Sample Collection and Preservation

Importance Importance Safety Safety Quantities Quantities Sampling utensils Sampling utensils Sample Types Sample Types Collection Methods Collection Methods Preservation Preservation Storage Storage Hold times Hold times COCs COCs

Why we sample To verify compliance for NPDES To verify compliance for NPDES To determine if our processes are efficient To determine if our processes are efficient

Some Basics Must be representative Must be representative Consider your collection point Consider your collection point Consider the analysis Consider the analysis Sample containers must be clean and free from interference Sample containers must be clean and free from interference Must be handled right to avoid degradation, contamination, compromising Must be handled right to avoid degradation, contamination, compromising Correct collection and preservation Correct collection and preservation Low level mercury Low level mercury Biological Biological

Safety

Safety Assess the potential for hazards Assess the potential for hazards Physical Physical leaning, stretching, pulling, lifting leaning, stretching, pulling, lifting Awkward positions Awkward positions Constituents Constituents Toxic, biological, pathogens Toxic, biological, pathogens Entry: skin, eyes, nose, mouth Entry: skin, eyes, nose, mouth

Safety General PPE Gloves Gloves Eye protection Eye protection Ventilate area if vapors may be present Ventilate area if vapors may be present Specific PPE Specific PPE Containment suits Containment suits Special gloves, boots Special gloves, boots

Sampling utensils

Collection CollectionStorage

Collection Containers Manual Manual Dippers Dippers Buckets Buckets Automated Automated Flow based Flow based Time based Time based

Manual Grab samples or composite grab Grab samples or composite grab Mix well before transfer Mix well before transfer Proper container Proper container Rusty coffee cans are probably not the right container……. Rusty coffee cans are probably not the right container…….

Automated Usually 24 hour Usually 24 hour Flow based more accurate than time based Flow based more accurate than time based Clean tubing Clean tubing 2 sets- one cleaning, one in use 2 sets- one cleaning, one in use Wear on tubing could change volume pumped Wear on tubing could change volume pumped Calibrate pump frequently Calibrate pump frequently NPDES states to pull at least 100ml NPDES states to pull at least 100ml

Collection Containers Dedicate containers Dedicate containers Clean containers well Clean containers well Use detergents that are free of interference/contamination potential Use detergents that are free of interference/contamination potential Rinse with DI water 3 X Rinse with DI water 3 X Dry completely Dry completely Container should not interfere with analysis Container should not interfere with analysis

A word about “C” Organic Carbons Organic Carbons Can not use plastic containers to collect VOC, TOC, or any C’s Can not use plastic containers to collect VOC, TOC, or any C’s It will contaminate sample It will contaminate sample

Storage Bottles Glass or plastic Glass or plastic Hard glass (pyrex) is preferred Hard glass (pyrex) is preferred Silica, sodium, and boron may be leached from soft glass but not plastic Silica, sodium, and boron may be leached from soft glass but not plastic Use glass for all organics (VOC, semi VOC, pesticides, PCBs, oil and grease) Use glass for all organics (VOC, semi VOC, pesticides, PCBs, oil and grease) Avoid plastic when possible- phthalate esters can contaminate sample Avoid plastic when possible- phthalate esters can contaminate sample

Storage Bottles Use amber glass bottles to avoid photodegradation Use amber glass bottles to avoid photodegradation Caps are important too! Caps are important too! No paper liners No paper liners Use foil or PTFE liners Use foil or PTFE liners Be aware that metal liners can contaminate samples for metals Be aware that metal liners can contaminate samples for metals

Quantities

How Much do you need Most methods tell you the minimum quantity needed Most methods tell you the minimum quantity needed Give yourself some extra Give yourself some extra For pre-preserved containers For pre-preserved containers Make sure that the quantity collected is the right volume. Don’t fill ¼ full if the bottle needs to be full. Make sure that the quantity collected is the right volume. Don’t fill ¼ full if the bottle needs to be full.

Sample Types Sample Types

Grab Sample Provide “snapshot” Provide “snapshot” Used for process control Used for process control Short hold time Short hold time Used when samples are not variable Used when samples are not variable Used for testing that requires immediate analysis Used for testing that requires immediate analysis Cl2, pH, temp, organic, volatiles Cl2, pH, temp, organic, volatiles Several grabs over time course to show variability Several grabs over time course to show variability

Composite Sample Represent heterogeneous matrix Represent heterogeneous matrix Can be set to represent flow based Can be set to represent flow based Can result in loss or dilution of analyte Can result in loss or dilution of analyte Can result in increase interferences Can result in increase interferences Can not be used on certain tests Can not be used on certain tests Cl2, pH, temp Cl2, pH, temp

Control Samples Field blank Field blank Usually DH20 transferred from one container to another while at sampling site Usually DH20 transferred from one container to another while at sampling site Usually low level contaminates Usually low level contaminates Lab blank Lab blank Usually DH2O analyzed in tandem Usually DH2O analyzed in tandem Tests for contamination/proper technique Tests for contamination/proper technique Indicates background levels Indicates background levels

Collection Methods

How to collect - Grab Pole dippers Pole dippers Secure container Secure container Submerge container Submerge container Buckets Buckets Start downstream and move into flow Start downstream and move into flow Direct Direct Start downstream and move into flow Start downstream and move into flow

How to collect - Composite Set Sampler to collect flow based or timed Set Sampler to collect flow based or timed Determine potential for contamination from tubing Determine potential for contamination from tubing Tubing should be clean Tubing should be clean Tubing should be located in area that is representative Tubing should be located in area that is representative Don’t rest on bottom Don’t rest on bottom Avoid dead areas Avoid dead areas Needs to be in center of flow Needs to be in center of flow

How to collect Same location every time Same location every time TOC and some volatiles should not be put into plastic containers TOC and some volatiles should not be put into plastic containers Transfer quickly with minimal exposure to air Transfer quickly with minimal exposure to air Don’t transfer multiply times Don’t transfer multiply times Cap container quickly Cap container quickly Label the container Label the container Time, date, location, collector Time, date, location, collector

Composite Collection bottle should be refrigerated Collection bottle should be refrigerated Clean tubing and collection bottle Clean tubing and collection bottle Collection bottle should be large enough to mix sample Collection bottle should be large enough to mix sample Mix the right way Mix the right way Too little and not enough mix of settlables Too little and not enough mix of settlables Too much and incorporate air/analyte loss Too much and incorporate air/analyte loss

Receiving Waters For stream sampling, make sure you enter downstream of where you will take sample For stream sampling, make sure you enter downstream of where you will take sample Move upstream to gather your samples if you have multiple sites Move upstream to gather your samples if you have multiple sites Change gloves frequently Change gloves frequently

Filling bottles Minimize exposure to air when transferring Minimize exposure to air when transferring Don’t overfill pre-preserved bottles Don’t overfill pre-preserved bottles Put preserve in bottle after sample Put preserve in bottle after sample Leave headroom for biologicals Leave headroom for biologicals No air bubbles for volatiles No air bubbles for volatiles

What do you do with those caps? Handle caps with care Handle caps with care Setting them on the ground risks contamination Setting them on the ground risks contamination Setting them upright risks contamination Setting them upright risks contamination Holding them risks contamination Holding them risks contamination Depends on the surroundings…… Depends on the surroundings……

Low Level Mercury Two people Two people Dirty hands/clean hands technique Dirty hands/clean hands technique One person only handles the sample containers One person only handles the sample containers One person collects sample, pours into sample container One person collects sample, pours into sample container

Composite Grabs NPDES states “at least” 8 grabs of at least 100 mls over periodic intervals during working hours NPDES states “at least” 8 grabs of at least 100 mls over periodic intervals during working hours Collect each grab and refrigerate Collect each grab and refrigerate Mix equal amounts of grabs together Mix equal amounts of grabs together Mix well Mix well Example: radium in sludge Example: radium in sludge

Soapbox Time Wear gloves Wear gloves Protects you Protects you Protects the sample Protects the sample DEET DEET Lotions/soap Lotions/soap Do you know where your hands have been? Do you know where your hands have been?

Preservation

Preservation Limited to: pH control pH control Chemical addition Chemical addition Amber or opaque bottles Amber or opaque bottles Refrigeration Refrigeration Filtration Filtration Freezing Freezing

Why Preserve Retard biological action Retard biological action Retard hydrolysis of chemical compounds Retard hydrolysis of chemical compounds Reduce volatility of analyte Reduce volatility of analyte

Preservation Depends on Analysis Depends on Analysis Some acids can degrade plastics- be careful Some acids can degrade plastics- be careful

Storage

Storage Ice or refrigerate immediately Ice or refrigerate immediately Keep temperature from fluctuating Keep temperature from fluctuating Preserve immediately if bottle is not pre- preserved Preserve immediately if bottle is not pre- preserved Some samples are stored at room temp Some samples are stored at room temp

Hold times

Begins when sample is collected Begins when sample is collected Depends on analyte Depends on analyte Rule of thumb: Rule of thumb: The quicker it’s analyzed, the better The quicker it’s analyzed, the better

COCs

Many Faces of COCs Labels Labels Seals for bottles Seals for bottles Facility bench sheets/ Field log books Facility bench sheets/ Field log books Analysis request sheet (COC) Analysis request sheet (COC) Record of delivery to laboratory Record of delivery to laboratory Receipt and logging of sample Receipt and logging of sample Assignment of sample Assignment of sample

Chain of Custody Traceability Traceability Shows who handled sample from collection, preservation, storage, and analysis. Shows who handled sample from collection, preservation, storage, and analysis. Allows for routine control of samples and also aides in litigation issues Allows for routine control of samples and also aides in litigation issues

Labels Permanent maker Permanent maker Attached to container Attached to container Lists the following: Lists the following: Date and time of collection Date and time of collection Facility Facility Location Location Type of sample Type of sample Preservative Preservative Analysis Analysis Collector Collector

COC Usually from Lab Usually from Lab Fill out completely Fill out completely Sample name, date and time of sample Sample name, date and time of sample Type of sample Type of sample Preservative Preservative Bottle and volume Bottle and volume Analysis needed Analysis needed

NPDES permit fine print

(10) Monitoring and records. (a) Samples and measurements taken for the purpose of monitoring shall be representative of the monitored activity. (a) Samples and measurements taken for the purpose of monitoring shall be representative of the monitored activity. (b) The permittee shall retain records of all monitoring information, including all calibration and maintenance records, and all original strip chart recordings for 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 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. (b) The permittee shall retain records of all monitoring information, including all calibration and maintenance records, and all original strip chart recordings for 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 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. (c) Records of monitoring information shall include: (c) Records of monitoring information shall include: 1. The date, exact place, and time of the sampling or measurements; 2. The individual(s) who performed the sampling or measurements; 3. The date(s) analysis were performed; 4. The individual(s) who performed the analyses; 5. The analytical techniques or methods used; and 6. The results of such analyses. (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 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 perform maintenance procedures on all monitoring and analytical instrumentation at intervals to ensure accuracy of measurements. (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 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 perform maintenance procedures on all monitoring and analytical instrumentation at intervals to ensure accuracy of measurements.

NPDES Requirements All calibration and maintenance Records All calibration and maintenance Records Yearly maintenance of balance etc Yearly maintenance of balance etc Replacement date of probes Replacement date of probes Thermometer calibrations Thermometer calibrations Pipettes Pipettes Original strip chart recordings Original strip chart recordings Required Reports Required Reports Keep for 3 years Keep for 3 years

Bench Sheets Date, exact location, collector and time of sample Date, exact location, collector and time of sample Date, time, analyst, and method for each test Date, time, analyst, and method for each test Record results in proper units Record results in proper units Include time points for analysis Include 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 instruments need to be recorded Daily temperatures and calibration of instruments need to be recorded

Rumors EPA, IEPA are taking a closer look at paperwork. EPA, IEPA are taking a closer look at paperwork. Make sure you have it written down Make sure you have it written down Make sure you have a copy Make sure you have a copy If you don’t have SOPs, make sure you can at least support your procedure If you don’t have SOPs, make sure you can at least support your procedure

Resources CFR has hold times and preservatives CFR has hold times and preservatives Standard Methods 1-33 has hold times, preservatives and container types and size Standard Methods 1-33 has hold times, preservatives and container types and size NPDES NPDES EPA/ IEPA EPA/ IEPA FVOA FVOA

Don’t worry so much….. “Complete and unequivocal preservation of samples, whether domestic wastewater, industrial wastes, or natural waters, is a practical impossibility because complete stability for every constituent never can be achieved. At best, preservation techniques only retard chemical and biological changes that inevitably continue after sample collection” “Complete and unequivocal preservation of samples, whether domestic wastewater, industrial wastes, or natural waters, is a practical impossibility because complete stability for every constituent never can be achieved. At best, preservation techniques only retard chemical and biological changes that inevitably continue after sample collection”

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