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==PFAS Sources==
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==Sediment Porewater Dialysis Passive Samplers for Inorganics (Peepers)==  
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[[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]] have been used in coatings for textiles, paper products, and cookware; in some firefighting foams; and have a range of applications in the aerospace, photographic imaging, semiconductor, automotive, construction, electronics, and aviation industries<ref name="ITRC2020">Interstate Technology and Regulatory Council (ITRC), 2020. Technical/Regulatory Guidance: Per- and Polyfluoroalkyl Substances (PFAS), PFAS-1. ITRC, PFAS Team, Washington DC. Website:  https://pfas-1.itrcweb.org/ &nbsp;&nbsp; [https://pfas-1.itrcweb.org/wp-content/uploads/2020/04/ITRC_PFAS_TechReg_April2020.pdf  Free Download from ITRC].&nbsp;&nbsp; [[Media: ITRC_PFAS-1.pdf | Report.pdf]]</ref><ref name="KEMI2015">Swedish Chemicals Agency (KEMI), 2015. Occurrence and use of highly fluorinated substances and alternatives, Report 7/15. ISSN 0284-1185. Article number 361 164.  [[Media: KEMI2015.pdf | Report.pdf]]</ref><ref name="USEPA2021">US Environmental Protection Agency (USEPA), 2021. Basic Information on PFAS.  [https://www.epa.gov/pfas/basic-information-pfas#tab-1 Website]</ref>. Although PFAS and PFAS-containing products have been manufactured since the 1950s, PFAS were not widely documented in environmental samples until the early 2000s. Understanding PFAS manufacturing history, past and current uses, and waste management over the last six to seven decades is necessary for the identification of potential environmental sources of PFAS, possible release mechanisms, and associated pathway-receptor relationships.
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Sediment porewater dialysis passive samplers, also known as “peepers,” are sampling devices that allow the measurement of dissolved inorganic ions in the porewater of a saturated sediment. Peepers function by allowing freely-dissolved ions in sediment porewater to diffuse across a micro-porous membrane towards water contained in an isolated compartment that has been inserted into sediment. Once retrieved after a deployment period, the resulting sample obtained can provide concentrations of freely-dissolved inorganic constituents in sediment, which provides measurements that can be used for understanding contaminant fate and risk. Peepers can also be used in the same manner in surface water, although this article is focused on the use of peepers in sediment.  
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<div style="float:right;margin:0 0 2em 2em;">__TOC__</div>
 
<div style="float:right;margin:0 0 2em 2em;">__TOC__</div>
  
 
'''Related Article(s):'''
 
'''Related Article(s):'''
  
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* [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]]
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*[[Contaminated Sediments - Introduction]]
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* [[PFAS Transport and Fate]]
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*[[Contaminated Sediment Risk Assessment]]
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*[[In Situ Treatment of Contaminated Sediments with Activated Carbon]]
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*[[Passive Sampling of Munitions Constituents]]
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*[[Sediment Capping]]
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*[[Mercury in Sediments]]
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*[[Passive Sampling of Sediments]]
  
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'''Contributor(s):''' [[Dr. Sheau-Yun (Dora) Chiang]] and [[Dr. Alexandra Salter-Blanc]]
 
  
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'''Key Resource(s):'''
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'''Contributor(s):'''  
  
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*[https://pfas-1.itrcweb.org/wp-content/uploads/2020/04/ITRC_PFAS_TechReg_April2020.pdf  Per- and Polyfluoroalkyl Substances (PFAS), PFAS-1. ITRC 2020.]<ref name="ITRC2020"/>
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*Florent Risacher, M.Sc.
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*Jason Conder, Ph.D.
  
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==Introduction==
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'''Key Resource(s):'''
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[[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]] are a complex family of more than 3,000 manmade fluorinated organic chemicals<ref name="Wang2017">Wang, Z., DeWitt, J.C., Higgins, C.P., and Cousins, I.T., 2017. A Never-Ending Story of Per- and Poly-Fluoroalkyl Substances (PFASs)? Environmental Science and Technology, 51(5), pp. 2508-2518.  [https://doi.org/10.1021/acs.est.6b04806 DOI: 10.1021/acs.est.6b04806]&nbsp;&nbsp; [[Media: Wang2017.pdf | Open access article.]]</ref> although not all of these are currently in use or production. PFAS are produced using several different processes. Fluorosurfactants, which include perfluoroalkyl acids (PFAAs) (see [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | PFAS]] article for nomenclature) and side-chain fluorinated polymers, have been manufactured using two major processes: [[Wikipedia: Electrochemical fluorination | electrochemical fluorination (ECF)]] and [[Wikipedia: Telomerization | telomerization]]<ref name="KEMI2015"/>. ECF was licensed by 3M in the 1940s<ref name="Banks1994">Banks, R.E., Smart, B.E. and Tatlow, J.C. eds., 1994. Organofluorine Chemistry: Principles and Commercial Applications. Springer Science and Business Media, New York, N. Y. [https://link.springer.com/book/10.1007/978-1-4899-1202-2 DOI: 10.1007/978-1-4899-1202-2]</ref> and used by 3M until 2001. ECF produces a mixture of even and odd numbered carbon chain lengths of approximately 70% linear and 30% branched substances<ref name="Concawe2016">Concawe (Conservation of Clean Air and Water in Europe), 2016.  Environmental fate and effects of poly- and perfluoroalkyl substances (PFAS).  Report No. 8/16. Brussels, Belgium. [[Media:Concawe2016.pdf | Report.pdf]]</ref>. Telomerization was developed in the 1970s<ref name="Benskin2012a">Benskin, J.P., Ahrens, L., Muir, D.C., Scott, B.F., Spencer, C., Rosenberg, B., Tomy, G., Kylin, H., Lohmann, R. and Martin, J.W., 2012. Manufacturing Origin of Perfluorooctanoate (PFOA) in Atlantic and Canadian Arctic Seawater. Environmental Science and Technology, 46(2), pp. 677-685.  [https://doi.org/10.1021/es202958p DOI: 10.1021/es202958p]</ref>, and yields mainly even numbered, straight carbon chain isomers<ref name="Kissa2001">Kissa, E., 2001. Fluorinated Surfactants and Repellents, Second Edition. Surfactant Science Series, Vol. 97. Marcel Dekker, Inc., CRC Press, New York. 640 pages. ISBN: 9780824704728</ref><ref name="Parsons2008">Parsons, J.R., Sáez, M., Dolfing, J. and De Voogt, P., 2008. Biodegradation of Perfluorinated Compounds. Reviews of Environmental Contamination and Toxicology, 196, pp. 53-71. Springer, New York, NY.  [https://doi.org/10.1007/978-0-387-78444-1_2 DOI: 10.1007/978-0-387-78444-1_2]&nbsp;&nbsp; Free download from: [https://www.researchgate.net/profile/Jan_Dolfing/publication/23489065_Biodegradation_of_Perfluorinated_Compounds/links/0912f5087a40c9d5df000000.pdf ResearchGate]</ref>.  PFAS manufacturers have provided PFAS to secondary manufacturers for production of a vast array of industrial and consumer products.
 
  
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During manufacturing, PFAS may be released into the atmosphere then redeposited on land where they can also affect surface water and groundwater, or PFAS may be discharged without treatment to wastewater treatment plants or landfills, and eventually be released into the environment by treatment systems that are not designed to mitigate PFAS (see also [[PFAS Transport and Fate]]). Industrial discharges of PFAS were unregulated for many years, but that has begun to change. In January 2016, New York became the first state in the nation to regulate PFOA as a hazardous substance followed by the regulation of PFOS in April 2016. Consumer and industrial uses of PFAS-containing products can also end up releasing PFAS into landfills and into municipal wastewater, where it may accumulate undetected in biosolids which are typically treated by land application.  
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*A review of peeper passive sampling approaches to measure the availability of inorganics in sediment porewater<ref>Risacher, F.F., Schneider, H., Drygiannaki, I., Conder, J., Pautler, B.G., and Jackson, A.W., 2023. A Review of Peeper Passive Sampling Approaches to Measure the Availability of Inorganics in Sediment Porewater. Environmental Pollution, 328, Article 121581. [https://doi.org/10.1016/j.envpol.2023.121581 doi: 10.1016/j.envpol.2023.121581]&nbsp;&nbsp;[[Media: RisacherEtAl2023a.pdf | Open Access Manuscript]]</ref>
  
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==Industrial Sources==
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*Best Practices User’s Guide: Standardizing Sediment Porewater Passive Samplers for Inorganic Constituents of Concern<ref name="RisacherEtAl2023">Risacher, F.F., Nichols, E., Schneider, H., Lawrence, M., Conder, J., Sweett, A., Pautler, B.G., Jackson, W.A., Rosen, G., 2023b. Best Practices User’s Guide: Standardizing Sediment Porewater Passive Samplers for Inorganic Constituents of Concern, ESTCP ER20-5261. [https://serdp-estcp.mil/projects/details/db871313-fbc0-4432-b536-40c64af3627f Project Website]&nbsp;&nbsp;[[Media: ER20-5261BPUG.pdf | Report.pdf]]</ref>
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PFAS are used in many industrial and consumer applications, which may have released PFAS into the environment and impacted drinking water supplies in many areas of the United States<ref name="EWG2017">Environmental Working Group (EWG) and Northeastern University Social Science Environmental Health Research Institute, 2017. Mapping A Contamination Crisis. [https://www.ewg.org/research/mapping-contamination-crisis Website]</ref>. Both in the United States (US) and abroad, primary manufacturing facilities produce PFAS and secondary manufacturing facilities use PFAS to produce goods. Environmental release mechanisms associated with these facilities include air emission and dispersion, spills, and disposal of manufacturing wastes and wastewater. Potential impacts to air, soil, sediment, surface water, stormwater, and groundwater are present not only at primary release points but potentially over the surrounding area<ref name="Shin2011">Shin, H.M., Vieira, V.M., Ryan, P.B., Detwiler, R., Sanders, B., Steenland, K., and Bartell, S.M., 2011. Environmental Fate and Transport Modeling for Perfluorooctanoic Acid Emitted from the Washington Works Facility in West Virginia. Environmental Science and Technology, 45(4), pp. 1435-1442. [https://doi.org/10.1021/es102769t DOI: 10.1021/es102769t]</ref>. Some of the potential primary and secondary sources of PFAS releases to the environment are listed here<ref name="ITRC2020"/>:
 
  
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* '''Textiles and leather:''' Factory or consumer applied coating to repel water, oil, and stains. Applications include protective clothing and outerwear, umbrellas, tents, sails, architectural materials, carpets, and upholstery
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*[https://serdp-estcp.mil/projects/details/db871313-fbc0-4432-b536-40c64af3627f/er20-5261-project-overview Standardizing Sediment Porewater Passive Samplers for Inorganic Constituents of Concern, ESTCP Project ER20-5261]
  
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==Introduction==
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Biologically available inorganic constituents associated with sediment toxicity can be quantified by measuring the freely-dissolved fraction of contaminants in the porewater<ref>Conder, J.M., Fuchsman, P.C., Grover, M.M., Magar, V.S., Henning, M.H., 2015. Critical review of mercury SQVs for the protection of benthic invertebrates. Environmental Toxicology and Chemistry, 34(1), pp. 6-21. [https://doi.org/10.1002/etc.2769 doi: 10.1002/etc.2769]&nbsp;&nbsp; [[Media: ConderEtAl2015.pdf | Open Access Article]]</ref><ref name="ClevelandEtAl2017">Cleveland, D., Brumbaugh, W.G., MacDonald, D.D., 2017. A comparison of four porewater sampling methods for metal mixtures and dissolved organic carbon and the implications for sediment toxicity evaluations. Environmental Toxicology and Chemistry, 36(11), pp. 2906-2915. [https://doi.org/10.1002/etc.3884 doi: 10.1002/etc.3884]</ref>. Classical sediment porewater analysis usually consists of collecting large volumes of bulk sediments which are then mechanically squeezed or centrifuged to produce a supernatant, or suction of porewater from intact sediment, followed by filtration and collection<ref name="GruzalskiEtAl2016">Gruzalski, J.G., Markwiese, J.T., Carriker, N.E., Rogers, W.J., Vitale, R.J.,  Thal, D.I., 2016. Pore Water Collection, Analysis and Evolution: The Need for Standardization. In: Reviews of Environmental Contamination and Toxicology, Vol. 237, pp. 37–51. Springer. [https://doi.org/10.1007/978-3-319-23573-8_2 doi: 10.1007/978-3-319-23573-8_2]</ref>. The extraction and measurement processes present challenges due to the heterogeneity of sediments, physical disturbance, high reactivity of some complexes, and interaction between the solid and dissolved phases, which can impact the measured concentration of dissolved inorganics<ref>Peijnenburg, W.J.G.M., Teasdale, P.R., Reible, D., Mondon, J., Bennett, W.W., Campbell, P.G.C., 2014. Passive Sampling Methods for Contaminated Sediments: State of the Science for Metals. Integrated Environmental Assessment and Management, 10(2), pp. 179–196. [https://doi.org/10.1002/ieam.1502 doi: 10.1002/ieam.1502]&nbsp;&nbsp; [[Media: PeijnenburgEtAl2014.pdf | Open Access Article]]</ref>. For example, sampling disturbance can affect redox conditions<ref name="TeasdaleEtAl1995">Teasdale, P.R., Batley, G.E., Apte, S.C., Webster, I.T., 1995. Pore water sampling with sediment peepers. Trends in Analytical Chemistry, 14(6), pp. 250–256. [https://doi.org/10.1016/0165-9936(95)91617-2 doi: 10.1016/0165-9936(95)91617-2]</ref><ref>Schroeder, H., Duester, L., Fabricius, A.L., Ecker, D., Breitung, V., Ternes, T.A., 2020. Sediment water (interface) mobility of metal(loid)s and nutrients under undisturbed conditions and during resuspension. Journal of Hazardous Materials, 394, Article 122543. [https://doi.org/10.1016/j.jhazmat.2020.122543 doi: 10.1016/j.jhazmat.2020.122543]&nbsp;&nbsp; [[Media: SchroederEtAl2020.pdf | Open Access Article]]</ref>, which can lead to under or over representation of inorganic chemical concentrations relative to the true dissolved phase concentration in the sediment porewater<ref>Wise, D.E., 2009. Sampling techniques for sediment pore water in evaluation of reactive capping efficacy. Master of Science Thesis. University of New Hampshire Scholars’ Repository. 178 pages. [https://scholars.unh.edu/thesis/502 Website]&nbsp;&nbsp; [[Media: Wise2009.pdf | Report.pdf]]</ref><ref name="GruzalskiEtAl2016"/>.
  
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To address the complications with mechanical porewater sampling, passive sampling approaches for inorganics have been developed to provide a method that has a low impact on the surrounding geochemistry of sediments and sediment porewater, thus enabling more precise measurements of inorganics<ref name="ClevelandEtAl2017"/>. Sediment porewater dialysis passive samplers, also known as “peepers,” were developed more than 45 years ago<ref name="Hesslein1976">Hesslein, R.H., 1976. An in situ sampler for close interval pore water studies. Limnology and Oceanography, 21(6), pp. 912-914. [https://doi.org/10.4319/lo.1976.21.6.0912 doi: 10.4319/lo.1976.21.6.0912]&nbsp;&nbsp; [[Media: Hesslein1976.pdf | Open Access Article]]</ref> and refinements to the method such as the use of reverse tracers have been made, improving the acceptance of the technology as decision making tool.
  
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==Peeper Designs==
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[[File:RisacherFig1.png|thumb|300px|Figure 1. Conceptual illustration of peeper construction showing (top, left to right) the peeper cap (optional), peeper membrane and peeper chamber, and (bottom) an assembled peeper containing peeper water]]
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[[File:RisacherFig2.png | thumb |400px| Figure 2. Example of Hesslein<ref name="Hesslein1976"/> general peeper design (42 peeper chambers), from [https://www.usgs.gov/media/images/peeper-samplers USGS]]]
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[[File:RisacherFig3.png | thumb |400px| Figure 3. Peeper deployment structure to allow the measurement of metal availability in different sediment layers using five single-chamber peepers (Photo: Geosyntec Consultants)]]
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Peepers (Figure 1) are inert containers with a small volume (typically 1-100 mL) of purified water (“peeper water”) capped with a semi-permeable membrane. Peepers can be manufactured in a wide variety of formats (Figure 2, Figure 3) and deployed in in various ways.
  
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Two designs are commonly used for peepers. Frequently, the designs are close adaptations of the original multi-chamber Hesslein design<ref name="Hesslein1976"/> (Figure 2), which consists of an acrylic sampler body with multiple sample chambers machined into it. Peeper water inside the chambers is separated from the outside environment by a semi-permeable membrane, which is held in place by a top plate fixed to the sampler body using bolts or screws. An alternative design consists of single-chamber peepers constructed using a single sample vial with a membrane secured over the mouth of the vial, as shown in Figure 3, and applied in Teasdale ''et al.''<ref name="TeasdaleEtAl1995"/>, Serbst ''et al.''<ref>Serbst, J.R., Burgess, R.M., Kuhn, A., Edwards, P.A., Cantwell, M.G., Pelletier, M.C.,  Berry, W.J., 2003. Precision of dialysis (peeper) sampling of cadmium in marine sediment interstitial water. Archives of Environmental Contamination and Toxicology, 45(3), pp. 297–305. [https://doi.org/10.1007/s00244-003-0114-5 doi: 10.1007/s00244-003-0114-5]</ref>, Thomas and Arthur<ref name="ThomasArthur2010">Thomas, B., Arthur, M.A., 2010. Correcting porewater concentration measurements from peepers: Application of a reverse tracer. Limnology and Oceanography: Methods, 8(8), pp. 403–413. [https://doi.org/10.4319/lom.2010.8.403 doi: 10.4319/lom.2010.8.403]&nbsp;&nbsp; [[Media: ThomasArthur2010.pdf | Open Access Article]]</ref>, Passeport ''et al.''<ref>Passeport, E., Landis, R., Lacrampe-Couloume, G., Lutz, E.J., Erin Mack, E., West, K., Morgan, S., Lollar, B.S., 2016. Sediment Monitored Natural Recovery Evidenced by Compound Specific Isotope Analysis and High-Resolution Pore Water Sampling. Environmental Science and Technology, 50(22), pp. 12197–12204. [https://doi.org/10.1021/acs.est.6b02961 doi: 10.1021/acs.est.6b02961]</ref>, and Risacher ''et al.''<ref name="RisacherEtAl2023"/>. The vial is filled with deionized water, and the membrane is held in place using the vial cap or an o-ring. Individual vials are either directly inserted into sediment or are incorporated into a support structure to allow multiple single-chamber peepers to be deployed at once over a given depth profile (Figure 3).
  
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==Peepers Preparation, Deployment and Retrieval==
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[[File:RisacherFig4.png | thumb |300px| Figure 4: Conceptual illustration of peeper passive sampling in a sediment matrix, showing peeper immediately after deployment (top) and after equilibration between the porewater and peeper chamber water (bottom)]]
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Peepers are often prepared in laboratories but are also commercially available in a variety of designs from several suppliers. Peepers are prepared by first cleaning all materials to remove even trace levels of metals before assembly. The water contained inside the peeper is sometimes deoxygenated, and in some cases the peeper is maintained in a deoxygenated atmosphere until deployment<ref>Carignan, R., St‐Pierre, S., Gachter, R., 1994. Use of diffusion samplers in oligotrophic lake sediments: Effects of free oxygen in sampler material. Limnology and Oceanography, 39(2), pp. 468-474. [https://doi.org/10.4319/lo.1994.39.2.0468 doi: 10.4319/lo.1994.39.2.0468]&nbsp;&nbsp; [[Media: CarignanEtAl1994.pdf | Open Access Article]]</ref>. However, recent studies<ref name="RisacherEtAl2023"/> have shown that deoxygenation prior to deployment does not significantly impact sampling results due to oxygen rapidly diffusing out of the peeper during deployment. Once assembled, peepers are usually shipped in a protective bag inside a hard-case cooler for protection.
  
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Peepers are deployed by insertion into sediment for a period of a few days to a few weeks. Insertion into the sediment can be achieved by wading to the location when the water depth is shallow, by using push poles for deeper deployments<ref name="RisacherEtAl2023"/>, or by professional divers for the deepest sites.  If divers are used, an appropriate boat or ship will be required to accommodate the diver and their equipment. Whichever method is used, peepers should be attached to an anchor or a small buoy to facilitate retrieval at the end of the deployment period.
  
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During deployment, passive sampling is achieved via diffusion of inorganics through the peeper’s semi-permeable membrane, as the enclosed volume of peeper water equilibrates with the surrounding sediment porewater (Figure 4). It is assumed that the peeper insertion does not greatly alter geochemical conditions that affect freely-dissolved inorganics. Additionally, it is assumed that the peeper water equilibrates with freely-dissolved inorganics in sediment in such a way that the concentration of inorganics in the peeper water would be equal to that of the concentration of inorganics in the sediment porewater.
  
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After retrieval, the peepers are brought to the surface and usually preserved until they can be processed. This can be achieved by storing the peepers inside a sealable, airtight bag with either inert gas or oxygen absorbing packets<ref name="RisacherEtAl2023"/>. The peeper water can then be processed by quickly pipetting it into an appropriate sample bottle which usually contains a preservative (e.g., nitric acid for metals). This step is generally conducted in the field. Samples are stored on ice to maintain a temperature of less than 4°C and shipped to an analytical laboratory. The samples are then analyzed for inorganics by standard methods (i.e., USEPA SW-846). The results obtained from the analytical laboratory are then used directly or assessed using the equations below if a reverse tracer is used because deployment time is insufficient for all analytes to reach equilibrium.
  
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==Equilibrium Determination (Tracers)==
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[[File:NewellMatrixDiffFig1.PNG | thumb |500px| Figure 1.  Diffusion of a dissolved solute (chlorinated solvent) into lower ''K'' zones during loading period, followed by diffusion back out into higher ''K'' zones once the source is removed <ref name="Sale2007">Sale, T.C., Illangasekare, T.H., Zimbron, J., Rodriguez, D., Wilking, B., and Marinelli, F., 2007. AFCEE Source Zone Initiative. Air Force Center for Environmental Excellence, Brooks City-Base, San Antonio, TX. [https://www.enviro.wiki/images/0/08/AFCEE-2007-Sale.pdf Report.pdf]</ref>]]
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The equilibration period of peepers can last several weeks and depends on deployment conditions, analyte of interest, and peeper design. In many cases, it is advantageous to use pre-equilibrium methods that can use measurements in peepers deployed for shorter periods to predict concentrations at equilibrium<ref name="USEPA2017">USEPA, 2017. Laboratory, Field, and Analytical Procedures for Using Passive Sampling in the Evaluation of Contaminated Sediments: User’s Manual. EPA/600/R-16/357.&nbsp;&nbsp; [[Media: EPA_600_R-16_357.pdf | Report.pdf]]</ref>.  
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Matrix Diffusion can have major impacts on solute migration in groundwater and on cleanup time following source removal.  As a groundwater plume advances downgradient, dissolved contaminants are transported by [[Wikipedia: Molecular diffusion | molecular diffusion]] from zones with larger hydraulic conductivity (''K'') into lower ''K'' zones, slowing the rate of contaminant migration in the high ''K'' zone. However, once the contaminant source is eliminated, contaminants diffuse out of low ''K'' zones, slowing the cleanup rate in the high ''K'' zone (Figure 1).  This process, termed ‘back diffusion’, can greatly extend cleanup times.
 
  
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The impacts of back diffusion on aquifer cleanup have been examined in controlled laboratory experiments by several investigators<ref name="Doner2008">Doner, L.A., 2008. Tools to resolve water quality benefits of upgradient contaminant flux reduction. Master’s Thesis, Department of Civil and Environmental Engineering, Colorado State University.</ref><ref name="Yang2015">Yang, M., Annable, M.D. and Jawitz, J.W., 2015. Back Diffusion from Thin Low Permeability Zones. Environmental Science and Technology, 49(1), pp. 415-422.  [https://doi.org/10.1021/es5045634 DOI: 10.1021/es5045634] Free download available from: [https://www.researchgate.net/publication/269189924_Back_Diffusion_from_Thin_Low_Permeability_Zones ResearchGate]</ref><ref name= "Yang2016">Yang, M., Annable, M.D. and Jawitz, J.W., 2016. Solute source depletion control of forward and back diffusion through low-permeability zones. Journal of Contaminant Hydrology, 193, pp. 54-62. [https://doi.org/10.1016/j.jconhyd.2016.09.004 DOI: 10.1016/j.jconhyd.2016.09.004] Free download available from: [https://www.researchgate.net/profile/Minjune_Yang/publication/308004091_Solute_source_depletion_control_of_forward_and_back_diffusion_through_low-permeability_zones/links/5a2ed2c44585155b6179f489/Solute-source-depletion-control-of-forward-and-back-diffusion-through-low-permeability-zones.pdf ResearchGate]</ref><ref name="Tatti2018">Tatti, F., Papini, M.P., Sappa, G., Raboni, M., Arjmand, F., and Viotti, P., 2018. Contaminant back-diffusion from low-permeability layers as affected by groundwater velocity: A laboratory investigation by box model and image analysis. Science of The Total Environment, 622, pp. 164-171. [https://doi.org/10.1016/j.scitotenv.2017.11.347 DOI: 10.1016/j.scitotenv.2017.11.347]</ref>.  The video in Figure 2 shows the results of a 122-day tracer test in a laboratory flow cell (sand tank)<ref name="Doner2008"/>.  The flow cell contained several clay zones (''K'' = 10<sup>-8</sup> cm/s) surrounded by sand (''K'' = 0.02 cm/s).  During the loading period, water containing a green fluorescent tracer migrated from left to right with the water flowing through the flow cell, while also diffusing into the clay.  After 22 days, the fluorescent tracer is eliminated from the feed, and most of the green tracer is quickly flushed from the tank’s sandy zones.  However, small amounts of tracer continue to diffuse out of the clay layers for over 100 days.  This illustrates how back diffusion of contaminants out of low ''K'' zones can maintain low contaminant concentrations long after the contaminant source as been eliminated.
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Although the equilibrium concentration of an analyte in sediment can be evaluated by examining analyte results for peepers deployed for several different amounts of time (i.e., a time series), this is impractical for typical field investigations because it would require several mobilizations to the site to retrieve samplers. Alternately, reverse tracers (referred to as a performance reference compound when used with organic compound passive sampling) can be used to evaluate the percentage of equilibrium reached by a passive sampler.
  
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[[File: GreenTank.mp4 | thumb |500px| Figure 2. Video of dye tank simulation of matrix diffusion]]
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Thomas and Arthur<ref name="ThomasArthur2010"/> studied the use of a reverse tracer to estimate percent equilibrium in lab experiments and a field application. They concluded that bromide can be used to estimate concentrations in porewater using measurements obtained before equilibrium is reached. Further studies were also conducted by Risacher ''et al.''<ref name="RisacherEtAl2023"/> showed that lithium can also be used as a tracer for brackish and saline environments. Both studies included a mathematical model for estimating concentrations of ions in external media (''C<small><sub>0</sub></small>'') based on measured concentrations in the peeper chamber (''C<small><sub>p,t</sub></small>''), the elimination rate of the target analyte (''K'') and the deployment time (''t''):
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In some cases, matrix diffusion can maintain contaminant concentrations in more permeable zones above target cleanup goals for decades or potentially even centuries after the primary sources have been addressed. At a site impacted by [[Wikipedia: Dense non-aqueous phase liquid | Dense Non-Aqueous Phase Liquids (DNAPL)]], [[Chlorinated Solvents | trichloroethene (TCE)]] concentrations in downgradient wells declined by roughly an order-of-magnitude (OoM) when the upgradient source area was isolated with sheet piling. However, after this initial decline, TCE concentrations appeared to plateau or decline more slowly, consistent with back diffusion from an underlying aquitard.  Numerical simulations indicated that back diffusion would cause TCE concentrations in downgradient wells at the site to remain above target cleanup levels for centuries<ref name="Chapman2005"/>.
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</br>
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{|
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| || '''Equation&nbsp;1:'''
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|&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;[[File: Equation1r.png]]
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|-
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| Where: || ||
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|-
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| || ''C<small><sub>0</sub></small>''|| is the freely dissolved concentration of the analyte in the sediment (mg/L or &mu;g/L), sometimes referred to as ''C<small><sub>free</sub></small>
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|-
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| || ''C<small><sub>p,t</sub></small>'' || is the measured concentration of the analyte in the peeper at time of retrieval (mg/L or &mu;g/L)
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|-
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| || ''K'' || is the elimination rate of the target analyte
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|-
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| || ''t'' || is the deployment time (days)
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|}
  
−
One other implication of matrix diffusion is that plume migration is attenuated by the loss of contaminants into low permeability zones, leading to slower plume migration compared to a case where no matrix diffusion occurs.  This phenomena was observed as far back as 1985 when Sudicky et al. observed that “A second consequence of the solute-storage effect offered by transverse diffusion into low-permeability layers is a rate of migration of the frontal portion of a contaminant in the permeable layers that is less than the groundwater velocity.”<ref name="Sudicky1985"> Sudicky, E.A., Gillham, R.W., and Frind, E.O., 1985. Experimental Investigation of Solute Transport in Stratified Porous Media: 1. The Nonreactive Case. Water Resources Research, 21(7), pp. 1035-1041. [https://doi.org/10.1029/WR021i007p01035 DOI: 10.1029/WR021i007p01035]</ref> In cases where there is an attenuating source, matrix diffusion can also reduce the peak concentrations observed in downgradient monitoring wells.  The attenuation caused by matrix diffusion may be particularly important for implementing [[Monitored Natural Attenuation (MNA)]] for contaminants that do not completely degrade, such as [[Metal and Metalloid Contaminants | heavy metals]] and [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]].
+
The elimination rate of the target analyte (''K'') is calculated using Equation 2:
 +
</br>
 +
{|
 +
| || '''Equation&nbsp;2:'''
 +
|&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;[[File: Equation2r.png]]
 +
|-
 +
| Where: || ||
 +
|-
 +
| || ''K''|| is the elimination rate of the target analyte
 +
|-
 +
| || ''K<small><sub>tracer</sub></small>'' || is the elimination rate of the tracer
 +
|-
 +
| || ''D'' || is the free water diffusivity of the analyte (cm<sup>2</sup>/s)
 +
|-
 +
| || ''D<small><sub>tracer</sub></small>'' || is the free water diffusivity of the tracer (cm<sup>2</sup>/s)
 +
|}
  
−
==SERPD/ESTCP Research==
+
The elimination rate of the tracer (''K<small><sub>tracer</sub></small>'') is calculated using Equation 3:
 +
</br>
 
{|  
 
{|  
−
The SERDP/ESTCP programs have funded several projects focusing on how matrix diffusion can impede progress towards reaching site closure, including:
+
| || '''Equation&nbsp;3:'''
 +
|&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;[[File: Equation3r2.png]]
 
|-
 
|-
−
|
+
| Where: || ||
−
*[https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-1740 SERDP Management of Contaminants Stored in Low Permeability Zones, A State-of-the-Science Review] <ref name="Sale2013"/>
 
 
|-
 
|-
−
|  
+
| || ''K<small><sub>tracer</sub></small>'' || is the elimination rate of the tracer
−
*[https://www.serdp-estcp.org/Tools-and-Training/Environmental-Restoration/Groundwater-Plume-Treatment/Matrix-Diffusion-Tool-Kit ESTCP Matrix Diffusion Toolkit]<ref name="Farhat2012">Farhat, S.K., Newell, C.J., Seyedabbasi, M.A., McDade, J.M., Mahler, N.T., Sale, T.C., Dandy, D.S. and Wahlberg, J.J., 2012. Matrix Diffusion Toolkit. Environmental Security Technology Certification Program (ESTCP) Project ER-201126.  [[Media:Farhat2012ER-201126UsersManual.pdf | User’s Manual.pdf]]  Website: [https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-201126 ER-201126]</ref>
 
 
|-
 
|-
−
|  
+
| || ''C<small><sub>tracer,i</sub></small>''|| is the measured initial concentration of the tracer in the peeper prior to deployment (mg/L or &mu;g/L)
−
*[https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-200530 ESTCP Decision Guide]<ref>Sale, T. and Newell, C., 2011. A Guide for Selecting Remedies for Subsurface Releases of Chlorinated Solvents. Environmental Security Technology Certification Program (ESTCP) Project ER-200530. [[Media: Sale2011ER-200530.pdf | Report.pdf]]  Website: [https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-200530 ER-200530]</ref>
 
 
|-
 
|-
−
|
+
| || ''C<small><sub>tracer,t</sub></small>'' || is the measured final concentration of the tracer in the peeper at time of retrieval (mg/L or &mu;g/L)
−
*[https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-201426 ESTCP REMChlor-MD: the USEPA’s REMChlor model with a new matrix diffusion term for the plume]<ref name="Farhat2018">Farhat, S. K., Newell, C. J., Falta, R. W., and Lynch, K., 2018. A Practical Approach for Modeling Matrix Diffusion Effects in REMChlor. Environmental Security Technology Certification Program (ESTCP) Project ER-201426.  [https://enviro.wiki/images/0/0b/2018-Falta-REMChlor_Modeling_Matrix_Diffusion_Effects.pdf  User’s Manual.pdf]  Website: [https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-201426 ER-201426]</ref>
+
|-
 +
| || ''t'' || is the deployment time (days)
 
|}
 
|}
−
[[File:ADRFig3.png | thumb| left |400px| Figure 3.  Comparison of tracer breakthrough (upper graph) and cleanup curves (lower graph) from advection-dispersion based (gray lines) and advection-diffusion based (black lines) solute transport<ref name="ITRC2011">Interstate Technology and Regulatory Council (ITRC), 2011. Integrated DNAPL Site Strategy (IDSS-1),  Integrated DNAPL Site Strategy Team, ITRC, Washington, DC. [https://www.enviro.wiki/images/d/d9/ITRC-2011-Integrated_DNAPL.pdf Report.pdf]  Free download from: [https://itrcweb.org/GuidanceDocuments/IntegratedDNAPLStrategy_IDSSDoc/IDSS-1.pdf ITRC]</ref>.]]
 
  
−
==Transport Modeling==
+
Using this set of equations allows the calculation of the porewater concentration of the analyte prior to its equilibrium with the peeper water. A template for these calculations can be found in the appendix of Risacher ''et al.''<ref name="RisacherEtAl2023"/>.
−
Several different modeling approaches have been developed to simulate the diffusive transport of dissolved solutes into and out of lower ''K'' zones<ref>Falta, R.W., and Wang, W., 2017. A semi-analytical method for simulating matrix diffusion in numerical transport models. Journal of Contaminant Hydrology, 197, pp. 39-49.  [https://doi.org/10.1016/j.jconhyd.2016.12.007 DOI: 10.1016/j.jconhyd.2016.12.007]</ref><ref>Muskus, N. and Falta, R.W., 2018. Semi-analytical method for matrix diffusion in heterogeneous and fractured systems with parent-daughter reactions. Journal of Contaminant Hydrology, 218, pp. 94-109.  [https://doi.org/10.1016/j.jconhyd.2018.10.002 DOI: 10.1016/j.jconhyd.2018.10.002]</ref>.  The [https://www.serdp-estcp.org/Tools-and-Training/Environmental-Restoration/Groundwater-Plume-Treatment/Matrix-Diffusion-Tool-Kit Matrix Diffusion Toolkit]<ref name="Farhat2012"/> is a Microsoft Excel based tool for simulating forward and back diffusion using two different analytical models<ref name="Parker1994">Parker, B.L., Gillham, R.W., and Cherry, J.A., 1994. Diffusive Disappearance of Immiscible Phase Organic Liquids in Fractured Geologic Media. Groundwater, 32(5), pp. 805-820. [https://doi.org/10.1111/j.1745-6584.1994.tb00922.x DOI: 10.1111/j.1745-6584.1994.tb00922.x]</ref><ref>Sale, T.C., Zimbron, J.A., and Dandy, D.S., 2008. Effects of reduced contaminant loading on downgradient water quality in an idealized two-layer granular porous media. Journal of Contaminant Hydrology, 102(1), pp. 72-85. [https://doi.org/10.1016/j.jconhyd.2008.08.002 DOI: 10.1016/j.jconhyd.2008.08.002]</ref>.  Numerical models including [https://en.wikipedia.org/wiki/MODFLOW MODFLOW]/[https://xmswiki.com/wiki/GMS:MT3DMS MT3DMS]<ref name="Zheng1999">Zheng, C. and Wang, P.P., 1999. MT3DMS: A Modular Three-Dimensional Multispecies Transport Model for Simulation of Advection, Dispersion, and Chemical Reactions of Contaminants in Groundwater Systems; Documentation and User’s Guide. Contract Report SERDP-99-1 U.S. Army Engineer Research and Development Center, Vicksburg, MS. [https://www.enviro.wiki/images/3/32/Mt3dmanual.pdf User’s Guide.pdf]  [https://xmswiki.com/wiki/GMS:MT3DMS MT3DMS website]</ref> have been shown to be effective in simulating back diffusion processes and can accurately predict concentration changes over 3 orders-of-magnitude in heterogeneous sand tank experiments<ref>Chapman, S.W., Parker, B.L., Sale, T.C., Doner, L.A., 2012. Testing high resolution numerical models for analysis of contaminant storage and release from low permeability zones. Journal of Contaminant Hydrology, 136, pp. 106-116. [https://doi.org/10.1016/j.jconhyd.2012.04.006 DOI: 10.1016/j.jconhyd.2012.04.006]</ref>. However, numerical models require a fine vertical discretization with short time steps to accurately simulate back diffusion, greatly increasing computation times<ref>Farhat, S.K., Adamson, D.T., Gavaskar, A.R., Lee, S.A., Falta, R.W. and Newell, C.J., 2020. Vertical Discretization Impact in Numerical Modeling of Matrix Diffusion in Contaminated Groundwater. Groundwater Monitoring and Remediation, 40(2), pp. 52-64. [https://doi.org/10.1111/gwmr.12373 DOI: 10.1111/gwmr.12373]</ref>.  These issues can be addressed by incorporating a local 1-D model domain within a general 3D numerical model<ref>Carey, G.R., Chapman, S.W., Parker, B.L. and McGregor, R., 2015. Application of an Adapted Version of MT3DMS for Modeling Back‐Diffusion Remediation Timeframes. Remediation, 25(4), pp. 55-79. [https://doi.org/10.1002/rem.21440 DOI: 10.1002/rem.21440]</ref>.
 
  
−
The [[REMChlor - MD]] toolkit is capable of simulating matrix diffusion in groundwater contaminant plumes by using a semi-analytical method for estimating mass transfer between high and low permeability zones that provides computationally accurate predictions, with much shorter run times than traditional fine grid numerical models<ref name="Farhat2018"/>.
+
==Using Peeper Data at a Sediment Site==
 +
Peeper data can be used to enable site specific decision making in a variety of ways. Some of the most common uses for peepers and peeper data are discussed below.
  
−
==Impacts on Breakthrough Curves==
+
'''Nature and Extent:''' Multiple peepers deployed in sediment can help delineate areas of increased metal availability. Peepers are especially helpful for sites that are comprised of coarse, relatively inert materials that may not be conducive to traditional bulk sediment sampling. Because much of the inorganics present in these types of sediments may be associated with the porewater phase rather than the solid phase, peepers can provide a more representative measurement of C<small><sub>0</sub></small>. Additionally, at sites where tidal pumping or groundwater flux may be influencing the nature and extent of inorganics, peepers can provide a distinct advantage to bulk sediment sampling or other point-in-time measurements, as peepers can provide an average measurement that integrates the variability in the hydrodynamic and chemical conditions over time.
  
−
The impacts of matrix diffusion on the initial breakthrough of the solute plume and on later cleanup are illustrated in Figure 3<ref name="ITRC2011"/>. Using a traditional advection-dispersion model, the breakthrough curve for a pulse tracer injection appears as a bell-shaped ([[wikipedia:Gaussian function |Gaussian]]) curve (gray line on the right side of the upper graph) where the peak arrival time corresponds to the average groundwater velocity. Using an advection-diffusion approach, the breakthrough curve for a pulse injection is asymmetric (solid black line) with the peak tracer concentration arriving earlier than would be expected based on the average groundwater velocity, but with a long extended tail to the flushout curve.
+
'''Sources and Fate:''' A considerable advantage to using peepers is that C<small><sub>0</sub></small> results are expressed as concentration in units of mass per volume (e.g., mg/L), providing a common unit of measurement to compare across multiple media. For example, synchronous measurements of C<small><sub>0</sub></small> using peepers deployed in both surface water and sediment can elucidate the potential flux of inorganics from sediment to surface water. Paired measurements of both C<small><sub>0</sub></small> and bulk metals in sediment can also allow site specific sediment-porewater partition coefficients to be calculated. These values can be useful in understanding and predicting contaminant fate, especially in situations where the potential dissolution of metals from sediment are critical to predict, such as when sediment is dredged.
  
−
The lower graph shows the predicted cleanup concentration profiles following complete elimination of a source area.  The advection-dispersion model (gray line) predicts a clean-water front arriving at a time corresponding to the average groundwater velocity.  The advection-diffusion model (black line) predicts that concentrations will start to decline more rapidly than expected (based on the average groundwater velocity) as clean water rapidly migrates through the highest-permeability strata. However, low but significant contaminant concentrations linger much longer (tailing) due to diffusive contaminant mass exchange between zones of high and low permeability. A similar response to source remediation is seen in models such as the sand tank experiment shown in Figure 2, and also in field observations of plume contaminant concentrations in heterogeneous aquifers.
+
'''Direct Toxicity to Aquatic Life:''' Peepers are frequently used to understand the potential direct toxicity to aquatic life, such as benthic invertebrates and fish. A C<small><sub>0</sub></small> measurement obtained from a peeper deployed in sediment (''in situ'') or surface water (''ex situ''), can be compared to toxicological benchmarks for aquatic life to understand the potential toxicity to aquatic life and to set remediation goals<ref name="USEPA2017"/>. C<small><sub>0</sub></small> measurements can also be incorporated in more sophisticated approaches, such as the Biotic Ligand Model<ref>Santore, C.R., Toll, E.J., DeForest, K.D., Croteau, K., Baldwin, A., Bergquist, B., McPeek, K., Tobiason, K., and Judd, L.N., 2022. Refining our understanding of metal bioavailability in sediments using information from porewater: Application of a multi-metal BLM as an extension of the Equilibrium Partitioning Sediment Benchmarks. Integrated Environmental Assessment and Management, 18(5), pp. 1335–1347. [https://doi.org/10.1002/ieam.4572 doi: 10.1002/ieam.4572]</ref> to understand the potential for toxicity or the need to conduct toxicological testing or ecological evaluations.
  
−
<br clear="left" />
+
'''Bioaccumulation of Inorganics by Aquatic Life:''' Peepers can also be used to understand site specific relationship between C<small><sub>0</sub></small> and concentrations of inorganics in aquatic life. For example, measuring C<small><sub>0</sub></small> in sediment from which organisms are collected and analyzed can enable the estimation of a site-specific uptake factor. This C<small><sub>0</sub></small>-to-organism uptake factor (or model) can then be applied for a variety of uses, including predicting the concentration of inorganics in other organisms, or estimating a sediment C<small><sub>0</sub></small> value that would be safe for consumption by wildlife or humans. Because several decades of research have found that the correlation between C<small><sub>0</sub></small> measurements and bioavailability is usually better than the correlation between measurements of chemicals in bulk sediment and bioavailability, C<small><sub>0</sub></small>-to-organism uptake factors are likely to be more accurate than uptake factors based on bulk sediment testing.
 +
 
 +
'''Evaluating Sediment Remediation Efficacy:''' Passive sampling has been used widely to evaluate the efficacy of remedial actions such as active amendments, thin layer placements, and capping to reduce the availability of contaminants at sediment sites. A particularly powerful approach is to compare baseline (pre-remedy) C<small><sub>0</sub></small> in sediment to C<small><sub>0</sub></small> in sediment after the sediment remedy has been applied. Peepers can be used in this context for inorganics, allowing the sediment remedy’s success to be evaluated and monitored in laboratory benchtop remedy evaluations, pilot scale remedy evaluations, and full-scale remediation monitoring.
  
 
==References==
 
==References==
−
 
 
<references />
 
<references />
  
 
==See Also==
 
==See Also==
−
 
+
*[https://vimeo.com/809180171/c276c1873a Peeper Deployment Video]
−
*[http://www.gsi-net.com/en/publications/useful-groundwater-resources/colorado-state-matrix-diffusion-video.html Matrix Diffusion Movie]
+
*[https://vimeo.com/811073634/303edf2693 Peeper Retrieval Video]
−
*[https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-1737 Impact of Clay-DNAPL Interactions on Transport and Storage of Chlorinated Solvents in Low Permeability Zones]
+
*[https://vimeo.com/811328715/aea3073540 Peeper Processing Video]
−
*[https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-200320 Prediction of Groundwater Quality Improvement Down-Gradient of ''In Situ'' Permeable Treatment Barriers and Fully Remediated Source Zones]
+
*[https://sepub-prod-0001-124733793621-us-gov-west-1.s3.us-gov-west-1.amazonaws.com/s3fs-public/2024-09/ER20-5261%20Fact%20Sheet.pdf?VersionId=malAixSQQM3mWCRiaVaxY8wLdI0jE1PX Fact Sheet]
−
*[https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Groundwater/Persistent-Contamination/ER-201032 Determining Source Attenuation History to Support Closure by Natural Attenuation]
 
−
*[https://www.coursera.org/learn/natural-attenuation-of-groundwater-contaminants/lecture/2R7yh/matrix-diffusion-principles Coursera Matrix Diffusion Online Lecture]
 

Latest revision as of 21:47, 14 October 2024

Sediment Porewater Dialysis Passive Samplers for Inorganics (Peepers)

Sediment porewater dialysis passive samplers, also known as “peepers,” are sampling devices that allow the measurement of dissolved inorganic ions in the porewater of a saturated sediment. Peepers function by allowing freely-dissolved ions in sediment porewater to diffuse across a micro-porous membrane towards water contained in an isolated compartment that has been inserted into sediment. Once retrieved after a deployment period, the resulting sample obtained can provide concentrations of freely-dissolved inorganic constituents in sediment, which provides measurements that can be used for understanding contaminant fate and risk. Peepers can also be used in the same manner in surface water, although this article is focused on the use of peepers in sediment.

Related Article(s):


Contributor(s):

  • Florent Risacher, M.Sc.
  • Jason Conder, Ph.D.

Key Resource(s):

  • A review of peeper passive sampling approaches to measure the availability of inorganics in sediment porewater[1]
  • Best Practices User’s Guide: Standardizing Sediment Porewater Passive Samplers for Inorganic Constituents of Concern[2]

Introduction

Biologically available inorganic constituents associated with sediment toxicity can be quantified by measuring the freely-dissolved fraction of contaminants in the porewater[3][4]. Classical sediment porewater analysis usually consists of collecting large volumes of bulk sediments which are then mechanically squeezed or centrifuged to produce a supernatant, or suction of porewater from intact sediment, followed by filtration and collection[5]. The extraction and measurement processes present challenges due to the heterogeneity of sediments, physical disturbance, high reactivity of some complexes, and interaction between the solid and dissolved phases, which can impact the measured concentration of dissolved inorganics[6]. For example, sampling disturbance can affect redox conditions[7][8], which can lead to under or over representation of inorganic chemical concentrations relative to the true dissolved phase concentration in the sediment porewater[9][5].

To address the complications with mechanical porewater sampling, passive sampling approaches for inorganics have been developed to provide a method that has a low impact on the surrounding geochemistry of sediments and sediment porewater, thus enabling more precise measurements of inorganics[4]. Sediment porewater dialysis passive samplers, also known as “peepers,” were developed more than 45 years ago[10] and refinements to the method such as the use of reverse tracers have been made, improving the acceptance of the technology as decision making tool.

Peeper Designs

Figure 1. Conceptual illustration of peeper construction showing (top, left to right) the peeper cap (optional), peeper membrane and peeper chamber, and (bottom) an assembled peeper containing peeper water
Figure 2. Example of Hesslein[10] general peeper design (42 peeper chambers), from USGS
Figure 3. Peeper deployment structure to allow the measurement of metal availability in different sediment layers using five single-chamber peepers (Photo: Geosyntec Consultants)

Peepers (Figure 1) are inert containers with a small volume (typically 1-100 mL) of purified water (“peeper water”) capped with a semi-permeable membrane. Peepers can be manufactured in a wide variety of formats (Figure 2, Figure 3) and deployed in in various ways.

Two designs are commonly used for peepers. Frequently, the designs are close adaptations of the original multi-chamber Hesslein design[10] (Figure 2), which consists of an acrylic sampler body with multiple sample chambers machined into it. Peeper water inside the chambers is separated from the outside environment by a semi-permeable membrane, which is held in place by a top plate fixed to the sampler body using bolts or screws. An alternative design consists of single-chamber peepers constructed using a single sample vial with a membrane secured over the mouth of the vial, as shown in Figure 3, and applied in Teasdale et al.[7], Serbst et al.[11], Thomas and Arthur[12], Passeport et al.[13], and Risacher et al.[2]. The vial is filled with deionized water, and the membrane is held in place using the vial cap or an o-ring. Individual vials are either directly inserted into sediment or are incorporated into a support structure to allow multiple single-chamber peepers to be deployed at once over a given depth profile (Figure 3).

Peepers Preparation, Deployment and Retrieval

Figure 4: Conceptual illustration of peeper passive sampling in a sediment matrix, showing peeper immediately after deployment (top) and after equilibration between the porewater and peeper chamber water (bottom)

Peepers are often prepared in laboratories but are also commercially available in a variety of designs from several suppliers. Peepers are prepared by first cleaning all materials to remove even trace levels of metals before assembly. The water contained inside the peeper is sometimes deoxygenated, and in some cases the peeper is maintained in a deoxygenated atmosphere until deployment[14]. However, recent studies[2] have shown that deoxygenation prior to deployment does not significantly impact sampling results due to oxygen rapidly diffusing out of the peeper during deployment. Once assembled, peepers are usually shipped in a protective bag inside a hard-case cooler for protection.

Peepers are deployed by insertion into sediment for a period of a few days to a few weeks. Insertion into the sediment can be achieved by wading to the location when the water depth is shallow, by using push poles for deeper deployments[2], or by professional divers for the deepest sites. If divers are used, an appropriate boat or ship will be required to accommodate the diver and their equipment. Whichever method is used, peepers should be attached to an anchor or a small buoy to facilitate retrieval at the end of the deployment period.

During deployment, passive sampling is achieved via diffusion of inorganics through the peeper’s semi-permeable membrane, as the enclosed volume of peeper water equilibrates with the surrounding sediment porewater (Figure 4). It is assumed that the peeper insertion does not greatly alter geochemical conditions that affect freely-dissolved inorganics. Additionally, it is assumed that the peeper water equilibrates with freely-dissolved inorganics in sediment in such a way that the concentration of inorganics in the peeper water would be equal to that of the concentration of inorganics in the sediment porewater.

After retrieval, the peepers are brought to the surface and usually preserved until they can be processed. This can be achieved by storing the peepers inside a sealable, airtight bag with either inert gas or oxygen absorbing packets[2]. The peeper water can then be processed by quickly pipetting it into an appropriate sample bottle which usually contains a preservative (e.g., nitric acid for metals). This step is generally conducted in the field. Samples are stored on ice to maintain a temperature of less than 4°C and shipped to an analytical laboratory. The samples are then analyzed for inorganics by standard methods (i.e., USEPA SW-846). The results obtained from the analytical laboratory are then used directly or assessed using the equations below if a reverse tracer is used because deployment time is insufficient for all analytes to reach equilibrium.

Equilibrium Determination (Tracers)

The equilibration period of peepers can last several weeks and depends on deployment conditions, analyte of interest, and peeper design. In many cases, it is advantageous to use pre-equilibrium methods that can use measurements in peepers deployed for shorter periods to predict concentrations at equilibrium[15].

Although the equilibrium concentration of an analyte in sediment can be evaluated by examining analyte results for peepers deployed for several different amounts of time (i.e., a time series), this is impractical for typical field investigations because it would require several mobilizations to the site to retrieve samplers. Alternately, reverse tracers (referred to as a performance reference compound when used with organic compound passive sampling) can be used to evaluate the percentage of equilibrium reached by a passive sampler.

Thomas and Arthur[12] studied the use of a reverse tracer to estimate percent equilibrium in lab experiments and a field application. They concluded that bromide can be used to estimate concentrations in porewater using measurements obtained before equilibrium is reached. Further studies were also conducted by Risacher et al.[2] showed that lithium can also be used as a tracer for brackish and saline environments. Both studies included a mathematical model for estimating concentrations of ions in external media (C0) based on measured concentrations in the peeper chamber (Cp,t), the elimination rate of the target analyte (K) and the deployment time (t):

Equation 1:      Equation1r.png
Where:
C0 is the freely dissolved concentration of the analyte in the sediment (mg/L or μg/L), sometimes referred to as Cfree
Cp,t is the measured concentration of the analyte in the peeper at time of retrieval (mg/L or μg/L)
K is the elimination rate of the target analyte
t is the deployment time (days)

The elimination rate of the target analyte (K) is calculated using Equation 2:

Equation 2:      Equation2r.png
Where:
K is the elimination rate of the target analyte
Ktracer is the elimination rate of the tracer
D is the free water diffusivity of the analyte (cm2/s)
Dtracer is the free water diffusivity of the tracer (cm2/s)

The elimination rate of the tracer (Ktracer) is calculated using Equation 3:

Equation 3:          Equation3r2.png
Where:
Ktracer is the elimination rate of the tracer
Ctracer,i is the measured initial concentration of the tracer in the peeper prior to deployment (mg/L or μg/L)
Ctracer,t is the measured final concentration of the tracer in the peeper at time of retrieval (mg/L or μg/L)
t is the deployment time (days)

Using this set of equations allows the calculation of the porewater concentration of the analyte prior to its equilibrium with the peeper water. A template for these calculations can be found in the appendix of Risacher et al.[2].

Using Peeper Data at a Sediment Site

Peeper data can be used to enable site specific decision making in a variety of ways. Some of the most common uses for peepers and peeper data are discussed below.

Nature and Extent: Multiple peepers deployed in sediment can help delineate areas of increased metal availability. Peepers are especially helpful for sites that are comprised of coarse, relatively inert materials that may not be conducive to traditional bulk sediment sampling. Because much of the inorganics present in these types of sediments may be associated with the porewater phase rather than the solid phase, peepers can provide a more representative measurement of C0. Additionally, at sites where tidal pumping or groundwater flux may be influencing the nature and extent of inorganics, peepers can provide a distinct advantage to bulk sediment sampling or other point-in-time measurements, as peepers can provide an average measurement that integrates the variability in the hydrodynamic and chemical conditions over time.

Sources and Fate: A considerable advantage to using peepers is that C0 results are expressed as concentration in units of mass per volume (e.g., mg/L), providing a common unit of measurement to compare across multiple media. For example, synchronous measurements of C0 using peepers deployed in both surface water and sediment can elucidate the potential flux of inorganics from sediment to surface water. Paired measurements of both C0 and bulk metals in sediment can also allow site specific sediment-porewater partition coefficients to be calculated. These values can be useful in understanding and predicting contaminant fate, especially in situations where the potential dissolution of metals from sediment are critical to predict, such as when sediment is dredged.

Direct Toxicity to Aquatic Life: Peepers are frequently used to understand the potential direct toxicity to aquatic life, such as benthic invertebrates and fish. A C0 measurement obtained from a peeper deployed in sediment (in situ) or surface water (ex situ), can be compared to toxicological benchmarks for aquatic life to understand the potential toxicity to aquatic life and to set remediation goals[15]. C0 measurements can also be incorporated in more sophisticated approaches, such as the Biotic Ligand Model[16] to understand the potential for toxicity or the need to conduct toxicological testing or ecological evaluations.

Bioaccumulation of Inorganics by Aquatic Life: Peepers can also be used to understand site specific relationship between C0 and concentrations of inorganics in aquatic life. For example, measuring C0 in sediment from which organisms are collected and analyzed can enable the estimation of a site-specific uptake factor. This C0-to-organism uptake factor (or model) can then be applied for a variety of uses, including predicting the concentration of inorganics in other organisms, or estimating a sediment C0 value that would be safe for consumption by wildlife or humans. Because several decades of research have found that the correlation between C0 measurements and bioavailability is usually better than the correlation between measurements of chemicals in bulk sediment and bioavailability, C0-to-organism uptake factors are likely to be more accurate than uptake factors based on bulk sediment testing.

Evaluating Sediment Remediation Efficacy: Passive sampling has been used widely to evaluate the efficacy of remedial actions such as active amendments, thin layer placements, and capping to reduce the availability of contaminants at sediment sites. A particularly powerful approach is to compare baseline (pre-remedy) C0 in sediment to C0 in sediment after the sediment remedy has been applied. Peepers can be used in this context for inorganics, allowing the sediment remedy’s success to be evaluated and monitored in laboratory benchtop remedy evaluations, pilot scale remedy evaluations, and full-scale remediation monitoring.

References

  1. ^ Risacher, F.F., Schneider, H., Drygiannaki, I., Conder, J., Pautler, B.G., and Jackson, A.W., 2023. A Review of Peeper Passive Sampling Approaches to Measure the Availability of Inorganics in Sediment Porewater. Environmental Pollution, 328, Article 121581. doi: 10.1016/j.envpol.2023.121581   Open Access Manuscript
  2. ^ 2.0 2.1 2.2 2.3 2.4 2.5 2.6 Risacher, F.F., Nichols, E., Schneider, H., Lawrence, M., Conder, J., Sweett, A., Pautler, B.G., Jackson, W.A., Rosen, G., 2023b. Best Practices User’s Guide: Standardizing Sediment Porewater Passive Samplers for Inorganic Constituents of Concern, ESTCP ER20-5261. Project Website   Report.pdf
  3. ^ Conder, J.M., Fuchsman, P.C., Grover, M.M., Magar, V.S., Henning, M.H., 2015. Critical review of mercury SQVs for the protection of benthic invertebrates. Environmental Toxicology and Chemistry, 34(1), pp. 6-21. doi: 10.1002/etc.2769   Open Access Article
  4. ^ 4.0 4.1 Cleveland, D., Brumbaugh, W.G., MacDonald, D.D., 2017. A comparison of four porewater sampling methods for metal mixtures and dissolved organic carbon and the implications for sediment toxicity evaluations. Environmental Toxicology and Chemistry, 36(11), pp. 2906-2915. doi: 10.1002/etc.3884
  5. ^ 5.0 5.1 Gruzalski, J.G., Markwiese, J.T., Carriker, N.E., Rogers, W.J., Vitale, R.J., Thal, D.I., 2016. Pore Water Collection, Analysis and Evolution: The Need for Standardization. In: Reviews of Environmental Contamination and Toxicology, Vol. 237, pp. 37–51. Springer. doi: 10.1007/978-3-319-23573-8_2
  6. ^ Peijnenburg, W.J.G.M., Teasdale, P.R., Reible, D., Mondon, J., Bennett, W.W., Campbell, P.G.C., 2014. Passive Sampling Methods for Contaminated Sediments: State of the Science for Metals. Integrated Environmental Assessment and Management, 10(2), pp. 179–196. doi: 10.1002/ieam.1502   Open Access Article
  7. ^ 7.0 7.1 Teasdale, P.R., Batley, G.E., Apte, S.C., Webster, I.T., 1995. Pore water sampling with sediment peepers. Trends in Analytical Chemistry, 14(6), pp. 250–256. doi: 10.1016/0165-9936(95)91617-2
  8. ^ Schroeder, H., Duester, L., Fabricius, A.L., Ecker, D., Breitung, V., Ternes, T.A., 2020. Sediment water (interface) mobility of metal(loid)s and nutrients under undisturbed conditions and during resuspension. Journal of Hazardous Materials, 394, Article 122543. doi: 10.1016/j.jhazmat.2020.122543   Open Access Article
  9. ^ Wise, D.E., 2009. Sampling techniques for sediment pore water in evaluation of reactive capping efficacy. Master of Science Thesis. University of New Hampshire Scholars’ Repository. 178 pages. Website   Report.pdf
  10. ^ 10.0 10.1 10.2 Hesslein, R.H., 1976. An in situ sampler for close interval pore water studies. Limnology and Oceanography, 21(6), pp. 912-914. doi: 10.4319/lo.1976.21.6.0912   Open Access Article
  11. ^ Serbst, J.R., Burgess, R.M., Kuhn, A., Edwards, P.A., Cantwell, M.G., Pelletier, M.C., Berry, W.J., 2003. Precision of dialysis (peeper) sampling of cadmium in marine sediment interstitial water. Archives of Environmental Contamination and Toxicology, 45(3), pp. 297–305. doi: 10.1007/s00244-003-0114-5
  12. ^ 12.0 12.1 Thomas, B., Arthur, M.A., 2010. Correcting porewater concentration measurements from peepers: Application of a reverse tracer. Limnology and Oceanography: Methods, 8(8), pp. 403–413. doi: 10.4319/lom.2010.8.403   Open Access Article
  13. ^ Passeport, E., Landis, R., Lacrampe-Couloume, G., Lutz, E.J., Erin Mack, E., West, K., Morgan, S., Lollar, B.S., 2016. Sediment Monitored Natural Recovery Evidenced by Compound Specific Isotope Analysis and High-Resolution Pore Water Sampling. Environmental Science and Technology, 50(22), pp. 12197–12204. doi: 10.1021/acs.est.6b02961
  14. ^ Carignan, R., St‐Pierre, S., Gachter, R., 1994. Use of diffusion samplers in oligotrophic lake sediments: Effects of free oxygen in sampler material. Limnology and Oceanography, 39(2), pp. 468-474. doi: 10.4319/lo.1994.39.2.0468   Open Access Article
  15. ^ 15.0 15.1 USEPA, 2017. Laboratory, Field, and Analytical Procedures for Using Passive Sampling in the Evaluation of Contaminated Sediments: User’s Manual. EPA/600/R-16/357.   Report.pdf
  16. ^ Santore, C.R., Toll, E.J., DeForest, K.D., Croteau, K., Baldwin, A., Bergquist, B., McPeek, K., Tobiason, K., and Judd, L.N., 2022. Refining our understanding of metal bioavailability in sediments using information from porewater: Application of a multi-metal BLM as an extension of the Equilibrium Partitioning Sediment Benchmarks. Integrated Environmental Assessment and Management, 18(5), pp. 1335–1347. doi: 10.1002/ieam.4572

See Also

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