Passive Diffusion Bag Samplers by dffhrtcv3

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									                        Passive Diffusion Bag
                              Samplers

                          January 29, 2003
                     NJDEP Public Hearing Room
                      Sponsors: NJDEP & ITRC



1:00 - 1:10   Welcome
              Brian Sogorka, NJDEP Remediation Technology Manager


1:10 - 1:15   ITRC Diffusion Sampler Team Update
              George Nicholas, NJDEP, ITRC Team Leader


1:20 - 2:30   PDBS Deployment and Discussion of USGS Users Guide
              Dr. Don Vroblesky, USGS


2:30 – 2:40 Regulatory Considerations for PDBS
              George Nicholas, NJDEP, ITRC Team Leader


2:40 - 3:00   Field Study: Use of PDBS at Cape Canaveral FL
              Sandra Gaurin, BEM Systems Inc.


3:00 - 3:45   Additional Approaches for Diffusion Sampling
              Dr. Don Vroblesky, USGS NJ


3:45          Wrap-up
Regulatory Acceptance for New Solutions                                                                                 January 2003




                                                                                              Regulatory
                                                                                              Acceptance
                       Introduction                                                           for New Solutions

                                Brian Sogorka
                                NJDEP Remediation
                                                                                        Brian Sogorka, NJDEP
                                Technology Manager
                                                                                        ITRC Point of Contact
                                                                                        609-633-1344,
                                                                                        brian.sogorka@dep.state.nj.us




                      Purpose of ITRC                                         Other Participants

       ITRC is a state-led, national coalition of             • Industry representatives                • Host organization
       regulators and others working to                       • Academia
                                                                                                                  Environmental
                                                              • Public stakeholders                               Council of the States
        • improve state permitting processes and
                                                              • Federal agencies
        • speed implementation of new                                                                   • State organizations
          environmental technologies.                                   U.S. Department of Energy
                                                                                                                 Western Governors’
                                                                                U.S. Environmental               Association
                                                                                Protection Agency
                                                                                                                   Southern States
                                                                        U.S. Department of Defense                 Energy Board



   January 2003                                      3   January 2003                                                                     4




                   Products & Services                                  Active Technical Teams
                                                              • Alternative Landfill                 • Permeable Reactive Barriers
           • Regulatory and Technical Guidelines                Technologies                         • Radionuclides
           • Technology Overviews                             • Brownfields                          • Remedial Process Optimization
           • Case Studies                                     • Contaminated Sediments               • Risk Assessment Resources
                                                                                                       (NEW)
                                                              • DNAPL
           • Peer Exchange                                                                           • Sampling, Characterization,
                                                              • Diffusion Samplers                     and Monitoring
           • Technology Advocates                             • In Situ Bioremediation               • Small Arms Firing Range
           • Classroom Training Courses                       • In Situ Chemical Oxidation           • Unexploded Ordnance
           • Internet-Based Training Sessions                 • Mitigation Wetlands
                                                              • MTBE-Contaminated
                                                                Groundwater
   January 2003                                      5   January 2003                                                                     6




                                                                                                                                              1
Regulatory Acceptance for New Solutions                                                                                               January 2003


                         Nationwide Success                                                                  Contacts
                                                                                     Web Site:          http://www.itrcweb.org
                                                                                     Cochairs, ITRC Board of Directors:
                                                                                     Brian C. Griffin   Oklahoma Secretary of Environment
                                                                                     (405) 530-8995     bcgriffin@owrb.state.ok.us

                                                                                     Ken Taylor         SC Department of Health and
                                                                                     (803) 896-4011     Environmental Control
                                                                                                        taylorgk@dhec.state.sc.us

                                                                                     Program Director:
                                                                                     Rick Tomlinson     rickt@sso.org
                                                                                     (202) 624-3669

   January 2003                                                             7   January 2003                                                   8




                            Technical Program
                   ITRC Diffusion Sampler     Field Study: Use of PDBS at
                       Team Update                 Cape Canaveral FL
                      George Nicholas                Sandra Gaurin


                PDBS Deployment and           Additional Approaches for
           Discussion of USGS Users Guide        Diffusion Sampling
                  Dr. Don Vroblesky               Dr. Don Vroblesky


                  Regulatory Considerations
                          for PDBS
                       George Nicholas




   January 2003                                                             9




                                                                                                                                                   2
ITRC Diffusion Sampler Team Update                                                                                                                                           January 2003


                                                                                                         ITRC Diffusion Sampler Team Members

                                                                                            Michael Crain, Army Corps of Engineers             Hugh Rieck, AZ DEQ
                                                                                            402-697-2657 michael.e.crain@usace.army.mil        602-771-4196 Rieck.hugh@ev.state.az.us
                                    ITRC Diffusion Sampler                                  Theodore Ehlke, USGS                               Javier Santillan, PhD, HQ AFCEE/ERT
                                                                                            609-771-3924 tehlke@usgs.gov                       210-536-5207 javier.santillan@brooks.af.mil
                                    Team Update                                             Sandra Gaurin, BEM Systems, Inc.
                                                                                            908-598-2600 Ext. 157 sgaurin@bemsys.com
                                                                                                                                               Bruce Stuart, Missouri DNR
                                                                                                                                               573-751-1405 nrstuab@mail.dnr.state.mo.us
                                                                                            Bob Genau, DuPont                                  James Taylor, CA RWQB
                                                                                            302-992-6771 bob.genau@usa.dupont.com              916-255-3069 Taylorjd@rb5s.swrcb.ca.gov
                                                                                            Joseph Gibson, Alabama DEM                         John Tunks, Parsons
                                                                                            334-270-5603 glj@adem.state.al.us                  303-764-8740 john.tunks@parsons.com
                                                                                            Don Gronstal, AFRPA                                Brad Varhol, EON Products
                                    George Nicholas, NJDEP                                  916-643-3672 x211 dgronsta@afbda1.hq.af.mil        800-474-2490 diffusion@eonpro.com
                                                                                            Alt E-Mail: gronstal.don@email.mcclellan.af .mil
                                    Team Lead                                               Ron Hoeppel, NFESC
                                                                                                                                               Don Vroblesky, PhD, USGS
                                                                                                                                               803-750-6115 vroblesk@usgs.gov
                                    609-984-6565, George.Nicholas@dep.state.nj.us           805-982-1655 hoeppelre@nfesc.navy.mil
                                                                                                                                               Mark Weegar, Texas Commission on Environmental Quality
                                                                                            Thomas Imbrigiotta, USGS                           512-239-2360 mweegar@tceq.state.tx.us
                                                                                            609-771-3914 timbrig@usgs.gov
                                                                                                                                               LtCol. Daniel Welch, DLA Support Service
                                                                                            Mark Malinowski, CA DTSC                           703-767-6255 daniel_welch@hq.dla.mil
                                                                                            916-255-3717 Mmalinow@dtsc.ca.gov
                                                                                                                                               Rod Whitten, AFRPA/EV
                                                                                            Dee O'Neill, Columbia Analytical Services          415-977-8885 Rod.whitten@brooks.af.mil
                                                                                            360-577-7222 doneill@caslab.com
                                                                                                                                               Richard Willey, EPA Region 1
                                                                                            David Randolph, TN - Superfund                     617-918-1266 willey.dick@epa.gov
                                                                                        2   615-532-0908 David.Randolph@state.tn.us




                    Order a Diffusion Sampler
                          Resource CD

                                              The recently prepared Diffusion
                                              Sampler Resource CD contains nearly
                                              70 articles and presentations on
                                              various diffusion samplers, as well as
                                              the ITRC training video and the
                                              AFCEE/Parsons field sampling video.
                                              Much of the material is available on
                                              this website, but the CD has the
                                              advantage of being searchable. It's
                                              free. To receive a copy of the CD email
                                              your request for the 'Diffusion Sampler
                                              CD' and your mailing address to
                                              itrc@wpi.org, or call 540-557-6071.




   3




                    Future Work for ITRC
                   Diffusion Sampler Team
       Website Development
           Enhance website and track PDBS performance, post information on
           lessons learned and keep updated on advances in passive sampling
           approaches


                   ITRC Diffusion Sampler Information Center
                      http://DiffusionSampler.itrcweb.org
                                                                                                                  Thank You!
       Additional Guidance:
           Decision Tree, Position Paper, Cost performance template

       Continue to Serve as Information Resource
           For State / Federal Regulators, Stakeholders, RP’s, Consultants
   5                                                                                    6




                                                                                                                                                                                                        1
PDBS Deployment and Discussion of USGS Users Guide                                                                                           January 2003


                                                                                               Presentation Overview

        Polyethylene Diffusion Bag (PDB)                                               Background on diffusion samplers
                                                                                       Theory – Why diffusion samplers work,
                   Samplers
                                                                                       field applications of PDB samplers
               Sometimes called Passive Diffusion Bag
                                                                                       Question and Answer Period 1
                             Samplers
                                                                                       Discussion of User’s Guide and practical applications
                            By Don A. Vroblesky                                        Data interpretation – comparison between different
                           U.S. Geological Survey                                      methods
                               Columbia, S.C.                                          Questions and Answer Period 2
                            (vroblesk@usgs.gov)

  1                                                                                2




                Typical Applications of Passive                                                 Passive Diffusion Bag
                Diffusion Bag (PDB) Samplers                                                      (PDB) Samplers
           Long-term monitoring of VOCs in wells
                                                                                       PDB samplers are used to obtain ambient
           Delineating contaminant stratification                                      concentrations of volatile organic compounds (VOCs) in
               This information can aid in site characterization                       wells.
               More accurate identification of the contaminated horizon can            Why are they a desirable alternative?
               be an aid in optimizing remediation by allowing more accurate              Very inexpensive (about $16-$26 ea) (typically 40-60% cost
               targeting by the remediation effort.                                       savings over conventional methods)
                                                                                          Sampling - rapid and easy with minimal field equipment required
                                                                                          Disposable, so no equipment decon is needed between wells
                                                                                          Potential to eliminate pumps and reduce waste water
                                                                                          Sometimes can provide information difficult to obtain with
                                                                                          conventional methodologies
                                                                                          Practical for use for access is a problem or discretion is desirable
                                                                                          Not subject to interferences from alkalinity or turbidity.



  3                                                                                4




                 Typical Water-Filled PDB
                                                                                                               Principle
                         Samplers

                                                                                       Law of Diffusion                       Fick’s Law
        PDB sampler                                                                                                               The rate of diffusive
      without protective
                                                                                          Compounds tend to
                                                                   PDB sampler                                                    mass transfer through a
            mesh                                                                          migrate from an area                    unit area (J) is
                                                                   attached to
                                                                                          of high concentration                   proportional to the
                                                                   bailer bottom                                                  difference in
                                                                                          to an area of low
      PDB sampler with                                                                                                            concentrations (C1-C2)
       protective mesh
                                                                                          concentration until                     divided by the distance
                                                                                          equilibrium is                          separating those
                                                                                          achieved                                concentrations (L). The
                                                                                                                                  constant of
                                                                                                                                  proportionality is also
      Must purchase from                                                                                                          called the diffusivity, or
        vendor or obtain                                                                                         (C 1 − C 2)      diffusion coefficient (D).
      license from USGS                                                                Fick’s Law:     J =D
         (703 648:4344)                                                                                               L
  5                                                                                6




                                                                                                                                                                 1
PDBS Deployment and Discussion of USGS Users Guide                                                                                                                                                      January 2003


                                                                                                                                                         Groundwater and
                                             Principle                                                                                                   Contaminant Flow
                                             Law of Diffusion (cont.)
                                                             Cb
         Concentration




                         Low Concentration
                               Area
                                                                                Before
                                                                              equilibration
                                                    Mass Transfer
                                                     by Diffusion


                              Cs                    High Concentration Area                                 Cross Section View

                              Cs                                Cb
         Concentration




                                                                                 After
                                              L                               equilibration
                                           Poly-
                                         ethylene
                                         membrane


  7                                                                                           8




                                Diffusion Samplers                                                                                                  Lab Tested VOCs in PDB
                                 Deployed in Well                                                                                                          Samplers
                                                                                                       Tested compounds showing good correlation (11 or less percent difference)
                                                                                                  Benzene                                      2-Chlorovinylether cis-1,2-Dichloroethene                    1,1,1-Trichloroethane

                                                                                                                                               DBChloroMethane                trans-1,2-Dichloroethene 1,1,2-Trichloroethane
                                                                  Cross Sectional                 BDCMethane

                                                                       View                       Brom oform                                   Dibrom oMethane                1,2-Dichloropropane           Trichloroethene

                                                                                                  Chlorobenzene 1,2-DCBenzene                                                 ci s-Dichloropropene          TCFMethane
       Diffusion                                                                                  Carbon Tet.                                  1,3-DCBenzene                  EDB                           1,2,3-TCPA
       Samplers
                                                                                                  Chloroethane                                 1,4-DCBenzene                  trans-1,3-DCPE                1,1,2,2-PCA

                                                                                                  Chloroform                                   DCFMethane                     Ethyl benzene                 Tetrachloroethene
                                                                    Avg. Diffusion                Chlorom ethane 1,2-Dichloroethane Naphthalene                                                             Vinyl chloride
        Weight                                                    Sampler size 1 to 2                                                          1,1-Dichlorethene              Toluene                       Xylenes
                                                                    feet in length
                                                                                                                   Tested compounds showing poor correlation (> 20 percent difference)
                                                                                                  Acetone*                                     MTBE                           Styrene                       MIBK*

  9                                                                                           10                                    Vroblesky and Campbell (2000), *Sivavec (2000, 2001, GE Corp., written commun.)




                            Limitations of PDB Samplers                                                                                          Lab Tests of PDB Samplers



       PDB sampler results are an integration of
                                                                                                  Inside Diffusion Sampler (µg/L)




       concentrations over the equilibration time
                                                                                                      Concentration in Water




                                                                                                                                     60                                                 1000
       associated with the most recent part of the
       deployment period                                                                                                                      TCE                                                PCE
                                                                                                                                     40
                                                                                                                                                                          p                                                    p
                                                                                                                                                                     hi                                                   hi
                                                                                                                                                                   ns                    100                            ns
                                                                                                                                                            t io                                                 t io
       Not appropriate for some compounds                                                                                            20                  ela                                                  ela
                                                                                                                                                       1R                                                   1R
                i.e. MTBE, acetone, most semi-volatiles, most ions                                                                                1:                                                   1:
       Rely on water movement through the well                                                                                        0                                                   10
                                                                                                                                          0       20           40               60          10               100                   1000
       Constitute point samples                                                                                                           Concentration in Water Outside Diffusion Sampler (µg/L)
                not necessarily a disadvantage


  11                                                                                          12




                                                                                                                                                                                                                                          2
PDBS Deployment and Discussion of USGS Users Guide                                                                                                                               January 2003


                                 Conventional Well                                                          PDB vs. Purge-and-Sample under
                                 Sampling Methods                                                                   Field Conditions

                                                                                                                                          100       PCE

       Two standard methods                                                                                                               10




                                                                                                              Diffusion Sampler (µg/L)
                                                                                                                                           1
         Purge-and-Sample                                                                                                                       1          10        100
                                                                                                                                          100




                                                                                                                  Concentration in
                                                                                                                                                    TCE
                      Remove 3 or more casing volumes of water prior to                                                                   10
                      collecting a sample
                                                                                                                                           1
                                                                                                                                                1               10         100
                                                                                                                                          10
                                                                                                                                                    1,1-DCA
         Low-Flow (LF) or Low-Volume Sampling                                                                                              1
                      Slowly purge with no drawdown until field parameters                                                                0.1
                      stabilize prior to collecting a sample                                                                                    0.1             1          10
                                                                                                                                          10
                                                                                                                                                    c-1,2-DCE                    Davis, CA (Jan. 1999)
                                                                                                                                           1

                                                                                                                                          0.1
                                                                                                                                                0.1             1          10
                                                                                                          Concentration Using Purge-and-Sample Method (µg/L)
  13                                                                                                 14




                       BTEX Data From Fractured-Rock
                                                                                                                                         Multiple PDB Samplers
                                  Aquifer

                                                                              NSWC, Louisville, KY
                                           Benzene
                               1000        Toluene
          PDB Sampler (µg/L)




                                           Ethylbenzene
           Concentration in




                                           Xylenes

                               100



                                10



                                 1
                      1       10      100    1000
           Concentration Using Purge-and-Sample Method (µg/L)
  15                                                                                                 16




                           TCE Stratification in 10-Ft                                                        Low-flow Sampling effects near
                                Well Screens                                                                         TCE stratification

                      50
         Depth (ft)




                                                Well MW-5

                      60                                               LF bladder pump
                           0         400     800      1200
                                                                       LF peristaltic pump
                      30                                               PDB sample
         Depth (ft)




                                               Well MW-12

                                                                     NAS North Island, CA
                      40
                           0    2000  4000    6000   8000    10000
                                 TCE Concentration (mg/L)

  17                                                                                                 18




                                                                                                                                                                                                         3
PDBS Deployment and Discussion of USGS Users Guide                                                                                                                                January 2003

                 Comparison of PDB and Purge Sampling
                          Methods at Well 18S                                             Switched to Multiple PDB samplers
                  (deployment of single PDB sampler in                                    and Low-Flow Sampling at Well 18S
                 approximate center of screened interval)

                                      PDB      Purge-and-                                                                                             30

                                    Sampler     Sample




                                                                                                                               Depth (TOC), in feet
                                                                                 These data imply that                                                32
                                    Method      Method                           the low-flow sampling
                                     (µg/L)      (µg/L)                          results can be a                                                     34
                                                                                 mixture of waters
               Total                                                             within the screened
              1,2-DCE                130           650                           interval
                                                                                                                                                      36


                                                                                                                                                      38
                                                                                                                                                           0     200 400 600 800 1000 1200 1400 1600 1800
                TCE                  570           2,300                                                                                                                         µg/L
                                                                                                                                                               Low-flow PDB
                                              4-casing-volume                                                                                                   sample sample
                                                                                                                                                                         Total 1,2-Dichloroethene
    Fridley, MN (Nov. 1999)                        purge                        Fridley, MN (May 2000)                                                                        Trichloroethene
  19                                                                       20




              Varying degrees of mixing during                                            Relation between well sampling
                         sampling                                                              and well construction

        Thus, diffusion samplers typically constitute a point sample.
        Useful for targeting the high concentrations. Avg.
        concentrations for a screened interval are obtained by multiple             In some cases, VOC stratification in a well and
        samplers.                                                                   disagreement between sampling methods can
                                                                                    result from inadequate wells.
        Low-flow samples sometimes constitute an approximate point
        sample (selected horizons at NAS North Island) providing no
        information on average concentrations in a well screen. In other            Examples include wells that connect zones of
        wells, LF samples constitute a mixed sample over varying
        intervals.                                                                  significantly different hydraulic head or contaminant
                                                                                    concentration.
        3 or more casing-volume purge sampling averages aqueous
        concentrations even more by mixing, sometimes inducing flow
        from horizons not in the vicinity of the well screen.                       CONSIDER THE FOLLOWING EXAMPLES:



  21                                                                       22




                                Heat-Pulse Flowmeter                                                      Heat-Pulse Flowmeter
                                                                                                                                                                             0          2        4
          Fractu                                                                    Fractu                                                                                        Downward
                re                                                                        re
                                     High                                                                                                                                           Flow
                                     Head
                     Borehole




                                                                                               Borehole


                                                                                                            Groundwater Flow




                                                                                                                                                                                                     Depth




                                     Low
                                     Head



              ture                                                                      ture
          Frac                         Borehole                                     Frac                                                               Borehole
                                       Flowmeter                                                                                                       Flowmeter



  23                                                                       24




                                                                                                                                                                                                             4
PDBS Deployment and Discussion of USGS Users Guide                                                                                                                                                                                                                                                                                  January 2003


                                                     High TCE Concentrations in the                                                                                                                                                  Differing Source Waters for PDB
                                                           Zone of Stagnation                                                                                                                                                               and Purge Methods
                                                     100                                                                                                                                                                                                              TCE (µg/L)
                                                                            Well PO2-2R                                                                                            Low-permeability                                                               5    10 15 20                   25
                                                     105
                                                                                                                              Zone                                                 aquifer
                                                                                                                                                                                                                                                             20                                                                     CS
                                                                                                                               of                                                  VOCs were                                                                                       PCE
                                                                                                                                                                                                                                                                                   TCE                                             Sand
                                                     110                                                                    Downward                                               higher in purged                                                                                                                                              Water
                              Depth BLS (ft)




                                                                                                                                                                                   sample than in                                                                                                                                  S&G           Level
                                                                                                                              Flow




                                                                                                                                                                                                                                                                                                       Flow during pumping
                                                                              Fracture                                                                                             PDB sample.
                                                     115                                                                                                                                                                                                     40




                                                                                                                                                                                                                                                Depth (ft)
                                                                             Purge-and-Sample                                                                                      PDB samples                                                                                                                                Fractured
                                                                                                                                                                                                                                                                         PDB                                                    Silty
                                                     120                                                                                                                           were local.                                                                         Samplers                                                 Clay
                                                                                                                                                                                   Pumped sample
                                                                    Diffusion
                                                     125             Sample                                                Zone of No                                              was from above                                                            60




                                                                                                                                                                                                                                                                                         Screen
                                                                                                                                                                                   the screen.
                                                                                                                           Measurable
                                                     130                                                                                                                                                                                                                                                                           Sand
                                                                                                                              Flow
                                                                                                                                                                                                                                                             80
                                                     135                                                                                                                                                                                                       40      80 120 160                                                            0.0 0.5 1.0
                                                        0                   200         400                 600                                                                (Davis Global                                                                           PCE (µg/L)                                                            Pumped flow
                                                                                                                                            (Data from Peter                   Comm., CA,:                                                                                                                                                      (gpm)
                                                      TCE Concentration (µg/L)                                                             Church, USGS, CT)                   Well DMW-5)
  25                                                                                                                                                                    26




                                                Pumps and PDBs at Andersen                                                                                                                                                                Well IRP-31, Andersen
                                                   AFB, Guam, April 2002                                                                                                                                                                  AFB, Guam, April 2002

                                                                                                                  40                                                                                   440
                        250                                                                                                                                                                                                                                                                                                        PDB        Low flow
                                                                                                                             Sample IRP-39A                                                                                         Most inflow
                                                                                                                                                                                                       445
    PDB sample (ug/L)




                                                                                              PDB sample (ug/L)
                                                                                e




                                                                                                                  30
                                                                              nc




                        200
                                                                                                                                                                         Depth, in feet
                                                                            de




                                                                                                                                                                                                       450
                                                                       on
                                                                        p
                                                                      es




                                                                                                                                                         e
                                                                    rr




                                                                                                                                                       nc




                        150                                                  Sample IRP-31A
                                                                 Co




                                                                                                                                                    de




                                                                                                                  20                                                                                   455
                                                                                                                                            on
                                                             1
                                                           1:




                                          Sample
                                                                                                                                          sp




                                          IRP-39A
                                                                                                                                        re




                        100                                                                                                                                                                                                                                                                                                              Typical
                                                                                                                                      or




                                                                                                                                                                                                       460
                                                                                                                                     C




                                                                                                                                                                                                                                                                                                                                         pumped-
                                                                                                                                      1
                                                                                                                                   1:




                                                                                                                  10
                         50                                                    TCE                                                                        PCE                                          465
                                                                                                                                                                                                                                                                                                                                         sample
                                                                                                                                                                                                                                                                                                                                         collection
                                                                                                                                                                                                                                                                                                                                         depth
                          0                                                                                        0
                              0                 50         100       150       200     250                             0      10               20            30    40                                  470
                                                                                                                                                                                                                               0         10          20                30          40 0                                      100          200            300
                                               Pumped sample(ug/L)                                                         Pumped sample (ug/L)
                                                                                                                                                                                                                                    % Flow entering well                                                                      TCE (ug/L)
                                                                                                                                                                                                                                   while pumping at 0.5 gpm


  27                                                                                                                                                                    28




                                                                                                                                                                                                                                    Contaminant Profile May Provide
                                                           Well IRP-39, Andersen
                                                                                                                                                                                                                                     Clues Regarding Contaminant
                                                           AFB, Guam, April 2002                                                                                                                                                             Degradation
                                                                                                                                                                                                                          Changes in TCE/DCE Ratio Along Vertical Profile in Screened Interval
                                                                                                                                                                                      Depth, in feet below land surface




                        600                                                                                                                                                                                               20                                                             20
                                                                                                                                                                                                                                                                  Well 24-S                                                                   Well 8-S
                                                                                                                                                                                                                          22                                                             22
                        605
                                                                                                          Low flow
                                                                                       Pump                                                                                                                               24
    Depth, in feet




                                                                                                                                                                                                                                                                                         24
                        610
                                                                                                                                                                                                                          26
                                                                                                                                                                                                                                                                                         26
                        615                            Most inflow                                                                                                                                                        28
                                                                                                                                                                                                                                                                                         28
                        620                                                                                                                                                                                               30

                                                                                                                                                                                                                          32                                                             30
                        625
                                                                                                                                                                                                                          34                                                             32
                                                                                                                                                                                                                                   200        400              600           800              0                         200      400        600           800
                        630
                              0                10     20     30       40       50 10     15   20                   25       30 0          10         20      30   40                                                                     Micrograms per liter                                                             MIcrograms per liter

                              % flow entering the                                         TCE (ug/L)                                      PCE (ug/L)                                                                                                                        Sample
                              well while pumping                                                                                                                                                                                                                             after   PDB
                                                                                                                                                                                                                                                                            purging Sample
                                   at 0.5 gpm                                                                                                                                                Vroblesky and Petkewich, 2000, USGS                                                              1,2-DCE
                                                                                                                                                                                                     WRI Report 00-4246
                                                                                                                                                                                                                                                                                              TCE

  29                                                                                                                                                                    30




                                                                                                                                                                                                                                                                                                                                                                5
PDBS Deployment and Discussion of USGS Users Guide                                                                                          January 2003

                                                                                                    “Users Guide For Polyethylene-Based Passive
                                                                                                      Diffusion Bag Samplers To Obtain Volatile
                         Questions and Answers                                                       Organic Compound Concentrations In Wells”




                                                                                           Available for download from:      Multi-Agency Document
                                                                                                                               U.S. Geological Survey
                                                                                           In the links page at the end of     U.S. Air Force
                                                                                                     this presentation         U.S. Naval Facilities
                                                                                                        OR                     Engineering Command
                                                                                                                               U.S. EPA
                                                                                              http://www.itrcweb.org           Federal Remediation
                                                                                                                               Technologies Roundtable
                                                                                                http://www.frtr.gov
                                                                                                                               Defense Logistics Agency
                                                                                             http:www.sc.er.usgs.gov/          U.S. Army Corps of
                                                                                                                               Engineers
                                                                                                    publications               Interstate Technology
                                                                                                                               Regulatory Cooperation
                                                                                                                               Work Group (ITRC)

  31                                                                                 32




                                                                                                          User’s Guide Part 2:
                   PDB Sampler User’s Guide. Part 1
                                                                                                              Field Tests

                Executive summary
                Introduction                                                                   Comparison to purge-and-sample
                   Summary of limitations and advantages                                          Davis Global Commun., CA (Vroblesky and others)
                PDB sampler deployment                                                            McClellan AFB, CA (McClellan AFB EMD)
                Sampler and sample recovery                                                       NIROP Fridley, MN (Vroblesky and Petkewich)
                Determining applicability                                                      Comparison to low-flow sampling
                   Influences of hydraulic and chemical heterogeneity on                          NAS North Is., CA (Vroblesky and Peters)
                   sample quality
                   Comparison of PDB sampling to conventional                                     Hanscom AFB, MA (Church)
                   methodologies                                                                  NIROP Fridley, MN (Vroblesky and Petkewich)
                Quality control and assurance                                                  Comparison to a variety of methods
                Summary                                                                           (Tunks and others)
                References

  33                                                                                 34




                         Comparison of Methods                                                      Deployment of PDB sampler with
                          (AFCEE/Parsons Eng.)                                                       attached weight (Eon sampler)
  CRITERIA                USGS PDB       DMLS        MICROPURGE CONVENTIONAL
  Ease of use             Excellent       Fair           Poor               Fair
  Labor hours per
  sample
                            0.66            1            2.75               3.66
  IDW Generation
                             <1            <1              100              500
  (liters)
                                                                                          Protective                                            Diffusion Bag
  Costs for dedicated
                            Low           High           Low               High           Mesh                                                  (inside mesh
  equip.
                                                                                          Sock                                                  sock)
  Between-well decon.      Minimal        High         Moderate        Moderate

  Immediacy of results      Slow          Slow           Rapid             Rapid
                                                                                           Weight
  Analytes other than
                                                                                           Hanger                                                Filling and
                             No           Yes              Yes              Yes
  VOCs?                                                                                                                                          Sampling
  Evaluation of VOC
  stratification?
                          Possible      Possible        Partial              No                                                                  Port
                                                                                           Weight
  OK MNA sampling?           No            No              Yes             Partial
  Cost per Sample           $65           $555           $308              $444
  35                                                                                 36




                                                                                                                                                                6
PDBS Deployment and Discussion of USGS Users Guide                                                                            January 2003


                                                                                         Commercially Available
                  Field Filling PDB Sampler
                                                                                         Prefilled PDB Sampler




                                                                                                                   Sampler       Weight

  37                                                                       38




                   Methods of Attaching PDB                                        Two Approaches to Measuring the Line to
                 Samplers to the Line or Weight                                      Determine the PDB Attachment Point


       The PDB sampler can be
       attached to the weighted line
       by a variety of methods.                                                 Weight suspended above the well bottom
           Wire ties through a knot                                                Measure the line and attach the PDB sampler at a
           Stainless steel clamp                                                   distance corresponding to the depth of the target zone
           Direct attachment to the                                                Be careful that the line doesn’t slip or stretch
           weigh
       Nonbuoyant nonstretch rope                                               Rest weight on the well bottom
       can be used as the line,                                                    Attach the PDB sampler to the line at a distance from
       however, stainless steel line is
       preferable                                                                  the bottom of the weight equal to the distance from the
                                                                                   well bottom to the target horizon
       Sufficient weight should be                                                 Usually this involves less measuring than measuring
       added to counterbalance the                                                 the line from the top down.
       buoyancy of the PDB samplers



  39                                                                       40




                Things to Consider When Measuring                                       Consider the Screen Length
                     From the Bottom Upward                                              Deploying PDB Samplers


         Measure the well depth                                                 Screen length/saturated interval 5 ft or less
             Compare measured and reported (from well logs) depths to              PDB sampler in the center
             the well bottom                                                    Screen length 5-10 ft
             This is to check on whether
                                                                                   Advisable initially to use multiple PDB samplers to
                 sediment has accumulated in the bottom of the well,
                                                                                   ascertain the presence of contaminant stratification
                 there is a non-screened section of pipe (sediment sump)
                 below the well screen, and                                     Screen length >10 ft
                 on the accuracy of well-construction records.                     Only use in conjunction with borehole flow meters or
         If there is an uncertainty regarding length or placement                  other techniques to characterize vertical variability in
         of the well screen, then an independent method, such                      hydraulic conductivity and contaminant distribution or
         as video imaging of the well bore, is strongly suggested.                 use strictly for qualitative reconnaissance purposes



  41                                                                       42




                                                                                                                                              7
PDBS Deployment and Discussion of USGS Users Guide                                                                                                                              January 2003


                                                    Equilibration of selected                                                          PDB Sampler Equilibration in Lab
                                                  compounds in PDB samplers                                                                       Studies

                                             1.0
                                                                            Benzene          PCE                Vroblesky          48 hours for TCE and several tested compounds at 25 C
       samplers to concentrations outside
       Ratio of concentrations within PDB




                                                                            EDB              Toluene
                                             0.5              25 oC                                                and
                                                                            cDCE             TCE
                                                                                                                Campbell,          (Vroblesky, 2000, USGS)
                                                                            Napht            Total xylenes
                                                                                                               2000, USGS
                                            0.0
                of PDB Samplers




                                            1.0
                                                                                                                                   93 to 166 hours for VC and some chloroethenes
                                                                             PCE                   TCE                             and 48 to 72 hours for BTEX compounds and selected
                                            0.5
                                                                            trans-1,2-DCE         1,1-DCE Sivavec,and              dichlorobenzenes at 10 C (Sivavec and Baghel, 2000,
                                                              10 oC         Chloroethane      cis-1,2-DCE Baghel 2000,
                                                                            Vinyl Chloride      1,1,1-TCA                          2001 General Electric Company)
                                                                            1,2-DCA              1,1-DCA    GE Co.
                                            0.0
                                                                                                                                   But samplers should equilibrate long enough for well
                                              1.0                                                                                  water, contaminant distribution, and flow dynamics to
                                                                               Benzene           O-Xylene
                                                                               Toluene           1,3-DCB
                                                                                                                   Sivavec,        restabilize (2 weeks for permeable formations,
                                              0.5                 10 oC        Ethylbenzene                        2001, GE        possibly longer for poorly permeable formations)
                                                                                                 1,4-DCB
                                                                               m-&p-Xylene       1,2-DCB             Co.
                                              0.0
                                                    0   24   48     72     96      120     144    168        192
  43                                                                      Hours                                               44




                                            One water-transfer method is to insert
                                                                                                                                         Attaching a Bottom-Discharge
                                                a discharge tube through the
                                                        polyethylene                                                                                Device




                                      Inserting the tube                          Transferring water
                                         through the                                to a VOA vial
                                      polyethylene into
  45                                  the PDB sampler                                                                         46




                                            Water Also can be Removed Simply by
                                                                                                                                        Determining applicability of
                                            Cutting the Sampler Open and Gently
                                                   Pouring into VOA Vials                                                                     PDB Samplers

                                                                                                                                   Common approach is to do a side-by-side
                                                                                                                                   comparison to conventional technology
                                                                                                                                      Particularly important in wells with high temporal
                                                                                                                                      chemical variability


                                                                                                                                   In Wells with low temporal chemical variability,
                                                                                                                                   comparison of PDB-sampler results to historical
                                                                                                                                   concentrations may be adequate.




  47                                                                                                                          48




                                                                                                                                                                                           8
PDBS Deployment and Discussion of USGS Users Guide                                                                                                   January 2003

                                                                                      If PDB-sampler VOC concentrations
                              Data Evaluation                                         are higher than VOC concentrations
                                                                                          from the conventional method


       i In general, if the results agree in a range deemed                 i Then the PDB sampler probably adequately
         acceptable by local, state, and Federal regulatory                    represent ambient conditions
         agencies and meet the site-specific data-quality
         objectives, then a PDB sampler may be approved for use                0   This is because there is a greater potential for dilution
         in that well to monitor ambient VOC concentrations.                       from mixing during sampling using conventional
                                                                                   technology




  49                                                                   50




                  If the conventional method VOC                                     The decision on whether to use PDB
                concentrations are higher than PDB-                                  samplers in such situations depends
                sampler VOC concentrations – then:                                      on the data quality objectives


       i Uncertain whether the PDB sampler or the                           i If the goal is to determine and monitor higher
         conventional sampler conc.’s represent local                          concentrations or to examine contaminant stratification
         conditions.                                                           within the screened interval
          0   Further testing (borehole flowmeter and/or multiple              0   PDB samplers may be appropriate
              PDB samplers) can be used to clarify the situation.           i If the goal is to determine the average concentrations
       i PDB samplers may be more locally representative if                    for the entire screened interval
         the pumped samples                                                    0   An average of multiple PDB samplers may be appropriate.
          0   Mixed chemically stratified zones                                0   A pumped sample may produce an average concentration
          0   Incorporated water containing higher concentrations                  across the screened interval, but several field tests suggest
              from other areas not adjacent to the screened interval               that low-flow samples sometimes constitute approximate
                  along inadequate well seals                                      point samples and sometimes constitute an average
                  through fractured clay                                           concentration over intervals that may vary from well to well


  51                                                                   52




                   Vertical stratification of                                       Comparisons of PDB samplers to
                             VOCs                                                     conventional methodologies

       i In areas where vertical stratification of                          i Resulting concentrations may                          50
                                                                              differ because each methodology
                                                                                                                             Depth (ft)




         VOCs is anticipated, using multiple PDB
         samplers may more fully characterize the                             is sometimes influenced in
         contaminated horizon than using a single                             different ways by aquifer                                                     LF as approx.
                                                                                                                                                            point sample
         PDB sampler.                                                         hydraulic and chemical                                60
                                                                                                                                               0     400     800 1200
          0   Particularly true in well screens 10 ft or longer,              heterogeneity
              but significant VOC stratification has been                                                                                 32
                                                                                   PDB sampler: typically an                                               LF as average
                                                                                                                       Depth (ft)




                                                                               0
              observed in intervals less than 5 ft                                                                                        34                  sample
                                                                                   approximate point sample
       i Because of the influences of chemical and                             0   3-Casing-volume purge-and-                             36
         hydraulic heterogeneity, discussed earlier,                               sample: integrates water over a                        38
         it is advisable that both the vertical                                    relatively large area                                       400   800    1200   1600
                                                                                                                                                      TCE (ug/L)
         distribution of VOCs and the potential for                            0   Low-flow sampling: Sometimes
                                                                                                                                                       LF bladder pump
         intra-borehole flow be determined in wells                                an approximate point sample and
                                                                                                                                                       LF peristaltic pump
         having screens longer than 10 ft.                                         other times an average
                                                                                                                                                       Diffusion sample
                                                                                   concentration over a larger area.
  53                                                                   54




                                                                                                                                                                             9
PDBS Deployment and Discussion of USGS Users Guide                                                                            January 2003


                             Quality control and
                                                                                                           Question & Answers
                                 assurance
    Replicate samples
       At least 10 percent are recommended.                                                                                Helpful Hint:
    Fill water blank                                                                                                     Securely Attach
                                                                                                                          the Line at the
       Tests should be done on the PDB sampler fill water since some VOCs introduced
       in the fill water (such as acetone) will not readily diffusion out (false positive).
                                                                                                                            Well Head

    Trip blanks
       Required for lab filled PDBS to determine whether contaminants have affected the
       samplers during shipment or prior to deployment.
                                                                                                                            Thank you for
    Equipment blanks                                                                                                    attending this ITRC
       Required for field-filled PDBS.                                                                                     training course.
         Note: Blanks are taken at the time of sampler deployment and sent immediately for analysis


  55                                                                                                  56




                                                                                                                                              10
Regulatory Considerations for PDBS                                                                                                               January 2003


                    Regulatory Aspects of Passive
                       Diffusion Bag Samplers
                                                                                                 PDB Sampler Perception


       i Regulatory Considerations / Requirements                                    i Focus – A Different Sample Collection Method
          0   Regulatory requirements specific to diffusion samplers
                                                                                        Once the PDB Sampler is retrieved from the well, all other
              have not been identified that would preclude their use
                                                                                        sampling issues (I.e., sample containers, preservation, chain
          0   Major deterrent to deployment is lack of standard method
                                                                                        of custody, analysis, etc….) are identical to conventional
              in States Sampling Procedures Manuals
                                                                                        sampling methodologies
          0   Strong reluctance to switch from methods already in use
          0   Technical performance of the Diffusion Sampler is a key
              issue (this is technical not regulatory)

       i Regulatory Acceptance
          0   Summary of State experience

   1                                                                            2




                                Applicability                                                         Deployment Issues

        i Recommended for long term monitoring at well                              i PDB samples represent a “point sample” so you must
           characterized sites                                                         accurately measure PDB sampler position in well
        i Sentinel wells: problem w/unknown contam. depth                                 0 Use    “As built” well diagrams for well info
                                                                                          0 Measure     total depth of well, compare to “as-built”
        i Contaminants of concern must be appropriate for PDBS
                                                                                    i Must assess potential for vert. stratification
        i Due to inability to detect iron, sulfate, nitrate, and
                                                                                          0 At   least initially, use multiple bags to vert. profile well
           manganese, PDBS currently not recommended for
                                                                                          0 based    on site conditions, may need to re-assess
           evaluation of Natural Attenuation processes
                                                                                    i Important to eval. potential for vertical flow in well
              [note: PDB samplers can detect DO, Methane, and breakdown prod]
                                                                                          0 High   potential in bedrock or unconsolidated w/clay & silt
                                                                                          0 Use    heat pulse flow meter or similar device


   3                                                                            4




                      EQULIBRATION TIMES                                                         Performance Evaluation


        2-week minimum                                                                i Simple site conditions – comparison to historic data
                                                                                         acceptable
               0   may need longer timeframe in tight formations to
                   allow stabilization of water column
                                                                                      i More complicated site conditions: side-by-side
               0   Field studies show longer deployments, up to 3-                       comparisons appropriate
                   months, did not encounter problems [i.e. bio-fouling,
                   bag rupture]                                                       i Poor correlation DOES NOT indicate failure

                                                                                      i Identify and agree upon evaluation criteria before
                                                                                         deployment


   5                                                                            6




                                                                                                                                                            1
Regulatory Considerations for PDBS   January 2003




            Thank You!


   7




                                               2
Field Study: Use of PDBS at Cape Canaveral FL                                                                                       January 2003


                                                                                                               Table of Contents
                                                                                                                       Presenters


  Overview of PDB Implementation                                                                       Sandra Gaurin
          and Utilization                                                                              John McGann, PG
    at the Cape Canaveral Air Force Station, Florida

  Presented by:                          Presented to:
                  100 Passaic Avenue     New Jersey Department of Environmental Protection
                  Chatham, NJ 07928
                  908-598-2600


                                       January 2003




                            Table of Contents
                             Presentation Agenda



         Section I – Background                                                                                   Section I
         Section II – Sampling Program
                                                                                                                   Background
         Section III – Results
         Section IV – Conclusion




                                                                                             Section


         PDB Implementation and Utilization at CCAFS                                           I
                                   Background

  PDB samplers first evaluation in a pilot study
       2 inactive space launch complexes
            SLC 11                                                                                                Section II
            SLC 12
       Detailed site characterization including vertical
       delineation completed during the RFI and CMS stages of
                                                                                                                Sampling Program
       the RCRA process
  Long Term Monitoring (LTM)
       Conducted since 1998 at the 2 sites
       Monitoring for chlorinated solvent VOCs in groundwater




                                                                                                                                              1
Field Study: Use of PDBS at Cape Canaveral FL                                                                                              January 2003

                                                                                    Section                                                        Section


      PDB Implementation and Utilization at CCAFS                                   II           PDB Implementation and Utilization at CCAFS       II
                        Sampling Program                                                            Sampling Program – PDB Installation

  October 2000, pilot study
     Compare the analytical results between PDB samplers and low-flow
     purge sampling techniques
     PDB sampling at 11 monitoring wells at the 2 adjacent launch
     complexes
        One pre-filled PDB sampler per each study well
        Dedicated stainless steel harness custom designed for each well to ensure
        PDB sampler installation in middle of well screened interval
        PDB samplers installed for 6 week equilibrium period, installed on
        09/12/2000, retrieved on 10/26-27/2000, prior to low-flow sampling
        Samples collected by both methods analyzed for VOC by SW846 8260




                                                                                    Section                                                        Section


      PDB Implementation and Utilization at CCAFS                                   II           PDB Implementation and Utilization at CCAFS       II
           Sampling Program – PDB Retrieval                                                         Sampling Program – Sample Collection




                                                                                                                                                   Section


                                                                                                 PDB Implementation and Utilization at CCAFS       III
                                                                                                                   Results

                                                                                              PDB sampler results correspond with the results of
                                                                                              low-flow sampling
                          Section III                                                         Estimated cost saving of 40% using PDB samplers
                                                                                              instead of low-flow purging at CCAFS VOC LTM
                                                                                              sites
                                 Results
                                                                                              Based on pilot study results, 45th Space Wing
                                                                                              Installation Restoration Program obtained
                                                                                              concurrence from Florida DEP and USEPA to use
                                                                                              PDB samplers for LTM at CCAFS sites with
                                                                                              groundwater VOC contamination only




                                                                                                                                                             2
  Field Study: Use of PDBS at Cape Canaveral FL                                                                                                                                                                                                                   January 2003

                                                                                                                                                           Section                                                                                                                        Section


                      PDB Implementation and Utilization at CCAFS                                                                                          III                          PDB Implementation and Utilization at CCAFS                                                       III
                             Results – Analytical Results Comparison                                                                                                                                    Results – Cost Comparison
                   Sample ID:       L11-09        DBL11-09        L11-19       DBL11-19        L11-20      DBL11-20    L11-21      DBL11-21    L11-22      DBL11-22

   Analyte           Date:          25-Oct-00      25-Oct-00     25-Oct-00      25-Oct-00      27-Oct-00   27-Oct-00   27-Oct-00   27-Oct-00   26-Oct-00    26-Oct-00     Task          Diffusion Sampling                                    Low-Flow LTM

Volatile Organic Compounds
   1,1-Dichloroethene                      2U            2U             2U                2U       4U           2U          2U          2U          2U             2U
   cis-1,2-Dichloroethene                3.4           4.6              2U                2U     138          126         4.3         2.6         1.5 J          1.8 J    Setup         Install sampler and harness                           None
   trans-1,2-Dichloroethene                2U          1.3 J            2U                2U     14.2         12.5          2U          2U          2U             2U
   Trichloroethylene                       2U            2U             2U                2U       4U           2U          2U          2U          2U             2U                   Installation cost will include sampler, harness and
   Vinyl chloride                        8.5           8.6              1U                1U     65.3         51.2       10.3         4.3         2.6            3.1                    labor - 0.5 manhour (2-man team, 15 minutes.)
                   Sample ID:        L12-01       DBL12-01        L12-02       DBL12-02        L12-06      DBL12-06    L12-09      DBL12-09    L12-09I     DBL12-09I


   Analyte           Date:          26-Oct-00      26-Oct-00     26-Oct-00      26-Oct-00      27-Oct-00   27-Oct-00   26-Oct-00   26-Oct-00   26-Oct-00    26-Oct-00
                                                                                                                                                                          Sampling      Retrieve sampler, open and pour into VOC vial         Purge well, collect samples with
Volatile Organic Compounds                                                                                                                                                                                                                    perstaltic pump, manage IDW
   1,1-Dichloroethene                     2U             2U            2U             4U            2U          2U          2U          2U          2U               2U
   cis-1,2-Dichloroethene                 2U             2U          53.7           101            15         67.9          2U          2U        2.8                2U                 Sampling cost will include labor - 1 manhour          Sampling cost will include peristaltic pump,
   trans-1,2-Dichloroethene               2U             2U            2            4.2             2U         3.7          2U          2U          2U               2U
   Vinyl chloride                         1U             1U          18.5            44             1U         3.1          1U          1U        3.4                1U
                                                                                                                                                                                        (2-man team, 0.5 hour)                                battery, tubing, meter(s) for pH, conductance,
                                                                                                                                                                                                                                              temperature and turbidity, IDW management
  Notes:                                                                                                                                                                                                                                      and labor - 3 manhours (2-man team, 1.5
  Non-detected values presented in blue
  Detected values presented in red
                                                                                                                                                                                                                                              hours
  Analyses were performed by SW846 8260
  DB - Sample IDs with the DB prefix were collected using PDB samplers
  J - Result is detected below the reporting limit and/or is an estimated concentration                                                                                   Analytical    VOCs                                                  VOCs
  U - Non-detected, value indicates MDL (method detection limit)




                                                                                                                                                                                                                                                                                          Section


                                                                                                                                                                                        PDB Implementation and Utilization at CCAFS                                                       IV
                                                                                                                                                                                                                       Conclusion

                                                                                                                                                                                  PDB samplers currently being used at 5 sites at
                                                                                                                                                                                  CCAFS
                                                            Section IV                                                                                                                 Sampling results used to evaluate and adjust the LTM
                                                                                                                                                                                       sampling and analysis programs
                                                                                                                                                                                       2 of the 5 sites were granted No Further Action after 2
                                                                  Conclusion                                                                                                           consecutive PDB sampling events without any VOC
                                                                                                                                                                                       detections above applicable screening criteria (regulatory
                                                                                                                                                                                       action levels) and a final round of confirmatory sampling
                                                                                                                                                                                       with PDB samplers and low-flow sampling techniques
                                                                                                                                                                                  The use of PDB samplers is now evaluated with the
                                                                                                                                                                                  addition of each new VOC LTM site at CCAFS




                                           Thank You!




                                                                                                                                                                                                                                                                                                    3
Additional Approaches for Diffusion Sampling                                                                                                      January 2003

                                                                                                             Passive Vapor Diffusion
                  U.S. Geological Survey
                                                                                                                    Sampler


                   Alternate and New
                                                                                                        Empty
                 Approaches in Passive                                                                   vial
                 Sampling Technology                                                                                                                Empty vial
                                                                                                                                                    inside two
                                                                                                                                                   polyethylene
                                                                                                                                                       bags
                                                                                                          Cap
                                        Don A. Vroblesky

                                                                                                                         U.S. Geological Survey                   2




               Contaminated Groundwater                                                                          Distribution of VOCs in
                 Discharge to a Stream                                                                           Fractured-Rock Aquifer
                                       Site for
                                    Vapor Diffusion
                                     Deployment
                                                                                                Greenville, SC


                                                               Stream

                                            Plume                                 Aquifer
                                   Groundwater Flow




                                             U.S. Geological Survey                         3                            U.S. Geological Survey                   4




       VOCs in diffusion samplers at                                                                      VOCs in diffusion samplers at
             Little Rocky Creek, SC                                                                             Little Rocky Creek, SC
                                 1000
                                                                              =




                                 400
                                    =




                                                                                                   Diffusion samplers
        Relative Concentration




                                                                                                   show primary VOC
            of VOCs (ppm)




                                                                                                   discharge zones are
                                                                                                   at intersection of
                                                                                                   creek and fractures
                                 200




                                   0
                                        0              400              800
                                             Distance Downstream (ft)

                                             U.S. Geological Survey                         5                            U.S. Geological Survey                   6




                                                                                                                                                                      1
Additional Approaches for Diffusion Sampling                                                                                                                                                                                                      January 2003

                                                                                                               VOC Changes in Diffusion
           Plan View of Little Rock Creek
                                                                                                             Samplers, Little Rocky Creek
                                        Greenville, SC


                                                                                                         10000




                                                                                                                                                                                                  BEGAN PUMPING FROM AQUIFER
                                                                                    VOCs, in ppb (v/v)
                                                                                                          1000




                                                                                                                                             AIR-ROTARY DRILLING
                                                                                                           100


           Exposed rock                                                                                      10
           VOCs (µL/L)
           Bubbles from nearby rock drilling                                                                     1
           Sampling site                                                                                                   Jan         Feb                               Mar         Apr                                 May                Jun                  Jul
                                                                                                                                                                                     1994

                                   U.S. Geological Survey                      7                                                             U.S. Geological Survey                                                                                                    8




                                                                                            TCE in Bald Cypress Tree cores
           TNX Upper Flood Plain                                                                                           Savannah River Site, SC (Jan-Feb 1998)
                                                                                                                       Upper
                                                                                                                                                                                                                                           TNX Area
                                                                                                                     Floodplain
                                                                                                                                                                           3,577
                                                                                                                         822

                                                                                                                                                                                                                                             ow
                                                                                                    Lower                                 1,187                                                                                            Fl
                                                                                                  Floodplain                         1,857                                                                                             W
                                                                                                                                            625                                                                                    G
                                                                                                                               327
                                                                                                            ch
                                                                                                         Dit                           180

                                                                                                                                                                         <40                                                           300 FEET


                                                                                                             Cored Bald Cypress trees
                                                                                                         TCE in tree cores (nM/L)
                                                                                                             >1,000               100-299
                                                                                                                 300-999                                   <50

                                                                                             822                 TCE in groundwater, 8/97 (µg/L)

                                   U.S. Geological Survey                      9                                                             U.S. Geological Survey                                                                                                    10




       c-DCE in Bald Cypress Tree Cores                                                              TCE and c-1,2-DCE in Diffusion
                  Savannah River Site, SC (Jan-Feb 1998)                                                   Samplers Beneath Ditch
                                                                    TNX Area                              August 25, 1997, TNX facility, Savannah River Site, SC
                                               55
                  13                                                                                                     400                                                                                                                        50


                                                                      ow
                             22                                     Fl
                                                                W                                                                                                                                                                                   40
                                                            G                                                            300
                       <5      16 6
          ch
                                                                                                                                                                                                                                                         cDCE (ppb)




       Dit
                                                                                                             TCE (ppb)




                              <5                                                                                                                                                                                                                    30


                                          <5
                                                                                                                         200            Lower                                                                                    Upper
                                                                300 FEET
                                                                                                                                      floodplain                                                                               floodplain           20


            Cored Bald Cypress trees                                                                                     100
                                                                                                                                                                                     TCE
                                                                                                                                                                                                                                                    10
       c-DCE in tree cores (nM/L)
           >60                 10-20                                                                                                                                           DCE
                                                                                                                           0                                                                                                                        0
               21-60                <10                                                                                        0      100                          200         300          400                                  500          600

                                                                                                                                            Distance along traverse (ft)
      22       c-DCE in groundwater, 8/97 (µg/L)

                                   U.S. Geological Survey                      11                                                            U.S. Geological Survey                                                                                                    12




                                                                                                                                                                                                                                                                            2
Additional Approaches for Diffusion Sampling                                                                                                                  January 2003

                                                                                                  Diffusion Samplers Beneath
       USER’S GUIDE FOR PVD SAMPLERS
                                                                                                   Johns Pond, MMR, Mass.

                                               USGS Water Resources
                                              Investigations Report 02-
                                                        4186.

                                                                                                                                                     John's
                                                 Available online at                                                                                 Pond
                                            http://ma.water.usgs.gov/pu
                                             blications/wrir/default.htm                                                   TCE
                                                                                                                                                    TCE, PCE


                                                                                                                                                     Diffusion
                                                                                                                     200 FEET                        Samplers
                                                                                (Savoi et al, 2000,
                                                                                USGS WRI 4017)

                           U.S. Geological Survey                          13                                              U.S. Geological Survey                        14




                   Mass. Military Reservation                                                          Mass. Military Reservation
                          Cape Cod                                                                            Cape Cod
                                                           1000 FEET
                                   VOCs




                                                                                                                                 TCE
                                           Massachusetts                                                                         PCE
                                              Military
                                            Reservation                                                                                             TCE
                                                                                                      Ashumet Pond


                                                                                                                                                    PCE
                                                                                                                                                              John's
                                                                                                                                                              Pond
                                                                                                                                        TCE


                                          VO V                                                                                                                250 FEET
                                            Cs O
                                                C   s
                            Ashumet
   (Savoi et al, 2000,       Pond                       John's
                                                                                (Savoi et al, 2000,
   USGS WRI 4017)                                       Pond
                                                                                USGS WRI 4017)

                           U.S. Geological Survey                          15                                              U.S. Geological Survey                        16




     Probable contaminant transport
                                                                                              Nylon-screen diffusion sampler
    beneath Ashumet and John’s Pond




                           U.S. Geological Survey                          17                                              U.S. Geological Survey                        18




                                                                                                                                                                              3
Additional Approaches for Diffusion Sampling                                                                         January 2003

        Plastic Jar and Nylon-Mesh                 Tributary to West Fork Trinity
                  Sampler                             River, Fort Worth, Texas




                 U.S. Geological Survey    19                          U.S. Geological Survey                                 20




        Arsenic in GW. Diffusion Sampler            Arsenic in GW (July 1999) and Diffusion
            Locations, Ft. Worth, TX                  Samplers (July 2000), Ft Worth, TX




                 U.S. Geological Survey    21                          U.S. Geological Survey                                 22




                                                  Sulfate in nylon-screen and low-flow
       Nylon mesh jars in LDPE tubing           samples, NAS Fort Worth JRB, March 2001


                                                                                      18



                                                                                                                   Sand
                                                                                      20
                                                                     Depth (ft bls)




                                                                                                                 Silty sand

                                                      Nylon-screen                    22
                                                      sample
                                                      Low-flow
                                                      sample
                                                                                      24


                                                                                                                   Sand

                                                                                      26
                                                                                        55   60   65   70   75
                                                                                           Sulfate (mg/L)        Lithology

                 U.S. Geological Survey    23                          U.S. Geological Survey                                 24




                                                                                                                                   4
Additional Approaches for Diffusion Sampling                                                                                                                                                                                                                                                                               January 2003

                                                  Nylon-mesh diffusion samplers, NAS                                                                                                                                    Iron in nylon-screen and low-flow samples,
                                                     Forth Worth JRB, March 2001                                                                                                                                              NAS Fort Worth JRB, March 2001




                                                                                                                                                                                         Nylon-screen samples (mg/L)
                                                                                                                                                                                                                       20
                                        250




                                                                                             Diffusion-jar samples, in µg/L
                                                                                                                              140
  Diffusion-jar samples, in µg/L




                                        200         Calcium                                                                   120            Chloride                                                                  15
                                                                                                                              100
                                        150
                                                                                                                              80                             n
                                                                                                                                                          tio
                                                                                                                                                        la                                                                                                                                                         Aerobic nylon-screen
                                                                                                                                                      Re                                                               10                              n
                                        100                   tio
                                                                 n                                                            60                  1                                                                                                 tio
                                                            la                                                                                  1:                                                                                                la                                                               sample
                                                          Re                                                                  40                                                                                                               Re                                                                  Anaerobic nylon-screen
                                                      1                                                                                                                                                                                    1
                                        50         1:                                                                                                                                                                                   1:                                                                         sample
                                                                                                                              20
                                                                                                                                                                                                                        5
                                         0                                                                                     0
                                              0    50           100   150     200      250                                          0   20    40       60        80   100 120 140

                                                   Pumped samples, in µg/L                                                               Pumped samples, in µg/L
                                                                                                                                                                                                                        0
                                                                                                                                                                                                                            0       5                  10                           15               20

                                                                                                                                                                                                                                Low-flow samples (mg/L)

                                                                              U.S. Geological Survey                                                                                25                                                                     U.S. Geological Survey                                                                                26




                                              Comparison of Fe(II) and Fe(total), NAS                                                                                                                                           Typical types of dialysis
                                                  Fort Worth JRB, March 2001                                                                                                                                                          membranes
                                                                                                                                                                                                           Cellulose ester or acetate                                                               Regenerated cellulose
                                   25
                                                                                                                                                                                                           Polyvinylidene fluoride (PVDF)                                                           Others (ie polylcarbonate,
                                                                                                                                                                                                           Polysulfone                                                                              polyester)
                                                                                    Iron(II)
                                   20                                               Total iron
                                                                                                                                                                                                                                   Membrane Compatibility Table
  Iron (mg/L)




                                   15                                                                                                                                                                                             Cellulose                                                                               Regenerated
                                                                                                                                                                                                                                                                    PVDF                          Polysulfone
                                                                                                                                                                                                                                    Ester                                                                                  Cellulose
                                   10                                                                                                                                                                        Benzene                  G                                          G                        N                    G
                                                                                                                                                                                                             Toluene                  G                                          G                        N                    G
                                   5
                                                                                                                                                                                                              Xylene                  G                                          G                        N                    G
                                                                                                                                                                                                               PCE                    G                                          G                        N                    G
                                   0
                                                          Nylon-            Low-flow                                                                                                                           TCE                    N                                          N                        N                    G
                                                          screen             sample                                            Nylon-screen                      Low-flow
                                                          sample                                                                  sample                          sample                                        CT                    G                                          G                        N                    G
                                                                                                                                                                                                                CF                    N                                          F                        N                    G
                                                                                                                                                                                                              Ethers                  N                                          F                        N                    G
                                                                              U.S. Geological Survey                                                                                27                                                                     U.S. Geological Survey                                                                                28




                                                                                                                                                                                                                                  One type of Regenerated
                                              Regenerated Cellulose Dialysis
                                                                                                                                                                                                                                 Cellulose Dialysis Sampler
                                         Used by many researchers since about 1976 in
                                                                                                                                                                                                                                                                                                  Well Sampling Technique Comparison
                                         lakebed studies.                                                                                                                                                                                                                                                Trichloroethene, 2002
                                         Ronen and others used a multi-level sampler with                                                                                                                                                                                        1000000.00



                                         cellulose-based membranes for dialysis in wells in                                                                                                                                                                                       100000.00



                                         1987 – The multilevel sampler later became the                                                                                                                                                                                            10000.00


                                         commercially available DMLS sampler.
                                                                                                                                                                                                                                                              Low-Flow Purging




                                                                                                                                                                                                                                                                                    1000.00
                                                                                                                                                                                                                                                                 TCE (µg/L)




                                         Tom Imbrigiotta and Ted Ehlke (USGS) tried a                                                                                                                                                                                                100.00



                                         simpler configuration in wells with success in the                                                                                                                                                                                           10.00



                                         late 1990s.                                                                                                                                                                                                                                   1.00


                                                                                                                                                                                                                                                                                       0.10


                                                                                                                                                                                                                                                                                       0.01
                                                                                                                                                                                                                                                                                           0.01    0.10   1.00   10.00    100.00   1000.00 10000.00 100000.0 1000000.
                                                                                                                                                                                                                                                                                                                                                       0        00

                                                                                                                                                                                              Ted Ehlke, USGS, Trenton, N.J.                                                                               Dialysis Membrane Diffusion Sampler
                                                                                                                                                                                                                                                                                                                       TCE (µg/L)


                                                                              U.S. Geological Survey                                                                                29                                                                     U.S. Geological Survey                                                                                30




                                                                                                                                                                                                                                                                                                                                                                        5
Additional Approaches for Diffusion Sampling                                                                                                                                                                                                               January 2003

                                                                                                                                                   Chloride in dialysis samples and low-
                         Dialysis Bag on Perforated Tube                                                                                           flow samples, Hickam AFB, July 2001




                                                                                                                    in dialysis samples (mg/L)
                                                                                                                                                      10000




                                                                                                                              Chloride
                                                                                                                                                                                                                                                 ce
                                                                                                                                                                                                                                       d    en
                                                                                                                                                           1000                                                                     on
                                                                                                                                                                                                                               sp
                                                                                                                                                                                                                            rre
                                                                                                                                                                                                                       Co
                                                                                                                                                                                                             1:1

                                                                                                                                                                 100


                                                                                                                                                                                   100                             1000                                    10000
                                                                                                                                                                                                    Chloride
                                                                                                                                                                                          in low-flow samples (mg/L)
                                 Vroblesky and others, 2002, USGS WRI 02-4031


                                                      U.S. Geological Survey                                   31                                                                                  U.S. Geological Survey                                              32




              Sulfate in dialysis and low-flow samples,                                                                                           Iron in dialysis and low-flow samples,
                       Hickam AFB, July 2001                                                                                                              Hickam AFB, July 2001

                                                                                                                                                                           4
    in dialysis samples (mg/L)




                                                                                                                                              in dialysis samples (mg/L)
                                 1000                                                                                                                                               Unfiltered LF sample,
                                                                                                                                                                                    Fe(total)
                                                                                                                                                                                                                                        e
                                                                                                                                                 Iron concentrations
                                                                                                                                                                                    Filtered LF sample,                             c
                                                                                                                                                                           3        Fe(II)                                       en
                                                                                                                                                                                                                              nd
                                                                                                                                                                                                                         po
                                  100
                                                                                       nc
                                                                                          e
                                                                                                                                                                                                                  rr   es
                                                                                   e                                                                                                                         Co
                                                                                nd
               SO4




                                                                                                                                                                           2
                                                                         sp
                                                                            o                                                                                                                          1:1
                                                                     rre
                                                                  Co
                                   10                         1:1
                                                                                                                                                                           1


                                      1                                                                                                                                    0
                                          1            10                100                       1000                                                                        0               1                       2                         3                 4
                                                              SO4                                                                                                                                 Iron concentrations
                                                  in low-flow samples (mg/L)                                                                                                                  in low-flow samples (mg/L)


                                                      U.S. Geological Survey                                   33                                                                                  U.S. Geological Survey                                              34




                         Benzene in dialysis, PDB, and low-flow                                                                               BTEX in dialysis, PDB, and low-flow samples,
                           samples, Hickam AFB, July 2001                                                                                        Well 01MW12, Hickam AFB, July 2001

                                                                                                                                              12                                         12                        12                                 12
                                                                                                                                                           A.                                  B.                           C.                             D.
                                                     Well
                         16                                                                                                                   14                                         14                        14                                 14
                                                   01MW02A
     Depth BTOC (feet)




                                                                                                                                              16                                         16                        16                                 16
                                                                                                                            Depth (ft BTOC)




                         18
                                                                                                                                              18                                         18                        18                                 18


                                                                                                                                              20                                         20                        20                                 20
                         20

                                                               PDB sample                                                                     22                                         22                        22                                 22

                         22                                    Dialysis sample
                                                                                                                                              24                                 24                24              24
                                                               Low-flow sample                                                                       0               400 800 1200 0 200 400 600 800 0 400 800 1200 0    400 800
                                                                                                                                                                     Benzene,        Toluene          Ethylbenzene    m,p-Xylene
                                                                                                                                                                      (µg/L)          (µg/L)             (µg/L)         (µg/L)
                         24                                                                                                                                                                     Dialysis sample
                                  0           5      10      15       20                      25          30                                                                                    Passive diffusion bag sample
                                                     Micrograms per liter                                                                                                                       Low-flow sample

                                                      U.S. Geological Survey                                   35                                                                                  U.S. Geological Survey                                              36




                                                                                                                                                                                                                                                                            6
Additional Approaches for Diffusion Sampling                                                                                                                                                                 January 2003

                   Dialysis membrane with                                                            Comparison of Regenerated Cellulose Dialysis and PDB
                   coating after two weeks                                                             for TCE analysis, Andersen AFB, Guam (April 2002)
                                                                                                                           555                                445                                 490




                                                                                                     Depth, in feet BTOC
                                                                                                                           560
                                                                                                                                                              450                                 495

                                                                                                                           565
                                                                                                                                                              455                                 500
                                                                                                                           570

                                                                                                                                                              460                                 505
                                                                                                                           575

                                                                                                                                              IRP-3                                   IRP-31                          IRP-51
                                                                                                                           580                                465                                 510
                                                                                                                                 40     60    80      100           0        100    200     300         5   10   15   20       25
                                                                                                                                      TCE (mg/L)                            TCE (mg/L)                      TCE (mg/L)
                                                                                                                                                                        EXPLANATION
                                                                                                                                                               RG             PDB           Low flow
                                                                                                                              22-23 days                    DIALYSIS
                                                                                                                                                                  Lab               Lab
                                                                                                                             equilibration.                                                       Lab
                                                                                                                                                                    Field           Field



                                        U.S. Geological Survey                                  37                                                              U.S. Geological Survey                                              38




                 Dry regenerated cellulose                                                                                           Pretreated regenerated
                   dialysis membranes                                                                                             cellulose dialysis membrane
     Available as dry rolls: cheaper (About $110-180 for a 30-m roll)                                                        About $178 for a 10-M roll
       but requires cleaning
           May contain glycerol, sulfide, and metals                                                                         Pretreated to remove metals and glycerol.
       Cleaning steps                                                                                                        Cleaning requirements
           Soak in DI water for 15 minutes                                                                                        Rinse with distilled water
           Heat (80 oC) precut membrane for 30 min while stirring in
           large container of sodium bicarbonate
           Soak in Na2 EDTA solution for 30 minutes
           Soak and stir in DI water for 30 min at 80 oC
           Store cooled membrane in refrigerator in a solution of
           sodium azide, sodium benzoate, or ethanol
           Before use, wash thoroughly with distilled water and
           dialysis buffer.



                                        U.S. Geological Survey                                  39                                                              U.S. Geological Survey                                              40




                Semipermeable Membrane
                                                                                                                                                               SUMMARY
                   Devices (SPMDs)
                                                                           Historically used                                 PVD samplers are simple, rapid tools for mapping
                                                                           as a surrogate for                                VOC-discharge zones.
                                                                               determining                                   Diffusion samplers can be used for H2, organic, and
   Triolein (lipid) in                                                     bioconcentration                                  inorganic solutes.
   sleeve of LDPE                                                               of organic                                   Types of diffusion samplers include polyethylene,
                                                                            contaminants in
                                                                                                                             nylon screens, dialysis membranes.
                                                                              fish tissue in
                                                                             surface water.                                  Dialysis membranes typically require pre-use
                                                                                                                             preparation and not allowing them to dry before use.
                                                                                Not yet
                                                                              extensively                                    Care must be taken when sampling for iron and
                                                                               tested in                                     other solutes that rapidly react with oxygen because
                                                                             groundwater                                     of the potential for precipitation.
                                                                             applications.
                         contact Dr. Jim Huckins: James Huckins@usgs.gov
                              or Dr. Jim Petty: Jim Petty@usgs.gov

                                        U.S. Geological Survey                                  41                                                              U.S. Geological Survey                                              42




                                                                                                                                                                                                                                         7
Additional Approaches for Diffusion Sampling   January 2003




           Thank You!


                 U.S. Geological Survey   43




                                                         8

								
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