40cfr method update rule

Curtis & Tompkins, Ltd.

40CFR METHODS UPDATE RULE (MUR)

Effective 4/11/07 The USEPA published updates to the Clean Water Act (CWA) and Safe Drinking Water Act (SDWA) that became effective on April 11, 2007. These rules may affect your projects immediately, or may be phased in as NPDES or other permits are updated; verify your implementation requirements with your regulators! The sections of 40CFR (Code of Federal Regulations, Section 40) that are affected include parts 122, 136, 141, 143, 430, 455 and 4665. 40CFR122: NPDES Program. Specifies use of the methods listed in 40CFR136; updated

sampling requirements for grab and composite samples; added E.coli and Enterococci to the list of permitted parameters.

40CFR136: CWA Program. Updated holding times and preservation requirements; removed

most of the methods published by the USEPA as “Methods for Chemical Analysis of Water & Wastes” (EPA-600/4-79-020) with methods published in “Standard Methods for the Examination of Water & Wastewater” (SMWW), ASTM and AOAC; withdrew use of Freon-based extraction methods for Oil & Grease and replaced them with hexane-based methods; added flexibility to method modifications.

40CFR141 & 143: SDWA Program. Allows use of newer methods, as listed in tables. 40CFR430: Amended Effluent Limitation Guidelines for pulp, paper, and paperboard point

sources; approved new method for chlorinated phenolics in waste water. 40CFR455: Moved Pesticide Active Ingredient table (Table 7) to 40CFR136 Table 1-G. 40CFR465: Amended Effluent Limits for coil coating point sources; updated method

references. SAMPLING REQUIREMENTS 40 CFR 136.3 Bottle & Preservation requirements in this section supersede any specified in older methods Cooler & refrigerator temperature now specified as < 6.0°C, instead of 2-6°C. Water samples should not be frozen but < 2°C is now acceptable. For those analyses with holding times previously listed as “as soon as possible” (ie: pH, dissolved oxygen, residual chlorine) 40CFR136 Table 2 now lists the holding time as 15 minutes, essentially requiring analysis to be done in the field. Sample preservation must be done within 15 minutes of collection. Sample preservation must be within 15 minutes after collection of grab samples, composite samples, or aliquots taken from a composite taken automatically over time.

Curtis & Tompkins, Ltd. July 2007

Curtis & Tompkins, Ltd.

Curtis & Tompkins, Ltd. July 2007

For Dissolved Metals, the samples must be filtered and then preserved within 15 minutes of collection. For Ortho-Phosphate, samples must be filtered within 15 minutes of collection. METHODS The updates include methods for Organics, Metals, and Inorganic (Wet Chemistry) methods however for C&T the changes primarily affect the Wet Chemistry analyses. For these parameters, most of the EPA numbers have been dropped in favor of SMWW methods. The table below lists the new method numbers along with the methods C&T has historically reported for these analyses. C&T is required to report the new method numbers, unless specifically directed by the client to report the old number for NPDES compliance. If the old number is required, it should be documented on the Chain-of-Custody for the applicable samples. INFORMATION & REFERENCES The text of the MUR, including details affecting organics and metals parameters, can be found through the websites listed below: March 12, 2007 Federal Register notice: http://www.epa.gov/fedrgstr/EPA-WATER/2007/March/Day-12/w1073.htm Print-version: http://www.epa.gov/fedrgstr/EPA-WATER/2007/March/Day-12/w1073.pdf Frequently Asked Questions (FAQ): http://www.epa.gov/waterscience/methods/update2003/questions.html Background documents: http://www.regulations.gov/fdmspublic/component/main?main=DocketDetail&d=EPA-HQ-OW-2003-0070

http://www.epa.gov/fedrgstr/EPA-WATER/2007/March/Day-12/w1073.htm






















































http://www.epa.gov/fedrgstr/EPA-WATER/2007/March/Day-12/w1073.pdf















http://www.epa.gov/waterscience/methods/update2003/questions.html


























http://www.regulations.gov/fdmspublic/component/main?main=DocketDetail&d=EPA-HQ-OW-2003-0070



























































GENERAL CHEMISTRY SAMPLE CONTAINERS & HOLDING TIMES Curtis & Tompkins, Ltd. General Chemistry Parameters New Method Previous

C&T Method Holding Time8 Water Soil

Minimum Volume Water Soil

Water Sampling Container Preservative9

Acidity SM 2310B EPA 305.1 14 days - - 100 mL - - 250mL P None Alkalinity (as CaCO3) SM 2320B EPA 310.1 14 days NS5 100 mL - - 250mL P None Ammonia Nitrogen SM 4500NH3-D EPA 350.3 28 days - - 100 mL - - 250mL P H2SO4 Asbestos Various Various NS5 NS5 1 L 50 g 1L P None Bicarbonate Alkalinity SM 2320B EPA 310.1 14 days - - 100 mL - - 250mL P None Bioassay, %survival NPDES NPDES 36 hr - - 5 gallons - - 5gal cube None Bioassay, screen CCR Title 22 CCR Title 22 36 hr 36 hr 500 mL 200 g 1L G None Biochemical Oxygen Demand (BOD) SM 5210B EPA 405.1 48 hr - - 600 mL - - 1L P None Carbon, Total Organic SM 5310C EPA 415.2 28 days - - 40 mL - - 2 x 40mL VOA H2SO4 Walkley-Black Walkley-Black - - NS5 - - 25 g - - - - Carbon, Total Inorganic SM 5310C EPA 415.2 28 days - - 40 mL - - 2 x 40mL VOA H2SO4 Carbonate Alkalinity SM 2320B EPA 310.1 NS5 - - 100 mL - - 250mL P None Cation Exchange Capacity EPA 9081 EPA 9081 - - 6 mo - - 10 g - - - - Chemical Oxygen Demand (COD) SM 5220D EPA 410.4 28 days - - 100 mL - - 250mL P H2SO4 COD, Filtered SM 5220D EPA 410.4 28 days - - 100 mL - - 250mL P H2SO4 Chloride EPA 300.0 EPA 300.0 28 days - - 100 mL - - 250mL P None Chlorine, Residual SM 4500Cl-G EPA 330.5 15 min - - 100 mL - - 250mL G Foil wrapped Coliform, Fecal 6 hr - - 100 mL - - sterile 100mL Na2S2O3 Color SM 2120B EPA 110.2 48 hr - - 50 mL - - 250mL G None Conductivity SM 2510B EPA 120.1 24 hr4 - - 100 mL - - 250mL P None Corrosivity to Steel (NACE) EPA 1110A EPA 1110A NS5 NS5 1 L 1000 g 1L G None Chromium, Hexavalent EPA 7196A EPA 7196A 24 hr10 30 days 100 mL 40 g 500mL P None SM 3500Cr-D SM 3500Cr-D 24 hr10 - - 100 mL - - 500mL P None EPA 7199 EPA 7199 24 hr10 - - 50 mL - - 250mL P None Cyanide SM 4500Cn-E EPA 335.2 14 days 14 days 500 mL 5 g 500mL P NaOH EPA 9010/9014 EPA 9010C/9014 14 days 14 days 500 mL 5 g 500mL P NaOH Cyanide, Amenable SM 4500Cn-E EPA 335.2 14 days 14 days 500 mL 5 g 500mL P NaOH EPA 9010/9014 EPA 9010C/9014 14 days 14 days 500 mL 5 g 500mL P NaOH Cyanide, Reactive SW846 Ch.7 SW846 Ch.7 NS5 NS5 25 mL 10 g 500mL P None Density ASTM or AOCS ASTM or AOCS NS5 - - 200 mL - - 250mL P or G None Dissolved Oxygen SM 4500O-G EPA 360.1 15 min - - 100 mL - - 250mL G None Dissolved Sulfide SM 4500S2-D EPA 376.2 7 days - - 50 mL - - 500mL P NaOH Ferrous Iron (Fe2+) SM 3500FeD SM 3500FeD in field - - 50 mL - - 100mL P or G HCL Ferric Iron (Fe3+) SM 3500FeD SM 3500FeD 24 hr - - see Notes - - 2 x 100mL P see Notes (6) Flash Point EPA 1010A EPA 1010A NS5 - - 60 mL NA 250mL P None Fluoride EPA 300.0 EPA 300.0 28 days 28 days 100 mL 10 g 250mL P None Free Liquids (Paint Filter Test) EPA 9095B EPA 9095B NS5 NS5 100 mL 50 g 500mL wide None Halogens, Total Organic EPA 9020 EPA 9020 28 days 28 days 200 mL 10 g 250mL P or G H2SO4 Hardness, as CaCO3 EPA 130.2 EPA 130.2 6 mo. - - 100 mL - - 250mL P HNO3

Curtis & Tompkins, Ltd. July 2007 page 3 of 6





Hexavalent Chromium EPA 7196A EPA 7196A 24 hr10 30 days 100 mL 40 g 500mL P None SM 3500Cr-D SM 3500Cr-D 24 hr10 - - 100 mL - - 500mL P None EPA 7199 EPA 7199 24 hr10 - - 50 mL - - 250mL P None Ignitability SW846 Ch.7 SW846 Ch.7 - - NS5 - - 10 g - - None Iron, Ferrous (Fe2+) SM 3500FeD SM 3500FeD 24 hr - - 50 mL - - 100mL P HCL Iron, Ferric (Fe3+) SM 3500FeD SM 3500FeD 24 hr - - see Notes - - 2 x 100mL P see Notes (6) MBAS (Surfactants) SM 5540C EPA 425.1 48 hr - - 250 mL - - 1L P None Moisture CLP-SOW CLP-SOW - - NS5 - - 25 g - - None Nitrate Nitrogen EPA 300.0 EPA 300.0 48 hr - - 100 mL - - 250mL P None Nitrite Nitrogen EPA 300.0 EPA 300.0 48 hr - - 100 mL - - 250mL P None Nitrate/ Nitrite Nitrogen EPA 300.0 EPA 300.0 28 days - - 100 mL - - 250mL P None Nitrogen, Ammonia SM 4500NH3-D EPA 350.3 28 days 28 days 100 mL 10 g 250mL P H2SO4 Nitrogen, Total Kjeldahl (TKN) SM 4500NH3-C EPA 351.4 28 days 28 days 50 mL 5 g 1L P H2SO4 Oil & Grease, Petroleum (H.E.M.-SG) EPA 1664A EPA 1664A 28 days - - 1 L - - 1L G HCL Oil & Grease, Total (H.E.M.) 28 days - - 1 L - - 1L G HCL Organic Carbon, Total SM 5310C EPA 415.2 28 days - - 40 mL - - 2 x 40mL VOA H2SO4 Walkley-Black Walkley-Black - - NS5 - - 25 g - - - - Organic Lead CA LUFT7 CA LUFT7 14 days 14 days 100 mL 50 g 250mL P None Ortho-phosphate Phosphorus SM 4500P-E EPA 365.2 48 hr11 - - 50 mL - - 100mL P None Oxygen Demand, Biochemical SM 5210B EPA 405.1 48 hr - - 600 mL - - 1L P None Oxygen Demand, Chemical SM 5220D EPA 410.4 28 days - - 100 mL - - 250mL P H2SO4 Oxygen, Dissolved SM 4500O-G EPA 360.1 15 min - - 100 mL - - 250mL G None Paint Filter Test EPA 9095 EPA 9095 NS5 NS5 100 mL 50 g 500mL wide None Perchlorate EPA 314.0 EPA 314.0 28 days - - 100 mL - - 250mL P None PH SM 4500H+B EPA 150.1 15 min 100 mL 250mL P None

EPA 9040C/

9045D EPA 9040C/ 9045D 24 hr 14 days 100 mL 50 g 250mL P None Phenolic Compounds EPA 420.1 EPA 420.1 28 days - - 500 mL - - 1L G H2SO4 Phosphate, ortho- SM 4500P-E EPA 365.2 48 hr - - 50 mL - - 100mL P None Phosphate, Total SM 4500P-E EPA 365.2 28 days 28 days 50 mL 10 g 250mL P H2SO4 Reactive Cyanide SW846 Ch.7 SW846 Ch.7 NS5 NS5 25 mL 10 g 500mL P None Reactive Sulfide SW846 Ch.7 SW846 Ch.7 NS5 NS5 25 mL 10 g 500mL P None Residual Chlorine SM 4500Cl-G EPA 330.5 15 min - - 50 mL - - 100mL G None Resistivity SM 2510B EPA 120.1 28 days - - 100 mL - - 250mL P None Salinity SM 2520B SM 2520B NS5 - - 250 mL - - 250mL G wax seal Silica SM 4500SiO2-C EPA 370.1 28 days 28 days 50 mL 10 g 100mL P None Solids, Settleable SM 2540F EPA 160.5 48 hr - - 1 L - - 1L G None Solids, Total Dissolved SM 2540C EPA 160.1 7 days - - 100 mL - - 250mL P None Solids, Total Suspended SM 2540D EPA 160.2 7 days - - 100 mL - - 250mL P None Solids, Total Volatile SM 2540E EPA 160.4 7 days NS5 100 mL 50 g 250mL P None Sulfate EPA 300.0 EPA 300.0 28 days - - 100 mL - - 250mL P None Sulfide SM 4500S2-D EPA 376.2 7 days - - 50 mL - - 500mL P NaOH + ZnAc






Sulfide, Dissolved SM 4500S2-D EPA 376.2 7 days - - 50 mL - - 500mL P NaOH Sulfide, Reactive SW846 Ch.7 SW846 Ch.7 NS5 NS5 25 mL 10 g 500mL P None Sulfite SM 4500SO3-B EPA 377.1 15 min - - 100 mL - - 500mL P None Surfactants (MBAS) SM 5540C EPA 425.1 48 hr - - 250 mL - - 1L P None Total Dissolved Solids (TDS) SM 2540C EPA 160.1 7 days - - 100 mL - - 250mL P None Total Inorganic Carbon SM 5310C EPA 415.2 28 days 28 days 40 mL 25 g 2 x 40mL VOA H2SO4 Total Kjeldahl Nitrogen (TKN) SM 4500NH3-C EPA 351.4 28 days 28 days 50 mL 5 g 1L P H2SO4 Total Organic Carbon (TOC) SM 5310C EPA 415.2 28 days - - 40 mL - - 2 x 40mL VOA H2SO4 Walkley-Black Walkley-Black - - NS5 - - 25 g - - - - Total Organic Halogens (TOX) EPA 9020B EPA 9020B 28 days 28 days 200 mL 10 g 250mL P or G H2SO4 Total Suspended Solids (TSS) SM 2540D EPA 160.2 7 days - - 100 mL - - 250mL P None Total Volatile Solids SM 2540E EPA 160.4 7 days NS5 100 mL 50 g 250mL P None Tributyl Tin GC/FPD GC/FPD NS5 NS5 1 L 10 g 1L P or G None Turbidity SM 2130B EPA 180.1 48 hr - - 100 mL - - 250mL G None Viscosity ASTM methods ASTM methods NS5 - - 25 mL - - 50mL P None General Minerals New Method

(MUR 4/11/07) Previous




Alkalinity (as CaCO3) SM 2320B EPA 310.1 14 days NS5 100 mL - - 250mL P None Chloride, Sulfate EPA 300.0 EPA 300.0 28 days - - 100 mL - - 250mL P None Conductivity SM 2510B EPA 120.1 24 hr4 - - 100 mL - - 250mL P None PH SM4500H+B EPA 150.1 15 min - - 100 mL - - 250mL P None Total Dissolved Solids (TDS) SM 2540C EPA 160.1 7 days - - 100 mL - - 250mL P None

Ca, Fe, Mg, Na, Zn, Hardness EPA 200.7 or

6010B EPA 200.7 or

6010B 6 mo 6 mo 100 mL - - 250mL P HNO3 Optional Analysis (can be added to list): Surfactants (MBAS) SM 5540C EPA 425.1 48 hr - - 250 mL - - 1L P None Ion Chromatography Method Holding Time8

Water Soil Minimum Volume Water Soil


Bromide EPA 300.0 28 days NS5 100 mL 1 g 250mL P None Chloride EPA 300.0 28 days NS5 100 mL 1 g 250mL P None Fluoride EPA 300.0 28 days NS5 100 mL 1 g 250mL P None Nitrate-Nitrogen EPA 300.0 48 hr NS5 100 mL 1 g 250mL P None Nitrite-Nitrogen EPA 300.0 48 hr NS5 100 mL 1 g 250mL P None Sulfate EPA 300.0 28 days NS5 100 mL 1 g 250mL P None Hexavalent Chromium EPA 7199 24 hr10 N/A 50 mL - - 250mL P None10 Perchlorate EPA 314.0 28 days N/A 100 mL - - 250mL P None


GENERAL CHEMISTRY SAMPLE CONTAINERS & HOLDING TIMES Curtis & Tompkins, Ltd. NOTES: LEGEND:

4.) Holding time for conductivity may be extended to 28 days if the samples are filtered within 24 hours of collection. mg/L: milligrams per liter (ppm)

5.) NS: No holding time is specified in the regulations for these methods. µg/L: micrograms per liter (ppb)

6.) Ferric Iron (Fe 3+) is the difference between total and ferrous iron. mg/Kg: milligrams per kilogram (ppm)

Requires submission of two polyethylene bottles, one preserved with HCl and one with HNO3. µg/Kg: micrograms per kilogram (ppb)

7.) CA LUFT: California Department of Health Services Leaking Underground Fuel Tank Manual, October 1989. VOA: Amber VOA Vial

8.) Holding times specified in 40CFR 136.3 Table 2 (Clean Water Act/ NPDES, 2006) and SW-846 Table 2-36 Rev.3 G: Amber Glass

9.) Samples should be kept at < 60C from time of collection until analysis. Preserved containers can be supplied by C&T. P: Polyethylene

HCL: hydrochloric acid to pH<2; H2SO4: sulfuric acid to pH<2; NaOH: sodium hydroxide to pH > 12; ZnAc: Zinc Acetate.

10.) Holding time can be extended to 28 days by preservation with EPA 218.6 buffer to pH 9.3 – 9.7.

11.) Samples for Ortho-phosphate must be filtered within 15 minutes of collection and analyzed within 48 hours.


40cfr method update rule

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