SW-846 Method 5035A

Presented by: Kyle F. Gross AWAL Laboratory Director

Overview

• History of soil VOA analysis • Summary of Method 5035A • Data indicating problems with method 5030 • Advantages of 5035A over 5030 • Regulatory status of 5035A • Choosing a concentration level • Sample vials and collection techniques • Analytical instrumentation • How to ship methanol

History of Soil VOA Analysis

• Bellar & Lichtenberg, “Determinating Volatile Organics in µg/L Levels by GC”, EPA, 1974 • Speis, “Determination of Purgeable Organics in Sediment”, EPA, 1980 • Method 624 promulgated 1984 • Method 5030 promulgated 1986 • Method 8260B promulgated 1996 • Method 5030B promulgated 1996

SW-846

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Method 5035A

• Method 5035 (promulgated in 1997) is a method for the collection, preservation, and analytical preparation of soil samples for volatile compound analysis. • A new version of method 5035 (5035A July 2002) is available 8 . • The purpose of this method is to reduce the loss of volatile compounds from sampling to preparation for analysis. • Studies have demonstrated, in some cases, an increase in volatile concentration by 2-3 orders of magnitude using method 5035A over method 5030. • The primary approved volatile analytical methods are 8260B, 8021B, and 8015B.

Risk Assessment

• It is critical to understand that risk based criteria for volatile compounds is based on true concentrations. Regulatory criteria is not based on negatively biased data collected by using method 5030 to collect and preserve soil samples.

Loss of TCE From a Field Sample Stored in an Uncovered Core Barrel Liner Held in a Plastic Bag (18 o C) 2

100 90 80 70 60 50 40 30 20 10 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60

Time in Minutes

Loss of VOCs Due to Microbial Degradation 2 Storage at 21 o C

4 3.5

3 2.5

2 1.5

1 0.5

0 0 1 2 3 4 5 6 7

Time in Days

8 9 10 11 12 13 14 TCE E-Ben p-Xyl

Loss of VOCs Due to Microbial Degradation 2 Storage at 4 o C

4 3.5

3 2.5

2 1.5

1 0.5

0 0 1 2 3 4 5 6 7

Time in Days

8 9 10 11 12 13 14 TCE E-Ben p-Xyl

Loss of VOCs Due to Microbial Degradation 2 Storage at -12 o C

4 3.5

3 2.5

2 1.5

1 0.5

0 0 1 2 3 4 5 6 7

Time in Days

8 9 10 11 12 13 14 TCE E-Ben p-Xyl

Loss of VOCs Due to Microbial Degradation Storage of Ethylbenze at Differing Temperatures 2

3 2.5

2 1.5

1 0.5

0 0 1 2 3 4 5 6 7

Time in Days

8 9 10 11 12 13 14 E-Ben (21 C) E-Ben (4 C) E-Ben (-12 C)

Advantages of 5035A over 5030

• Reduces loss of volatile compounds by as much as 2 - 3 orders of magnitude.

2,3 • Significantly slows the action of microbial degradation on aromatic volatiles by better sample preservation.

2,3 • Reduces laboratory contamination (methylene chloride and acetone) since the vials are never opened in the laboratory if the closed loop purge and trap system is employed.

• The person collecting the sample has complete control over what portion of the sample is analyzed.

Site Remediation

• TCE compound of concern • Site criteria 100 µg/kg (PPB) • Method 5030B/8260B = 50 µg/kg • Method 5035A/8260B = 200 µg/kg • What is your liability?

• If you used 5030B for soils you knowingly used a method proven to be significantly biased negatively.

Method 5035A Requirements

• Mandatory in 24 states (AK, AZ, CA, CT, DE, FL, GA, HI, IL, IN, LA, ME, MA, MI, MN, NJ, NC, ND, OH, PA, SC, TX, WV, WI,) for at least one program. One more this year (WA).

• Highly recommended by the USEPA Office of Solid Waste.

6 • Mandatory in Region III, and IX and strongly recommended in other regions (I, II).

• Mandatory for some federal government programs (CLP 4 USACE 5 ).

& • Mandatory for many other DOD projects.

• Probably required in most states soon.

Method 5035A, Concentration Levels

• Low Level (0.5 - 250 µg/kg for 5 gram sample) • High Level (> 250 µg/kg for 10 gram sample)

Method 5035A, Choosing a Level

• For unknown sites with full range data requirements, dual level sampling is recommended.

• For high level sites collect high only.

• For low level sites collect low level and high level is optional as a backup.

• If resampling is very costly or difficult, collect three replicates for low and 2 replicates for high level.

Method 5035A, Vial Preparation LOW LEVEL SOIL

• 40 ml amber VOA vial with Teflon/silicon septa • Add magnetic stir bar • Add 0.2 g of NaHSO 4 for each gram of sample expected (AWAL recommends skipping this step) • Seal and label • Weigh vial to nearest 0.01g and record on label

Low Level Vials

Before and After Sample Collection

Method 5035A, Sample Collection LOW LEVEL SOIL

• Add 5 g soil (or less if necessary) +/- 10% using the sampling tool and record sample ID on label • Collect min. of 2 vials (3 preferred) at each location • Collect min. of 5 vials for each designated MS/MSD • Collect additional 5 or 10 g sample in empty vial for TS • Wipe soil from vial lip and seal • Freeze with dry ice or cool to 4 o C (if NaHSO 4 is used as a preservative) and transport to lab in darkness

Method 5035A, Vial Preparation HIGH LEVEL SOIL

• 40 ml amber VOA vial with Teflon/silicon septa • Add 10 ml of methanol • Mark methanol meniscus on the vial • Seal and label • Weigh to nearest 0.01 g and note on label

High Level Vials

Before and After Sample Addition

Method 5035A, Sample Collection HIGH LEVEL SOIL

• Check VOA vial weight (+/- 0.1 g required) or note if methanol level is at the marked meniscus.

• Add 5 or 10 g. soil to vial +/- 10%.

• If methanol does not cover soil add less sample to new vial.

• Wipe soil from lip and seal.

• Collect additional 10 g sample in empty vial for TS.

• Cool to 4 o C and transport in darkness.

EnCore Sampler

Method 5035A, EnCore Sampler

• In lieu of the previous methods an EnCore Sampler may be used.

• AWAL does not recommend the use of an EnCore Sampler.

• EnCore sampler has a 48 hour holding time and requires additional sample handling in the laboratory that increases the chance of analyte loss and contamination. In addition, this method is the most expensive of all the method 5035A options. Not permitted in two states (DE and FL) that require 5035A.

Agilent 5973 Closed Loop GC/MS

Tekmar Solatek 72 Closed Loop P&T

Shipment of Methanol or Sodium Bisulfate

7 Methanol and Sodium Bisulfate are considered flammable or corrosive liquids respectively by DOT • Small Quantity Exception (49 CFR 173.4), container limit 30ml/vial and 500ml/cooler. Shipping paper not required, but air waybill must be marked “Dangerous Good in Excepted Quantities”. Marking: “49 CFR 173.4 (a)(10)” • Limited Quantity Exception (49 CFR 172.101 Hazardous Materials Table Column 8A) not recommended due to additional labeling, required DOT training and other red tape.

• Hazardous Materials Shipment (49 CFR 172.101 Table, Column 9A/9B) not recommended due to additional labeling, required DOT training and other red tape.

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References

USEPA, Office of Solid Waste and Emergency Response, “Test Methods for Evaluating Solid Waste”, Final Update III, December 1996 USACE, CRREL, Hewitt, Alan D., “Storage and Preservation of Soil Samples for Volatile Compound Analysis”, May 1999 Environmental Testing and Analysis, Hewitt, Alan D., “Frozen Storage of Soil Samples for VOC Analysis”, September/October 1999 USEPA, Contract Laboratory Program, “Statement of Work for Organic Analysis Muti Media, Multi-Concentration OLM04.1”, September 1998 USACE, “Sample Collection and Preparation Strategies for Volatile Organic Compounds in Solids” October 1998 USEPA, Office of Solid Waste and Emergency Response, Memorandum to RCRA Senior Policy Analysts Regions I - X, “Clarification Regarding Use of SW-846 Methods”, From: Elizabeth Cotsworth - Acting Director, August 7, 1998 USACE, HQ Environmental Division Lessons, “Shipment of Methanol or Sodium Bisulfate Preserved Environmental Samples”, October 20, 1999 USEPA, Office of Solid Waste and Emergency Response, “Test Methods for Evaluating Solid Waste”, “Method 5035A”, Draft Revision 1, July 2002