ISMR 2007 Operator Continuing Education Credit Class

“Three Phases of a Water Sampling Event”

Jim Risch, Environmental Chemist 1IDEM OLQ Chemistry Services Section

(317) 233-6541, jrisch@idem.IN.gov

Rodger Wilson, Project ManagerStandard Laboratories, Inc.

(812) 473-1814, rwilson@standardlabs.com

Three Phases of a Water Sampling Event

• Planning

• Implementation

• Assessment

Reference Toolbox

• “Guidance on Systematic Planning Using the Data Quality Objectives Process,” EPA QA/G-4, February 2006. http://www.epa.gov/QUALITY/qs-docs/g4-final.pdf

• “Standard Methods for the Examination of Water and Wastewater,” 20th Edition, January 1999. http://www.standardmethods.org/

• “Guidance to the Performance and Presentation of Analytical Chemistry Data,” July 1998.

http://www.in.gov/idem/rules/policies/sw/performpresanalychemdata.pdf

Goals: You should be able to ..

• Locate regulations related to water sampling for mining operations

• Write a Sampling and Analysis Plan (SAP) based on a sampling objective.

• Recognize and use various types of equipment for collecting samples.

You should be able to …

• Document a sampling event and deliver samples to the laboratory.

• Generally understand relevant laboratory procedures.

• Use the report of the analytical results to make project decisions.

312 IAC 25-4: Coal Mining and Reclamation Operations; Permitting

Procedures• 312 IAC 25-4-31 Surface Mining Permit

Applications; Environmental Resources Information

• 312 IAC 25-4-72 Underground Mining Permit Application; Environmental Resources Information

• 327 IAC 5: Industrial Wastewater Pre-Treatment Programs and NPDES

• 327 IAC 15: NPDES General Rule Program

• 40 CFR 434: Coal Mining Point Source Category BPT, BAT, BCT Limitations and New Source Performance Standards

IB. Establishing a Sampling Objective

Begin by:• Determining if sample collection is needed for

your project.

• Determining if sample collection is possible for your particular project.

• Getting a general idea of the costs.

Is Sample Collection Needed? Consider:

• Organizing and performing a sampling event requires a significant input of time, money and effort.

• Is there a more efficient way to get the answers you need?

• Can you make your case with pictures and documentation instead?

• Does your project require sampling?

EXAMPLE:“Stadium Site Soil Contains Arsenic”

• “The 350,000 tons of waste will contain more than 6,000 pounds of arsenic.”

• “The state’s own testing found high levels of arsenic but then the high numbers are removed. Removing the higher numbers lowers the arsenic level on paper.”

• Courtesy wishtv.com

Example: Lake Discharge Permit Levels

“Chicago cries foul over Indiana wastewater: State has said oil refinery can pour more pollutants into Lake Michigan.”

Source: Indianapolis Star

Lessons

• People are paying attention

• Media reports can be misleading

• It pays to be conscientious about sampling issues

Is Sample Collection Possible?

• Do you have legal access to the sample location? Will the property owner or RP know you are there?

• Is there enough material to sample?(esp. ground water or storm water)

• Are site conditions currently suitable for sampling ? How’s the weather?

Some Typical Lab Charges- Based on one (1) water sample with a 30-day turn around time

• 8 RCRA metals: $100-$140• Total Petroleum Hydrocarbons: $40-$100• Ammonia, Nitrate, and TKN: $45-$65• Volatile Organics: $125-$300• Semi-Volatile Organics: $225-$450• PCBs: $90-$100• Cyanide and Sulfide: $50-$100

Other Expenses

• Sampler’s paid time on project• Transportation to and from facility• Per diem and overnight stays• Facility costs• Disposable equipment and PPE• Tech. staff paid time for review• Follow-up sampling events

Establishing a Sampling Objective (2)

Now you can:• Establish the objective for the sampling event

before you invest the time, money, and effort to collect the samples.

• A sampling objective must include the decision you want to be able to make.

• Data

• Quality

• Objectives

• “Guidance on Systematic Planning Using the Data Quality Objectives Process,” EPA QA/G-4, February 2006.

What is the DQO Process?

• The DQO process is a strategic planning approach based on the Scientific Method that is used to prepare for a data collection activity.

• The DQO process provides a systematic procedure for determining when and where to collect samples, how many samples to collect, etc.

The DQO Process

• 1. State the Problem

• 2. Identify the Goal of the Study• 3. Identify Information Inputs• 4. Define the Boundaries of the Study• 5. Develop the Analytic Approach• 6. Specify Performance or Acceptance Criteria• 7. Develop the Plan for Obtaining Data

Problem Statement +

Goal of Study =

Complete Sampling Objective

Establishing Goal for Sampling Project - Consider:

• What are you trying to accomplish? What do you want the chemist to be able to tell you?

• What are the Parameters of Interest (constituents of concern, target analytes, etc.) and corresponding Action Levels (if available)?

• What is the end-use of the analytical results?

Before you sample, consider:

• Is sample collection possible?

• Is sample collection needed?

• How much is this event going to cost?

• What are you trying to decide?

I. Planning Phase

C. Preparing the SAP

• Sampling and Analysis Plan (SAP)

• “Test Methods for Evaluating Solid Waste, Physical/Chemical Methods,” (SW-846) Chapter Nine

Sampling and Analysis Plan (SAP)

• Brief Site History and Sampling Objective

• Steps for Collecting Samples

• Documentation and Field Measurements

• Steps for Delivering Samples to Lab, Maintaining Custody, and Analytical Methods with related QA/QC

Representative Sample

1. Has the properties and chemical composition of the population from which it was collected.

2. Has the above in the same average proportions as are found in the population.

Important Decisions when trying to Collect Representative Samples

• Choice of Location(s)

• Number of Samples

• Type of Samples (soil, water, air)

• Choice of Equipment

• Equipment Management (skill and training of sampler)

• Sample Preservation

Ask/Tell Your Chemist:

• Explain your Sampling Objective

• What analytical methods will be used based on the sampling objective? (watch detection limits)

• What bottles and preservatives needed?

• What are the sample holding times?

Ask/Tell Your Chemist (2):

• Is extra sample volume needed for MS/MSD sample preparation?

• Can IDEM-required data deliverables be provided with the results?

• What about shipping samples?

Recommendation

• Send a copy of your draft SAP to the regulatory agency for review and comment before you collect samples.

Locations determined for you:(in most cases)

• Drinking Water Wells

• Ground Water Monitoring Wells

• Liquid Waste Tanks

• Split-Sampling with Site Representative

Locations determined by judgment (easy)

• Visible contaminant release to surface water, flowing away from the site.

• “Worst Case” soil, lagoon, or waste pile

• Drums and Tank Removal Pits

Locations determined by judgment (challenging)

• Ground water well placement

• Soil Gas and/or Vapor Intrusion

• Characterization of soil on site with limited or no available information

Collecting Samples:Grab or Composite?

• Grab: Single sample from one location at one point in time.

• Composite: A specified number of random grab samples are collected and combined into a single sample prior to analysis. (not for VOCs)

The SAP should also include:

• Matrices to be sampled (soil, ground water, drinking water, waste, etc.).

The SAP should also include:

• Detailed procedures for collecting samples. (See next section of presentation)

• Laboratory Test Methods, Field Test Methods, and QA/QC Protocol.

• Containers, Preservatives and Holding Times.

Laboratory Methods

SW-846 on Line: Test Methods for Evaluating Solid Waste, Physical and Chemical Methodshttp://www.epa.gov/epaoswer/hazwaste/test/1_series.htm

• “Standard Methods for the Examination of Water and Wastewater,” 20th Edition, January 1999. http://www.standardmethods.org/

Analytical Methods for Drinking Water (EPA & Non-EPA )http://www.epa.gov/safewater/methods/methods.html

ASTM Methodshttp://www.astm.org

Field Duplicates

• Two samples collected at same place and time and then stored in separate containers and analyzed independently.

• Why needed? Indicates if the sampling procedure has a significant effect on the precision of the analytical results.

Field Duplicate Precision

Result 1 (ppm) Result 2 (ppm) RPD

50 1 192

24 25 4

<5 6 ?

Dedicated Equipment?

• Ideally, dedicated or disposable sampling equipment will be used in order to avoid extensive field decontamination.

• When sample collection equipment will be decontaminated and reused, plan on collecting an Equipment Blank.

Preservatives

• Plan on being able to keep samples cold (approx. 4 degrees C) from the time they are collected until the time they are delivered to the laboratory.

• Water sample containers often have a chemical preservative added at the lab prior to shipment. Be careful!

Holding Times

• Storage time allowed between sample collection and sample analysis when designated preservation and storage techniques are employed.

• Fecal/Total Coliform, Hexavalent Chromium, Nitrate (unpreserved), and BOD tests have short holding times.

The SAP should also include:

• Chain of Custody procedure and form. Possession of the samples must be documented from the time of collection until the time of delivery to the lab.

• Shipping and transport requirements

Why are the SAP and Field QA/QC Samples So Critical?

• Ensure that data generated are accurate and precise with a minimum bias.

• Ensure that data are defensible if and when projects go to litigation.

• Ensure consistency in data collection for long-term projects.

• Ensure that representative samples are submitted for analysis.

II. IMPLEMENTATION PHASE

A. Sampling and Test Equipment

Advantages of Low-Flow (Micro-Purge) Sampling:

• Less strain on the formation

• Reduction in sample turbidity

• Reduction in need for sample filtration

• Less overall sampling time

• Less expensive overall

• Lowers impact of sample collection on the precision & accuracy of results

Low-Flow Sampling References

• Micro-Purge Sampling for Monitoring Wells by OLQ Geological Services

• Technical Guidance on Low-Flow Purging & Sampling and Passive Sampling by Nielsen

• Low-Flow (Minimal Drawdown) Ground-Water Sampling Procedures by Puls & Barcelona

Items of Concern when using Low-Flow Sampling

• Well needs to be installed properly.

• Well screen must be clear.

• Pump intake must be in well screen.

• Drawdown must be minimized.

• Sampler must be trained.

• Must have good reasons for choosing low-flow over traditional methods.

Filtering Water Samples

• “Sampling and Analysis of Ground Water for Metals at Remediation Sites”

http://www.in.gov/idem/rules/policies/sw/w0057_npd.html

II. Implementation Phase

B. Documenting the Sampling Event

Don’t Forget:

• Good sampling procedures and complete field documentation are key elements in generating legally defensible and scientifically valid analytical data.

• Make sure all samplers for the project read and follow the procedures in the sampling and analysis plan.

Documentation Options – Written Records

• Dedicated Site Field Book

• Sample Bottle Labels & Seals

• Chain-of-Custody and Courier Manifest Forms

• Field Memos, Field Sheets, and Technical Reports

Documentation Options:Audio-Visual Records

• 35 mm Slides

• Still Photographs (Polaroid-Type?)

• Video Tape

• Other Recorded Audio and/or Video

Audio-Visual RecordsPlease Consider:

• May be necessary to obtain permission to record field events.

• Must advise people involved in event that they are being recorded.

• In litigation, courts may restrict use of audio-visual materials.

Field Documentation

• Include documentation procedure and copies of forms in SAP.

• Record sufficient information so that anyone can reconstruct the sampling without reliance on the collector’s memory.

All Field Documentation

• Use only black, permanent ink.

• Cross out any mistakes or changes with a single line and then initial and date the change.

• Make sure all documentation is legible.

Field Measurements

• Provide instructions for calibration, measurement, and equipment decontamination in the SAP.

• Document all measurements and include appropriate units.

Please Remember:

• Your written observations could be as important to the overall case as the analytical results. Comments should be as detailed and objective as possible.

• “If you didn’t write it down, you didn’t do it.”

Delivery to Lab:Containers

• If possible, use containers supplied by the laboratory (match with analysis).

• Containers must be properly capped and labeled.

• Samples must be properly preserved (ice).

Sample Custody Chain

• Must be completed before samples can be transferred to the lab.

• Possession of the samples must be documented from the time of collection until the time of delivery to the lab.

• DO NOT identify the site location or the field duplicate on the Custody Chain. You may note the blank and MS/MSD.

Chain of Custody Reference

• USEPA “Chain-of-Custody Procedures for Samples and Data”

http://www.epa.gov/apti/coc/

When you need to ship samples, remember:

• Pack and seal coolers to avoid container breakage. Use bubble wrap, tape, etc.

• Seal the containers and/or seal the ice in plastic bags. Use lots of ice.

• Custody and Shipping Form copies

II. Implementation Phase

C. Laboratory Procedures

How Does a Sample Move through the Laboratory?

• Project Management/Scheduling

• Container Preparation

• Sampling Assistance

• Sample Receiving

• Sample Storage

• Internal Sample Custody Chain

Analytical Activities

• Sample Preparation

• General Chemistry Analysis

• Metals Analysis

• Organic Analysis – GC/MS

• Organic Analysis – GC and other

• Clean up and Disposal

After the Analysis

• Lab QA/QC Evaluation

• Information Storage & Data Package Assembly

• Technical Support and Interpretation

III. Assessment Phase

Assessment Steps

• Review sampling documentation to check agreement with SAP.

• Review laboratory documentation to assess quality of results.

• Determine if analytical results are usable for meeting established sampling objectives.

Remember ...

If your project objectives were clearly defined and you had the time to plan for the sampling event, assessing the results should be a straight-forward procedure.

Review Sampling Documentation

• Was the field documentation complete and acceptable?

• Were the samples properly preserved? (esp. delivered to lab at 2-6 oC)

• Was a complete chain-of-custody maintained and provided for review?

QA/QC Documents are needed because:

• In most sampling projects, analytical results that are scientifically valid and legally defensible are required.

• The precision and accuracy of the analytical results are judged by review of the QA/QC documents.

Review Laboratory QA/QC Documentation

• QA/QC Section usually divided into sub-sections, according to sample matrix type and analyte type (VOCs, metals, etc.)

• All required documentation submitted?

• Acceptable analytical methods and associated detection limits utilized?

Review Laboratory QA/QC Documentation (2)

• Samples analyzed within holding times?

• Initial and continuing calibration and instrument tuning (if applicable) information acceptable?

• Method blanks acceptable?

Review Laboratory QA/QC Documentation (3)

• Matrix spike / matrix spike duplicate (MS/MSD) results acceptable?

• If not, were the Laboratory Control Sample (LCS) results acceptable?

• How are the sample results affected?

Finally, Review the Analytical Results

• Comment on the analytes detected in the samples and whether set action levels were exceeded.

• Summarize the results - with data qualifications - as they relate to the objectives for the sampling project.

• Include recommendations for additional activities needed for the site.