acid, and sodium nitroprusside. Consult the appropriate Material Safety Data Sheets (MSDS) before use. Prepare these reagents in a fume hood. If eye or skin contact occurs, flush with large volumes of water. Always wear safety splash goggles or shield for eye protection and protective clothing when working with these reagents.


2.19 Appropriate disposal of wastes from these analyses is the responsibility of the analyst. See Section 7.0 for disposal methods.


2.21 A new analyst who will perform analyses of Total Kjeldahl Nitrogen (TKN) using this method must be first trained by an experienced analyst who is proficient in this analysis. The new analyst must demonstrate proficiency in this analysis by performing a satisfactory QC test batch (see QA SOP). Upon successful completion of the test batch, the analyst will be permitted to perform the entire total Kjeldahl nitrogen analysis.





3.3 Minimum sample volume to be collected for autoanalyzer analysis: 250 mL

3.4 If preservation is required in the Study Plan, pack the sample container containing the collected sample in ice or refrigerate for travel to laboratory. Samples collected for TKN analysis alone may be preserved with H2SO4 to lower the pH below 2. Samples collected for multiple analyses should NOT be preserved in this manner to prevent interference in other analytical procedures.

3.5 Upon arrival at the laboratory, samples are stored at 4° C prior to analysis. Maximum refrigerated holding times are as follow: preserved with H2SO4 - 28 days; unpreserved – 48 hours.



4.1 The method detection limit based on low-level standards (2% of maximum working range) is mg/L (Section 16).

4.2 The Working Linear Range is 0.5 to 2.0 mg/L.

4.3 The Method Reporting Limit (MRL) is 0.2 mg/L.


5.1 Calcium and magnesium ions may be present in sufficient concentrations to cause precipitation interference. 5% EDTA is used to prevent this. See section 7.2.

5.2 Sample turbidity and color can interfere with this method. Samples are allowed to settle after digestion prior to analysis. See section 9.1.



6.1 Autoanalyzer II

6.2 Block digester-40 and controller

6.3 NCWQR Manifold for Ammonia (see Figure 17.1)


6.5 Chemware TFE (Teflon boiling stones), Markson Science, Inc., Box 767, Delmar, CA 92014). Rinsed with distilled water before use.


6.7 Digestion tubes for block digester. Rinsed at least three times with distilled water before use. Any discolored or otherwise damaged tubes are disposed and replaced with new as needed.

6.8 Autoanalyzer tubes. Soaked in acetic acid, scrubbed with a brush and rinsed at least three times with distilled water before use. Any discolored or otherwise damaged tubes are disposed and replaced with new as needed.


7.1 Stock solutions:

7.1.1 Phosphate buffer solution, 0.5 M: Dissolve 70g Na2HPO4 in 800 ml distilled water; add 22g NaOH; dissolve and dilute to 1 L. Assign a six month expiry.

7.1.2 NaOH solution, 5 N: Dissolve 200g NaOH in 900 ml of distilled water, allow to cool to touch, dilute to 1 L. Assign a six month expiry.

7.1.3 Urea solution: Dissolve 2.1276 g urea in distilled water and bring to volume in a 1 Liter volumetric flask. 1 mL of this solution provides 1.0 mg NH3-N. Assign a one month expiry.

7.2 Digestion reagents – assign a six-month expiry to these reagents.

7.2.1 Mercuric sulfate: Dissolve 2.0 g red mercuric oxide (HgO) in 25 mL of 5 N sulfuric acid.


7.2.2 Digestion reagent: (Sulfuric acid-mercuric sulfate potassium sulfate solution): Dissolve 134 g of K2SO4 in 700 mL of distilled water and 200 mL of concentrated H2SO4. Add the mercuric sulfate solution (see 7.2.1) and dilute to 2.0 liters.

7.3 Autoanalyzer solutions

7.3.1 Complexing reagent: Dissolve 30g EDTA Disodium salt in 600 ml distilled water. Add 0.5g KCl and 100 ml 0.5M phosphate buffer. Set pH to 11 with 5N NaOH and dilute to 1 L. Add 5ml of Brij-35 wetting agent. Assign a six month expiry.

7.3.2 Sodium Nitroprusside: Dissolve 0.25 g sodium nitroprusside in 1 L of distilled water. Assign a six month expiry.

7.3.3 Assign a six month expiry.

7.3.4 Sodium Hypochlorite solution: Mix 500 mL of household bleach (5.25%) with 500 mL ammonia-free distilled water. Assign a one month expiry.

7.3.5 Sulfuric acid 0.1% (0.036 N): Add 1 mL conc. sulfuric acid to 1 L of distilled water. Assign a six month expiry.

7.3.6 Sodium hydroxide - EDTA solution: Add 80 g NaOH and 20g Na4EDTA up to 1000 mL with distilled water. Assign a six month expiry

7.3.7 Sulfuric acid rinse water (1.26 N): Add 35 mL conc. sulfuric acid to 1 L of distilled water. Assign a six month expiry.

7.4 Standards

7.4.1 Distilled water is used as the blank.

7.4.2 Standards: 0.5, 1, or 2 mL of urea standard (see 7.1.3) brought up to 1L for 0.5, 1.0, or 2.0 mg/L standards, respectively.



8.1 The autoanalyzer system is interfaced with the laboratory computer, and software provided by the manufacturer is used to produce a calibration curve. The software is NAP version 3.1.

8.2 Place pairs of standards at the end of the run of samples, with a pair of blanks followed by a pair of 0.5 mg/L standards, a pair of 1 mg/L standards, and a pair of 2 mg/L standards, and analyze as


if they were samples. Sample analysis is done under computer control, and the measured absorbances are transferred electronically to a computer file.





9.3 Add 25 mL of sample to a digestion vial. Then add 4mL digestion reagent (see 7.2.2) using an auto pipette.

9.4 Add 4 to 8 Teflon boiling stones. Too few boiling chips will cause the sample to boil over.

9.5 With Block Digester in automatic mode, set low and high temperature at 180°C and 360°C respectively. Place tubes in digester. The block is preset at the low temperature time for 1.5 hours and the high temperature time For 3.5 hours. The block must cool below 100°C before the next set of samples can be digested.

9.6 Cool sample after digestion and add back 10 mL ammonia-free distilled water with an autopipette. Mix thoroughly in the digestion vial, pre-rinse autoanalyzer tube with the sample, then pour sample into tube and place in the autosampler tray.

9.7 Calibration standard tubes are pre-rinsed with standard solution prior to filling with standard solutions..and pouring into an autoanalyzer vial for analysis.

9.8 Allow turbid samples to settle overnight before analysis. To avoid aspirating solids into the autoanalyzer, insure that the autosampler tubing is set at an appropriate height above any sedimentation.



10.2 Check the level of all reagent containers to assure an adequate supply. Fill acid water (7.3.7) reservoir.


10.3 Heater coil and lamp are left on continuously during normal laboratory operation. If autoanalyzer is shut off completely, allow a minimum of 60 minutes for warm up.

10.4 Turn on the autoanalyzer and allow it to warm up for 5-10 minutes.

10.5 Call up the sample list from the VAX into the autoanalyzer computer.

10.6 Arrange sample tray beginning with a high-range standard as a “primer”.

10.7 Examine the electronic trace. After a stable baseline has been obtained start the sample run by starting the computer program which runs the autoanalyzer.

10.8 Absorbance values are transferred electronically and, together with the concentration values in the standards chosen by the analyst, are used to produce a calibration curve by least squares linear fit. The correlation coefficient (R2) for the calibration absorbances past the requirement state in Table 16.5.

10.9 Run samples, including duplicates, check standards and spike. Lastly, the 7 calibration standards. After calibration curve is created, the autoanalyzer will run 2 washes.

10.9.1 All sample concentrations must be within the range covered by standards. For any sample with a concentration exceeding this range, re-analyze the sample; prepare dilution and begin with step 9.3.


10.10 Daily shut-down procedures: Remove all reagent and sample lines, place in distilled water and pump for 10 minutes. Open platens. Return reagents to storage and leave instrument in stand-by mode.

11.0 CALCULATIONS

11.1 Calculated concentrations are provided by the computer at the end of the sample run. Concentrations are corrected for any dilutions which have been applied.


12.1 Standards are run at the end of each tray: a blank followed by standards in order of increasing concentration. Quality control data must pass the Instrument Performance Verification parameters in Table 16.5.





12.2 Digested samples are analyzed before the remainder of the sample is discarded, allowing for re-analysis if necessary.






12.4.4 Laboratory blanks address possible sources of contamination in laboratory glassware and/or autoanalyzer tubing.




13.2 Results are reported in mg/L (i.e., parts-per-million or ppm) to hundredths of a milligram.




14.6 Autoanalyzer tubing is replaced when it reaches 200 hours of use, to avoid atypical system operation, which can range from irregular peak shape and non-reproducible peak times to outright rupture of the tubing.


14.8 Periodically, as needed: clean rollers with isopropyl alcohol and oil them; clean platens with distilled water; change lamps; replace flow cells and replace dialysis membrane. Refer to schedules in the Autoanalyzer II Maintenance Manual.

15.0 REFERENCES

15.4 Method 351.2- Revision 2.0. Edited by J. O’Dell. Determination of total kjeldahl nitrogen by semi-automated colorimetry. EPA 600/R-93/100: Environmental Monitoring Systems Laboratory, Office of Research and Development, US EPA. Cincinnati, Ohio. 1993.

15.5 Technicon AA II system operation manual. Technical publication # TA1-0170-20. Technicon Instruments Corporation, Tarrytown, NY. 1970.

15.6 Standard Methods for the Examination of Water and Wastewater, Method 4500-Norg and 4500-N G "Nitrogen ammonia – automated phenate method", 19th Edition of Standard Methods. 1995.


16.0 TABLES, DIAGRAMS, FLOW CHARTS, AND VALIDATION DATA

Tubing sizes:

mL/min

color code 1. 2.00 green/green 2. 0.32 black/black 3. 0.80 red/red 4. 0.42 orange/orange 5. 0.32 black/black

mL/min

color code Flow Cell: 30mm x 1.0 Filter: 630 nm

Figure 16.1. Autoanalyzer Configuration: TKN in Water and Sediment Samples

Rinse solution

Complexing reagent Alkaline phenol Hypochlorite Nitroprusside Pull through

Air

1

3

4 5

6

7

8

waste

4.7 mL

45°CFlow Cell

waste

pull through

10 turns10 turns

10 turns

2SampleSulfuric Acid

Sodium hydroxide - EDTA 9

10

Dialysis membrane

6. 0.42 orange/orange 7. 0.80 red/red 8. 0.32 black/black 9. 0.42 orange/orange 10. 0.42 orange/orange


Table 16.1 Method Detection Limit. The ;method detection limit quoted in Section 1.5 was calculated from the standard deviation of 10 low-level standards (0.5 mg/L) analyzed in a single run on July 17, 2006, as MDL = t0.5,n-1 * s

Trial TKN (mg/L) 1 0.4229 2 0.5054 3 0.4867 4 0.4940 5 0.4922 6 0.5062 7 0.4898 8 0.5038 9 0.4931 10 0.4822 Mean 0.4876 Std. Dev. 0.0241 MDL 0.0680

Table 16.2 NAP Version 4.3 Parameters for tknhigh Peaks per Screen 40 Theshold 1Decimal Places 4 Ascending Slope 0.3Chart Speed 60 Descending Slope(-) 0.2Start Ignore Time 200 Apex Points 6Initial Baseline 70 Plateau Points 5Final Baseline 180 Integration Points 3Filter Level 12 Order of Fit FirstInverse Chemistry No R^2 Lower Limit 0

Table 16.3 NAP Version 4.3 tknhigh Standard SettingsStandard 1 0Standard 2 0.5Standard 3 1.0Standard 4 2.0

Table 16.4 NAP Version 4.3 tknhigh Sampler TimesAspirate Time 80Cycle Time 90

Table 16.5 Instrument Performance Verification Parameters


Check Standard 0.64 - 0.86 mg/L



17.0 CHANGE HISTORY17.1 Version 1 – Initial issuing of SOP; version author, Anne Stearns. 17.2 Version 2 – Update cleaning procedure; include MRL value in Section 4.3; include Instrument

Performance Verification in Section 12.1; insert Instrument Performance Verification parameters table 16.5; version author, Aaron Roerdink.

17.3 Version 3 – Change method from phenol to salicylate;


Table of Contents

1.0 SCOPE AND APPLICATION 1502.0 SAFETY AND TRAINING 1503.0 SAMPLE COLLECTION AND RECEIPT 1504.0 METHOD PERFORMANCE VALIDATION AND WORKING LINEAR RANGE 151 5.0 INTERFERENCES AND CORRECTIVE MEASUREMENTS 1526.0 EQUIPMENT AND SUPPLIES 1527.0 REAGENTS AND STANDARDS 1528.0 CALIBRATION PROCEDURES 1539.0 SAMPLE PREPARATION. 15410.0 ANALYTICAL PROCEDURE 15411.0 CALCULATIONS 15512.0 QUALITY CONTROL REQUIREMENTS 15513.0 DATA REPORTING REQUIREMENTS 15614.0 PREVENTATIVE MAINTENANCE 15715.0 REFERENCES 15717.0 CHANGE HISTORY 158


1.0 SCOPE AND APPLICATION 1.1 This method covers the determination of fluoride, chloride, nitrite-N, nitrate-N, and sulfate in

filtered water samples. 1.2 INSTRUMENTATION: Dionex DX320 or Dionex ICS20000 and Chromeleon 6.80 1.3 Representative validation data for this method is presented in Table 16.1.

2.0 SAFETY AND TRAINING 2.1 The toxicity or carcinogenicity of each reagent used in this method has not been fully

established. Each chemical should be regarded as a potential health hazard and exposure to these compounds should be as low as reasonably achievable.

2.2 The laboratory has a current awareness file of OSHA regulations regarding the safe handling of

the chemicals specified in this method. A reference file of material data safety sheets (MSDS) is available in Gillmor 327 to all personnel involved in the chemical analysis.

2.3 Concentrated hydrochloric or acetic acids present various hazards and are moderately toxic and

extremely irritating to skin and mucus membranes. Prepare these reagents in a fume hood. If eye or skin contact occurs, flush with large volumes of water. Always wear safety splash goggles or shield for eye protection and protective clothing when working with these reagents.

2.4 All personnel handling environmental samples known to contain or to have been in contact with

human waste should be immunized against known disease causative agents. 2.5 Appropriate disposal of wastes from these analyses is the responsibility of the analyst. See

section 7.3 for disposal methods. 2.6 A new analyst who will perform analyses of anions using the IC method herein must be first

trained by an experienced analyst who is proficient at performing this analysis. The new analyst must demonstrate proficiency in this analysis by performing a satisfactory QC test batch (see QC SOP). Upon successful completion of the QC test batch, the analyst will be permitted to perform IC anion analysis.

3.0 SAMPLE COLLECTION AND RECEIPT 3.1 Appropriate sample quantities and collection techniques (grab, composite, etc.) are designated by

the project leader and depend on the goals of the project. Care must be taken to assure that the sample is representative of the body of water under study. Refer to the appropriate Study Plan for details of sampling requirements.



3.3 Minimum sample volume to be collected for ion chromatograph analysis: 100 mL 3.4 If preservation is required in the Study Plan, pack the sample container containing the sample in

ice or refrigerate for travel to laboratory. 3.5 Upon arrival at the laboratory, samples are stored at 4° C prior to analysis. Samples to be

processed the same day as arrival do not need to be refrigerated. Maximum refrigerated holding times are as follow: chloride, fluoride and sulfate - 28 days; nitrate – 48 hours (28 days if chlorinated); nitrite – 48 hours.

3.6 Sample collector must initial and date chain of custody form for samples delivered. Samples

received by parcel delivery must be accompanied by chain of custody paperwork. Laboratory analyst must sign and date chain of custody upon receipt. See QAP for chain of custody documents.

4.0 METHOD PERFORMANCE VALIDATION AND WORKING LINEAR RANGE 4.1 Method detection limits based on analysis of low level standards, and normal working ranges,

are shown in table 4.1 below. See QA SOP for methods for determination of MDL and section 16.0 for Validation Data.

Table 4.1 Method Detection Limits for Anions

Method Detection Limit

Working Range

Concentration Used in MDL Study

Date of MDL Study

Parameter

(mg/L) (mg/L) (mg/L) Fluoride*

0.12 0 - 5 0.2 05-2008 Chloride 0.46 0 - 500 1.0 05-2008 Nitrite-N 0.005 0 - 10 0.020 05-2008 Nitrate-N 0.079 0 - 50 0.1 05-2008 Sulfate 0.33 0 - 500 1.0 05-2008

*Fluoride is included for information only.


5.0 INTERFERENCES AND CORRECTIVE MEASUREMENTS 5.1 Samples preserved with mercuric chloride will not be accepted for analysis. Low molecular

weight organic acids can interfere with chloride and fluoride determination. Run times are adjusted when samples are suspected of containing high concentrations of organic acids.

6.0 EQUIPMENT AND SUPPLIES 6.1 Dionex DX320 with Eluent Generator or Dionex ICS2000 with Eluent Generator 6.2 Mettler AE-163 Analytical Balance. Capable of weighing to 0.01 mg. 6.3 Membrane filter apparatus, GN-6 Metricel membrane disc filters (0.45 μm, 47 mm diameter) 6.4 Glass volumetric pipets, volumetric flasks and plastic containers for standard preparation.

Minimum cleaning rinse once with tap water and then three times with distilled water. 6.5 Plastic IC vials with filter caps. Autosampler vials are soaked in dilute acetic acid, scrubbed with

a brush, and rinsed at least 3 times with distilled water prior to use. Filter caps are rinsed with distilled water prior to use. Any discolored or otherwise damaged caps or vials are disposed and replaced with new as needed.

7.0 REAGENTS AND STANDARDS 7.1 Stock solutions – all reagents are analytical reagent grade or equivalent unless otherwise noted.

7.1.1 Nitrite standard stock solution: Dissolve 6.072 g KNO2 in 800 mL of water and dilute to 1 L. 1 mL of this stock solution in 1 L of distilled water provides a concentration of 1.0 g N/L. Assign a one month expiry, store in plastic and refrigerate.

7.1.2 Fluoride standard stock solution: Dissolve 2.21 g NaF in 800 ml of water and dilute to 1

L. 1 mL of this stock solution in 1 L of distilled water provides a concentration of 1.0 g F-/L. Assign a six month expiry, store in plastic and refrigerate.

7.1.3 Chloride standard stock solution: Dissolve 21.023 g KCl in 800 mL of water and dilute

to 1 L. 1 mL of this stock solution in 1 L of distilled water provides a concentration of 10.0 g Cl-/L. Assign a six month expiry, store in plastic and refrigerate.

7.1.4 Nitrate standard stock solution: Dissolve 7.218 g KNO3 in 800 mL of water and dilute to

1 L. 1 mL of this stock solution in 1 L of distilled water provides a concentration of 1.0 g N/L. Assign a six month expiry, store in plastic and refrigerate.


7.1.5 Sulfate standard stock solution: Dissolve 18.139g K2SO4 in 800 mL of water and dilute to 1 L. 1 mL of this stock solution in 1 L of distilled water provides a concentration of 10.0 g SO4

-2/L. Assign a six month expiry, store in plastic and refrigerate. 7.2 Ion Chromatograph Solutions are prepared from stock solutions (see Section 7.1) unless

otherwise noted.

7.2.1 Reagent blank: Distilled Water >18 M�/cm resistively. 7.2.2 Eluent generator reagent: DIONEX Elugen EGC II KOH cartridge. 7.2.3 Working standards contain all analytes (chloride, fluoride, nitrite, nitrate, and sulfate) and

are prepared by the analyst. Assign a one month expiry for these standards, except nitrite which must be prepared daily.

7.2.3.1.Primary standard: add 1 mL F- stock, 2 mL NO2

- stock, 10 mL each of Cl-, NO3-

and SO4-2 stock; bring up to 1L with distilled water. (Standard 4)

7.2.3.2.Secondary standards: 10% (Standard 1), 20% (Standard 2), 50% (Standard 3), of

primary standard (prepared by dilution of primary standard, Standard 4), and 200% (Standard 5) and 500% (Standard 6) for standard curve generation (prepared by adding 1 mL F- stock, 2 mL NO2

- stock, 10 mL each of Cl-, NO3- and

SO4-2 stock to a 500 mL volumetric flask and a 200 mL volumetric flask,

respectively. Dilute with distilled water.) 7.2.3.3.Tertiary standards (“I cups”): “I Cup 1” is prepared by 10 % dilution of Standard

1 (see Section 7.2.3.2). “I Cup 2” is the primary standard (Standard 4, see Section 7.2.3.1) retained from the previous week and is used for check standard verification during batch run.

7.2.4 QC check standards – prepared by Quality Assurance Coordinator (QAC) using same

method as analyst and are incorporated when applicable. 7.3 Disposal of sample and reagent wastes: All sample and reagent wastes from this analysis are

rinsed down the sink with copious amounts of water.

8.0 CALIBRATION PROCEDURES 8.1 The Ion Chromatograph (IC) Dionex DX320 and ICS2000 systems are interfaced to a computer

with software for data collection. The software provided by the manufacturer, Chromeleon 6.80, produces a calibration curve with associated statistical data on the curve fit. The software uses this data to assign values to each standard or sample.


8.2 Place calibration standards at the beginning of the batch of samples in order of increasing concentration, and analyze as if they were samples. Sample analysis is done under computer control, and the measured conductivities are transferred automatically and instantaneously to a computer file.

8.3 After the calibration standards are complete, a least squares fit is applied to the conductivities for

the standards to create a calibration for the run. The regression relationship, its correlation coefficient value, and the calculated concentrations in the standards are reported on an electronic report at the end of the batch run, along with the concentrations in the samples.

9.0 SAMPLE PREPARATION. 9.1 Obtain sample. Sign and date chain of custody form. 9.2 Using chain of custody information, analyst enters sample ID into computer database manually

by keyboard 9.3 Filter the sample: assemble filtration apparatus with 0.45 �m filter, rinse filter with at least 200

mL of distilled water, drain off any excess water after rinsing, then filter sample.

9.3.1 If the sample is a finished drinking water sample, filtration should not be necessary. 9.4 Rinse the autosampler vial two times with sample, then fill completely with sample. Place cap on

vial and snap into place, evacuating excess sample, and place vial in the autosampler tray.

10.0 ANALYTICAL PROCEDURE10.1 Set up the DX320 (see Appendix A) or ICS2000 (see Appendix B)

10.1.1 Set autosampler to take one-half of the sample volume for analyzing. 10.1.2 Assemble autosampler vials in trays – maximum 20 field samples per batch. Include one

distilled water blank for every 20 samples, or one per sample set if less than 20 samples 10.1.3 Standards should be at room temperature before autosampler analysis is performed. 10.1.4 Include 2 tertiary check standards for every 20 samples, plus one additional primary

check standard at the end of the batch in addition to the 6 in-house calibration standards used.

10.1.5 Replicates, spiked blanks and samples are to be included in a sample run. See sections

12.3 and 12.4 for complete explanation.


10.2 Check the level of distilled water supply for eluent generation and eluent generator cartridge

containers to confirm presence of reagents for adequate volumes for runs. Refill distilled water or replace eluent generator cartridge as needed before beginning batch analysis. Software indicates eluent level – order new eluent when level reaches 15%, and replace before level reaches 5%.

10.3 Turn on the DX320 or ICS2000 system and allow to warm-up for 30 to 60 minutes. 10.4 Enter the sample list into computer file manually using keyboard. 10.5 Start the sample batch. Autosampler flushes sample path at the beginning of each sample using

sample contents to reduce carryover. At the end of each sample, a report is electronically generated to allow the analyst to check the sample results. At the end of the batch, a summary report is recorded electronically in the database memory.

10.6 Daily shut-down procedures: Place the DX320 or ICS2000 system in standby. 10.7 Analyst views the standard curves and peak graphs from the data to verify accuracy of data

generated. The data is then transferred electronically by the analyst to the laboratory VAX computer as well as a backup server.

10.8 If error is suspected, analyst follows QC protocol (section 12.0). If necessary, analyst can use

remaining half of filtered samples to re-process batch.

11.0 CALCULATIONS 11.1 Calculated concentrations are provided by the computer at the end of the sample run and account

for any dilutions that have been applied.

12.0 QUALITY CONTROL REQUIREMENTS 12.1 Following the analytical batch run, the computer calculates a calibration curve from the

standards and applies it to the samples to determine their concentrations. An electronic report of concentrations is assessed by the analyst.

12.1.1 Visually inspect analyte secondary standard peaks to look for skew in peak shape. 12.1.2 Visually inspect primary and tertiary standard values to verify conformity with standard

curve.


12.1.3 Visually inspect blank results to verify purge quality of autosampler and detect evidence of contamination.

12.2 The least squares fit of the standards used for calibration must have a correlation coefficient of at

� 0.995. The calibration is acceptable if primary and tertiary check standards reflect 85 - 115% or better recovery of all analytes.

12.2.1 If the calibration is unacceptable, routine operation is suspended until the source of the

poor calibration is determined and corrected. 12.2.2 Once the problem is identified, calibration and check standards are run and evaluated for

acceptability. If acceptable calibration is achieved, the routine analysis of samples is resumed.

12.3 If a sample value is outside the expected range but the check standard run before and after the

sample are within acceptable limits (12.2), the analyst may re-test the sample.

12.3.1 Any re-test must include a minimum of 4 vials: the sample in question bracketed between two check standards, plus a reagent blank.

12.3.2 The analyst will assign a new ID to the sample being re-tested. The original ID along

with the new ID will be entered into the QC log for future reference. 12.4 Replicates, blanks and spikes are included in every sample batch and must be analyzed a

minimum of one each for every 20 samples.


12.4.2 Laboratory replicates also address the precision of the method, but only represent

laboratory methods. 12.4.3 Field blanks address possible sources of contamination of sample containers prior to

sample collection. 12.4.4 Laboratory blanks address possible sources of contamination in laboratory glassware

and/or IC tubing. 12.4.5 Spikes reflect the presence of matrix interference.



13.1 Results are reported in mg/L (i.e., parts-per-million or ppm): chloride and sulfate to tenths of a milligram; fluoride to hundredths of a milligram; nitrite and nitrate to thousandths of a milligram.

13.2 Results are electronically stored and retrieved according to the Quality Assurance Plan. 13.3 If desired, printed reports can be generated by the analyst.

14.0 PREVENTATIVE MAINTENANCE 14.1 Systematic filtration of all samples reduces chance of autosampler tubing obstruction 14.2 Periodic cleaning of autosampler tubing: fill 6 autosampler vials with 1N HCl, followed by 18

vials with distilled water, run in flush mode.

14.3 Replace guard filter as needed to protect column function.

15.0 REFERENCES 15.1 Method 300.1- Determination of inorganic anions in drinking water by Ion Chromatography,

Revision 1.0. J. D. Pfaff, D. P. Hautman and D. J. Munch. NERL Office of Research and Development, US EPA. Cincinnati, Ohio. 1997.

15.2 Standard Methods for the Examination of Water and Wastewater, Method 4110B, "Anions by

Ion Chromatography", 19th Edition of Standard Methods. 1995. 15.3 Dionex, System DX320 Operation and Maintenance Manual, Dionex Corp., Sunnyvale,

California. 1996. 15.4 Code of Federal Regulations 40, Ch. 1, Pt. 136, Appendix B.


16.0 TABLES, DIAGRAMS, FLOWCHARTS AND VALIDATION DATA Table 16.1 Method Detection Limit. The method detection limits quoted in Section 4.1 were calculated from the standard deviation of 10 standards analyzed on the ICS2000 during May, 2008, as MDL = t.01,n-1

Tray No. Chloride Nitrite Nitrate Sulfate9147 1.1 0.018 0.091 1.19147 1.1 0.019 0.100 1.29148 1.0 0.014 0.076 1.09149 1.2 0.020 0.011 1.29151 1.5 0.020 0.119 1.49151 1.1 0.019 0.091 1.19152 1.0 0.016 0.078 1.09153 1.4 0.017 0.086 1.29153 1.2 0.019 0.092 1.19155 1.2 0.017 0.086 1.1

Average 1.2 0.018 0.083 1.1Std Dev 0.1619 0.0019 0.0280 0.1174

MDL 0.457 0.005 0.079 0.331

Table 16.2 Instrument Performance Verification Parameters.

Analyte Fluoride* Chloride Nitirite Nitrate SulfateR2 � 0.995 � 0.995 � 0.995 � 0.995 � 0.995

Duplicate ± 20% ± 20% ± 20% ± 20% ± 20%Check Standard Icup 1 NA 0.75 -1.25 mg/L 0.017 - 0.023 mg/L 0.075 - 0.125 mg/L 0.75 -1.25 mg/LCheck Standard Icup 2 NA 85 - 115 mg/L 1.7 - 2.3 mg/L 8.5 - 11.5 mg/L 85 - 115 mg/LPeak Gaussian Factor 0.8-1.15 0.8-1.15 0.8-1.15 0.8-1.15 0.8-1.15

*Fluoride data is for information only


17.0 CHANGE HISTORY 17.1 Version 1 – Initial issuing of SOP; version author, Anne Stearns. 17.2 Version 2 – Update MDL data; include Instrument Performance Verification parameters in Table

16.2; add statement on cleaning without detergent; version author, Aaron Roerdink. 17.3 Version 3 – Add ICS2000 to SOP; change concentrations for NO2

- standards; add Appendix A and B, instrumental method; update MDL data; revise IPV parameters; version author, Aaron Roerdink


Appendix A -- Method information for DX320 -4.0 Flow = 2.00 Concentration = 32 Curve = 5 Pressure.LowerLimit = 200 Pressure.UpperLimit = 3000 %A.Equate = "DI Water" LoadPosition Data_Collection_Rate = 5.0 Temperature_Compensation = 1.7 DS3_Temperature = 30 SRS_Current = 300 -3.9 Flow = 2.00 Concentration = 0.20 Curve = 5 -2.300 Pump_ECD_Relay_1.Closed ;Push load button (AS40) -2.200 Pump_ECD_Relay_1.Open 0.000 Pump_ECD.Autozero Flow = 2.00 Concentration = 0.20 Curve = 5 InjectPosition Duration=60.00 ECD_1.AcqOn 1.000 Concentration = 0.20 Curve = 5 6.000 Concentration = 6. Curve = 5 10.000 Concentration = 32.00 Curve = 5 13.500 ECD_1.AcqOff Concentration = 32.00 Curve = 5 Wait Ready End


Appendix B Method information for ICS2000 Pressure.LowerLimit = 200 [psi] Pressure.UpperLimit = 3000 [psi] %A.Equate = "%A" CR_TC = On Pump_InjectValve.State LoadPosition Data_Collection_Rate = 5.0 [Hz] CellTemperature.Nominal = 30.0 [°C] ColumnTemperature.Nominal = 35.0 [°C] Suppressor_Type = ASRS_4mm ; Pump_ECD.Hydroxide = 60.0 ; Pump_ECD.Recommended Current = 149 ; Pump_ECD.Carbonate = 0.0 ; Pump_ECD.Bicarbonate = 0.0 ; Pump_ECD.Tetraborate = 0.0 ; Pump_ECD.Other eluent = 0.0 Suppressor_Current = 149 [mA] ECD_Total.Step = 0.20 [s] ECD_Total.Average = Off Channel_Pressure.Step = 0.20 [s] Channel_Pressure.Average = Off Flow = 1.00 [ml/min] -2.300 Pump_ECD_Relay_1.Closed Duration=8.00 0.000 Concentration = 10.00 [mM] Curve = 5 Autozero ECD_1.AcqOn ECD_Total.AcqOn Channel_Pressure.AcqOn Pump_InjectValve.InjectPosition Duration=30.00 Concentration = 10.00 [mM] Curve = 5 12.000 Concentration = 60.00 [mM] Curve = 5 14.000 Concentration = 60.00 [mM] Curve = 5 Concentration = 10.00 [mM] Curve = 5 ECD_1.AcqOff ECD_Total.AcqOff Channel_Pressure.AcqOff End


Table of Contents

1.0 SCOPE AND APPLICATION 1632.0 SAFETY AND TRAINING 1633.0 SAMPLE COLLECTION AND RECEIPT 1634.0 METHOD PERFORMATION VALIDATION AND WORKING LINEAR RANGE 164 5.0 INTERFERENCES AND CORRECTIVE MEASUREMENTS 1646.0 EQUIPMENT AND SUPPLIES 1647.0 REAGENTS AND SUPPLIES 1658.0 CALIBRATION PROCEDURES 1669.0 SAMPLE PREPARATION 16610.0 ANALYTICAL PROCEDURES 16611.0 CACULATIONS 16712.0 QUALITY CONTROL REQUIREMENTS 16813.0 DATA REPORTING REQUIREMENTS 16914.0 PREVENTATIVE MAINTENANCE 16915.0 REFERENCES 16916.0 TABLES, DIAGRAMS, FLOW CHARTS AND VALIDATION DATA 17017.0 CHANGE HISTORY 173



1.1 This method covers the determination of ammonia N in water. The applicable range of this method is 0.01 to 1 mg/L NH3 as N.





2.3 Sodium hydroxide and phenol present various hazards and are moderately toxic and extremely irritating to skin and mucus membranes. Phenol and sodium nitroprusside can cause rapid lowering of blood pressure from high exposure. Prepare these reagents in a fume hood. If eye or skin contact occurs, flush with large volumes of water. Always wear safety splash goggles or shield for eye protection and protective clothing when working with these reagents.



2.6 A new analyst who will perform analyses of ammonia using the Traacs method herein must be first trained by an experienced analyst who is proficient at performing this analysis. The new analyst must demonstrate proficiency in this analysis by performing a satisfactory QC test batch (see QC SOP). Upon successful completion of the QC test batch, the analyst will be permitted to perform Traacs ammonia analysis.



3.8 HDPE sample containers, sample glassware, and reagent glassware are cleaned with tap water, and then rinsed with Type II reagent (processed through a reverse osmosis system) water before


use. If contamination is observed in the Reagent blank, sample containers and glassware is cleaned with detergent. For grab samples, rinse sample containers with sample water before filling container for analysis. Autosampler is equipped with a line purge cycle after each sample is drawn. Label sample containers to identify location, date, collector’s initials and time of sample.

3.9 Minimum sample volume to be collected for Traacs analysis: 100 mL.

3.10 If preservation is required in the Study Plan, pack the sample container containing the collected sample in ice or refrigerate for travel to laboratory. Samples collected for multiple analyses should NOT be preserved in this manner to prevent interference in other analytical procedures.

3.11 Upon arrival at the laboratory, samples are stored at 4° C prior to analysis. Maximum refrigerated holding times are as follow: preserved with H2SO4 - 28 days; unpreserved – 48 hours.

3.12 Sample collector must initial and date chain of custody form for samples delivered. Samples received by parcel delivery must be accompanied by chain of custody paperwork. Laboratory analyst must sign and date chain of custody upon receipt. See QAP for chain of custody documents.

4.0 METHOD PERFORMATION VALIDATION AND WORKING LINEAR RANGE

4.1 The method detection limit based on low-level standards (5% of maximum working range) is 0.0257 mg/L (Section 16).

4.2 The Working Linear Range is 0.01 to 1 mg/L.


5.1 Calcium and magnesium ions may be present in sufficient concentrations to cause precipitation interference. 5% EDTA is used to prevent this. See section 7.2.

5.2 Sample turbidity and color can interfere with this method. Samples are filtered prior to analysis. See section 9.1.


6.1 Traacs 800

6.2 NCWQR Manifold for Ammonia (see Figure 17.1)

6.3 Mettler AE-163 Analytical Balance. Capable of weighing to 0.01 mg.



6.5 Traacs tubes. Soaked in acetic acid, scrubbed with a brush and rinsed at least three times with distilled water before use. Any discolored or otherwise damaged tubes are disposed and replaced with new as needed.

7.0 REAGENTS AND SUPPLIES

7.1 All reagents are analytical reagent grade unless otherwise noted. Different volumes of stated solutions may be prepared as long as concentrations were maintained.

7.2 Stock solutions

7.2.1 Phosphate buffer solution, 0.5 M: Dissolve 70 g Na2HPO4 in 800 ml distilled water; add 22g NaOH; dissolve and dilute to 1 L. Assign a six month expiry.

7.2.2 NaOH solution, 5 N: Dissolve 200g NaOH in 900 ml of distilled water, dilute to 1 L. Assign a six month expiry.

7.2.3 Ammonium chloride solution: Dissolve 0.3819 g NH4Cl in distilled water and bring to volume in a 1 Liter volumetric flask. 100 mg/L NH3-N. Assign a one month expiry.

7.3 Traacs solutions

7.3.1 Complexing reagent: Dissolve 30g EDTA Disodium salt in 600 ml distilled water. Add 0.5g KCl and 100 ml 0.5M phosphate buffer. Set pH to 11 with 5N NaOH and dilute to 1 L. Add 5ml of Brij-35 wetting agent. Assign a six month expiry.

7.3.2 Sodium Nitroprusside: Dissolve 0.25g sodium nitroprusside in 1 L of distilled water. Assign a six month expiry.

7.3.3 Alkaline Phenol: Weigh 64g of 50% w/w NaOH solution; add 100 ml of liquid phenol(~90%) then dilute to 1 L. Assign a six month expiry.

7.3.4 Sodium Hypochlorite solution: Mix 500 mL of household bleach (5.25%) with 500 mL ammonia-free distilled water. Assign a one month expiry.

7.4 Calibration Standards

7.4.1 Distilled water is used as the blank.

7.4.2 10 mg/L Off-scale Standard. Use 50 mL of the ammonium chloride stock solution (see 7.2.3); bring up to 500 mL with distilled water. Assign a one week expiry.


7.4.3 1 mg/L On-scale Standard. Take 50 mL of off-scale standard (see 7.4.2) and bring up to 500 mL with distilled water. Assign a one week expiry.

7.4.4 Low-range standards: For 100 mL quantities: 10, 20, or 50 mL of 1 mg/L on-scale standard (see 7.4.3) brought up to 100mL for 0.1, 0.2, or 0.5 mg/L standards, respectively.




8.2 Place calibration standards at the beginning of the run of samples, beginning with the blank followed by standards in order of increasing concentration and analyze as if they were samples. Sample analysis is done under computer control, and the measured absorbances are transferred electronically to a computer file.



9.1 Obtain sample from storage; sign and date chain of custody form.


9.3 Filter the sample through a 0.45 μm membrane filter. Filter must be pre-washed with at least 200 mL of distilled water prior to sample filtration.



10.0 ANALYTICAL PROCEDURES



10.2 Check the level of all reagent containers to assure an adequate supply. Fill distilled water reservoir.

10.3 Heater coil and lamp are left on continuously during normal laboratory operation. If Traacs is shut off completely, allow a minimum of 60 minutes for warm up.

10.4 Turn on the Traacs and allow to warm-up for 5-10 minutes.

10.5 Retrieve the sample list from the VAX into the Traacs computer.

10.6 Arrange sample tray beginning with a high-range standard as a “primer”, followed by distilled water blank.

10.7 Examine the electronic trace. After a stable baseline has been obtained start the sample run by starting the computer program which runs the Traacs.

10.8 Begin with 7 calibration standards. After calibration curve is created, the Traacs will run 2 washes.

10.9 Absorbance values are transferred electronically and, together with the concentration values in the standards chosen by the analyst, are used to produce a calibration curve by least squares linear fit. The correlation coefficient on the calibration absorbances must be at least 0.99 for an acceptable calibration curve. Less than 0.99 results require the analyst to re-run the calibration curve procedure (10.8 and 10.9).

10.10 Next, run samples, including duplicates, check standards and spikes. Lastly, two “I-cup” check standards (5% and 95% of mid-range calibration standard) are run for every 20 samples

10.10.1 Sample concentrations must be within the range covered by the accompanying standards. For any sample with a concentration exceeding this range, dilute the remaining portion of sample with a known volume of ammonia-free distilled water sufficiently that the concentration will fit within the range, and re-analyze.


10.11 Daily shut-down procedures: Remove all reagent and sample lines, place in distilled water, and pump for 10 minutes. Remove all lines from distilled water, pump air for 10 minutes, and finally turn off pumps. Return reagents to storage.

11.0 CACULATIONS11.1 Calculated concentrations are provided by the computer at the end of the sample run.




12.1 Standards are run at the beginning of each tray: a blank followed by standards in order of increasing concentration. The least squares fit of the standards used for calibration must have a correlation coefficient of at least 0.99, and the absorbances of the standards must be compatible with previous experience. The calibration is acceptable if check standards reflect 95% or better recovery of all analytes.


12.1.2 An unacceptable calibration may indicate contaminated or poorly prepared standards. Inspect bench sheets - analyst or QC coordinator for evidence of calculation or other error.




12.4 Replicates, blanks and spikes are included in every sample batch and must be analyzed a minimum of one each for every 20 samples.








13.1 Results are reported in mg/L (i.e., parts-per-million or ppm) to the hundredth of a milligram.






15.0 REFERENCES

15.1 Method 350.1- Revision 2.0. Edited by J. O’Dell. Determination of ammonia nitrogen by semi-automated colorimetry. EPA 600/R-93/100: Environmental Monitoring Systems Laboratory, Office of Research and Development, US EPA. Cincinnati, Ohio. 1993.


15.3 Standard Methods for the Examination of Water and Wastewater, Method 4500-N G, "Nitrogen ammonia – automated phenate method", 19th Edition of Standard Methods. 1995.


16.0 TABLES, DIAGRAMS, FLOW CHARTS AND VALIDATION DATA

Rinse

Complexing

Alkaline

Hypochlorite Nitroprussid

Pull

Air

1

3 4

5

6

7

8

waste

4.7 mL

45°

Flow

waste

Tubing sizes: mL/min color code

1. 2.00 green/green 2. 0.32 black/black 3. 0.80 red/red 4. 0.42 orange/orange

mL/min color code

5. 0.32 black/black


7 0.80 red/red

8. 0.32 black/black

Flow Cells: 30mm x 1.0 (low range) 50 mm x 1.0 (high range) Filter: 630 nm

10 turns 10 turns 10 turns

Figure 16.1 Autoanalyzer Configuration: NH3

2 Sampl

Low range High

Rinse

Complexing reagent Alkaline

Hypochlorite Nitroprusside Pull

Air

1

3 4

5

6

7

8

wast

4.7

45°

Flow

wast

Tubing sizes:

mL/mi

color code

1. 2.00 green/green

2. 0.32

3. 0.80 red/red


mL/min

color code 5. 0.32

6. 0.42

7 0.80 red/red

8. 0.32

50 mm x 1.0 (high range) Filter: 630 nm

10 turns 10 turns 10 turns

Figure 16.1 Autoanalyzer Configuration: NH3

2 Sampl

Low

High


Table 16.1 The method detection limit quoted in Section 4.0 was calculated according to the Quality Assurance Standard Operating Procedure (QA-SOP) using the data from Table 16.1. The sample for MDL determination was Icup 20070403 and analyzed from April 3rd to April 25th, 2007.

Sample Date mg/L Ammonia4/3/2007 0.0471844/3/2007 0.0527844/3/2007 0.0653644/3/2007 0.0718424/3/2007 0.0672104/3/2007 0.0697464/3/2007 0.0447334/4/2007 0.0488644/4/2007 0.0496584/4/2007 0.0730404/4/2007 0.0777934/11/2007 0.0491634/11/2007 0.0524664/11/2007 0.0612594/11/2007 0.0536584/11/2007 0.0548734/12/2007 0.0296094/12/2007 0.0642744/17/2007 0.0554444/17/2007 0.0503964/17/2007 0.0610234/17/2007 0.0479244/18/2007 0.0504204/19/2007 0.0720644/19/2007 0.0688824/24/2007 0.0641914/24/2007 0.0603984/24/2007 0.0692884/25/2007 0.0587044/25/2007 0.0624024/25/2007 0.059575Average 0.058524Std Dev 0.010468

MDL 0.025720 t = 2.457 Table 16.2 NAP Version 3.1 Parameters for AMMONIA.MTH



Unitsmg/L

soluble ammonia



Table 16.3 NAP Version 3.1 AMMONIA.MTH Standard Settings Standard 1 0.0Standard 2 0.1Standard 3 0.2Standard 4 0.5Standard 5 1.0

Table 16.4 NAP Version 3.1 AMMONIA.MTH and NH3HIGH.MTH Dilution Concentrations

Cycle 1 10.00Cycle 2 0.00

Table 16.5 NAP Version 3.1 AMMONIA.MTH and NH3HIGH.MTH Sampler Times Aspirate Time 25Cycle Time 30

Table 16.6 NAP Version 3.1 Parameters for NH3HIGH.MTH



Unitsmg/L

soluble ammonia



Table 16.7 NAP Version 3.1 NH3HIGH.MTH Standard Settings Standard 1 0.0Standard 2 N/AStandard 3 N/AStandard 4 N/AStandard 5 1.0Standard 6 2.0Standard 7 5.0Standard 8 10.0

17.0 CHANGE HISTORY17.1 Version 1 -- Initial issuing of Standard Operating Procedure; Version Author, Anne Stearns 17.2 Version 2 – Update MDL and MDL Data; correct working linear range; correct NAP software

version; remove “Semi” from title; remove preservation statement for ammonia analysis only; Version Author, Aaron Roerdink.

17.3 Version 3 – Update the cleaning procedure; Version Author, Aaron Roerdink.


Table of Contents 1.0 Scope and Application 1762.0 Safety and Training 1763.0 Sample Collection and Receipt 1764.0 Method Performance Validation and Working Linear Range 1775.0 Interferences and Corrective Measurements 1776.0 Equipment and Supplies 1777.0 Reagents and Standards 1788.0 Calibration Procedures 1799.0 Sample Preparation 17910.0 Analytical Procedure 17911.0 Calculations 18012.0 Requirements 18013.0 Data Reporting Requirements 18114.0 Preventive Maintenance 18115.0 References 18116.0 Tables, Diagrams, Flowcharts, and Validation data 18317.0 Change History 184


1.0 Scope and Application

1.1 This method covers the determination of soluble reactive silica in filtered water samples. The term soluble reactive silica refers to the analysis of filtered-water samples without digestion


2.0 Safety and Training



2.24 Specifically, concentrated nitric and hydrochloric acids present various hazards and are moderately toxic and extremely irritating to skin and mucus membranes. Use these reagents in a fume hood whenever possible and if eye or skin contact occurs, flush with large volumes of water. Always wear safety glasses or a shield for eye protection, protective clothing and observe proper mixing when working with these reagents.

2.25 The acidification of samples containing reactive materials may result in the release of toxic gases, such as cyanides or sulfides. Acidification of samples should be done in a fume hood.



2.28 A new analyst who will perform analyses of reactive silica using this method must be first trained by an experienced analyst who is proficient in this analysis. The new analyst must demonstrate proficiency in this analysis by performing a satisfactory QC test batch (see QA SOP). Upon successful completion of the test batch, the analyst will be permitted to perform the entire reactive silica analysis.

3.0 Sample Collection and Receipt




3.3 Minimum sample volume to be collected for Traacs analysis: 250 mL. The sample should be filtered through a 0.45 μm membrane filter before analysis.

3.4 If preservation is required in the Study Plan, pack the sample container containing the collected sample in ice or refrigerate for travel to laboratory.

3.5 Upon arrival at the laboratory, samples are stored at 4° C prior to analysis. Maximum refrigerated holding times are as follow: filtered and unpreserved – 28 days.


4.0 Method Performance Validation and Working Linear Range

4.1 The method detection limit based on low-level standards (0.4 mg/L) is 0.061 mg/L (Table 17.2).

4.2 The Working Linear Range is 0.1 to 20.0 mg/L.

5.0 Interferences and Corrective Measurements

5.1 Mercuric chloride leads to a background absorbance which increases over time. For samples known to be preserved with mercuric chloride, interference can be avoided by adding KCl to the mixed phosphorus reagent to provide a 0.1N KCl concentration. However, it is preferable to avoid the use of mercuric chloride as a preservative.

6.0 Equipment and Supplies

6.1 Technicon Traacs II

6.2 NCWQR Silica Manifold (see Figure 16.1)

6.3 Mettler AE-163 Analytical Balance. Capable of weighing to 0.01 mg.

6.4 Membrane filters for filtering – 0.45 �m


6.5 Volumetric pipets, plastic volumetric flasks and containers for standard preparation. Minimum cleaning required is rinsing once with tap water and three times with distilled water.

6.6 Traacs tubes. Soaked in acetic acid, scrubbed with a brush and rinsed at least three times with distilled water before use. Any discolored or otherwise damaged tubes are disposed and replaced with new as needed.

7.0 Reagents and Standards

7.1 Stock solutions – assign six-month expiry to these reagents

7.1.1 Sulfuric acid solution (0.1N H2SO4): Add 5.6 mL of conc. sulfuric acid to 800 mL of distilled water, mix and dilute to 2 Liter.

7.1.2 Sodium Lauryl Sulfate solution (15% SLS): Dissolve 150 g sodium lauryl sulfate in 900 mL distilled water and dilute to 1 Liter.

7.1.3 Silica Stock Standard 1000mg/L SiO2 : Dissolve 4.73 g of sodium metasilicate nonahydrate (Na2Mo7O24 – 9H2O) in 800 mL of distilled water in a 1L plastic volumetric flask and dilute to 1L.

7.2 Traacs solutions – prepare as needed

7.2.1 Ascorbic acid solution: Dissolve 58.9 g of ascorbic acid in 500 mL of distilled water and mix well. Add 50 mL of acetone and dilute to 1 L. Add 5 mL 15% SLS. Assign a one month expiry

7.2.2 Ammonium molybdate reagent. Mix 3.41g ammonium molybdate in 200 mL distilled water. Bring to 500 mL with 0.1N H2SO4. Add 5 mL SLS. Assign a one week expiry

7.2.3 Oxalic acid. Dissolve 43.6 grams of oxalic acid in 800 mL of distilled water and dilute to

1000 mL with distilled water. Add 5 mL of SLS. Assign a six month expiry.

7.3 Wash receptacle solution: distilled water.

7.4 Calibration Standards Assign a one week expiry to all solutions

7.4.1 The blank is distilled water.

7.4.2 Prepare silica standards 2.0, 5.0, 10.0, and 20.0 mg/L using 2.0, 5.0, 10.0, or 20.0 mL of the silica stock standard (see 7.1.4) brought up to 1 L with distilled water. (If desired, this standard can be combined with a phosphorus standard for soluble reactive phosphorus analysis. See SOP NCWQR Method 365.2, Section 7.3)



8.0 Calibration Procedures


8.2 Place standards at the beginning of the run of samples, with a blank followed by standards in order of increasing concentration, and analyze as if they were samples. Sample analysis is done under computer control, and the measured absorbances are transferred electronically to a computer file.


9.0 Sample Preparation



9.3 Filter the sample through a 0.45 μm membrane filter. Filter must be pre-washed with at least 200 mL of distilled water prior to sample filtration.



10.0 Analytical Procedure10.1 Close platens. Connect tubing using the configuration shown in Figure 16.1. 10.2 Check the level of all reagent containers to assure an adequate supply. 10.3 Heater coil and lamp are left on continuously during normal laboratory operation. If Traacs is

shut off completely, allow a minimum of 60 minutes for warm up. 10.4 Turn on the Traacs and allow it to warm up for 5-10 minutes. 10.5 Call up the sample list from the VAX into the Traacs computer. 10.6 Flush the sampler wash receptacle with about 25 mL of distilled water. 10.7 Examine the electronic trace. After a stable baseline has been obtained, start the sample run by

starting the computer program which runs the Traacs. 10.8 Absorbance values are transferred electronically and, together with the concentration values in


the standards chosen by the analyst, are used to produce a calibration curve by least squares linear fit. The correlation coefficient on the calibration absorbances must be at least 0.99 for an acceptable calibration curve. A result of less than 0.99 requires the analyst to re-run the calibration curve procedure (see steps 10.6 and 10.7).

10.9 Analysis results 10.9.1 All sample concentrations must be within the range covered by standards. For any sample with a concentration exceeding this range, dilute the remaining sample with a known volume of distilled water sufficiently that the concentration will fit within the range, and re-analyze.


10.10 Daily shut-down procedures: Open platens after pumping air for 10 minutes, remove all reagent and sample lines, place in distilled water, pump for 10 minutes, remove from distilled water, pump air for 10 minutes. Return reagents to storage. Leave in stand-by mode.

11.0 Calculations11.1 Calculated concentrations are provided by the computer at the end of the sample run.

Concentrations are corrected for any dilutions which have been applied.

12.0 Requirements

12.1 Standards are run at the beginning of each tray: a blank followed by standards in order of increasing concentration. The least squares fit of the standards used for calibration must have a correlation coefficient of at least 0.99, and the absorbances of the standards must be compatible with previous experience. The calibration is acceptable if check standards reflect 95% or better recovery of all analytes.














13.0 Data Reporting Requirements

13.1 Results are reported in mg/L (i.e., parts-per-million or ppm) to the hundredth of a milligram.

14.0 Preventive Maintenance





15.0 References

15.1 Method 370.1- “Silica, Dissolved (Colorimetric)” US EPA. 1978.



15.3 Standard Methods for the Examination of Water and Wastewater, Method 4500-SiO2 E. "Automated Method for Molybdate-Reactive Silica", 21st Edition of Standard Methods. 2005.

Title: Honey Creek TWG Revision Number: <#1>

Revision Date: <6/12/2009> of 238

16.0 Tables, Diagrams, Flowcharts, and Validation data

Figure 16.1 Autoanalyzer Configuration: SiO 2 in Water Samples

Flow

Filter: 660 nm

Tubing sizes:

mL/min

color code

1. 0.111 orange/white2. 0..381 3. 0.151 black/black4. 0.574 orange/yellow 5. 0.050 orange/green

10mm x 0.5 (Traacs)

Air waste20 turns 2.3 mL

Sample

Ascorbic Acid Oxalic Acid

1

5

34

6

37°C

Flow Cell

we

pt

5 turnsMolybdate 2

Deionized water

5 turns 5 turns Flow cell

pull through


Table 16.1 Method Detection Limit. The method detection limit quoted in Section 1.5 was calculated from the standard deviation of 10 low-level standards (0.4 mg/L) analyzed in a single run on June 23, 2006, as MDL = t.01,n-1 * s

Trial SiO2 (mg/L) 1 0.4409 2 0.4495 3 0.4214 4 0.4493 5 0.4591 6 0.4531 7 0.4585 8 0.4473 9 0.4365 10 0.3876 Std. Dev. 0.0216 MDL 0.0610

Table 16.2 NAP Version 4.3 Parameters for SIO2.MTHPeaks per Screen 20 Theshold 1Decimal Places 4 Ascending Slope 0.2Percent Full Scale 100 Descending Slope(-) 8Chart Speed 60 Apex Points 5Start Ignore Time 360 Plateau Points 10Initial Baseline 70 Integration Points 5Final Baseline 120 Corrections ONFilter Level 5 Order of Fit First

Unitsmg/L

soluble silica



Table 16.3 NAP Version 4.3 SIO2.MTH Standard Settings Standard 1 20.0Standard 2 10Standard 3 4Standard 4 2Standard 5 0.0

Table 16.4 NAP Version 4.3 SIO2.MTH Dilution Concentrations


Cycle 1 200.00Cycle 2 0.00

Table 16.5 NAP Version 4.3 SIO2.MTH Sampler Times Aspirate Time 50Cycle Time 60

17.0 Change History17.1 Version 1 – Initial issuing of SOP; version author, Anne Stearns. 17.2 Version 2 – Update cleaning procedure; correct references; version author, Aaron Roerdink


Appendix B-4

Water Quality in Ohio Rivers and Streams

Project Study Plan

Version 1.1 June 27, 2008

Prepared by R. Peter Richards, Senior Research Scientist

Anne M. Stearns, Research Associate National Center for Water Quality Research

Heidelberg College 310 E. Market Street Tiffin, Ohio 44883

(419) 448-2198


1. OBJECTIVES This Study Plan, implemented by the National Center for Water Quality Research (NCWQR), pertains to an on-going project that has been in operation since 1975. The project‘s objectives are to gather chemical water quality data for rivers and streams in Ohio, and to use that data to evaluate loads of the water quality constituents entering Lake Erie and the Ohio River, to detect and interpret trends in water quality, and to identify possible ecosystem and human health issues related to water quality. Data and understandings derived from the data are shared with local, state, and federal governmental agencies, with scientists and also with others who can benefit from them. Much of the data is made available at the NCWQR’s Ohio Tributary Loading Data website (http://wql-data.heidelberg.edu). In general, our data quality objectives are to sample frequently enough to resolve important environmental patterns, to achieve detection limits that are not more than 10% of the lowest concentrations of interest (MCLs, water quality standards, ecological thresholds, etc), and to attain the analytical accuracy and precision stated in each method’s standard operating procedure (SOP).

2. ISSUES This Study Plan is not driven by a single issue at a single location. Rather, it is motivated by an interest in understanding the impacts of land use of all types on surface water quality, whether in lakes, rivers or streams, and in helping to minimize negative impacts. Tributary Monitoring Stations are generally located at positions near the mouth of a river or near some physiographic transition. Stations on Lake Erie tributaries are located as close to the lake as possible while avoiding reversals of flow due to lake level rises during seiche events. On the other hand, the Scioto River station is located at Chillicothe, Ohio, at the boundary of glaciation. Below this point, the topography of the watershed is very different. Stations are located, whenever possible, at USGS gauging stations, so that flow data will be available at the same point, to facilitate load calculation. Georeferencing information about each station currently in operation is provided in the table and map in Appendix A. The major long-term issue addressed by this Study Plan is the eutrophication of Lake Erie and its control by reduction of phosphorus concentrations in the lake. This continuing study has helped to document achievement of the phosphorus target load of 11,000 metric tons P per year into Lake Erie starting in the mid-1980s. Also, this study has documented decreases in total phosphorus in the Maumee and Sandusky Rivers of about 40% between 1975 and 1995, and decreases in dissolved reactive phosphorus of more than 80%. More recently, the NCWQR has documented substantial increases in dissolved reactive phosphorus concentrations and loads, at the same time that Lake Erie is exhibiting increased phosphorus concentrations and related hypoxia and noxious algae blooms. Data from this Study Plan have helped to identify the importance of non-point pollution. The data document typical patterns of water quality response to storm runoff, from the leading peak of sediment


and sediment-attached parameters to the trailing peak of nitrite, due to its passage through tile systems. They also document the differences in concentration distributions as a function of flow that characterize systems dominated by point sources (high concentrations under ambient flow conditions) in contrast to those dominated by non-point sources (high concentrations during storm runoff, most of the load delivered in a short period of time). All of these patterns are important in understanding the ecology of these rivers, and assessing and addressing causes of impairment. Data from this project find use in many aspects of environmental management. The NCWQR data have been used by Ohio EPA in several TMDL studies. They are widely used in the development, calibration and validation of land-use/water quality models: at least four such projects are currently underway with funding from USDA and the Army Corps of Engineers. The data provide important insights into the issue of nutrient trading and the difficulties inherent in making it work. Suspended sediment data from the Maumee and Sandusky Rivers are being used to assess the water quality benefits of the Ohio Lake Erie Conservation Reserve Enhancement Project. Pesticide and nitrate data are important in evaluating the use of these rivers as raw water sources for drinking water supplies.

3. PARAMETER COVERAGE The parameters that are routinely measured in this project are shown in Table 3.1.

Table 3.1 Analytes, Analytical Equipment, and Methods of the Ohio Tributary Monitoring Program

Analytical Group Equipment Method Reference Total suspended solids Mettler Balance EPA Method 160.2* Nutrients and major ions Total phosphorus Total Kjeldahl nitrogen Ammonia nitrogen Soluble reactive phosphorus Silica Specific Conductance Nitrate nitrogen Nitrite nitrogen Chloride Fluoride Sulfate

Technicon AAII Technicon AAII Technicon TRAACS Technicon TRAACS Technicon TRAACS Technicon TRAACS Dionex Ion Chromatograph Dionex Ion Chromatograph Dionex Ion Chromatograph Dionex Ion Chromatograph Dionex Ion Chromatograph

EPA Method 365.1* EPA Method 351.2* EPA Method 350.1 EPA Method 365.1* EPA Method 370.1 EPA Method 120.1 EPA Method 300.1* EPA Method 300.1* EPA Method 300.1* EPA Method 300.1 EPA Method 300.1*

Current generation pesticides EPTC Butylate Phorate Pendamethalin Simazine Acetochlor Atrazine Terbufos Fonofos Metribuzin

Gas Chromatography/ Mass Spectroscopy (GC/MS) using a Varian Saturn II

EPA Method 507, solid phase extraction


Alachlor Linuron Metolachlor Chlorpyrifos

Table 3.1 Analytes, Analytical Equipment, and Methods of the Ohio Tributary Monitoring Program (cont)

Analytical Group Equipment Method Reference

Current generation herbicides Atrazine Alachlor Metolachlor Cyanazine

Immunoassay, Ohmicron RPA1 reader and tubes

Ohmicron Methods

Metals (major) Calcium Magnesium Sodium Potassium Strontium Barium Aluminum Iron Trace metals Copper Cadmium Lead Manganese Zinc

Varian 810 ICP-MS

EPA Method 200.8

*Note: Parameters identified with an asterisk are being submitted for the Credible Data Program at this time. All other parameters are for research purposes and may be submitted for Credible Data at a future date upon completion of additional auditing from the Ohio EPA Division of Environmental Services.

4. SAMPLING METHODS At all Tributary Monitory Stations, except the Muskingum, nutrient samples are taken three times per day using refrigerated ISCO autosamplers. Sample bases are collected and changed once per week. At a minimum during low flow periods, one sample per day is analyzed from the three collected. For periods of high flow (e.g., storm runoff events) all samples are analyzed. The Muskingum River is sampled manually once per day, samples are sent to the lab weekly, and all samples are analyzed. At all stations where autosamplers are used for sample collection, a submersible pump is used to deliver stream water to a sampling well located in the shed housing the autosampler. The peristaltic pumping system for the autosampler is used to move water from the sampling well to the adjacent autosampler. The submersible pump assures that a high-volume, well-mixed sample is is available to the autosampler. The submersible pump also supports more dependable winter collections. Timers in controlling the


submersible pumps allow hourly backflushing of the sampling lines and well. For samples for pesticide analyses, a separate refrigerated ISCO autosampler containing glass bottles is used between April 15 and August 15 for the Maumee River, Sandusky River, Honey Creek and Rock Creek stations. Three samples per day are analyzed from storm runoff events, and two samples per week during low flow periods. At the Scioto and Great Miami stations, pesticides are analyzed three times per day using the nutrient samples and immunoassay procedures. In addition, a weekly manual sample is analyzed using GC/MS. Pesticide samples are taken manually once a week at the Cuyahoga and Grand stations, and twice a week at the Muskingum station. All of these samples are analyzed using GC/MS. Between August 15 and April 15, two samples per month are collected at each station and analyzed using GC/MS. Analytical methods are listed in Table 3.1 in the previous section, and detailed in Standard Operating Procedure documents that are available upon request and are updated annually or whenever a change in procedure is made. Method detection limits are listed in Table 4.1.

Table 4.1 Method Detection and Minimum Reporting Limits

Analyte MDL Date of Study MRLSuspended Sediment * * 10 mg/L

Total phosphorus 0.056* Jun-06 0.05 mg/L Total Kjeldahl nitrogen 0.068* Jul-06 0.20 mg/L

Soluble reactive phosphorus 0.002* Jul-06 0.01 mg/L Nitrate nitrogen 0.011* Oct-06 0.11 mg/L Nitrite nitrogen 0.006* Oct-06 0.06 mg/L

Chloride 0.24* Oct-06 2.5 mg/L * Updated study to be performed in January 2008

5. SAMPLING LOCATIONS Sampling location information is presented in Appendix A; see also Table 1 and Figure 1 in Section 2.

6. SAMPLING SCHEDULE At all stations except the Muskingum, nutrient samples are taken three times per day using refrigerated ISCO autosamplers. The autosamplers are set to collect samples at 4:00, 12:00 and 20:00 hours. Sample bases are changed once per week. All samples from storm runoff events are analyzed. One sample per day (12:00 hour sample) is analyzed for samples taken during low flow periods. The Muskingum River is sampled manually once per day, samples are sent to the lab weekly, and all samples are analyzed. Between April 15 and August 15, pesticide samples are taken at the Maumee and Sandusky stations


using a separate autosampler pumping into glass bottles. Three samples per day are analyzed from storm runoff events, and two samples per week during low flow periods. At the Scioto and Great Miami stations, pesticides are analyzed three times per day using the nutrient samples and immunoassay procedures. In addition, a weekly manual sample is analyzed using GC/MS. Pesticide samples are taken manually once a week at the Cuyahoga and Grand stations, and twice a week at the Muskingum station. All of these samples are analyzed using GC/MS. Between August 15 and April 15, two samples per month are collected at each station and analyzed using GC/MS.

7. QA/QC PLANThe NCWQR maintains a Quality Assurance Plan (QAP) consistent with Ohio EPA’s “Manual of Surveillance Methods and Quality Assurance Practices”. The QAP, along with its corresponding Standard Operating Procedures (SOP’s), is described in a separate document available upon request, and incorporated into this document by reference.

8. WORK PRODUCTS

No work products will be produced for Ohio EPA on an automatic, regular basis. Chemical measurements collected during this study will be made available to the director of Ohio EPA upon request, as will any available interpretations of those measurements such as load calculations and trend analyses.

9. QUALIFIED DATA COLLECTORS AND OTHER PERSONNEL

Name Address QDC? Phone Email** David B. Baker # NCWQR* Yes 419 448-2941 dbaker R. Peter Richards NCWQR Yes 419 448-2240 prichard Anne M. Stearns NCWQR Yes 419 448-2204 astearns Jack W. Kramer NCWQR Yes 419 448-2373 jkramer Aaron Roerdink NCWQR Yes 419 448-2250 aroerdin D. Ellen Ewing NCWQR Yes 419 448-2199 eewing Barbara J. Merryfield NCWQR Yes 419 448-2199 bmerryfi

# Lead Project Manager * NCWQR: National Center for Water Quality Research, address on cover of this document. ** All email addresses are @heidelberg.edu

10. LEVEL 3 QUALIFIED DATA COLLECTOR AND LEAD PROJECT MANAGER DOCUMENTATIONDocumentation for all Qualified Data Collectors (QDC’s) and Lead Project Managers is maintained in Gillmor 327.


11. CONTRACT LABORATORY INFORMATION No contract laboratory will be used for this project. All analysis will be completed within the NCWQR and by NCWQR personnel.

12. SCIENTIFIC COLLECTOR’S PERMIT The NCWQR believes that this requirement is not applicable for this Study Plan or the type of sampling undertaken in this study.

13. DIGITAL PHOTO CATALOG OF SAMPLING LOCATIONS The NCWQR believes that this requirement is not applicable for this Study Plan or the type of sampling undertaken in this study. The NCWQR will maintain the photographic catalog if requested by the Director.

14. VOUCHER SPECIMENS This requirement is not applicable for this Study Plan; biological sampling is not being done in this study.


Document History First draft version 0.1 started September 7, 2006 Version 0.1 completed October 23, 2006 Version 1.0 completed December 7, 2007 Version 1.1 completed June 27, 2008


Appendix A

Table 1. Characteristics of the ten major Ohio Tributary Monitoring Program stations Land use above station, by percent*

River

Drainage Area above Station (sq.mi.)

Agri-

culture**

Urban

Wooded

Other***

Maumee R. at Waterville USGS 04193500 Lat, long: 41.50019, -83.712777

6,330 89.9 1.2 7.3 1.6

Sandusky R. near Fremont USGS 04198000 Lat, long: 41 18 29, 83 09 32

1,253 84.1 0.9 13.0 2.0

Honey Creek at Melmore**** USGS 04198 Lat, long: 41 01 20, 83 06 35

149

Rock Creek at Tiffin**** USGS 04198 Lat, long: 41 06 49, 83 10 06

34.6 82 2 16 0

Vermilion River at Mill Hollow USGS 04198 Lat, long: 41.38194, -82.31657

262

Cuyahoga R. at Independence USGS 04208000 Lat, long: 41 23 43, 81 37 48

708 30.4 9.6 50.1 9.9

Grand R. at Painesville USGS 04212100 Lat, long: 41 43 08, 81 13 41

686 40.0 0.9 45.2 13.1

Muskingum R. at McConnelsville USGS 03150000 Lat, long: 39.651395, -81.862592

7,420 52.0 1.7 43.4 2.9

Scioto R. at Chillicothe USGS 03231500 Lat, long: 39 20 29, 82 58 16

3,854 80.2 4.6 12.9 2.3

Great Miami R. below Miamisburg USGS 03271601 Lat, long: 39.636832, -84.291886

2,685 82.1 4.7 10.3 2.9

* Source: ODNR Division of Real Estate and Land Management


own

MAUMEE

SANDUSKYCUYAHOGA

GRAND

GREAT MIAMI

SCIOTO MUSKINGUM

0 10 20 30 40 50 MI

0 20 40 60 80 KMSampling Stations

** Includes open urban/suburban areas such as lawns *** Includes shrub/scrub lands, open water, non-forested wetlands, barren ground **** A tributary of the Sandusky River

Figure 1. Locations of the Ohio Tributary Monitoring Program stations


Appendix B


(This is a pdf document produced from Pete’s FileMaker Pro database)


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The Honey Creek Targeted Watershed Project

Work Plan and Detailed Budget (Revision of December 21, 2007)

Contact Information Dr. David B. Baker, Project Director National Center for Water Quality Research Heidelberg College 310 East Market Street Tiffin, OH 44883 Telephone: 419 448-2941 E-mail: [email protected]: 419 448-2345 Project Location:

This project will primarily be conducted in the Honey Creek Watershed (HUC 04100011-080 (HUC = Hydrological Unit Code)) of northwestern Ohio. Honey Creek is a major tributary of the Sandusky River (HUC 04100011) which drains into Sandusky Bay and Lake Erie.

Project Duration:

This project is projected to occur during a five year period beginning in January 2008 and concluding in December 2012. (These beginning and ending dates may be adjusted depending on grant processing issues within the U.S. Environmental Protection Agency.)

Project Abstract:

Water resource protection efforts since the early 1980s in the Honey Creek Watershed and other northwestern Ohio agricultural watersheds have focused on reducing the export of suspended solids and particulate phosphorus to Lake Erie, primarily through the use of conservation tillage, and more recently, streamside buffers. Tributary monitoring programs show that successes in reducing particulate pollutants have been accompanied by increased export of both dissolved reactive phosphorus and nitrate, which pose threats to Lake Erie and public water supplies, respectively. Meanwhile, TotalMaximum Daily Load (TMDL) studies have revealed the need to address impaired biological communities, especially in the headwater streams of Ohio’s agricultural watersheds.

In this project, strategies outlined in the state-approved Honey Creek Watershed Action Plan will be implemented. These include sets of Best Management Practices (BMPs) that simultaneously address the causes of both the increased dissolved nutrient export and the impaired biological communities. BMP targeting will be used to maximize reductions in soluble phosphorus export. Program outputs will be measured in terms of acres, types, and locations of BMPs adopted; while environmental outcomes


will be measured through a continuation of pollutant export studies and initiation of a stratified sampling program to assess stream habitat and biological community recovery.

Purpose of This Document

This document is intended to amplify the work plan and budget outlined in the proposal which the National Center for Water Quality Research (NCWQR) submitted to the U.S. Environmental Protection Agency, Targeted Watershed Grants Program, Implementation Grant Program Request for Proposals 2006/2007. Our Honey Creek Targeted Watershed Project Proposal was selected by the U.S. Environmental Protection Agency for support, pending submission of an acceptable work plan and detailed budget. In particular, this document lists the major work tasks and associated outputs under each of the four major project components (project administration, project outreach and education, project implementation, and project outcome monitoring). Detailed budgets are presented for each of the major project components. This work plan also is accompanied by the various applications, certifications and assurances listed on the Checklist For Applications: Required Items To Be Submitted.

Overview of this Document

This document presents a brief overview of the project, including a description of the major environmental goals (outcomes) of the project. This is followed by work plans for each of the four major components of the project. Detailed budgets for each component are then presented. Accordingly, the outline for the balance of this document is as follows.

Topic .............................................................................................................................Page Abbreviations and Acronyms ..............................................................................................4 I. Project Overview and Goals .............................................................................................5

A. Environmental problems and watershed planning....................................................5 B. Project Outcomes ......................................................................................................6

II. Work Plan........................................................................................................................6 A. Project Administration ..............................................................................................6

1. General Description .............................................................................................6 2. Work tasks ...........................................................................................................6 3. Work task timeline...............................................................................................7 4. Work task outputs ................................................................................................7 5. Work task staffing................................................................................................8

B. Project Outreach and Education................................................................................8 1. General Description .............................................................................................8 2. Work tasks ...........................................................................................................8 3. Work task timeline...............................................................................................8 4. Work task outputs ................................................................................................9 5. Work task staffing................................................................................................9


C. Project BMP Implementation....................................................................................9 1. General Description .............................................................................................9 2. Work tasks .........................................................................................................10 3. Work task timeline.............................................................................................11 4. Work task outputs ..............................................................................................12 5. Work task staffing..............................................................................................12

D. Project Outcome Monitoring ..................................................................................12 D.(1) Project Outcome Monitoring – Chemical Monitoring Program ........................13

1. General Description ...........................................................................................13 2. Work tasks .........................................................................................................13 3. Work task timeline.............................................................................................13 4. Work task outputs ..............................................................................................14 5. Work task staffing..............................................................................................14

D.(2) Project Outcome Monitoring – Biological and Habitat Monitoring Program ...15 1. General Description ...........................................................................................15 2. Work tasks .........................................................................................................15 3. Work task timeline.............................................................................................17 4. Work task outputs ..............................................................................................18 5. Work task staffing..............................................................................................18

III. Detailed Budget (Based on revised SF-424 A)............................................................18 A. Project Administration ............................................................................................19

1. Detailed Budget .................................................................................................19 2. Budget Justification ...........................................................................................20

B. Project Outreach and Education..............................................................................20 1. Detailed Budget .................................................................................................20 2. Budget Justification ...........................................................................................21

C. Project BMP Implementation..................................................................................21 1. Detailed Budget .................................................................................................22 2. Budget Justification ...........................................................................................22

D. Project Outcome Monitoring ..................................................................................23 1. Detailed Budget .................................................................................................23 2. Budget Justification ...........................................................................................23

IV. Quality Assurance Narrative Statement ......................................................................24 V. Other Forms, Assurances ............................................................................................24 VI. Biosketches/short vitae ................................................................................................24 V1. Work Plan Appendix...................................................................................................25


Abbreviations and Acronyms BMPs = Best Management Practices (for reducing nonpoint source pollution) Coalition = Sandusky River Watershed Coalition

(see http://www.sanduskyriver.org/watershed/) CREP = Conservation Reserve Enhancement Program (a USDA program) DRP = dissolved reactive phosphorus (a specific type of dissolved phosphorus) EQIP = Environmental Quality Incentive Program (a USDA program) FSA = Farm Service Agency (a USDA agency) HHEI = Headwaters Habitat Evaluation Index (an OEPA habitat index for headwater streams) HUC = Hydrological Unit Code NCWQR = National Center for Water Quality Research (Heidelberg College, formerly the Water

Quality Laboratory (WQL)) NRCS = Natural Resource Conservation Service (a USDS agency) OEPA = Ohio Environmental Protection Agency PP = particulate phosphorus (phosphorus attached to particles, especially suspended sediments. QAPP = Quality Assurance Project Plan QDC = Qualified Data Collector (designation used by the Ohio EPA as part of their credible data

progam) QHEI = Qualitative Habitat Evaluation Index SS = suspended solids (primarily eroded soil particles suspended in water) STORET = EPA’s data STOrage and RETrieval system SWCD = Soil and Water Conservation District (county level organizations that support and operate soil

and water conservation programs) WAP = Watershed Action Plan (an integrated water resource protection plan, generally developed for

HUC-11 sized watersheds.) WSOS = Wood, Sandusky, Ottawa, Seneca (counties) Community Action Commission, Inc. (The parent

organization of the Sandusky River Watershed Coalition) TMDL = Total Maximum Daily Load (a program to integrate pollutant reduction from multiple sources) USDA = U.S. Department of Agriculture


I. Project Overview and Goals A. Environmental problems and watershed planning:

The major water quality problems within the Honey Creek watershed include high export of dissolved reactive phosphorus (DRP) that impacts Lake Erie, high nitrate concentrations that impact public water supplies, and impaired aquatic communities, particularly in headwater streams (streams with drainage areas <20 square miles). The primary causes of the biological impairments are degraded stream habitat, especially siltation; altered stream flow regimes, specifically lowered base flows and increased peak flows (both aspects of increasing stream “flashiness”); and stream channel modification. Solutions to all of the above problems involve working with the agricultural sector. Other problems, such as impacts from small town sewage treatment plants and failing private sewage treatment systems are being addressed by the Ohio Environmental Protection Agency (OEPA) and county health departments respectively.

Conservation efforts related to water resource protection were initiated in the Honey Creek Watershed in 1979 as part of U.S. Army Corps of Engineers’ Lake Erie Wastewater Management Study. In the Honey Creek Project, area Soil and Water Conservation Districts (SWCDs) evaluated the feasibility of using conservation tillage to achieve significant reductions in erosion and in the associated export of suspended sediments (SS) and particulate phosphorus (PP). Detailed Lake Erie tributary loading studies initiated by NCWQR had already indicated that agricultural phosphorus loading exceeded point source loading to Lake Erie, and that the restoration of Lake Erie would require nonpoint load reduction. Multi-state nonpoint source phosphorus reduction programs were subsequently built upon conservation tillage. The NCWQR’s tributary monitoring programs, including the station on Honey Creek, continue to document the outcomes of the sediment and phosphorus reduction programs and to identify emerging problems.

To support broader nonpoint source pollution control efforts at the watershed level, diverse stakeholders formed the Sandusky River Watershed Coalition (Coalition) in 1997. In 2001, the Coalition published The Sandusky River Watershed: Resource Inventory and Management Plan (http://www.sanduskyriver.org/watershed/index.php?page=Resource+Inventory). The Coalition was instrumental in advancing the OEPA’s scheduled TMDL study, so that in 2001 detailed biological and water quality studies were completed by the OEPA for the upper two-thirds of the watershed (http://www.epa.state.oh.us/dsw/documents/2001SanduskyTSD.pdf) and, in 2004, the Total Maximum Daily Loads for the Upper Sandusky River Watershed was published by the OEPA (http://www.epa.state.oh.us/dsw/tmdl/SanduskyRiverUpperTMDL.html). The Coalition has started the preparation of watershed action plans (WAPs) for each of the 14 11-digit hydrological units in the Sandusky that will implement the TMDL findings. The first of these, the Honey Creek WAP (http://www.sanduskyriver.org/watershed/index.php?page=Home/Watershed+ Planning/Honey+Creek+WAP/), has received full approval by ODNR and OEPA. This project implements major portions of that action plan.

The overall approach utilized by the Coalition in addressing agricultural nonpoint pollution problems in the Sandusky Watershed is that of adaptive management, a process of ongoing interaction among planning, implementation and monitoring. The Coalition, led by its coordinator, is associated with a 501(c)(3) nonprofit organization (WSOS, Inc.). It focuses on watershed planning and a variety of outreach efforts. Area SWCDs, which are units of local government, lead implementation programs, with support from local U. S. Department of Agriculture (USDA)


agencies. The NCWQR is associated with the science departments of Heidelberg College, a private institution of higher education. The NCWQR focuses on monitoring, research activities and adaptive management programs within the watershed and throughout Ohio and the Lake Erie Basin. B. Project Outcomes:

The anticipated outcomes of implementing the project practices are: (1) reduction of phosphorus export by 25%, as called for in the Honey Creek TMDL and WAP, with

a focus on DRP reduction; through the focus on dissolved phosphorus sources, we look to achieve a 35% reduction is DRP export.

(2) information on the extent of stream habitat recovery and biological community restoration that can occur through natural channel recovery processes as facilitated by upland erosion control, buffer strips and water management practices;

(3) a reverse in the current upward trend of stream flashiness, as measured using the Richards-Baker Index at the Honey Creek Melmore stream gage;

(4) a 50% reduction in the amount of time nitrate concentrations exceed the drinking water standards from a current average of 8.9% during the 2000-2004 period to 4.5% of the time during the last two years of the project period (as corrected for weather related variations in nitrate export). Other outcomes of this grant will be its impacts on state water resource protection and

restoration policy, particularly in relation to the problems of increasing DRP loading to Lake Erie and biological restoration of major proportions of agricultural headwater streams.

II. Work Plan A. Project Administration

1. General Description - The responsibilities of assuring that the overall project is proceeding according to the detailed work plans laid out for the major project components, including BMP implementation, outreach and education, and outcome monitoring, falls to the project director and constitutes much of the work to be accomplished under Project Administration. The project director will participate in various public meetings to provide an overview of project goals and organization and aid in the development of a project brochure. Other sub-components under Project Administration include the provision of financial oversight, the filing of annual financial status reports and semiannual work plan progress reports, production of the final project report and attendance at least one National Targeted Watershed meetings. Most of the work of Project Administration will be ongoing throughout the five year grant period.

2. Work tasks for Project Administration- a. Project oversight: Assure timely progress in all components of the grant. Oversee project

team meetings, project integration, and project adjustments. b. Prepare and submit annual financial status reports and payment requests c. Collate, prepare and submit quarterly work performance reports. d. Receive invoices from and process payments to contractors, quarterly throughout the grant

period. e. Oversee NCWQR components of project budget, quarterly throughout grant period.


f. Provide overview presentations on the Honey Creek Targeted Watershed Project to various audiences at local, regional and state meetings.

g. Attend and participate in a minimum of one National Targeted Watersheds Conference. h. Aid in development of project brochures, news releases and other education and outreach

activities. i. Prepare final project report.

3. Work task timeline – See Table 1.

Table 1. Timeline for Project Administration Project Administration Task Timeline

Project Year, beginning January 2008 (estimated project start date).

Task Jan. 2008

July 2008

Jan. 2009

July 2009

Jan. 2010

July 2010

Jan. 2011

July 2011

Jan. 2012

July 2012

a. Project oversight x x x x x x x x x x b. Annual Financial Status

Reports x x x x x

c. Quarterly Performance Reports (4/yr for 5 years)

x,x x,x x,x x,x x,x x,x x,x x,x x,x x,x

d. Process invoices and contractor payments.

x x x x x x x x x x

e. Oversee NCWQ project budgets

x x x x x x x x x x

f. Provide project presentations

x x x x x x x x x x

g. Attend National Targeted Watershed Conferences

x x

h. Aid in project brochure development, and communications

x x x x x x x x x x

i. Prepare final report x x

4. Work task outputs - The tasks described in part II.A.2 (Work Tasks, Project Administration) and scheduled according to the timeline (II.A.3.) will result in the following specific outputs. a. Annual Financial Status Reports b. Quarterly Performance Reports c. Ledger sheets and files supporting expenditures d. Presentations and lists thereof e. Attendance at National Targeted Watershed Conference(s) f. Project brochure (See Outreach and Education Component), news releases g. Final report for project

5. Work task staffing - The following persons will be responsible for conducting the work tasks described above. For Dr. Baker’s work experience and qualifications, see his biosketch in the


supplementary material. David B. Baker, Project Director Nancy Miller, Administrative Assistant, NCWQR

B. Project Outreach and Education 1. General Description- The Outreach and Education component of this project will convey

information about the need for the project, the project goals, and the ways farmers can participate in the project to residents of Honey Creek Watershed. As such, the Outreach and Education component will help pave the way for farmer adoption of BMPs supported by this project under the implementation program.

Outreach and Education will be accomplished by a variety of means including development and distribution of a project brochure, holding of public meetings in the Honey Creek Watershed, preparation of news releases and articles for publication in newspapers and newsletters, sponsorship of field days to demonstrate various combinations of BMPs for nutrient management.

Other activities under this component will be to convey the lessons learned from this project to surrounding areas, including adjacent watershed groups, state officials and representatives of federal agencies.

2. Work tasks a. Organize meetings for residents of the Honey Creek Watershed to present need for the project,

project goals, and various means to meet those goals. Two meetings will be held in year one and single annual meetings thereafter.

b. Prepare a project brochure and distribute it through the three Soil and Water Conservation District offices (Seneca, Crawford and Huron counties), county Farm Bureau organizations, county extension agents, and various agribusinesses operating in the Honey Creek Watershed. Revise brochure in year 3.

c. Prepare news releases for newspapers and newsletters to provide updates on BMP sign-up opportunities, project progress, and meetings.

d. Organize annual field days in the Honey Creek Watershed to highlight successful adoption of project BMPs.

e. Organize project conferences during year 2 and 4 to highlight project progress and issues. f. Report on project progress at state and regional meetings, years 1, 3 and 5. g. Complete quarterly progress reports for EPA Targeted Watershed reporting requirements.

3. Work task timeline - See Table 2.

Table 2. Timeline for Project Outreach and Education


Project Outreach and Education Timeline


Task Jan. 2008

July 2008

Jan. 2009

July 2009

Jan. 2010

July 2010

Jan. 2011

July 2011

Jan. 2012

July 2012

a. Organize Public Meetings for Honey Creek farmers

x x x x x x

b. Prepare and Distribute Project Brochure

x x x

c. Prepare news releases regarding project meetings, opportunities and progress

x x x x x x x x x x

d. Organize annual field days to highlight BMPs

x x x x

e. Organize Project Conferences

x x x x

f. Provide project presentations

x x x x x


x x x x x x x x x x

4. Work task outputs - The tasks described in part II.B.2 (Work Tasks, Project Administration) and

scheduled according to the timeline (II.B.3.) will result in the following specific outputs. a. Minutes and attendance sheets for public meetings b. Brochure and distribution records c. Copies of news releases and their distribution records d. Field days held, programs, and attendance records e. Conferences held, programs and attendance records. f.. Presentations held, associated power points on NCWQR Website. g. Quarterly progress reports for Outreach and Education component

5. Work task staffing - The following persons will be responsible for conducting the work tasks described above. For their experience and qualifications, see their biosketches in the supplementary material. John P. Crumrine, NCWQR Agricultural Project Coordinator Cynthia Brookes, Sandusky river Watershed Coordinator - Cindy will work through a contract

with the Sandusky River Watershed Coalition. C. Project BMP Implementation

1. General Description – The BMP implementation program will be the responsibility of the three soil and water conservation districts that operate within the Honey Creek Watershed. The Seneca SWCD will take the lead in this program and operate under a memorandum of


understanding with the other two SWCDs (Crawford and Huron). A conservation technician will be hired to work directly with farmers in the Honey Creek Watershed to engage them in those practices receiving incentive payments under this grant as well as in the adoption of various practices under the Lake Erie Conservation Reserve Enhancement Program (CREP) and the Environmental Quality Incentive Program (EQIP) programs (see Work Plan Appendix, Table 1 and Revised Table 2 from grant application for a list of eligible BMPs).

The overall strategy for meeting the environmental goals set forth for this project involves targeting BMPs to locations in the watershed that contribute high dissolved phosphorus runoff to area streams. These areas will be identified by implementing a stratified soil testing program that will characterize the phosphorus content in the upper two inches of the soil column. This data, together with field slope and proximity to streams and drainage ditches, will be used for targeting and incentive payment calculations (See Work Plan, Appendix Table 3, Revised Table 4 and Table 5). Incentive payments will be limited to fields deemed to be critical pollutant source areas by the above calculations. Many of the BMPs selected for this project have multiple and cumulative benefits relative to helping achieve project goals (Work Plan Appendix, Table 1).

The Outreach and Education component and the Outcome Monitoring component of this project contribute to the success of the implementation program. The environmental problems in the watershed, for both public water supplies and Lake Erie, will be communicated to Honey Creek farmers through the Outreach and Education program, based on local environmental data.

2. Work tasks

a. Prepare formal Memorandum of Understanding among the Crawford, Huron and Seneca Soil and Water Conservation Districts that will set forth project administrative and operational procedures. (First Quarter, 2008). Copies of the MOU will be sent to the project officer by April 30, 2008.

b. Create and organize a 10 to 12 member Project Advisory Group consisting of Soil and Water Conservation District Board Members, District Program Administrators, USDA agency representatives, farmers, fertilizer dealers and perhaps others. (First Quarter, 2008)

c. Hold Project Advisory Group meetings – two or three meetings the first year, at least one meeting per year there after. (Begin First Quarter 2008 and then quarterly throughout Project)

d. Advertise and secure a qualified conservation technician to coordinate completion of project tasks and lead practice implementation measures. (Second Quarter, 2008)

e. Assist with the preparation of a technical report to relate stratified soil test results to field level information on soils, crop rotations plus tillage and manure practices. (Begin 3rd Quarter, 2008 with annual updates the First Quarter of subsequent years)

f. Assist with the preparation of a project informational brochure for use with farmers, agricultural businesses and participating USDA agencies, NRCS and FSA. (First Half, 2008)

g. Prepare project participant enrollment documents to include required stratified phosphorus soil test data, practices planned/targeted and estimated incentive payment amounts. (Second Quarter, 2008)

h. Plan, schedule and approve farmer implementation of vertical soil test phosphorus practices


using field ranking and incentive payment methods set forth in Tables 2, 3, 4 and 5. (Begin Third Quarter, 2008 and then annually throughout Project)

i. Following approval of vertical soil test phosphorus practice implementation, process and prepare incentive payments to farmer participants. (Begin First Quarter, 2009 and then annually throughout Project)

j. Assist USDA – NRCS and FSA staff with planning, scheduling and approval of farmer implementation of CREP and EQIP practice targets per Table 2. (Begin First Quarter, 2008 and then annually throughout Project)

k. Assist annually with two or three information/education events and activities such as summer field days and winter seminars, as planned by the Outreach and Education component. (Begin First Quarter 2008 and then each year throughout the Project)

l. Complete quarterly progress reports on project tasks and practice implementation. 3. Work task timeline for Implementation Program – See Table 3.

Table 3. Timeline for Project BMP Implementation Program Project Implementation Task Timeline


Task Jan. 2008

July 2008

Jan. 2009

July 2009

Jan. 2010

July 2010

Jan. 2011

July 2011

Jan. 2012

July 2012

a. Prepare Memorandum of Understanding

x

b. Form Project Advisory Group

x

c. Hold Project Advisory Group Meetings

x x x x x x x x x x

d. Hire Conservation Technician

x

e. Assist in production of a stratified soil testing results report

x x x x x

f. Assist with prep. of project informational brochure

x x x

g. Prepare participant enrollment documents

x x

h. Implement BMP targeting program, including use of stratified soil testing

x x x x x x x x x

i. Process and prepare incentive payments to farmers

x x x x x x x x x

j. Assist with CREP and EQIP adoption in Honey Creek

x x x x x x x x x x


Watershed k. Assist with field days,

seminars and conferences x x x x x x x x x x

i. Complete quarterly progress reports

x x x x x x x x x x

4. Work task outputs –

a. Memorandum of Understanding b. Project Advisory Group membership list c. Project Advisory Group meeting minutes d. Contract with Conservation Technician f. Stratified soil testing data sets g. Project Brochure – see Outreach and Education component h. Assessments and prioritization lists of participant applications, based on targeting criteria i. Acres of each type of BMP implemented in critical areas, along with records of incentive

payments. j. New CREP and EQIP acres in the Honey Creek Watershed k. Field days and conferences held (See Outreach and Education component) l. Quarterly progress reports filed

5. Work task staffing - The following person will be responsible for conducting the work tasks

described above. For her experience and qualifications, see her biosketch in the supplementary material.

Tia Rice, Program Administrator, Seneca SWCD. Tia will work under a contract to the Seneca

SWCD. She will be assisted by a conservation technician who will be hired in year one and work full time in the Honey Creek Watershed on this project. The NCWQR’s agricultural project coordinator will work with the Seneca SWCD to coordinate district programs with other project components.

D. Project Outcome Monitoring

The outcome monitoring will determine whether the environmental improvement goals set forth for

this project are being met. This component of the project consists of two major areas – one focusing on habitat and biological community responses and the other on chemical and hydrological responses. The biological community assessments will include analyses of fish and invertebrate communities, accompanied by habitat evaluations, for agricultural drainage ditches that have had variable durations of recovery since the last major excavation of the ditch. We hypothesize that successes in upland erosion control and sediment trapping measures are extending the durations of time between major excavations and are thereby leading to a general improvement in biological communities in these ditches. The chemical and hydrological assessments will utilize the 30-year records of nutrient and stream flow data at the U.S. Geological Survey stream gage on Honey Creek at Melmore. The chemical monitoring at


that station will continue for the next five years with support from a grant from the Great Lakes Protection Fund to the NCWQR.

Since these two monitoring components differ greatly in their personnel, approaches and financing, detailed work plans are presented separately for each. However, a single detailed budget is provided for the monitoring component since all of the chemical monitoring is done under a contract to the NCWQR Tributary Loading Program. D.(1). Project Outcome Monitoring – Chemical and Hydrological Monitoring

1. General Description – The chemical transport station on Honey Creek at Melmore is one of 14 pollutant transport stations currently operated by the NCWQR in Ohio and Michigan. The transport station at Melmore was initiated in 1976 and current funding will continue the operation of that station through the 2012 Water Year.

Uniform sampling and analytical procedures are used for all 14 stations. All stations are located at or near U.S. Geological Survey stream gages. Automatic samplers are used to collect three samples per day throughout the year. Samples are returned to the NCWQR’s analytical laboratory at weekly intervals for analyses. During storm event days, all three samples are analyzed, while during non-storm runoff periods, a single sample per day is analyzed.

Analyses include suspended sediments, total and dissolved reactive phosphorus, nitrate, nitrite, ammonia and total Kjeldahl nitrogen, sulfate, silica, chloride and conductivity, and, at less frequent intervals, pesticides and trace metals. The analytical laboratory operates under a detailed quality assurance/quality control program. Details of the analytical procedures and sample collection procedures are available on the tributary loading website maintained by the NCWQR (http://wql-data.heidelberg.edu/). The chemical data will be used to determine if the goal of achieving a 25% reduction in phosphorus export has been achieved as well as a 50% decrease in the duration of time that nitrate concentrations exceed the drinking water standard. Stream flow data at the Melmore station will be analyzed to determine if progress has been made in reducing the flashiness of Honey Creek, as measured by the Richards-Baker Flashiness Index.

2. Work tasks a. Prepare and submit a chemical monitoring Quality Assurance Project Plan (first half year). b. Continue collection of samples at the Melmore gaging station using refrigerated automatic

samplers. (continuous for five years) c. Continue the analytical program for sediments, nutrients and pesticides. (continuous for five

years, annual outputs of chemical data sets). d. Transfer data to tributary loading website and to STORET, annually. e. Interpret chemical transport data in relation to weather conditions and past trends, annually

and provide feedback to project team and watershed residents. f. Utilize the Richards-Baker Flashiness Index to assess changes in stream flashiness, annually

and at end of project. g. Produce quarterly progress reports h. Produce final report on chemical and flashiness trends in relation to project BMP outputs.

(final year).

3. Work task timeline - See Table 4


Table 4. Timeline for Outcome Monitoring – Chemical Monitoring Program

Outcome Monitoring, Chemistry and Hydrology


Task Jan. 2008

July 2008

Jan. 2009

July 2009

Jan. 2010

July 2010

Jan. 2011

July 2011

Jan. 2012

July 2012

a. Prepare QAPP x x b. Continue sample collection

at Melmore Stream Gage x x x x x x x x x x

c. Continue analytical program for Melmore station on Honey Creek

x x x x x x x x x x

d. Transfer chemical data to STORET and NCWQR tributary loading website

x x x x x

e. Interpret and present data x x x x x x f. Calculate stream flashiness

and interpret data x x x x x


x x x x x x x x x x

h. Produce Final Reports and publications

x x x

4. Work task outputs

a. QAPP submitted b. Sample collection log sheets c. Analytical results – logs and computer files d. Data filed to STORET and the NCWQR tributary loading website e. Data presentations; associated power points on NCWQR website f. Presentations on stream flashiness and trends in flashiness g. Quarterly progress reports h. Final report and publications

5. Work task staffing - The following persons will be responsible for conducting the work tasks

described above. For their experience and qualifications, see their biosketches as listed in the Laboratory Quality Control Materials (to be included the QAPP).

The Honey Creek sampling station is one of 14 stations that comprise the NCWQR’s tributary loading program. Because (1) the supplies are purchased in bulk for this program, (2)


the analyses are done in large sets involving multiple stations, and (3) the collection routes are integrated, it is not feasible to track personnel and supply costs for individual stations. Instead, total program costs are tracked and the total costs are divided among the stations. Funding for individual stations is done on a contract basis with the current costs (2007 fiscal year) amounting to $27,810 per year per station.

Five NCWQR staff are involved in the tributary loading program. They are: Jack Kramer, B.S., Laboratory Manager Ellen Ewing, B.S., Laboratory Technician Barbara Merryfield, B.S., Laboratory Technician Aaron Roerdink, Ph.D., Quality Control Officer Anne Stearns, M.S., Laboratory Data Manager

The above staff members are aided by student workers drawn from the Heidelberg’s undergraduate environmental science program.

D.(2). Project Outcome Monitoring – Biological and Habitat Studies

1. General Description – Following disruption, streams tend to recover to more natural conditions. Such recovery has been observed in the drainage ditches and headwater streams of northwestern Ohio. However, frequent excavation of these ditches disrupts the improving habitat, leading to impaired biological communities and therefore lower habitat use designations. The success of various upland erosion control measures, such as no-till and reduced till, coupled with increased use of streamside buffers, has reduced the transport of sediment into and through the ditch and stream channels, resulting in longer intervals between excavation. Thus, these drainage/stream systems now have longer durations of recovery time. The objective of this study is to evaluate how far such recovery can go, in terms of meeting designated uses. If sufficient recovery appears to be occurring, management efforts could continue to focus on additional upland erosion control and water management efforts, rather than moving to major construction projects on the ditches themselves, such as construction of extra wide ditches, two stage ditches, or “natural channel design” systems. We will select 60 ditches for study over the first four years of the project, with time since the last excavation a major consideration. Other factors, such as drainage area, position in the drainage network, upstream corridor condition, etc., will also be considered.

2. Work tasks

a. Develop a QAPP for the biological and habitat assessment component. b. Develop channel segment selection criteria and apply those criteria to select a set of ditches

for the initial year of study. Repeat the process for years two, three and four, taking into consideration experience gained in previous years and opportunities to maximize knowledge gained. The careful selection of channel segments is crucial to the success of the monitoring component of this project. Thus, throughout the project period we will work with county personnel in Crawford, Huron, and Seneca counties in obtaining the historical records on county maintenance channels in the Honey Creek watershed and adjacent watersheds (Rock Creek, Broken Sword Creek, Sycamore Creek). County ditch maintenance records date back at least to the 1960s. We will initially discuss the project objectives and approach with the


Soil and Water Program Administrators in each county. Next we will contact the ditch maintenance supervisors in Seneca and Huron counties and the county engineer in Crawford County, who have responsibility for ditch maintenance in their respective counties. These personnel will be invaluable to the early success of the project in that they can suggest the best candidate channel segments based on their detailed knowledge of ditch maintenance in their respective counties and can assist in acquisition of the county data. Using maintenance records that are readily available at the local SWCD offices, and during the first six months of this project, we will select a number of candidate channel segments for on-site study based on specific combinations of physical and historical criteria.

c. Conduct habitat assessments in selected ditch segments. We will perform a Qualitative Habitat Evaluation Index (QHEI) assessment at each channel segment prior to conducting biological assessments. Krieger is certified by Ohio EPA as a Level 3 Qualified Data Collector (QDC) for the QHEI and therefore will perform all QHEI assessments with assistance of other personnel, and the QHEI forms and scores will be submitted to Ohio EPA for their information. In the event that a segment has a drainage area less than one square mile, we will conduct the QHEI and will also conduct the Headwaters Habitat Evaluation Index (HHEI) (Ohio EPA 2002). Stearns completed Ohio EPA training for the HHEI and applies the method in another ongoing project. In addition to the numerous habitat characteristics scored by the QHEI and HHEI, we will record additional characteristics on-site. These will include, among others, the extent of development of a “bench” or sill within the channel. The list of characteristics will be developed as part of the QAPP. We will also document each site with a set of digital photographs.

d. Conduct onsite fish assessments - Techniques will be adapted from those used by the contractors in their recently completed Ohio Lake Erie Protection Fund grant (http://www.epa.state.oh.us/oleo/Grant/freports/smallfinals/2006/sg293-06.pdf). Following identification and assessment, all fish will be released downstream of the stationary seine

e. Analyze fish data – Techniques will be adapted from those used by the contractors in their recently completed Ohio Lake Erie Protection Fund grant (http://www.epa.state.oh.us/oleo/Grant/freports/smallfinals/2006/sg293-06.pdf).

f. Conduct onsite invertebrate collections. To account for seasonal variations resulting from life cycles and for the possibility that some channels will not contain surface water during droughts, we will sample macroinvertebrates two times between May and September in each channel segment, once in May or June and again in August or September. If there is no water above the channel bottom, we will collect above-ground terrestrial invertebrates as well as any remaining aquatic invertebrates in order to characterize the biota of the segment during periods of no standing water. We will collect two separate invertebrate samples during each of our two visits to a given channel segment (for a total of four samples per channel segment each year). One sample will be a qualitative sample, in which we collect as many different taxa of aquatic macroinvertebrates from as many microhabitats within the channel segment as we can. This sample will permit us to compare the taxonomic richness and overlap among channel segments. The other sample will be semi-quantitative, applying a method adapted from USEPA’s Rapid Bioassessment Protocols ((Barbour et al. 1999); it will permit comparison of the relative contributions of taxa among channel segments.


Krieger maintains a current Wild Animal Permit from Ohio DNR. g. Process and analyze invertebrate samples. Samples will be processed in the laboratory by

sorting the invertebrates from the sample debris, and specimens will be identified to the lowest practical taxonomic level, which will be to genus for most insects and molluscs. Chironomid midges will only be identified to family unless sufficient funding is available to identify them to genus, and oligochaete worms will only be identified to class. Krieger is certified by Ohio EPA as a Level 3 Qualified Data Collector (QDC) for macroinvertebrate sampling and identification.

h. Present results at conferences. We will investigate the relationship of characteristics of the invertebrate and fish communities to features of the habitat and water chemistry. To do this, we will apply multivariate statistical techniques that may include principal components analysis, cluster analysis, and/or correspondence analysis. We will also compare the fish and invertebrate communities among the channel segments (and between years for channel segments sampled more than one year) using a variety of similarity and diversity indices. These results will then be presented at various conferences.

i. Prepare quarterly progress reports. These reports will be forwarded to the Project Director for submission to the EPA.

j. Input data into STORET. We will enter our biological and physical-chemical data into STORET as prescribed in the grant agreement.

3. Work task timeline – See Table 5

Table 5. Timeline for Biological and Habitat Studies Component:Habitat and Biology

Project Year, beginning January 2008. 1.a. is year one, first half. 1.b. is first year, second half.

Sub-component Jan. 2008

July 2008

Jan. 2009

July 2009

Jan. 2010

July 2010

Jan. 2011

July 2011

Jan. 2012

July 2012

a. Develop QAPP x b. Select channel

segments x x x x

c. Conduct habitat assessments

x x x x x x x x

d. Conduct on-site fish assessments

x x x x x x x x

e. Analyze fish data x x x x x x x x f. Conduct on-site

invert. surveys x x x x x x x x

g. Process & analyze inver-tebrate samples

x x x x x x x x

h. Present results at conferences

x x x x x x x x


i. Prepare quarterly progress reports

x x x x x x x x x x

j. Input data to STORET

x

x

x

x

x

x x

x

4. Work task outputs.

a. QAPP document b. List of selection criteria and procedures and resulting locations for year 1 studies c. Habitat forms and summary sheet d. Fish collection data sheets e. Fish community assessments for stream segments f. Field notes for invertebrate collections g. Laboratory notes on invertebrates founds in each stream segment and resulting diversity and

stream quality assessments. h. Presentations at conferences and associated PowerPoint available on website. i. Quarterly progress reports. j. Data in STORET

5. Work task staffing - The following persons will be responsible for conducting the work tasks described above. For their experience and qualifications, see their biosketches in the supplementary material.

Kenneth A. Krieger, Ph.D., Senior Research Scientist Anne Stearns, M.S., Laboratory Data Manager The fish collections, identification and data interpretation will be done by staff and students of the University of Toledo under contract. The University of Toledo team will be headed by Dr. Johann Gottgens.

III. Detailed Budget (based on revised SF-424 A) General Comments on Presentation of Detailed Budget Information

This budget section elaborates upon the budget presented in the attached Standard Form 424A. In

order to follow the sequence of components presented in the work plan, we have reorganized the SF 424A form that we submitted with the original proposal. In the attached SF 424A the components are presented in the order of 1. Administration, 2. Outreach/Education, 3. Implementation, and 4. Monitoring. An additional change from the original SF 424A occurs in the Implementation component. Now, the cost categories have been consolidated into two parts, 6.f. Contractual and 6. h. Other. Thus the cost categories a. – e. and j. for all components now reflect only those costs associated with the work of the NCWQR itself and not the contractors. The total costs for each component, as well as the breakdown between federal and local funding sources, have not changed.

A table showing the detailed costs for each major component of the project is presented below.


Each table contains the same Cost Categories shown in Standard Form 424A. However, the table contains the costs for each project year, as well as the total costs for that component of the project. The total costs match those presented in the attached Standard Form 424A.

In addition, each table lists the NCWQR personnel involved, their annual salary, the proportion of time allocated to the project component, the resulting amount of salary charged to the grant and the associated fringe benefit rates. An inflation factor of 3% per year was used to project salaries over the five year duration of the grant.

A copy of the Indirect Cost Rate for Heidelberg College is included in the supplementary materials. The rate is 59% of salaries, wages and fringe benefits. This rate is applied within each project component and applies only to the NCWQR staff salaries, wages and fringes. No indirect charges for Heidelberg are associated with any of the work contracted to outside entities.

Fringe benefit rates, as a percentage of total wages, vary for each worker, depending on their participation in various programs. Fringe benefits can include health care, retirement, social security, unemployment compensation, workman’s compensation and disability insurance. The percentage used in the tables reflects the percentage of the fringe benefits for each person in the most recently completed fiscal year. It is anticipated that actual fringe benefits percentages will change to a greater or lesser extent for each person during the five year duration of the grant.

The sources of cost sharing for each component are summarized in each Table and in the associated budget justification.

A. Project Administration 1. Detailed Budget – See Table 6

Table 6. Detailed Budget for Project Administration Cost Category 2008 2009 2010 2011 2012 Total

a. Personnel $9,206 $9,483 $9,767 $10,060 $10,361 $48,877 b. Fringe Benefits $978 $1,007 $1,037 $1,069 $1,101 $5,192 c. Travel $925 $925 $1,850 d. Equipment $0 e. Supplies (Office) $200 $100 $100 $100 $100 $600 f. Contractual $0 g. Construction $0 h. Other $0 i. Total Direct Charges $11,309 $10,590 $10,904 $12,154 $11,562 $56,519

j. Indirect Charges (59% of a. & b.) $6,009 $6,189 $6,375 $6,566 $6,762 $31,901

k. Totals $17,318 $16,779 $17,279 $18,720 $18,324 $88,420 Federal Total $9,793 $9,488 $9,771 $10,585 $10,363 $50,000 Local Match $7,525 $7,291 $7,508 $8,135 $7,961 $38,420

Source of local match: Heidelberg College, $28,420; National Machinery Foundation, $10,000. Details on Personnel Category

2008 2009 2010 2011 2012 TotalDavid B. Baker – Director Emeritus, NCWQR and Project Director

Annual Salary $75,840 $78,115 $80,459 $82,872 $85,359 Percent of time 10% 10% 10% 10% 10%


Amount $7,584 $7,812 $8,046 $8,287 $8,535 $40,264 Fringe (8.31%, FICA) $630 $649 $669 $689 $709 $3,346

Nancy Miller - Fiscal Administration Annual Salary $38,934 $40,102 $41,305 $42,544 $43,821 Percent of Time 4.17% 4.17% 4.17% 4.17% 4.17% Amount $1,622 $1,671 $1,721 $1,772 $1,827 $8,613

Fringe (21.43%- FICA, Health, Retirement,) $348 $358 $369 $380 $391 $1,846

Total Salaries $9,206 $9,483 $9,767 $10,059 $10,362 $48,877Total Fringe $978 $1,007 $1,038 $1,069 $1,100 $5,192

2. Budget Justification – Project Administration a. Personnel costs reflect estimated time allocations for the work plan.

c. Travel is for attendance at the required Targeted Watershed Conferences. Since submitting the grant proposal we have learned that the initial meeting is in Corpus Christi, Texas. Actual costs are as follows: Roundtrip airfare from Columbus, OH - $367.60; Hotel (OMNI Bayside and Marina Towers) $83/night x 5 nights plus 15% tax; ground transportation Tiffin to Columbus round trip 186 miles at $0.36 per mile; Airport parking - $12 per day for 6 days; meals $25 per day for 5.5 days. Total costs for this trip will be $1,121. In our original budgeting we estimated the costs of this trip to be $925. We will transfer needed funds from another budget category, when the exact totals of these costs become known.

e. Supply costs are for general office supplies (paper, notebooks, envelops, postage, etc.). For year one, we anticipate sending 200 mailings at $0.60 each, plus printing three 3ft x 4ft posters at $24.00 each. For years 2-5, we anticipate sending 75 mailings at $0.60., plus printing two posters at $24 each. The remaining balances of $8.00 first year and $7.00 years 2-5 will cover notebooks and other miscellaneous office supplies.

j. Indirect costs are calculated as 59% of total salaries and wages.

The local match, totaling $38,420, is provided by Heidelberg College ($28,420) and from a grant ($10,000) to the NCWQR from the National Machinery Foundation.

B. Project Outreach and Education

1. Detailed Budget – See Table 7.

Table 7. Detailed Budget for Outreach and Education Cost Category 2008 2009 2010 2011 2012 Total

a. Personnel $4,292 $4,420 $4,553 $4,690 $4,830 $22,785 b. Fringe Benefits $367 $378 $390 $401 $414 $1,950 c. Travel (local meetings) $200 $250 $250 $250 $250 $1,200 d. Equipment $0 e. Supplies (Office) $100 $50 $50 $50 $50 $300 f. Contractual $6,666 $6,667 $6,667 $20,000 g. Construction $0 h. Other $0


i. Total Direct Charges $11,625 $11,765 $11,910 $5,391 $5,544 $46,235 j. Indirect Charges $2,749 $2,831 $2,916 $3,004 $3,094 $14,594 k. Totals $14,374 $14,596 $14,826 $8,395 $8,638 $60,829 Federal Total $11,815 $11,998 $12,187 $6,900 $7,100 $50,000 Local Match $2,559 $2,599 $2,639 $1,494 $1,538 $10,829

Source of local match: Heidelberg College, $10,829. Contractual funds are designated to the Sandusky River Watershed Coalition for salary support for the the watershed coordinator in the work plan for the Outreach and Education activities. Details on Personnel Category

2008 2009 2010 2011 2012 Total

John Crumrine, Agricultural Project Coordinator Annual Salary $51,500 $53,045 $54,636 $56,275 $57,964 Percent of time 8.33% 8.33% 8.33% 8.33% 8.33% Amount $4,292 $4,420 $4,553 $4,689 $4,831 $22,785 Fringe (8.56%, FICA) $367 $378 $390 $401 $414 $1,950

Total Salaries $4,291 $4,420 $4,553 $4,689 $4,831 $22,785 Total Fringe $367 $378 $390 $401 $414 $1,950

2. Budget Justification a. The personnel budget involved the time of the NCWQR’s agricultural project coordinator in

the Outreach and Education program. c. Travel includes mileage for one round trip to Columbus each year (190 miles) plus, in the first

year, 10 round trips to meet with farmers in various locations in the Honey Creek Watershed, averaging about 36.5 miles per trip. In years 2-5, the number of trips to meet with farmers will increase to about 14. The current charge for college vehicles is $0.36 per mile.

e. The supplies budget is for office supplies, including paper, posters and miscellaneous office supplies. For year one, we anticipate delivering 600 pages of handouts at $0.05 each and printing 2 posters at $24 each. For each of years 2-5, we anticipate distributing 400 pages of handouts at $0.05 per page, and printing 1 poster at $24.00. The remaining balances of $22.00 in year one and $6.00 per year in years 2-5 will be used for miscellaneous expenses such as project notebooks, staples, file folders, paper clips, etc.

f. The contractual portion of the budget goes to the Sandusky River Watershed Coalition. These funds will cover about 10% of the watershed coordinator’s salary. Cynthia Brookes is the Coordinator of the Sandusky River Watershed Coalition. She will organize the field days in the watershed, work on the brochures and conferences and integrate the Honey Creek project with activities and programs in the rest of the Sandusky River Watershed. Cynthia Brookes in particular, and the Sandusky Coalition in general, are uniquely position to serve this role in this grant. In fact, this role for the Coalition is spelled out in the Honey Creek Watershed Action Plan, large portions of which will be implemented through this Targeted Watershed Grant.

g. The indirect cost rate is 59% of total salaries and fringe benefits.

The matching funds for this component ($10,829) are provided by Heidelberg College.


C. Project BMP Implementation 1. Detailed Budget

Table 8. Detailed Budget for BMP Implementation. Cost Category 2008 2009 2010 2011 2012 Total

a. Personnel b. Fringe Benefits c. Travel (local meetings) d. Equipment e. Supplies (Office)

f.1. Contractual, SWCD $52,276 $59,498 $61,072 $62,702 $64,390 $299,938 f.2. Contractual, Farmers $58,330 $116,670 $116,670 $58,330 $350,000 g. Construction h. Other $109,244 $218,506 $218,506 $109,244 $655,500 i. Total Direct Charges $52,276 $227,072 $396,248 $397,878 $231,964 $1,305,438 j. Indirect Charges k. Totals $52,276 $227,072 $396,248 $397,878 $231,964 $1,305,438 Federal Total $52,276 $117,828 $177,742 $179,372 $122,720 $649,938 Local Match* $0 $109,244 $218,506 $218,506 $109,244 $655,500

* Sources of Local Match: Farmer share of costs associated with BMP implementation. 2. Budget Justification f.1. Within the Sandusky River and Honey Creek Watersheds, the major responsibilities for

implementation of BMPs lie with the Soil and Water Conservation Districts and their partners in the Natural Resource Conservation Service, the Farm Service Agency and The Ohio State University Extension. Thus they are the existing groups in the best position to operate the implementation program. The three soil and water districts in the Honey Creek Watershed (Seneca, Crawford and Huron) have chosen the Seneca Soil and Water Conservation District to serve as the lead in this project. The contracted funds to the Seneca SWCD will cover their hiring of a full time conservation technician to work in the watershed, time for their current staff to work on the project, travel to meet with farmers in the watershed, supplies, and equipment, a project computer and a GPS (geographical positioning system) unit.

f.2. This amount will provide for incentive payments to farmers for achieving the targeted


implementation of BMPs. The acreages and associated amounts of payments for each BMP are shown in Table 2 (revised) of the Appendix to the Work Plan. The amount of the payments will be shown on participant enrollment documents that will be retained by the Seneca SWCD. The Seneca SWCD will also distribute the incentive payments to the individual participating farmers.

h. The “Other” portion of the Implementation Costs reflects the portion of the costs for BMP implementation bourn by the individual farmers who are receiving incentive payments for targeted BMP implementation. These costs are used as local match for the implementation portion of the project.

D. Project Outcome Monitoring 1. Detailed Budget (Note this budget includes the costs for the both parts of the Work Plan for

Outcome Monitoring (D.(1) and D.(2))

Table 9. Detailed Budget for Project Outcome Monitoring Cost Category 2008 2009 2010 2011 2012 Total

a. Personnel $22,374 $17,503 $11,848 $12,131 $17,003 $80,859 b. Fringe Benefits $2,531 $1,841 $1,579 $1,626 $2,580 $10,157 c. Travel $700 $700 $700 $700 $200 $3,000 d. Equipment $490 $490 e. Supplies (laboratory) $600 $600 $600 $600 $100 $2,500

f.1. Contractual (U. of T. $36,325 $38,341 $40,184 $18,176 $133,026 f.2. Contractual (NCWQR) $27,810 $28,644 $29,504 $30,389 $31,300 $147,647 g. Construction h. Other i. Total Direct Charges $90,830 $87,629 $84,415 $63,622 $51,183 $377,679 j. Indirect Charges $14,695 $11,414 $7,922 $8,117 $11,552 $53,700 k. Totals $105,525 $99,043 $92,337 $71,739 $62,735 $431,379 Federal Total $36,694 $34,439 $32,107 $24,945 $21,815 $150,000 Local Match $68,831 $64,604 $60,230 $46,794 $40,920 $281,379

Source of matching: Honey Creek chemical monitoring - $147,647, Great Lakes Protection Fund; U. of Toledo - $73,025; Heidelberg College - $60,707 Details on Personnel Category

2008 2009 2010 2011 2012 TotalKenneth A. Krieger- Senior Research Scientist

Annual Salary $65,863 $67,839 $69,874 $71,970 $74,129 Percent of time 12.50% 8.33% 8.33% 8.33% 12.50% Amount $8,233 $5,653 $5,823 $5,998 $9,266 $34,973

Fringe (21.66%, FICA, Health, Retirement) $1,783 $1,224 $1,261 $1,299 $2,007 $7,574

Anne Stearns - Research Associate Annual Salary $41,000 $42,230 $43,497 $44,802 $46,146


Percent of Time 20.833% 16.667% 8.333% 8.333% 14.167% Amount $8,542 $7,038 $3,625 $3,733 $6,537 $29,476

Fringe (8.76%, FICA) $748 $617 $318 $327 $573 $2,582 Student Wages (hourly) $5,600 $5,600 $2,400 $2,400 $1,200 $16,411Total Salaries* $22,375 $17,502 $11,848 $12,131 $17,003 $80,859Total Fringe* $2,531 $1,841 $1,579 $1,626 $2,580 $10,157*Totals may differ slightly from lines a. and b. above because of rounding.

2. Budget Justification a. The personnel cost shown reflect the work involved in the invertebrate sampling,

identification, and analyses together with the habitat analyses and report writing. c. The travel costs include approximately 30 round trips to sampling sites each year. These trips

will cover both the selection of stream reaches for study, as well as two collections at each site each year. The average round trip distance is estimated to be 46 miles, and the cost is $0.36 per mile. An additional $200 per year is set aside for travel to meetings to present the results of the study.

d. The equipment purchases cover replacement nets for sample collection equipment. Specifically the estimate covers three D-Frame nets with a unit cost of $163. The resulting cost of $489 was rounded to $490 to cover a portion of the shipping charges.

e. The supplies budget will cover miscellaneous laboratory supplies, including specimen vials and preservatives. For each of the first four years, ½ of case of vials will be used, with a unit cost of $532 per case. In the fifth year, 1/10 of a case will be used. Preservatives required for the project include ethanol. The unit cost for ethanol is $95 per 20 liters. In each of the first four years, 3.5 units of ethanol will be used. In the final year 0.5 units will be used. The combined costs of the above supplies are $599 per year for the first four years, which we rounded to $600. for the fifth year, the cost is $101, which we rounded to $100.

f.1. The portion of the Contractual budget covers a contract with the University of Toledo to complete the fish community assessments. This portion of the budget and the associated U. of Toledo matching money has been developed by Dr. Johan Gottgens. He was selected to participate in this project because of his interest and experience in the topic of fish communities in agricultural ditches, as reflected in his recently completed Ohio Lake Erie Protection Fund grant on this topic.

f.2. This contract is to the Tributary Loading Program of the NCWQR. As explained in the detailed work plan above (page 13), the Honey Creek station is one of 14 stations operated by our laboratory. Since this program is run as a unit, it is not feasible to directly separate out the costs for an individual station. Instead, the total program costs are allocated to the participating stations. The entire amounts shown for this part of the contract are part of the local match for this project. Funds for the operation of this station are derived from a grant from the Great Lakes Protection Fund.

Matching funds for this component of the project come from Heidelberg College $60,707, the

Great Lakes Protection Fund ($147,647), the University of Toledo ($73,025).


IV. Quality Assurance Narrative Statement – To be developed. See QAPP production as part of work plans for monitoring section.

V. Other Forms, Assurances – See attached set of forms and assurances. VI. Biosketches/short vitae – See attached set of Biosketches


Work Plan Appendix Note: These are tables included in the original grant application. Some have since been slightly

modified based on intervening circumstances. These “intervening circumstances” include the following: � Since the original proposal was submitted, the market price of wheat has doubled. � There is a greater understanding of the importance of phosphorus injection in conservation

tillage systems, as opposed to broadcast fertilizer applications. � Regional ethanol plant construction has created a greater demand for corn. In response to the above circumstances several new practices have been added to Tables 2 and 4. These new practices include phosphorus injection >5 inches, plow once system in a five year conservation tillage rotation, and zero phosphorus application. These three new practices would also be targeted based on criteria shown in Table 3.

Table 2 (Revised). Proposed practices, acre estimates of accomplishment by practice and incentive costs. PRACTICE 2008 2009 2010 2011 2012 Costs Grass Buffer 1 25 25 25 25 Tree Buffer 1 10 10 10 10 Permanent Wildlife Habitat 1 5 5 5 5 Field Windbreak 1 5 5 5 5 Wetland Restoration 1 5 5 5 5 Escarpment Treatment 1 25 25 25 25 Recharge Area Treatment 1 25 25 25 25 Waste Utilization 2 100 100 100 100 100 Pasture and Hayland Planting 2 50 50 50 50 50 Waste Storage Facility 2 (Number) 1 1 1 1 1

250 500 500 250 Annual Cover after Vertical P Soil Test 3 Incentive Cost, Grant Dollars $6250 $12500 $12500 $6250 $37500

1500 3000 3000 1500 Wheat after Vertical P Soil Test 3 Incentive Cost, Grant Dollars $45000 $90000 $90000 $45000 $180000

50 100 100 50 Hay after Vertical P Soil Test 3 Incentive Cost, Grant Dollars $2000 $4000 $4000 $2000 $12000

500 750 750 500 P Injection >5”after Vertical P Soil Test 3 Incentive Cost, Grant Dollars $10000 $15000 $15000 $10000 $50000

200 100 100 100 Plow Once System after Vert P Soil Test 3 Incentive Cost, Grant Dollars $4000 $2000 $2000 $2000 $10000

250 500 500 250 Zero P Application after Vert P Soil Test 3 Incentive Cost, Grant Dollars $5000 $10000 $10000 $5000 $30000

508 1017 1017 508 Nitrogen Application Reduction 3 Incentive Cost, Grant Dollars $5080 $10170 $10170 $5080 $30500 Controlled Drainage 1,3 * 50 100 100 50 GRANT TOTAL INCENTIVE COSTS $350000


1. Practices supported by Lake Erie CREP 2. Practices supported by EQIP 3. Practices supported by this grant. * Note: If implementation dollars through existing USDA programs are insufficient, some grant dollars may be moved from Wheat after Vertical P Soil Test to support six control structures impacting 300 acres. Research suggests that load reductions of as much as 50% are possible when soil water is held within fields during summer and winter periods. The six structures would cost an estimated $18,000. Table 3. Ranking fields for phosphorus reduction practices in the Targeted Project. Ranking Factors Weighting Criteria – 1 for first column; 2 for second; 3 for third Predominant Slope Mostly A, some B Mostly B, some A Mostly B, some C Surface P Soil Test >60 lbs/ac Bray P1 >120 lbs/ac Bray P1 >180 lbs/ac Bray P1 Proximity to Water Course (Stream, Sod Waterway, Ditch or Tile Blowout

Most of field is >2640 feet from water course

Most of field is between 2640 feet and 1320 feet from water course

Most of field is 0 to 1320 feet from water course

Example: Field 5 on Tract 3475 has mostly “A” slopes with some “B” slopes (score of “1”); has a surface (0 to 2 inches) Bray P1 Soil Test of 135 lbs/ac (score of “2”); and is located adjacent to a stream (score of “3”). Total score for Field 5 would be “6”. Note: In the scoring system proposed above, a field would need to score “6” or more to be selected for incentive payments. Table 4 (Revised). Incentive payments per acre by practice based on field score or rank. Incentive Practices

Ranking Score Annual Cover Crop

Wheat Planting

Hay Planting

P Injection >5 inches

Plow Once

System

Zero P Application

6 $20 $25 $30 $15 $10 $10 7 $25 $30 $40 $20 $20 $20 8 $30 $40 $50 $25 $30 $30 9 $35 $45 $60 $30 $40 $40

Table 5. Ranking the field and related incentives for nitrogen reduction for corn. Ratio: Commercial N/ac to Bushels/Ac Incentive Amount: $/Ac

>1.2 None 1.0 to 1.2 $5 0.8 to 1.0 $10 0.6 to 0.8 $20 0.4 to 0.6 $40


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