Sept 2006Sept 2006

Common Analytical Methods Common Analytical Methods & How To Review Lab Data& How To Review Lab Data

Blayne Hartman Ph.D.James Picker, Ph.D.

H&P Mobile GeochemistryCarlsbad, CA760-804-9678

www.handpmg.com

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Remember Us?Remember Us?

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• Three Primary Services:– Env. analysis: on-site & off-site (10 mobile)– Sample collection (direct-push)– Vapor intrusion/soil gas services

• Technical Training Nationwide– Lab methods– Vapor intrusion

• Countless Articles & Presentations

www.handpmg.com

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Seminar OverviewSeminar Overview• Review of Common Methods• Lab QA/QC Basics• Forensic Geochemistry • Common Lab Errors • How to Review Lab Data • Questions & (hopefully) Answers • Infamous Candle Quiz

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Common MethodsCommon Methods

“SW“SW--846” 846” -- HazHaz waste, sludge, groundwater waste, sludge, groundwater etc. 3000s, 5000s, 7000s, 8000s, etc. 3000s, 5000s, 7000s, 8000s, 9000s9000s

Methods and Guidance for Analysis of Methods and Guidance for Analysis of Water..drinking water, Water..drinking water, indind. effluent. 500s, . effluent. 500s, 600s, 1600s600s, 1600s

Standard Methods for the examination of Standard Methods for the examination of Water and WastewaterWater and Wastewater –– APHA, AWWAAPHA, AWWA

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e.g. GC/MS Methode.g. GC/MS MethodEPA Method 8260B

–Specifies GC/MS part only–Requires preparation method e.g.,

• EPA 5030 for water• EPA 5035 for soil

Some methods are all inclusive

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FuelsFuels• TRPH by 418.1 (IR)

– Fast, inexpensive ($30 to $40)– Good for heavier carbon ranges (C24+, oils)– Non-detects are reliable – Gives no idea of hydrocarbon type (petroleum?)

• TPH by CA-LUFT & EPA 8015b (GC) – Gives fingerprint of fuel type (gas, diesel,

kerosene)– Use either FID or GC/MS (gasoline, diesel?)– Inexpensive ($25 to $50)

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VOCsVOCs• 8021 (GC-PID/ElCD)

– Inexpensive ($30 to $50); not commonly used – Interferences on hot samples; non-detects reliable– Hard to do all the oxygenates– Second column confirmation rare

• VOCs by 8260 (GC/MS)– Less susceptible to interferences– Can do all oxygenates– Cost: $50 to $75, combo pricing $50 to $125– Second column confirmation not necessary

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SVOCsSVOCs• PAHs by 8100 (GC-FID) & 8310 (HPLC)

– Less expensive than GC/MS ($125)– Subject to interferences– Lower detection limits (HPLC)

• Method 8270 (GC/MS) – More expensive (~$200)– No interferences, DLs ~10x higher– 70+ compounds

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Pesticides & PCBsPesticides & PCBs• Methods 8080 & 8081 (GC-ECD)

– Less expensive than GC/MS– Subject to interferences– Lower detection limits (0.5 to 5 ppb)

• Method 8270 (GC/MS) – More expensive (~$150)– No interferences– Higher DLs (>100 ppb)

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MetalsMetals• Method 7000 (AA)

– Less expensive than ICAP (<$25)– Generally for select compounds (Hg)– Low detection limits (1 to 10 ppb)

• Method 6010 (ICAP)– More expensive (~$120 for Title 22)– More compounds in same run– Higher DLs (> 10 ppb)

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MetalsMetals

• Method 6020 (ICAP-MS)– More expensive than ICAP– Multiple metals– Lower detection limits (sub ppb)

• Method (XRF) – Fast, inexpensive, multiple compounds– Higher DLs (>10 ppm)– Field portable, not radioactive units exist

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Air & Soil Vapor Air & Soil Vapor VOCsVOCs• TO-14/15

– Required for Ambient Air, not Soil Gas– Expensive (~$200)– Lower detection limits (0.1 to 1 ppbv)– Subject to hardware

• 8021 & 8260– Better suited for soil gas with higher

concentrations– Less expensive ($75 to $125)– Can do in the field

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Basic Lab Quality Basic Lab Quality Assurance/Quality ControlAssurance/Quality Control

Began with EPA QAMS for EPA Programs

Current National Guidance by NELAC and NELAP

Quality System – Manual

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Quality System ComponentsQuality System Components

Purpose and objectives

Organization, Management, personnel

Physical facilities

Supplies equipment

Lab procedures

Sampling

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Quality System ComponentsQuality System ComponentsSample Handling

Document Control

Quality Control

Data Handling

Safety

Complaint Procedures

Test Methods

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Quality ControlQuality ControlCalibration – Initial, daily

Internal/External Standards

Blanks

Surrogates

Detection Limits

Lab Control Samples

Matrix Spiking

Performance Evaluation

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Calibration BasicsCalibration Basics• Initial Calibration (ICAL)

– Must do at multiple concentration levels– Average response factor (%RSD) < limit– Lowest conc near or at MDL– Some methods require second source confirm

• Continuing Calibration (CCAL) – Daily or within time window (12 hours)– Must be within acceptable range (%RPD)– Should be part of lab report

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Other QC VariablesOther QC Variables• Internal Standards

– Must do at multiple concentration levels– Average response factor (%RSD) < limit– Lowest conc near or at MDL– Some methods require second source confirm

• Surrogates – Daily or within time window (12 hours)– Must be within acceptable range (%RPD)– Should be part of lab report

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Some Lab BasicsSome Lab Basics• Matrix Interferences

– Flag when recoveries too low– Lab supposed to run blank spike (LCS)– If LCS in, proves matrix effect – LCS analysis should be included

• Higher DLs due to Dilutions – Instruments have calibration range– Must dilute samples to stay within range– MDL * dilution factor = Reported DL (RL)

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Lab Basics cont’Lab Basics cont’

• Flags – the Lab’s Disclaimer (“fine print”)

– “E” flag – Whoa, way too much &$X%! stuff– ”B” flag – “I just had lunch”– “J” flag - “I think it’s there but….”

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“J” Flags“J” Flags

• When the result is between the MDL and the EQL, the result should be given a “J” flag to indicate lack of precision.

• MDL (method detection limit) - The minimum amount of substance that can be measured with 99%confidence that the result is greater than zero.

• EQL (estimated or practical quantitation limit PQL) – The lowest concentration that can be reliably measured within specified limits of precision and accuracy under routine conditions. Nominally 5 to 10 times MDL

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Forensic GeoChemistryForensic GeoChemistry

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Fuel SignaturesFuel Signatures

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Fuel SignaturesFuel Signatures

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Oil by GCOil by GC--FID (FID (HumpologyHumpology))

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Fuel SignaturesFuel Signatures

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How to Review Lab DataHow to Review Lab Data

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Why Do You Need to Review DataWhy Do You Need to Review Data(Lab(Lab--onomicsonomics 101)101)

• Lab Prices are 1/5 1990 Prices– TPH/BTEX from $150 to $30

• Equipment & Salaries Have Increased• More Analyses/day Required to Keep $• Length of Day Still 24 Hours• Chargable Analyses/day Must Increase

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How Do Labs Do This? How Do Labs Do This? • By Automating Analyses

– Autosamplers running 24 hours– Computers interpreting data

• By Modifying Methods– Shorten preparation time– Shorten analysis time

• By Reducing QA/QC Runs– Less blanks & duplicates & reruns– Sharing matrix spikes– Analyzing out of calibration specs

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Typical Laboratory ShortcutsTypical Laboratory Shortcuts

• Sample Preparations• Shortening of Analytical Runs• Sharing Matrix Spikes• No ICAL• No CCAL• Not enough blanks• Reporting outside calibration range

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Common Mistakes to Look For Common Mistakes to Look For • Unexpected fuel product reported

– Misidentified by Software? Lab note?– Carry-over from previous sample?

• Low diesel/oil values for all samples– Instrument blanks – even if not in lab blank– Low diesel/oil values for all samples

• Low value after a hot sample– Carry over (especially if oil range or VOC)– Can’t always tell order of samples

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Common Mistakes to Look For Common Mistakes to Look For • High Sample Dilutions

– Blanks magnified so new contaminants– Detection levels increase

• Methylene Chloride/Acetone Hits – Common lab solvents– Acetone common in vapors

• TRPH (418.1) < TPH-GC– Integration error?– Blanks on GC analysis

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The Most Common GoofThe Most Common GoofWith Air & Soil Gas SamplesWith Air & Soil Gas Samples

1 ug/L Benzene equals: a) 1 ppbvb) 1 ppmvc) 330 ppbvd) None of the Above

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A Lawyer’s Guide to the A Lawyer’s Guide to the $30 Analysis $30 Analysis

• Was an ICAL Done?– Typically not part of lab report

• Were CCALs analyzed?– Should be part of lab report

• Were reported values within Cal range?• Were blanks run after hot samples?• Were matrix spikes run on your samples?• Were proper flags applied?

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A Few Words on the A Few Words on the Hottest Issue Currently Hottest Issue Currently

Out ThereOut There

(Hopefully not for (Hopefully not for CaltransCaltrans))

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What Is Vapor Intrusion?What Is Vapor Intrusion?

Key Assumptions:– Risk level (1 in 10,000? 100,000? 1,000,000?)– Toxicity of Compounds– Exposure Factors (time, rates, ventilation)

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The The DaDa Vapor CodeVapor Code(Newest Box(Newest Box--Office Blockbuster)Office Blockbuster)

• AEHS 2006, 2005, 2004 - 2007• AWMA Conf (9/06 – LA, 1/06)• Workgroups Everywhere (ASTM,

ITRC, EPA-OSWR, API) • EPA Seminars (2003 & 2004) • Requests for Training from >25 States

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Why Do You Care About VI?Why Do You Care About VI?(Risk Often More Perceived Than Real)(Risk Often More Perceived Than Real)

• Health & Safety of Occupants• EPA – RCRA/CERCLA:

Draft VI Guidance Exists • CA-EPA/DTSC: Guidance Exists• Individual Counties: SF, SD• ASTM New Phase 1 Standard• Attorneys & Citizen Groups

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CA SitesCA SitesAgencies with Policy/Guidance:Agencies with Policy/Guidance:

• San Diego DEH– Current TWG Revising Existing Guidance

• CA-DTSC (& LA-RWQCB)– Soil Gas Collection & Analysis Advisory– Vapor Intrusion “Guidance”– CHHSLs (thanks to OEHHA)

• EPA Region 9 – Follows the EPA Draft VI Guidance

• SF-RWQCB– Has own ESLs (“fail levels”)

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LowLow RBSLsRBSLs Mean More SitesMean More Sites(benzene 1e(benzene 1e--6 risk, default values)6 risk, default values)

* Federal EPA version

Some are Below or Near Lab DLs!

0.220.31.630’0.4

0.20.1

Soil (ug/kg)*

0.292.350’

0.151.320’0.091.010’

Soil Gas (ug/L)Water (ug/L)Depth

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Quiz #1Quiz #1

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Why Do You Care About It?Why Do You Care About It?(Risk Often More Perceived Than Real)(Risk Often More Perceived Than Real)

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The Candle Quiza) The Thin Oneb) The Fat Onec) They Both Burn Equallyd) Neither Onee) Why Are You Asking Us This

Irrelevant Question???