i c o i o g y a n d e n v i r o n m e n t , i n c . •" international Specialists in the Environment

350 Sansome Street #300, San Francisco, California 94104 Tel: (415) 981-2811, Fax: (415) 981-0801

SFUND RECORDS CTR

5138-00005

SFUND RECORDS CENTER 88224915

AR0055

March 2, 1998

Karen Nelson, START Project Officer Environmental Protection Agency 75 Hawthorne Street San Francisco, CA

Dear Ms. Nelson:

Enclosed please find the site-specific Quality Assurance Sampling Plan (QASP) for the removal assessment for the India Basin site, located in San Francisco, California.

Sincerely,

Thompson Chambers START Project Leader

Enclosure

cc: Chris Weden, USEPA Region IX, San Francisco, CA File

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QUALITY ASSURANCE SAMPLING PLAN

FOR:

India Basin Removal Assessment

TDD No.: 09-96-06-0002

Prepared By:

Carl Palladino Ecology and Environment, Inc.

Contract No: 68-W6-0010

Date: March 2, 1998

QASP Approvals

Ecology and Environment Inc., START:

Project Manager fa?

Date 1 -lb- fK

Quality Assurance Officer or Team Leader

Date

USEPA ERO:

On-Scene Coordinator Date

• • TABLE OF CONTENTS

Section Page

1.0 INTRODUCTION 1

2.0 BACKGROUND. 1

3.0 PROJECT OBJECTIVES 2 3.1 Data Use Objectives 2 3.2 Sampling Objectives . . 2 3.3 Data Quality Objectives 2

3.3.1 Data Quality Objective (DQO) Process 2 3.3.2 DQO Data Categories 2 3.3.3 DQO Quality Indicators 3

3.4 Action Levels 3

4.0 ANALYTICAL METHODS AND PROCEDURES . 3 4.1 Non-Definitive Methods and Procedures 3 4.2 Definitive Methods and Procedures 4

5.0 APPROACH AND SAMPLING METHODOLOGIES . 5 5.1 Strategy and Justification . . : 5 5.2 Sampling Equipment " . 5 5.3 Sample Collection 5 5.4 Sample Identification 5 ' 5.5 Sample Handling and Shipment 6 5.6 Sample Equipment Decontamination 6 5.7 Sample Documentation .6

6.0 QUALITY ASSURANCE REQUIREMENTS 6.1 Quality Control and Quality Assurance Samples

6.1.1 Replicate Sampling 6.1.2 Reference or Background Sampling 6.1.3 Field Generated Blank Samples 6.1.4 Matrix Spike/Matrix Spike Duplicates . . . 6.1.5 Performance Samples

6.2 Analytical 6.3 Data Validation 8

7.0 DISPOSAL OF INVESTIGATION DERIVED WASTE 8

8.0 ADDITIONAL DATA COLLECTION ! 8 8.1 Photographic : . . . 8

9.0 SCHEDULE OF SAMPLING ACTIVITIES . . 8

10.0 PROJECT ORGANIZATION AND RESPONSIBILITIES 9 10.1 Responsibilities 9 10.2 Deliverables 9

- • • ' '

TABLES

TABLE 1 ACTION LEVELS 3 TABLE 2 METHODS, DATA USE, AND QUALITY INDICATORS 4 TABLE 3 PRESERVATIVE AND CONTAINER REQUIREMENTS 5

APPENDICES J

APPENDIX A STANDARD OPERATING PROCEDURES

Quality Assurance Sampling Plan For:

India Basin Removal Assessment

TDD No.: 09-96-06-0002

1.0 INTRODUCTION

The U.S. Environmental Protection Agency (EPA) has directed Ecology and Environment, Inc. (E & E), Superfund Technical Assessment and Response Team (START) to conduct a removal assessment at a shipyard which contains various debris, hazardous materials and waste, and a suspected methamphetamine drug laboratory.

This investigation is being conducted under the USEPA Emergency Response Section (ERO) Quality Assurance Project Plan (QAPP) dated May 1995. As specified in the Office of Solid Waste and Emergency Response (OSWER) Directive 9360.4-01, the ERO QAPP does not contain site specific sampling elements. The specific field sampling and chemical analysis information pertaining to this investigation is addressed in this QASP document.

The Federal On-scene Coordinator (OSC), in order to expediently determine whether the site poses an eminent environmental or health threat, has deemed it necessary to immediately begin site activities concurrently with the development of the Data Quality Objectives (DQOs). The DQOs are being developed by the Federal OSC with the assistance of the START contract. The project's preliminary DQOs are specified in Section 3.0.

While this QASP is intended to accurately reflect the planned data gathering activities for this investigation, site conditions and additional USEPA direction may warrant modifications. All significant changes will be recorded in site records and reported as amendments in the post sampling document. This QASP does not portray aspects of the E & E START Quality Assurance program beyond the specifics required for this project. Thus, if the EPA OSC directs another agency or party with any responsibility specified in this QASP, the quality assurance and oversight requirements associated with that sampling will be as agreed upon between that agency or party and the OSC.

2.0 BACKGROUND

This site has a history of hazardous waste problems. In 1991, the EPA National Enforcement Investigation Center with the Ecology and Environment, Inc. Technical Assistance Team (TAT) conducted an investigation of the site, which was owned by Donco Industries. Samples of containers were collected and hazard categorized by the TAT. Results indicated potential metal and organic compound contamination. In 1993, the TAT conducted another investigation of the site. Soil samples were collected and analyzed for total and Toxicity Characteristic Leaching Procedure (TCLP) lead and copper. Results indicated that total copper ranged from 4 to 1,120 parts per million (ppm) and that TCLP copper was detected up to 30 ppm. Lead results ranged

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from not detected to 3,760 ppm but TCLP lead results did not exceed the Resource Conservation and Recovery Act (RCRA) regulatory limit of 5.0 ppm.

Investigations of the site ceased in 1994 pending access and security issues. These issues have been resolved and the EPA is recommencing the investigation.

3.0 PROJECT OBJECTIVES

3.1 Data Use Objectives

The data collected during this investigation will be used to help identify hazardous waste and to assist the Federal OSC's determination of whether a removal action is warranted.

3.2 Sampling Objectives

Liquid and solid container samples will be collected by the California Department of Toxic Substance Control (DTSC) for field hazard categorization by the START. Field hazardous categorization data will be used to help determine if samples meet federal or state RCRA characteristic waste criteria. Soil/solid samples will be collected for field analysis for metals by X-Ray Fluorescence (XRF) to help determine if the samples exceed California Total Threshold Limit Concentration (TTLC) values for metals, thus indicating a hazardous waste. Ten percent or more of the samples field screened will be analyzed by a commercial laboratory for confirmation.

Additional sampling to support USEPA actions will be directed by the Federal OSC if deemed necessary. Sampling will follow chain of evidence guidelines and will include photo documentation and written descriptions.

3.3 Data Quality Objectives

3.3.1 Data Quality Objectives (DQOs) Process

DQOs for this project will be established based on the use of the data. A description of the DQO process is described in the ERO QAPP and in EPA QA/.R-5.

3.3.2 DQO Data Categories

The removal assessment will involve the generation of non-definitive (ERO screening) screening plus 10 % definitive data and definitive data (Definition and requirement of these data categories are specified in the ERO QAPP).

Non-definitive (ERO screening) category data will include data resulting from direct reading field instruments, field X-Ray Fluorescence, and hazard categorization techniques. Screening plus 10% data will include data resulting from field XRF and hazard categorization for specific analytical parameters that have associated definitive data.

This investigation will generate non-definitive data which results from on-site analyses. Ten percent of the non-definitive data will be confirmed by definitive data which results from labora­tory analysis of collected samples. All laboratory data generated for this project is intended to meet the specification of definitive category data as defined in EPA QA/R5. All definitive analytical methods employed for this project will be methods approved by the EPA.

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A description of the specific requirements of each data category is located in section 6.0 and in the ERO QAPP.

3.3.3 DQO Quality Indicators

DQO Quality Indicators for this project have been developed following guidelines specified in the Region 9 ERO QAPP.

3.4 Action Levels

Data generated by this investigation will be compared to federal RCRA and California characteristic hazardous waste criteria. Hazard categorization results will be used to determine flash point, pH, some reactivity characteristics, and the presence of chlorinated substances. Field XRF will be used to determine total concentration of metals as compared to the California Total Threshold Limit Concentration (TTLC) values. Any substance which exceeds a regulatory limit as summarized in Table 1 will be considered a hazardous waste.

TABLE 1 ACTION LEVELS

Analyte of Concern Action Level Action Level Source Method of Analysis

Ignitability < 140 ° F RCRA Field Test or EPA SW-846 Method 1010/1020

Corrosivity > 12.5 pH or < 2 pH

RCRA Field Test or EPA SW-846 Method 9045

Chromium 2,50b mg/kg CA. TTLC XRF or CAM 17 Metals

Lead 1,000 mg/kg CA. TTLC XRF or CAM 17 Metals

Zinc 5,000 mg/kg CA. TTLC XRF or CAM 17 Metals

Copper 2,500 mg/kg CA. TTLC XRF or CAM 17 Metals

4.0 ANALYTICAL METHODS AND PROCEDURES

4.1 Non-Definitive (screening) methods and procedures

Samples will be field screened by either XRF or hazard categorization, depending on the matrix of the sample. Soil and solid samples suspected of metals contamination will be analyzed by the XRF instrument per DRAFT EPA Method 6200. Liquid samples or solid product samples will be hazard categorized (Appendix A for SOP).

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4.2 Definitive methods and procedures

Based on the field screening and characterization results, a portion of the samples will be analyzed for characterization using the EPA-approved analytical methods listed in Table 2. Method detection limits required of the analytical laboratories will be those specified in the individual methods, as a minimum. Samples collected for this effort are considered waste samples. Samples will, however, be cooled to 4 degrees centigrade and protected from sunlight in order to minimize any potential reaction due to a light sensitivity of the sample. Table 3 summarizes sample containers and holding times.

To provide analytical quality control for the analytical program of this QASP, the following measures will be utilized:

• All sample analyses will be conducted by a laboratory certified by the State of California for the analytical methods to be conducted.

• An additional volume of sample will be collected for one of the samples for metals analysis to be utilized for matrix spike/matrix spike duplicate (MS/MSD) analysis. Due to the expected high concentrations of analytes in the samples, a high concentration MS/MSD will be requested of the laboratory, if necessary.

• A CLP-type (Level IV) data package will be required from the laboratory for all resultant data.

TABLE 2 Methods, Data Use and Quality Indicators

Method Matrix Total Samples

and Field Duplicates

Matrix Spike and Matrix

Spike Duplicates

Method Detection (MDL)

DQO Data

Category Intended Data Use

EPA 9045 pH Liquid jjjjli 0 0.1 pH Definitive A

EPA IQ10/I020 Flashpoint Liquid 0 1°C Definitive A

EPA 6010A/7000s

series CAM 17 Metals

Solid 5 1 Per

Method Definitive A

DRAFT EPA 6200

Field XRF Solid 10 0

Per Method

Non-Definitive with 10% Definitive

A

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TABLE 3 Preservative and Container Requirements

Method Matrix Container Type Preservation Extraction

Holding Time

Analysis Holding Time

EPA 9045 pH

Liquid 4oz glass jar Cool to 4°C Not Applicable 7 days

EPA 1010/1020 Flashpoint Liquid 4 oz glass jar Cool to 4°C Not Applicable 7 days

EPA 6Q10A/700Q series

CAM 17 Metals Solid 8 oz glass jar Cool to 4°C Not Applicable

6 months, Mercury 28

days

5.0 APPROACH AND SAMPLING METHODOLOGIES

5.1 Strategy and Justification

Numerous containers and matrices of hazardous waste are suspected to be located on site. Containers, including drums, buckets, and cans, are expected to contain waste liquids, sludges, and solids. Waste sandblast grit released to native soils is expected to be sampled. All samples will be collected by DTSC, who will provide sample splits to the START for analysis. California Fish and Game will collect water and sediment samples from the bay, but splits will not be provided to the START for analysis.

For the sample splits, the START will identify, handle, and prepare all documentation and chain of custodies according to Region IX Removal Program guidelines and protocols. The analytical (QAO) QA Requirements and data validation requirements will be as mandated by EPA guidelines (OSWER Directive 9360.4-01). Other operating procedures that will be used in this sampling effort are included in the ERO QAPP.

5.2 Sampling Equipment

All samples will be collected according to DTSC protocols and SOPs.

53 Sample Collection

All samples will be collected according to DTSC protocols and SOPs.

5.4 Sample Identification

All samples will be collected according to DTSC protocols and SOPs.

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5.5 Sample Handling and Shipment

Each of the samples will be labeled and placed on ice in a cooler. The sample container lids and/or cooler lid will be secured with custody seals. All sample documents will accompany the samples to the laboratory.

The samples will be immediately delivered to the Curtis and Tompkins, Berkeley California for analysis.

5.6 Sample Equipment Decontamination

All samples will be collected according to DTSC protocols and SOPs.

5.7 Sample Documentation

All sample documents will be completed legibly, in ink. Any corrections or revisions will be made by lining through the incorrect entry and by initialing the error.

Field Logbook: The field logbook is essentially a descriptive note book detailing site activities and observations so that an accurate account of field procedures can be reconstructed in the writer's absence. All entries will be dated and signed by the individuals making the entries, and should include (at a minimum) the following:

1. Site name and project number. 2. Name(s) of personnel on-site. 3. Dates and times of all entries (military time preferred). 4. Descriptions of all site activities, includirijg site entry and exit times. 5. Noteworthy events and discussions. 6. Weather conditions. 7. Site observations. 8. Subcontractor information and names of on-site personnel.

Sample Labels: Samples submitted for laboratory analyses will clearly identify the particular sample, and includes the following:

1. Site name and number. 2. Date sample was taken.

Chain-of-Custody: A Chain-of-Custody record will be maintained for all samples submitted for laboratory analyses, from the time the sample is taken to its final deposition. Every transfer of custody will be noted and signed for, and a copy of this record kept by each individual who signed. When samples (or groups of samples) are not under direct control of the individual responsible for them, they must be stored in a locked container sealed with a Custody Seal. The Chain-of-Custody record includes (at minimum) the following:

1. Sample identification number. 2. Sample date. 3. Name(s) and signature(s) of sampler(s). 4. Signature(s) of any individual(s) with control over samples. 5. Requested analysis.

6 StuABhpitVQASP.ffpd

Custody Seals: Custody Seals demonstrate that a sample container has not been tampered with, or opened. The individual in possession of the sample(s) designated for laboratory analysis signs and dates the seal, affixing it in such a manner that the container cannot be opened without breaking the seal.

6.0 QUALITY ASSURANCE REQUIREMENTS

6.1 Quality Control and Quality Assurance Samples

6.1.1 Replicate Sampling

No replicate samples will be required for the removal assessment.

6.1.2 Reference or Background Sampling

One background soil sample will be collected if necessary.

6.1.3 Field Generated Blank Samples

No blank samples are required.

6.1.4 Matrix Spike/Matrix Spike Duplicates

One field sample for metal analysis will be designated as a QC sample for a matrix spike duplicate.

6.1.5 Performance Samples

Performance samples will not be submitted to the laboratory.

6.2 Analytical

The following requirements apply to the definitive data quality level:

1. Provide sample documentation in the form of field logbooks, appropriate field data sheets and chain-of custody forms.

2. Initial and continuing calibrations will be documented.

3. The detection limit will be determined by the laboratories according to the method requirements, and recorded, along with the data, where appropriate.

4. Analytes will be identified and quantified.

5. QC blanks will be analyzed.

6. Matrix spike recoveries will be documented.

7. Analytical error determination in the form of replicate samples must be performed on 10 percent of the samples.

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8. Total measurement error documenting the precision of the measurement system from sample acquisition through analysis will be determined.

6.3 Data Validation

Data generated under this plan will be evaluated in accordance with appropriate criteria contained in the Removal Program Data Validation Procedures which accompany OSWER Directive 9360.4-1. The assessment of data acceptability or usability will be provided as part of the final report for this investigation.

7.0 DISPOSAL OF INVESTIGATION DERIVED WASTE

For non-hazardous waste, materials will be doubled bagged in large drum liners and sent to a municipal landfill. Hazardous waste generated during the investigation will be double bagged, labeled, and left on-site.

8.0 ADDITIONAL DATA COLLECTION

8.1 Photographic

Photographic documentation will be collected by other agencies investigating the site. START will document site activities of the START members only with photographs. Photographs will be taken and entered into a separate photo log book. It is necessary to include the following information;

1. Date 2. Roll Number 3. Frame Number 4. Description of activity being photographed 5. Initials of person taking photograph

9.0 SCHEDULE OF SAMPLING ACTIVITIES

The proposed schedule of work is as follows:

Activity Start Complete

Prepare QASP 02-28-98 03-02-98

Field Activities 03-04*98 03-04-98

Receive Analytical Data/Data validation 03-06-98 04-06-98

Prepare, review, and finalize report TBD TBD TBD = To be determined

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10.0 PROJECT ORGANIZATION AND RESPONSIBILITIES

10.1 Responsibilities

The TM has the ultimate responsibility for decisions concerning project sampling needs, objectives and schedules. The E & E START Program Manager and the EPA Project Officer have the responsibility for coordinating resources requested by the TM for this project, and for the overall execution of the overall START program.

The START Project Manager is the primary contact point with the TM, and has the responsibility for the execution of decisions and courses of action deemed appropriate by the TM.

The Project Manager is also responsible for ensuring adherence to the sampling QA/QC plan throughout the sampling effort, and recording any deviations from the plan. In the absence of the Project Manager, a START Site Manager will assume the Project Manager's responsibilities.

The Region IX START QA Officer is responsible for auditing and reviewing the field activities and final deliverables, and proposing corrective action, if necessary, for nonconformity to this QASP and the Project Health and Safety Plan. No audits are planned for this activity.

The Key personnel and their responsibilities are listed below:

All samples will be analyzed by Curtis and Tompkins, located in Berkeley, California.

10.2 DELIVERABLES

The PM will keep the OSC informed of the technical and financial progress of this project. Activities under this project will be documented in trip, analytical and/or final reports. Activities will also be summarized in the appropriate formats for inclusion into the monthly and annual START reports.

The QASP, Data Validation Report Summary, and the Final Report will be included in the

deliverables. :

Task Monitor OSC Chris Weden

START Program Leader T.Chambers

Project Manager

Site Safety Officer

START QA Officer

C. Palladino

J. Gregory

H. Edwards

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APPENDIX A

STANDARD OPERATING PROCEDURE

October 20, 1988 HAZCAT.'tNG Field Chemistry for First Responders

Hazard Categorization (HAZCAT)

1.0 Introduction

The Hazard Categorization (Hazcat) System currently utilized by EPA Region IX TAT is comprised of a series of simple field chemistry tests designed to Identify the hazardous characteristics of an unknown chemical, mixture, or waste. A series of qualitative test-tube tests permits the unknown material to be classified into one of the following 9 categories:

i) ACID (liquid/solid)

ii) ACID OXIDIZER (1iquid/sol id )

iii) BASE (liquid/solid)

iv) BASE OXIDIZER (liquid/so 1 id)

v) FLAMMABLE (liquid/so 1Id)

vi) CHLORINATED HYDROCARBON

vii) CYANIDE (liquid/solid)

•iii) SULFIDE (liquid/solid)

ix) NON-HAZARDOUS (liquid/solid)

By thus classifying the hazardous material, any or all of the following tasks may be performed:

1.1 Assignment of hazardous waste characteristics according to RCRA (40 CFR, Section 261.20) definitions (ignitability, corrosivity, reactivity).

1.2 Assignment of DOT hazard class (49 CFR, Sections 171, 172) to permit placarding and manifesting of the material for transportation. ...... -

1.3 Rapid assessment of the materials present at a site, and the evaluation of their potential hazards to the populace and environment. TAT cannot access CERCLA funds for a removal action (40 CFR, Section 300.63) if the materials present are non-hazardous.

1.4 Selection of Immediate mitigative measures, such as the segregation of containers of Incompatible materials, or the neutralization of containment of a leaking substance with the appropriate material (i.e. soda ash for an acid spill).

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1.5 Bulking material into consolidated waste streams for subsequent disposal or treatment, thus reducing disposal/ transportation costs.

1.6 Reducing analytical costs by allowing the selection of a limited number of composite samples from each waste stream, instead of submitting many discrete samples to the laboratory.

2.0 The Hazcat Procedure

2.1 Sample Observation

Note the color, viscosity (i.e. water-like), turbidity and number of phases.

2.2 Water Solubility/Specific Gravity

A small quantity (approximately 0.2 mL or 0.1 gram of solid) is added to 3mL of de-ionized water in a test tube.

i) Note whether a temperature change occurs, and whether effervescence or fumes are produced, indicating that the sample is water-

• reactive.

il) If the sample completely dissolves in the water, giving no turbidity and forming a one phase

. .. solution, then the sample is soluble.

ill) If the sample is insoluble or immiscible, note whether its specific gravity is greater than one (it sinks) or less than one (it floats).

2.3 Determination of pH

This test is performed on a water/sample solution, since a pure

organic acid or base will not give a result.

Meter: Immerse the probe of a calibrated pH meter into the

sample solution and read the pH.

pH Paper: Dip the test strip into the liquid and compare the color obtained with the reference colors on the pack.

For solid samples, the test strip should be dipped Into a solution of the sample, or into an aqueous extract if the sample

is only sparingly soluble.

5-2

2.4 Oxidizer Test

This test is conducted on all water soluble samples.

i) Acidify a potassium iodide (KI) test strip with a few drops of 3M hydrochloric acid (HC1).

ii) Dip the strip into the liquid sample or aqueous-solution of the solid sample.

iii) if the test strip turns blue or black., the sample

is an oxidizer.

2.5 Sulfide Test

This test is performed when the pH of a sample is 7 or greater, since sulfides are not stable in acid solution. A detection

limit of about 50 ppm can be obtained.

i) The lead acetate test strip is acidified with a few drops of 3M HC1 and dipped into the sample, or contacted against the solid sample.

ii) The paper darkens if sulfides are present.

2.6 Cyanide Test

This test is performed when the pH of the solution is greater than 7, since cyanides are not stable in acid solutions. A detection limit of about 50 ppm can be obtained.

i) 5 mL of the sample, or 0.2g of the solid sample dissolved in 5 mL of water, is placed in a test

tube. 7

ii) If the pH is not already 11 or greater, add 2-3 drops of 50Z sodium hydroxide solution (NaOH) to

adjust the pH to 11.

iii) 3 drops of the rhodanine solution are added to the tube, which is gently swirled.

iv) 1 drop of the 0.02M silver nitrate (AgN03> is added. If cyanide is.-present, there is no color change. A negative cyanide result is characterized by a precipitate - or color change.

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2.7 Flammabi1ity Test

i) The HNu photoionization detector is used to take a head—space reading from the sample jar.

ii) A small quantity of the liquid sample is applied to a support medium, such as a cotton swab and ex—

posed to a flame (the BIC test).

Flammable: The sample ignites readily and vigorously on exposure to a flame source, and gives an HNu reading (10.2eV probe, 9.8 span) of greater than 200 units. The estimated flash point is approximately 100F or less.

Combustible: The sample ignites and will sustain a flame on exposure to the flame source, and gives an HNu. reading ( 10 . 2 e V / 9 . 8 span) of less than 200 units. Flash point

estimated at less than 200F.

Nonflammable: The sample is non—combustible and nonflammable if it does not ignite or burn after sustained exposure to the

flame source.

2.7 Chlorinated Hydrocarbons

For all liquid samples which are insoluble and have a specific

gravity of greater than 1.

A. Copper Wire Test (Beilstein Test)

i) Heat the copper wire in the flame of a propane torch until a yellow flame with no green colora­

tion is seen. -

ii) Air-cool the wire for 15 seconds,

iii) Dip wire into the sample.

iv) A green flame indicates that chlorinated compounds

are present.

2.8 PCB Screening

Kits are commercially available to test for the presence of PCB s semi-quantitatively (CLOR-N-OIL screening kit; McGraw Edison

kit) .

3.0 The Haxcat Kit

3.1 Reagents and Test Strips

A. pH Test - pH paper de-ionized water

5-4

B. Oxidizer Test - Potassium I o d i d e (KI) test strips 3M Hydrochloric Acid (HC1)

C. Sulfide Test - Lead Acetate/Starch test strips

3M HC1

D. Cyanide Test - 50Z sodium hydroxide solution ,nn. 7 Rhodanine solution (20.mg of para-amino-

benzalrhodanine in 100 ml of acetone) 0.02M silver nitrate Solution.

E. Chlorinated Hydrocarbon Test - Copper Wire Propane Torch.

3.2 Equipment

Test tubes (100) Test tube rack Test tube holder Disposable pipets(100) Wash bottle of deionized water (250 mL)

Copper wire Propane torch Garbage bags Kimwipes Cotton swabs Duct tape HHu Draeger pump & tubes Container inventory sheets Hazcat result sheets ~ ~

3.3 Reagents & Test Strips .=

Rhodanine solution (in acetone) (30 mL) 3M Hydrochloric Acid (30 mL) 5 0 Z Sodium hydroxide solution ( 3 0 mL) 0.02H Silver nitrate solution (30 mL) Potassium iodide test strips (2 packs) Lead acetate/starch test strips (2 packs)

pH test strips (2 packs) Deionized water (250 mL)

4.0 Personal Protective Clothing For HAZCAT

4 . 1 Sijal Suit

4 . 2 Canister Respirator with GMC-H organic vapor/acid gas

cartridges

4 . 3 Neoprene boots

4.4 Latex inner & neoprene outer gloves

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4.5 Hard hat with face shield (optional)

4.6 Acid Splash apron (optional)

Notes:

Genera 1

If the hazcat procedure is performed carefully, with attention to detail, little or no contamination of the gloves or other

protective clothing should occur: 1. The Sijal Suit offers the most complete protection

against acids, bases and organics. Saranex is^ an alternative, offering good protection against acids, bases, some organics and PCB's. However, Saranex offers poor protection against halogenated and aromatic hydrocarbons and has stitched seams which may

constitute a penetration pathway.

2. Canister - respir a. tors' are listed in preference to cartridge respirators since the canister is belt-mounted outside the breathing, zone and thus away from the area of maximum contaminant concentration during

sample handling.

3. If the samples are known to be principally halogenated and aromatic hydrocarbons, then viton gloves would afford better protection than neoprene. In general, neoprene gloves offer the best compromise when many classes of chemicals are to be handled, although their susceptibility to attack by halogenated hydrocarbons

should be noted.

5.0 Data Management

Field data (container markings, container size, etc. and hazcat test results) are recorded directly on the data sheets inclu e in Appendix A. In Region IX TAT, this data Is subsequently entered into a computer database, using a portable Compaq le computer. A database management program permits the samples o be grouped according to hazard class, so that print-outst o samples having similar chemical properties can be obtained. This is particularly important for large removal operations, in which thousands of drums may have been sampled, since it obviates

lengthy and tedious manual compilation of the data.

5-6

6.0 Compatibility Studies

For a removal action, it is usually desirable to consolidate compatible wastes from different containers in order to generate waste streams for disposal or treatment. Thus, it would be desirable to consolidate all cyanide wastes for one stream, and for example, all non-oxidizing acids (liquid) into another. However, it must be appreciated that the qualitative nature of hazcatting does not completely categorize a given sample since there is the possibility of incompatibilities between samples of the same hazard class. Therefore, a bench-top compatibility study must first be conducted using small quantities of each sample from a given class, so that any incompatibilities are detected before the materials are mixed in bulk.

Composite samples for each hazard class are thus prepared by taking small quantities (5-10 mL) of each sample of that class, and mixing them in an 8 oz. sample jar. The aliquot drawn from each sample should be proportional to the bulk amount of that material present on site. Therefore, the following composite might be prepared from ten containers, each of which were determined to be liquid cyanide wastes from the results of hazcatting.

Sample # Container Size ZFull Aliquot Taken (gallon) (mL)

1 55 100 5 2 55 50 2.5 3 10 100 1 4 100 100 10 5 25 100 2.5

Thus, the composite sample generated approximately reflects the composition.of the waste stream obtained when the bulk containers are mixed.

On addition of each constituent to the composite sample, the following observations are made:

i) I8 an effervescence observed?

ii) Is any gas/vapor evolved?

iii) la any heat generated?

iv) Is any solid precipitated?

A positive observation of i, ii or iii indicates incompatibility between the samples; they are probably not suitable for bulking into one consolidated waste stream. Perhaps only one sample gives such reactions. In this case, that sample would be disposed of as a separate waste stream (i.e. cyanide (reactive)).

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During the compositing process, the sample jar should at all times be pointed away from the person compositing, since adverse reactions do occur, and the solution can spray out of the jar. Care is essential in this process, as in the hazcatting procedure itself, during which the test tube mouth is always pointed away from the person conducting the tests.

In the open-air environment hazcatting processes • are not danger­ous, provided that the specified protective clothing is worn, and good laboratory practice in handling potentially dangerous chemi­cals is followed. It should always be remembered, however, that the potential for injury exists when high-concentration source samples are handled, so that caution must always be exercised.

7.0 Additional Tests

7.1 Draeger Tubes

Draeger tubes can provide valuable confirmation, particularly for the rhodanine/silver nitrate test for cyanide, which often proves ambiguous with dirty, opaque solutions in which a negative result (precipitation) is difficult to see. If a small (0.5 mL or less) portion of the sample is acidified to a pH of <5 with a few drops o£.3M HC1, hydrogen cyanide gas (HCH) is liberated, which can be detected with the hydrogen cyanide Draeger tube. Although HCN is extremely toxic (TLV =» 10 ppm) the small quantity generated by this test does not represent a health hazard to an operator wearing a respirator (equipped with. a GMC-H canister) operating in the open-air. It is imperative, however, that only a small quantity of the sample is acidified for this test.

Similarly, acidification of a small aliquot of a sulfide containing sample generates hydrogen sulfide (H2S; TLV; 10 ppm) which may be detected with a hydrogen sulfide Draeger tube. Again, less than 0.5 mL should be used for health and safety reasons.

Finally, when time is available and a site is better characterized so that the contaminants present or suspected of being present are known, specific Draeger tubes may be used to

c screen certain hazard classes. Examples are:

i) Flammable Liquids: Could be screened for acetone, alcohol, methyl ethyl ketone, or ethyl acetate.

ii) Acid Oxidizers: SO2 Draeger tube (sulfuric acid) NO2

Draeger tube (nitric acid)

iii) Acid Liquids: HF Draeger tube (hydrofluoric acid) HC1

Draeger tube (hydrochloric acid).

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7.2 Other Test Strips

Test strips are commercial 1y available to test for many metals (e.g. nickel, zinc and chromium) and many anions (e.g. sulfate, chromate, and nitrate) in aqueous solution. However, these are of limited use due to interferences which may occur when many species are present in the same solution.

7.3 PCB Test Kits

The CHLOR-N—OIL test kit permits the concentration of PCB's in transformer oils to be qualitatively measured. The sample is reacted with metallic sodium in the presence of a catalyst, stripping the chlorine from the PCB's to form sodium chloride, which is subsequently extracted.and determined colorimetrically.

McGraw Edison market a similar kit which uses a chloride ion electrode to determine the sodium chloride generated and is thus a little more quantitative. Both kits are easily used In the

field.

7.4 Pesticide Screening Kits

A qualitative field test is available for organophosphorous pesticides. Chlorinated pesticides give a positive copper wire test.

7.5 Physical Appearance

It is tempting, particularly for a chemist, to make a tentative identification of an unknown sample by its physical appearance. For example, nickel salts are green crystalline solids, giving clear green solutions in water; sodium cyanide is commercially available in white pellets, approximately 1/4" in length. However, an unknown material must never be identified solely by supposition based on color or physical appearance; these characteristics provide valuable corroborating evidence, but can be misleading, due to plethora of mixtures, formulations and contaminated materials existing on a hazardous waste site. Similarly, one should never assume that the labeling on a container is correct.

8.0 Ambiguous Results and Other Problems

8.1 A water soluble sample (an aqueous solution or some lower molecular weight organic species) cannot be a chlorinated hydrocarbon. If such a sample gives a positive copper wire test, it is simply a solution containing chloride ions. Hydrochloric acid, for example, gives a positive copper wire test, but is clearly not a chlorinated hydrocarbon.

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8.2 As commented previously, the cyanide test (and in some cases the sulfide and oxidizer tests) may give ambiguous results with certain dirty, opaque solutions. In this cas*s' , test may be repeated with diluted samples (using deionized water for dilution) or in the case of the oyan:L<ie_ and sulfide tests, confirmation may be obtained by acidifying

and testing with Draeger tubes.

Highly colored pure solutions (such as potassium permanganate, which is deep red-purple in color) may also cause difficulty because their color masks that of the pH paper or the oxidizer test strip. Again, the sample may be diluted with deionized water, because although this will change the pH of the solution, it will nol do so sufficiently to confuse the qualitative identification o acids and bases. (Potassium permanganate would hazcat as_ an oxidizer, and could be acid or basic according to the application for which it was formulated.)

8.3 Since the pH of a solution is a measure of the concentration of hydrogen ions in aqueous solutions, organic cannot usually be tested with pH paper. An aqueous extract must be prepared by shaking the sample with an equal volume of deionized water; the extract is then tested with p

paper.

8.4 Some samples may have more than one phase; an aqueous phase and an organic phase being fairly common. In this instance, both phases should be hazcatted separately. In these cases, the validity of the hazcat tests reflects the skill of the sampler who withdrew the sample from the drum/container. Vlthout a representative sample to work with, the person conducting the hazcatting cannot properly characterize the

material in the container.

9.0 Selective Application of HAZCAT Tests

In many cases, not all of the hazcatting tests prescribed in

section 2 need to be conducted on a given sample.

9.1 If a liquid is insoluble in water and forms a layer floating on the water surface (i.e. it has a specific gravity less than 1), then it is an organic material and need not be tested for cyanide and sulfide* In addition, since s specific gravity (SG) is less than 1 it cannot be a chlorinated hydrocarbon, all of which have SG s greater than 1. Since it could be an organic acid, however, the pH must

still be recorded by preparing an aqueous extrapt as

detailed in 8.3.

9.2 If an insoluble liquid sample has an SG>1, it is probably a chlorinated hydrocarbon. In this case proceed directly to

the copper wire test or PCB test kit, if availa e.

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9.3 If the pH of a sample is less than 7, the sample canno contain sulfide or cyanide, neither of which are^stable acid solution. thus, these tests can be dispensed with.

9.4 If a sample gives a positive oxidizer test, it cannot be sulfide or cyanide; in this case the sulfide would have been

oxidized to sulfate and the cyanide to cyanate.

10.0 Practical Experience

Participants in the training class will hazcat unknown (low-hazard) samples in the laboratory, following the

introductory lecture.

The forms to be used for the laboratory practical exercise

are contained in Appendix A.

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