Common Analytical Methods & How To Review Lab Data

1 Sept 2006 Sept 2006 Common Analytical Methods Common Analytical Methods & How To Review Lab Data& How To Review Lab DataBlayne Hartman Picker, Mobile GeochemistryCarlsbad, 9-062 Remember Us?Remember Us?Caltrans 9-063 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 & 9-064 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 QuizCaltrans 9-065 Common MethodsCommon Methods SW SW--846 846 --HazHazwaste, sludge, groundwater waste, sludge, groundwater etc.

2 3000s, 5000s, 7000s, 8000s, etc. 3000s, 5000s, 7000s, 8000s, 9000s9000sMethods and Guidance for Analysis of Methods and Guidance for Analysis of water, water, indind. effluent. 500s, . effluent. 500s, 600s, 1600s600s, 1600sStandard Methods for the examination of Standard Methods for the examination of Water and WastewaterWater and Wastewater APHA, AWWAAPHA, AWWAC altrans GC/MS GC/MS MethodzEPA Method 8260B Specifies GC/MS part only Requires preparation method , EPA 5030 for water EPA 5035 for soilSome Methods are all inclusiveCaltrans 9-067 FuelsFuels TRPH by (IR) Fast, inexpensive ($30 to $40) Good for heavier carbon ranges (C24+, oils) Non-detects are reliable Gives no idea of hydrocarbon type (petroleum?)

3 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)Caltrans 9-068 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 necessaryCaltrans 9-069 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+ compoundsCaltrans 9-0610 Pesticides & PCBsPesticides & PCBs Methods 8080 & 8081 (GC-ECD) Less expensive than GC/MS Subject to interferences Lower detection limits ( to 5 ppb) Method 8270 (GC/MS) More expensive (~$150)

4 No interferences Higher DLs (>100 ppb)Caltrans 9-0611 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)Caltrans 9-0612 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 existCaltrans 9-0613 Air & Soil Vapor Air & Soil Vapor VOCsVOCs TO-14/15 Required for Ambient Air, not Soil Gas Expensive (~$200) Lower detection limits ( to 1 ppbv) Subject to hardware 8021 & 8260 Better suited for soil gas with higher concentrations Less expensive ($75 to $125)

5 Can do in the fieldCaltrans 9-0614 Basic Lab Quality Basic Lab Quality Assurance/Quality ControlAssurance/Quality ControlBegan with EPA QAMS for EPA ProgramsCurrent National Guidance by NELAC and NELAPQ uality System Manual Caltrans 9-0615 Quality System ComponentsQuality System ComponentsPurpose and objectivesOrganization, Management, personnelPhysical facilitiesSupplies equipment Lab proceduresSamplingCaltrans 9-0616 Quality System ComponentsQuality System ComponentsSample HandlingDocument ControlQuality ControlData HandlingSafety Complaint ProceduresTest MethodsCaltrans 9-0617 Quality ControlQuality ControlCalibration Initial, dailyInternal/External StandardsBlanksSurrogatesDetection LimitsLab Control SamplesMatrix Spiking Performance EvaluationCaltrans 9-0618 Calibration BasicsCalibration Basics Initial Calibration (ICAL)

6 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 reportCaltrans 9-0619 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 reportCaltrans 9-0620 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)

7 Caltrans 9-0621 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 Caltrans 9-0622 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.

8 Nominally 5 to 10 times MDL Caltrans 9-0623 Forensic GeoChemistryForensic GeoChemistryCaltrans 9-0624 Fuel SignaturesFuel SignaturesCaltrans 9-0625 Fuel SignaturesFuel SignaturesCaltrans 9-0626 Oil by GCOil by GC--FID (FID (HumpologyHumpology))Caltrans 9-0627 Fuel SignaturesFuel SignaturesCaltrans 9-0628 Caltrans 9-0629 Caltrans 9-0630 Caltrans 9-0631 How to Review Lab DataHow to Review Lab DataCaltrans 9-0632 Why Do You Need to Review DataWhy Do You Need to Review Data(Lab(Lab--onomicsonomics101)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 IncreaseCaltrans 9-0633 How Do Labs Do This?

9 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 specsCaltrans 9-0634 Typical Laboratory ShortcutsTypical Laboratory Shortcuts Sample Preparations Shortening of Analytical Runs Sharing Matrix Spikes No ICAL No CCAL Not enough blanks Reporting outside calibration rangeCaltrans 9-0635 Common Mistakes to Look For Common Mistakes to Look For

10 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 samplesCaltrans 9-0636 Caltrans 9-0637 Caltrans 9-0638 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 ( ) < TPH-GC Integration error?