Sample Collection and Sample Collection and PreservationPreservation

ImportanceImportance SafetySafety QuantitiesQuantities Sampling utensilsSampling utensils Sample TypesSample Types Collection MethodsCollection Methods PreservationPreservation StorageStorage Hold timesHold times COCsCOCs

Why we sampleWhy we sample

To verify compliance for NPDES To verify compliance for NPDES

To determine if our processes are To determine if our processes are efficientefficient

Some Basics Some Basics Must be representativeMust be representative

Consider your collection pointConsider your collection point Consider the analysis Consider the analysis

Sample containers must be clean and Sample containers must be clean and free from interference free from interference

Must be handled right to avoid Must be handled right to avoid degradation, contamination, degradation, contamination, compromisingcompromising

Correct collection and preservationCorrect collection and preservation Low level mercuryLow level mercury BiologicalBiological

SafetySafety

SafetySafety Assess the potential for hazardsAssess the potential for hazards

Physical Physical leaning, stretching, pulling, lifting leaning, stretching, pulling, lifting Awkward positionsAwkward positions

ConstituentsConstituents Toxic, biological, pathogensToxic, biological, pathogens Entry: skin, eyes, nose, mouthEntry: skin, eyes, nose, mouth

SafetySafetyGeneral PPEGeneral PPE

GlovesGloves Eye protectionEye protection Ventilate area if vapors may be presentVentilate area if vapors may be present

Specific PPESpecific PPE Containment suitsContainment suits Special gloves, bootsSpecial gloves, boots

Sampling Sampling utensilsutensils

CollectionCollection

StorageStorage

Collection ContainersCollection Containers

ManualManual DippersDippers BucketsBuckets

AutomatedAutomated Flow basedFlow based Time basedTime based

ManualManual

Grab samples or composite grabGrab samples or composite grab Mix well before transferMix well before transfer Proper containerProper container

Rusty coffee cans are probably not the Rusty coffee cans are probably not the right container…….right container…….

AutomatedAutomated Usually 24 hour Usually 24 hour Flow based more accurate than time Flow based more accurate than time

basedbased Clean tubing Clean tubing

2 sets- one cleaning, one in use2 sets- one cleaning, one in use Wear on tubing could change volume Wear on tubing could change volume

pumpedpumped Calibrate pump frequently Calibrate pump frequently NPDES states to pull at least 100mlNPDES states to pull at least 100ml

Collection ContainersCollection Containers Dedicate containersDedicate containers Clean containers wellClean containers well Use detergents that are free of Use detergents that are free of

interference/contamination potentialinterference/contamination potential Rinse with DI water 3 X Rinse with DI water 3 X Dry completelyDry completely Container should not interfere with Container should not interfere with

analysisanalysis

A word about “C”A word about “C”

Organic CarbonsOrganic Carbons

Can not use plastic containers to Can not use plastic containers to collect VOC, TOC, or any C’scollect VOC, TOC, or any C’s

It will contaminate sampleIt will contaminate sample

Storage BottlesStorage Bottles

Glass or plasticGlass or plastic Hard glass (pyrex) is preferredHard glass (pyrex) is preferred

Silica, sodium, and boron may be Silica, sodium, and boron may be leached from soft glass but not plasticleached from soft glass but not plastic

Use glass for all organics (VOC, semi Use glass for all organics (VOC, semi VOC, pesticides, PCBs, oil and grease)VOC, pesticides, PCBs, oil and grease)

Avoid plastic when possible- phthalate Avoid plastic when possible- phthalate esters can contaminate sampleesters can contaminate sample

Storage BottlesStorage Bottles

Use amber glass bottles to avoid Use amber glass bottles to avoid photodegradationphotodegradation

Caps are important too!Caps are important too! No paper linersNo paper liners Use foil or PTFE linersUse foil or PTFE liners Be aware that metal liners can Be aware that metal liners can

contaminate samples for metalscontaminate samples for metals

QuantitieQuantitiess

How Much do you needHow Much do you need

Most methods tell you the minimum Most methods tell you the minimum quantity neededquantity needed

Give yourself some extraGive yourself some extra For pre-preserved containersFor pre-preserved containers

Make sure that the quantity collected is Make sure that the quantity collected is the right volume. Don’t fill ¼ full if the the right volume. Don’t fill ¼ full if the bottle needs to be full.bottle needs to be full.

Sample Sample TypesTypes

Grab Sample Grab Sample

Provide “snapshot”Provide “snapshot” Used for process controlUsed for process control Short hold timeShort hold time Used when samples are not variableUsed when samples are not variable Used for testing that requires immediate Used for testing that requires immediate

analysisanalysis Cl2, pH, temp, organic, volatilesCl2, pH, temp, organic, volatiles

Several grabs over time course to show Several grabs over time course to show variabilityvariability

Composite SampleComposite Sample

Represent heterogeneous matrixRepresent heterogeneous matrix Can be set to represent flow basedCan be set to represent flow based Can result in loss or dilution of Can result in loss or dilution of

analyteanalyte Can result in increase interferencesCan result in increase interferences Can Can notnot be used on certain tests be used on certain tests

Cl2, pH, tempCl2, pH, temp

Control SamplesControl Samples

Field blankField blank Usually DH20 transferred from one container to Usually DH20 transferred from one container to

another while at sampling siteanother while at sampling site Usually low level contaminatesUsually low level contaminates

Lab blankLab blank Usually DH2O analyzed in tandemUsually DH2O analyzed in tandem

Tests for contamination/proper techniqueTests for contamination/proper technique Indicates background levelsIndicates background levels

Collection Collection MethodsMethods

How to collect - GrabHow to collect - Grab Pole dippersPole dippers

Secure containerSecure container Submerge containerSubmerge container

BucketsBuckets Start downstream and move into flowStart downstream and move into flow

DirectDirect Start downstream and move into flowStart downstream and move into flow

How to collect - CompositeHow to collect - Composite Set Sampler to collect flow based or Set Sampler to collect flow based or

timedtimed Determine potential for contamination Determine potential for contamination

from tubingfrom tubing Tubing should be cleanTubing should be clean Tubing should be located in area that Tubing should be located in area that

is representativeis representative Don’t rest on bottomDon’t rest on bottom Avoid dead areasAvoid dead areas Needs to be in center of flowNeeds to be in center of flow

How to collectHow to collect

Same location every timeSame location every time TOC and some volatiles should not TOC and some volatiles should not

be put into plastic containersbe put into plastic containers Transfer quickly with minimal Transfer quickly with minimal

exposure to airexposure to air Don’t transfer multiply timesDon’t transfer multiply times Cap container quicklyCap container quickly Label the containerLabel the container

Time, date, location, collectorTime, date, location, collector

CompositeComposite Collection bottle should be refrigeratedCollection bottle should be refrigerated Clean tubing and collection bottleClean tubing and collection bottle Collection bottle should be large Collection bottle should be large

enough to mix sampleenough to mix sample Mix the right wayMix the right way

Too little and not enough mix of settlablesToo little and not enough mix of settlables Too much and incorporate air/analyte loss Too much and incorporate air/analyte loss

Receiving WatersReceiving Waters

For stream sampling, make sure you For stream sampling, make sure you enter downstream of where you will enter downstream of where you will take sampletake sample

Move upstream to gather your Move upstream to gather your samples if you have multiple sitessamples if you have multiple sites

Change gloves frequentlyChange gloves frequently

Filling bottlesFilling bottles

Minimize exposure to air when Minimize exposure to air when transferringtransferring

Don’t overfill pre-preserved bottlesDon’t overfill pre-preserved bottles Put preserve in bottle after sample Put preserve in bottle after sample

Leave headroom for biologicalsLeave headroom for biologicals No air bubbles for volatiles No air bubbles for volatiles

What do you do with those What do you do with those caps?caps?

Handle caps with careHandle caps with care Setting them on the ground risks Setting them on the ground risks

contaminationcontamination Setting them upright risks Setting them upright risks

contaminationcontamination Holding them risks contaminationHolding them risks contamination

Depends on the surroundings……Depends on the surroundings……

Low Level MercuryLow Level Mercury

Two people Two people Dirty hands/clean Dirty hands/clean

hands techniquehands technique One person only One person only

handles the sample handles the sample containers containers

One person collects One person collects sample, pours into sample, pours into sample containersample container

Composite GrabsComposite Grabs

NPDES states “at least” 8 grabs of at NPDES states “at least” 8 grabs of at least 100 mls over periodic intervals least 100 mls over periodic intervals during working hoursduring working hours

Collect each grab and refrigerateCollect each grab and refrigerate Mix equal amounts of grabs togetherMix equal amounts of grabs together Mix wellMix well Example: radium in sludgeExample: radium in sludge

Soapbox TimeSoapbox Time

Wear glovesWear gloves Protects youProtects you Protects the sampleProtects the sample

DEETDEET Lotions/soapLotions/soap Do you know where your hands have Do you know where your hands have

been? been?

PreservationPreservation

Preservation Limited to:Preservation Limited to:

pH controlpH control Chemical additionChemical addition Amber or opaque bottlesAmber or opaque bottles RefrigerationRefrigeration FiltrationFiltration FreezingFreezing

Why PreserveWhy Preserve

Retard biological actionRetard biological action

Retard hydrolysis of chemical Retard hydrolysis of chemical compoundscompounds

Reduce volatility of analyteReduce volatility of analyte

PreservationPreservation

Depends on AnalysisDepends on Analysis Some acids can degrade plastics- be Some acids can degrade plastics- be

carefulcareful

StorageStorage

StorageStorage

Ice or refrigerate immediatelyIce or refrigerate immediately Keep temperature from fluctuatingKeep temperature from fluctuating Preserve immediately if bottle is not Preserve immediately if bottle is not

pre-preservedpre-preserved Some samples are stored at room Some samples are stored at room

temptemp

Hold Hold timestimes

Hold timesHold times

Begins when sample is collectedBegins when sample is collected Depends on analyteDepends on analyte Rule of thumb:Rule of thumb:

The quicker it’s analyzed, the betterThe quicker it’s analyzed, the better

COCsCOCs

Many Faces of COCsMany Faces of COCs LabelsLabels Seals for bottlesSeals for bottles Facility bench sheets/ Field log booksFacility bench sheets/ Field log books Analysis request sheet (COC)Analysis request sheet (COC) Record of delivery to laboratoryRecord of delivery to laboratory Receipt and logging of sampleReceipt and logging of sample Assignment of sampleAssignment of sample

Chain of CustodyChain of Custody

TraceabilityTraceability Shows who handled sample from Shows who handled sample from

collection, preservation, storage, and collection, preservation, storage, and analysis.analysis.

Allows for routine control of samples Allows for routine control of samples and also aides in litigation issuesand also aides in litigation issues

LabelsLabels

Permanent makerPermanent maker Attached to containerAttached to container Lists the following:Lists the following:

Date and time of collectionDate and time of collection FacilityFacility LocationLocation Type of sampleType of sample PreservativePreservative Analysis Analysis CollectorCollector

COCCOC

Usually from LabUsually from Lab Fill out completelyFill out completely

Sample name, date and time of sampleSample name, date and time of sample Type of sampleType of sample PreservativePreservative Bottle and volumeBottle and volume Analysis neededAnalysis needed

NPDES permit fine printNPDES permit fine print

(10) Monitoring and records.(10) Monitoring and records.

(a) Samples and measurements taken for the purpose of monitoring shall be (a) Samples and measurements taken for the purpose of monitoring shall be representative of the monitored activity.representative of the monitored activity.

(b) The permittee shall retain records of all monitoring information, including all (b) The permittee shall retain records of all monitoring information, including all calibration and maintenance records, and all original strip chart recordings for calibration and maintenance records, and all original strip chart recordings for continuous monitoring instrumentation, copies of all reports required by this permit, continuous monitoring instrumentation, copies of all reports required by this permit, and records of all data used to complete the application for this permit, for a period and records of all data used to complete the application for this permit, for a period of at least 3 years from the date of this permit, measurement, report or application. of at least 3 years from the date of this permit, measurement, report or application. This period may be extended by request of the Agency at any time.This period may be extended by request of the Agency at any time.

(c) Records of monitoring information shall include: (c) Records of monitoring information shall include: 1.1. The date, exact place, and time of the sampling or measurements;The date, exact place, and time of the sampling or measurements;2.2. The individual(s) who performed the sampling or measurements;The individual(s) who performed the sampling or measurements;3.3. The date(s) analysis were performed;The date(s) analysis were performed;4.4. The individual(s) who performed the analyses;The individual(s) who performed the analyses;5.5. The analytical techniques or methods used; andThe analytical techniques or methods used; and6.6. The results of such analyses.The results of such analyses.

(d) Monitoring must be conducted according to test procedures approved under 40 CFR (d) Monitoring must be conducted according to test procedures approved under 40 CFR Part 136, unless other test procedures have been specified in this permit. Where no Part 136, unless other test procedures have been specified in this permit. Where no test procedure under 40 CFR Part 136 has been approved, the permittee must test procedure under 40 CFR Part 136 has been approved, the permittee must submit to the Agency a test method for approval. The permittee shall calibrate and submit to the Agency a test method for approval. The permittee shall calibrate and perform maintenance procedures on all monitoring and analytical instrumentation perform maintenance procedures on all monitoring and analytical instrumentation at intervals to ensure accuracy of measurements. at intervals to ensure accuracy of measurements.

NPDES RequirementsNPDES Requirements

All calibration and maintenance All calibration and maintenance RecordsRecords Yearly maintenance of balance etcYearly maintenance of balance etc Replacement date of probesReplacement date of probes Thermometer calibrationsThermometer calibrations PipettesPipettes

Original strip chart recordingsOriginal strip chart recordings Required ReportsRequired Reports Keep for 3 yearsKeep for 3 years

Bench SheetsBench Sheets Date, exact location, collector and Date, exact location, collector and

time of sampletime of sample Date, time, analyst, and method for Date, time, analyst, and method for

each testeach test Record results in proper units Record results in proper units Include time points for analysisInclude time points for analysis

time in /time out of oven, weighing, ect time in /time out of oven, weighing, ect Daily temperatures and calibration of Daily temperatures and calibration of

instruments need to be recordedinstruments need to be recorded

RumorsRumors

EPA, IEPA are taking a closer look at EPA, IEPA are taking a closer look at paperwork.paperwork.

Make sure you have it written downMake sure you have it written down Make sure you have a copyMake sure you have a copy If you don’t have SOPs, make sure If you don’t have SOPs, make sure

you can at least support your you can at least support your procedureprocedure

ResourcesResources

CFR has hold times and preservativesCFR has hold times and preservatives Standard Methods 1-33 has hold Standard Methods 1-33 has hold

times, preservatives and container times, preservatives and container types and sizetypes and size

NPDESNPDES EPA/ IEPAEPA/ IEPA FVOAFVOA

Don’t worry so much…..Don’t worry so much…..

““Complete and unequivocal preservation Complete and unequivocal preservation of samples, whether domestic of samples, whether domestic wastewater, industrial wastes, or natural wastewater, industrial wastes, or natural waters, is a practical impossibility waters, is a practical impossibility because complete stability for every because complete stability for every constituent never can be achieved. At constituent never can be achieved. At best, preservation techniques only retard best, preservation techniques only retard chemical and biological changes that chemical and biological changes that inevitably continue after sample inevitably continue after sample collection”collection”

Doesn’t mean we shouldn’t try.Doesn’t mean we shouldn’t try. Just need to be realisticJust need to be realistic Follow basic rulesFollow basic rules Be consistentBe consistent Analyze as soon as possibleAnalyze as soon as possible