1. Sampling: Your data is only as good as your field technicians.
Jeff Martin, Astrea Taylor,
& Nancy Zikmanis

2. Next Phase of the Project Life Cycle
PLANNING:
SAMPLING:
ASSESSMENT:
EVALUATION:
Plan for data collection using the DQO process Collect data using a SAP and FSOPs Verify that data meets DQOs Make data-based project decisions

3. What’s the Goal? Sampling & analysis objectives:
Collect representative samples
Obtain accurate and precise analytical data
Quality Assurance Project Plan (QAPP)
Laboratory QA/QC program
Field Standard Operating Procedures (FSOPs) (see handout)
VAP does not require QAPPs, but Ohio EPA encourages their use for accurate, representative data

4. Who Collects the Sample?
Field staff, usually not the CP or project manager
Field staff must know how to
Collect, handle & manage samples
Understand VAP DQOs for sample collection activities
Follow FSOPs
Communicate with the lab
COCs & VAP Certification
Contact lab for help when needed
Complete Chain of Custody (COC)

5. Field versus Lab Error
Most error (60 to 80%) associated with environmental sampling and analysis is due to field sampling error rather than lab error
Lab QA/QC programs provide strict management and performance control
QA/QC for field sampling activities? We need to rely on FSOPs – typically far less stringent than lab requirements

6. FSOP Purpose?
Standard written instructions that document the way sampling activities are performed to
Meet project data quality objectives
Comply with QAPP (if one exists)
Promote quality by properly and consistently implementing accepted methodology (Ohio EPA’s TGM, VAP TDCs)

7. FSOP Recommendations
Follow U.S. EPA and Ohio EPA technical guidance documents (Ohio EPA’s TGM, VAP TDCs)
Incorporate flexibility into field investigation as it moves forward
Solicit input from technical experts and field staff
U.S. EPA format:
Guidance for Preparing Standard Operating Procedures (SOPs), EPA QA/G-6 (EPA/600/B-07/001, April 2007)

8. FSOPs for Sampling In general, three groups of FSOPs:
Sampling media (soil, ground water, etc.)
Support (decon, field screening, etc.)
Transfer of samples from field to lab:
QA/QC samples (duplicates, blanks)
Sample management (preservation, handling, and shipment)
Chain of Custody

9. Maintaining Sample Integrity from the Field to the Laboratory
Important Concerns that Need Addressed by SOPs

10. Sampling Practices to Avoid Cross-Contamination
While sampling, don’t
Smoke or eat
Wear perfume or cologne
Handle fuels, solvents or other chemicals
Touch potentially contaminated surfaces
Regularly change sampling gloves, especially before filling sample containers
Use disposable or dedicated sampling equipment whenever possible

11. Any Issues?

12. Sampling Practices for Volatile Organic Compounds (VOCs)
For soils, use SW-846 Method 5035/5035A
For ground water (Method 8260B), use the low-flow sampling technique
Minimize sample agitation and aeration
Seal sample containers and place on ice ASAP

13. Methods 5035/5035A Low-Level Soil VOCs (< 200 ug/kg)
Goal is to collect and preserve soil samples in a manner that minimizes VOC loss
Studies indicate significant VOC loss from samples collected using the “bulk soil” or “jar” method (Method 5035A, July 2002, p. 46), problem for low-level VOC samples
Several options for collecting/preserving low- level VOC samples

14. Methods 5035/5035A Low-Level Soil VOCs (<= 200 ug/kg)
Sample collection options (coring devices):
EnCore™ Sampler (or similar devices):
Designed to collect and contain/transport a soil core
Sample may be transferred to a 40 ml VOA vial before shipment to lab
Terra Core Sampler™, Powerstop Handle™ and EasyDraw Syringe™ (or similar devices)
Designed to collect and transfer soil cores to VOA vials

15. Methods 5035/5035A Encore™ Samplers

16. Methods 5035/5035A Terra Core™ Samplers

17. Methods 5035/5035A Low-Level Soil VOCs (<= 200 ug/kg)
Sample preservation options:
Sealed VOA vial on ice (4o+/-2o C)
Sodium bisulfate (reacts with carbonate in soil)
Methanol (dilution factor, hazardous material/waste)
Freezing
Holding times:
48 hours on ice (4o+/-2o C) in VOA vial from collection to analysis or preservation (field or lab)
14 days after preservation to analysis

18. Methods 5035/5035A Low-Level Soil VOCs (<= 200 ug/kg)
What specific collection/preservation options should I use?
Ohio EPA recommends evaluating:
Need for low-level soil VOC analyses (DQOs?)
Site conditions (carbonate soils? soils with VOCs > 200 ug/kg? very loose or very dense soils?)
Difficulty/complexity of effort for field personnel to collect and preserve samples

19. Methods 5035/5035A Low-Level Soil VOCs (<= 200 ug/kg)
Most importantly, discuss the use of these methods with the laboratory and follow their recommended sampling and preservation procedures
Not all laboratories have the same capabilities or preferences
Don’t assume your laboratory will be able to accommodate every 5035/5035A option

20. Methods 5035/5035A Low-Level Soil VOCs (<= 200 ug/kg)
Certified Lab (CL) Rule, OAC (H)(6) states that the CL shall: “Perform analyses in accordance with the laboratory's standard operating procedures and quality assurance program plan approved by Ohio EPA whenever the laboratory produces certified data”

21. Methods 5035/5035A Low-Level Soil VOCs (<= 200 ug/kg)
Phase II Rule, OAC (D)(3)(a) states that field QA/QC procedures must include a: “Review of the laboratory’s quality assurance program plan and standard operating procedures for consistency with field quality assurance and quality control procedures”

22. Ground Water Sampling Issues (Reminder)
Sample representativeness?
Depends on adequacy of well development and sampling techniques:
Adequate well development?
Sufficient stabilization time between development and sampling?
Proper purging and sampling techniques, e.g., adequate purging prior to sampling?
Refer to Ohio EPA’s TGM Chapters 6 and 10

23. Ground Water VOC Samples
Filling 40 ml VOC vials with ground or surface water (zero headspace):
Fill slowly (100 mL/min) to minimize agitation and aeration
Form a meniscus and then slowly screw on cap to seal the sample
Check for bubbles by inverting vial and gently tapping it
Collect at least two vials for each sample

24. Ground Water VOC Samples
Air bubbles in 40 mL vials may be caused by
Insufficient meniscus when sealing the vial
Degassing after sample collection or during sample shipment
Reaction between the sample and preservative (HCl)
Air bubbles do not necessarily invalidate the sample
U.S. EPA studies indicate that bubbles smaller than ¼- inch (pea-sized) do not adversely affect the sample

25. Ground Water VOC Samples
If air bubbles are present in a 40 mL VOC vial immediately after sample collection…
Discard vial and collect another sample using a new vial
Don’t re-open and “top off” the vial, this may compromise the sample through
Additional exposure to ambient air
Loss of preservative

26. Ground Water VOC Samples
If air bubbles are noticed in a 40 mL VOC vial during sample cooler packing…
Recollect the sample if the bubble is ¼-inch (pea- sized) or greater in diameter
Otherwise, submit the sample to the laboratory
If sample reacts with preservative, may need to collect an unpreserved sample

27. Quality Assurance/Quality Control (QA/QC)
Minimize
Sources of sampling and analytical error
Potential cross-contamination
Maximize
Sample representativeness
Analytical data accuracy and precision

28. VAP Phase II QA/QC Procedures OAC 3745-300-07(D)(3)
Review lab QA/QC procedures – are field QA/QC procedures consistent?
QA/QC procedures, not limited to the following:
Equipment decontamination
QA/QC samples
Field instrument calibration
Documentation and record maintenance
Sampling handling, preservation and holding times
Chain of custody

29. QA/QC Samples Sample Type: When to Submit: Trip Blanks
Equipment (Rinsate) Blanks
Field Blanks
Filter Banks
Duplicate Samples
One (1) per sample cooler, VOCs only
If non-dedicated, non-disposable sampling equipment is used
Needed based on field conditions
Recommended for field filtering
One (1) per 20 samples, typically not collected for soil (due to soil matrix heterogeneity)

30. QA/QC Samples Matrix Spike / Matrix Spike Duplicate (MS/MSD):
Fill all containers that the lab provides (if four 1-L jars are required, don’t return only two)
Don’t use the most contaminated sample for the MS/MSD (may adversely affect the lab QA/QC results)
Follow the lab’s advice for the MS/MSD and other QA/QC samples (they know what they need)

31. Sample Management: Preservation
Prevents physical and chemical changes to sample during transportation and storage
Maintains representative constituent concentrations by
Reducing volatility
Preventing hydrolysis
Retarding biodegradation

32. Sample Management: Preservation
Methods generally used
pH control (add strong acid or base)
Chemical addition (stabilization other than pH control, e.g., Na2S2O3)
Temperature control (cool to 4o +/- 2o C)
Protection from light (amber glass sample containers)
Field staff need to understand the purpose of preservation and methods

33. Sample Management: Preservation
Preservatives may react with sample
VOC ground water sample containing carbonate minerals reacts with HCl preservative
Solution: collect an unpreserved sample
Sample holding time will be significantly shorter
Field staff need to inform lab (must understand the relationship between preservation and holding time requirements)

34. Sample Management: Preservation
Use pre-preserved sample containers or add preservatives in the field?
Most labs provide pre-preserved sample containers
May want to carry additional preservative in the field
Adding preservatives to containers in the field presents additional health & safety concerns (field staff need to be aware of potential hazards)

35. Sample Management: Preservation

36. Sample Management: Preservation
Temperature control – recommend using ice rather than ice substitute (“blue ice”)
Generally less effective at maintaining the required cooler temperature
Potential source of chemical cross-contamination
Propylene glycol
Styrene
Ammonium chloride

37. Sample Management: Preservation
Use sealable plastic bags to contain ice
Avoid immersing sample containers in water (damaged labels, cross-contamination)
Avoid leaking coolers; also use plastic cooler liner (or commercial shipper may not deliver)
About 1/3 of cooler should be ice
Avoid the use of “blue ice”
Ice is cheaper than resampling.

38. Sample Management: Preservation
Verification of proper temperature preservation:
Presence of ice in cooler
Measurement of internal cooler temperature
Temperature blank
Recommended
One per cooler
Don’t encase in ice or freeze

39. Sample Management: Containers & Labeling
Specifications per analytical methods (SW-846)
Generally provided by lab
Stockpiled containers from previous projects? Not recommended:
Loss of preservatives
Cross-contamination issues
Inconsistency with current project lab

40. Sample Management: Containers & Labeling
Labels may be completed in field or (mostly) pre- populated by laboratory
Labels should be waterproof and securely affixed to each sample container
Permanent marker or ink (legible if wet)
Protect completed labels with clear tape (except for pre-weighed containers)
Recommend completing and affixing label after sample container is filled

41. Sample Management: Containers & Labeling
Label information
Sample identification (per FSOP?)
Date and time collected (AM/PM or military time)
Analytical methods/constituents requested
Field staff need to be familiar with methods and their respective constituents
Preservatives
Name or initials of sampler

42. Sample Management: Shipping
Use coolers to ship samples (temperature preservation requirements)
Seal ice in plastic bags, use cooler liner
Ship containers upright
Use packing to protect glass containers, e.g., bubble wrap, styrofoam, etc.
Deliver to laboratory via commercial carrier (UPS, FedEx, etc.) or courier

43. Sample Management: Shipping

44. Sample Management: Shipping
Include the chain of custody (COC) form in the cooler (in a sealed plastic bag)
Use an individual COC for each cooler rather than a single COC for multiple coolers
What if the cooler with the COC doesn’t arrive at the lab with the other coolers?
If any cooler in a multiple cooler shipment under a single COC exceeds temp requirements, samples in all coolers will be flagged for temp

45. Sample Management: Shipping
Regulations (DOT), requirements (shipper)
Hazardous materials (LNAPL, methanol)?
Cooler weight?
Type of tape used, cooler labeling?
Securely seal cooler
Affix custody seal with protective tape

46. Sample Management: Shipping
Shipping method depends on holding times
Hexavalent chromium?
SVOCs by 8270?
Unpreserved VOCs by 8260?
Recommend sampling constituents with short holding times last
Important for field staff to understand analytical methods and holding time requirements

47. Sample Management: Shipping
Using a commercial shipper?
Should know drop off locations and business hours before sampling
Call locations to verify, just don’t rely on internet
Saturday delivery?
Complete appropriate shipping forms
Call the lab to confirm deliver location

48. Chain of Custody (COC)
COC form: critical communication between field samplers and the laboratory
Technical and legal record of samples collected, analyses requested and sample custody
Field staff must understand how to properly complete COC forms – what does this mean?

49. Chain of Custody (COC)
Field staff should understand the following to properly complete COC forms:
Project and contact information
Sample ID nomenclature
Analytical methods:
Method numbers/references
Container types and volume requirements
Preservative requirements
Holding times

50. Chain of Custody (COC)
Field staff should understand the following to properly complete COC forms (continued):
QA/QC samples (trip blanks, duplicates, etc.)
Type and quantity needed
How to designate/record on form
Information to include as comments or notes
Detection limit or certification requirements (VAP)
Highly contaminated samples or other matrix issues
Special sampling handling/processing requirements

51. Chain of Custody (COC)

53. Chain of Custody (COC) Review for accuracy and completeness
Don’t forget to sign COC with date & time
Retain a copy before shipping samples
Commercial carriers (e.g., UPS) will not sign a COC – Ohio EPA recommends retaining a copy of the shipping form for documentation of sample custody during transportation

54. Laboratory Interaction
Field staff need a lab contact to address:
Questions about method requirements (e.g., preservation, holding times)
Questions about VAP certification
Need for additional sample containers or supplies
Sample matrix concerns (highly contaminated samples, unpreserved samples)
Weekend delivery (sample receiving)

55. Laboratory Interaction
In most cases, the lab is a contractor retained by the consultant
Both the consultant and lab have common objectives:
Collect representative samples
Obtain accurate and precise analytical data
Mutual understanding, cooperation, and tact will greatly facilitate these objectives

56. Vapor Intrusion (VI) Sampling & Analysis
Gavin Armstrong

57. Vapor Intrusion (VI) Sampling & Analysis
Background:
Has been recognized as a potential pathway of contamination for almost 20 years.
In the late 1980s, the first vapor intrusion studies were carried out to evaluate potential health effects from chronic exposure to volatile organic compounds.
For labs, this has created an upward trend in the number of ambient air, indoor air, soil gas and sub-slab samples submitted each year for volatile organic compound (VOC) analyses.

58. Vapor Intrusion (VI) Sampling & Analysis
The primary compounds of concern are often chlorinated VOCs. Trichloroethene (TCE) and tetrachloroethene (PCE), in particular, are common targets of the investigations due to the health risks associated with these compounds and their breakdown products.

59. Sample Collection… Silicon-lined canister (Silonite®) Tedlar Bag
Varying sizes for GRAB v. TIMED Samples
GRAB Sample only

60. Canister v. Tedlar Bag Sampling Options

61. Canisters from the lab:
Pre-assembled
Assemble On-Site

63. Canister Cleanliness – HOW CLEAN IS CLEAN?
Should you request a “Certificate of Cleanliness” for each canister?

64. Laboratory Analysis: USEPA Method TO-15
The most frequently requested method for the analysis of VOCs for the range of air samples associated with vapor intrusion investigations.
A wide range of compounds (40 to 60) may be analyzed by EPA TO-15 including alkanes, alkenes, aromatics, halogenated VOCs, ketones, esters and some alcohols. (Some aldehydes and sulfides may also be evaluated using this method.)
Some variation among commercial environmental laboratories in the compound lists (must be specific when communicating with lab).
Results reported in μg/m3, ppbV, or both. YOU SHOULD REQUEST BOTH!!!
Compound lists can usually be tailored to meet project-specific objectives.

65. Summary Points
Communicate: >Talk to the lab about equipment/canisters Grab v. Time Integrated.
>Discuss reporting units – ASK FOR BOTH ug/m3 and ppbv.
>Discuss most appropriate method – TO or TO-15 SIM.
>“Certify” each canister? Or accept “batch” decon?
>Verify that lab has CURRENT VAP CERTIFICATION for the analysis.

66. Summary Points Communicate:
>Talk to the lab about equipment/canisters Grab v. Time Integrated.
>Discuss reporting units – ug/m3 and ppbv
ASK FOR BOTH!
>Discuss most appropriate method – TO-15 or TO-15 SIM.
>“Certify” each canister? Or accept “batch” decon?
>Verify that lab has CURRENT VAP CERTIFICATION for the analysis.

67. Any additional questions or comments?
Thanks for your time and attention!