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==PFAS Treatment by Electrical Discharge Plasma==
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==Sediment Porewater Dialysis Passive Samplers for Inorganics (Peepers)==  
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Plasma-based water treatment is a technology that, using only electricity, converts water into a mixture of highly reactive species including OH•, O, H•, HO<sub>2</sub>•, O<sub>2</sub>•<sup>‒</sup>, H<sub>2</sub>, O<sub>2</sub>, H<sub>2</sub>O<sub>2</sub> and aqueous electrons (e<sup>‒</sup><sub>aq</sub>), called a plasma<ref name="Sunka1999">Sunka, P., Babický, V., Clupek, M., Lukes, P., Simek, M., Schmidt, J., and Cernak, M., 1999. Generation of Chemically Active Species by Electrical Discharges in Water. Plasma Sources Science and Technology, 8(2), pp. 258-265. [https://doi.org/10.1088/0963-0252/8/2/006 DOI: 10.1088/0963-0252/8/2/006]</ref><ref name="MededovicThagard2009">Mededovic Thagard, S., Takashima, K., and Mizuno, A., 2009. Chemistry of the Positive and Negative Electrical Discharges Formed in Liquid Water and Above a Gas-Liquid Surface. Plasma Chemistry and Plasma Processing, 29(6), pp.455-473. [https://doi.org/10.1007/s11090-009-9195-x DOI: 10.1007/s11090-009-9195-x]</ref>. These highly reactive species rapidly and non-selectively degrade [[Wikipedia: Volatile organic compound |volatile organic compounds (VOCs)]]<ref name="Du2019">Du, C., Gong, X., and Lin, Y., 2019. Decomposition of volatile organic compounds using corona discharge plasma technology. Journal of the Air and Waste Management Association, 69(8), pp.879-899.  [https://doi.org/10.1080/10962247.2019.1582441 DOI: 10.1080/10962247.2019.1582441]  [https://www.tandfonline.com/doi/full/10.1080/10962247.2019.1582441 Open access article.]</ref>, [[1,4-Dioxane | 1,4-dioxane]]<ref name="Xiong2019">Xiong, Y., Zhang, Q., Wandell, R., Bresch, S., Wang, H., Locke, B.R. and Tang, Y., 2019. Synergistic 1,4-Dioxane Removal by Non-Thermal Plasma Followed by Biodegradation. Chemical Engineering Journal, 361, pp.519-527. [https://doi.org/10.1016/J.CEJ.2018.12.094 DOI: 10.1016/J.CEJ.2018.12.094]</ref><ref name="Ni2013">Ni, G.H., Zhao, Y., Meng, Y.D., Wang, X.K., and Toyoda, H., 2013. Steam plasma jet for treatment of contaminated water with high-concentration 1,4-dioxane organic pollutants. Europhysics Letters, 101(4), p.45001. [https://doi.org/10.1209/0295-5075/101/45001 DOI: 10.1209/0295-5075/101/45001]</ref>, and a broad spectrum of [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | per- and polyfluoroalkyl substances (PFAS)]] including perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), and short-chain PFAS<ref name="Stratton2015">Stratton, G.R., Bellona, C.L., Dai, F., Holsen, T.M. and Mededovic Thagard, S., 2015. Plasma-Based Water Treatment: Conception and Application of a New General Principle for Reactor Design. Chemical Engineering Journal, 273, pp.543-550. [https://doi.org/10.1016/j.cej.2015.03.059 DOI: 10.1016/j.cej.2015.03.059]</ref><ref name="Singh2019a">Singh, R.K., Multari, N., Nau-Hix, C., Anderson, R.H., Richardson, S.D., Holsen, T.M. and Mededovic Thagard, S., 2019. Rapid Removal of Poly- and Perfluorinated Compounds from Investigation-Derived Waste (IDW) in a Pilot-Scale Plasma Reactor. Environmental Science and Technology, 53(19), pp.11375-11382. [https://doi.org/10.1021/acs.est.9b02964 DOI: 10.1021/acs.est.9b02964]</ref><ref name="Singh2019b">Singh, R.K., Fernando, S., Baygi, S.F., Multari, N., Mededovic Thagard, S., and Holsen, T.M., 2019. Breakdown Products from Perfluorinated Alkyl Substances (PFAS) Degradation in a Plasma-Based Water Treatment Process. Environmental Science and Technology, 53(5), pp.2731-2738. [https://doi.org/10.1021/acs.est.8b07031 DOI: 10.1021/acs.est.8b07031]</ref>. A plasma reactor can simultaneously oxidize and reduce organics by producing a mixture of hydroxyl radicals and aqueous electrons, the latter of which act as strong reducing agents and could be the key species in removing PFAS and other non-oxidizable compounds. Additionally, the plasma process produces no residual waste and requires no chemical additions, although adding surfactants or injecting inert gas into the liquid phase can increase interfacial PFAS concentrations, exposing more of the PFAS to the plasma and therefore increasing removal efficiency.  
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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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*[[PFAS Ex Situ Water Treatment]]
 
  
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'''Contributor(s):'''
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*[[Contaminated Sediments - Introduction]]
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*Dr. Selma Mededovic Thagard
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*[[Contaminated Sediment Risk Assessment]]
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*Dr. Thomas Holsen
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*[[In Situ Treatment of Contaminated Sediments with Activated Carbon]]
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*Dr. Stephen Richardson, P.E
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*[[Passive Sampling of Munitions Constituents]]
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*Poonam Kulkarni, P.E.
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*[[Sediment Capping]]
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*Dr. Blossom Nzeribe
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*[[Mercury in Sediments]]
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*[[Passive Sampling of Sediments]]
  
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'''Key Resource(s):'''
 
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* [https://pfas-1.itrcweb.org/12-treatment-technologies/#12_2  PFAS – Per- and Polyfluoroalkyl Substances: 12.2 Field-Implemented Liquids Treatment Technologies. Interstate Technology Regulatory Council (ITRC).]  See also: [https://pfas-1.itrcweb.org/12-treatment-technologies/#12_5 12.5 Limited Application and Developing Liquids Treatment Technologies].
 
  
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* Physico-Chemical Processes for the Treatment of Per- And Polyfluoroalkyl Substances (PFAS): A review28<ref name="Nzeribe2019">Nzeribe, B.N., Crimi, M., Mededovic Thagard, S. and Holsen, T.M., 2019. Physico-Chemical Processes for the Treatment of Per- And Polyfluoroalkyl Substances (PFAS): A review. Critical Reviews in Environmental Science and Technology, 49(10), pp.866-915. [https://doi.org/10.1080/10643389.2018.1542916 DOI: 10.1080/10643389.2018.1542916]</ref>
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'''Contributor(s):'''
  
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* Low Temperature Plasma for Biology, Hygiene, and Medicine: Perspective and Roadmap<ref name="Laroussi2021">Laroussi, M., Bekeschus, S., Keidar, M., Bogaerts, A., Fridman, A., Lu, X.P., Ostrikov, K.K., Hori, M., Stapelmann, K., Miller, V., Reuter, S., Laux, C., Mesbah, A., Walsh, J., Jiang, C., Mededovic Thagard, S., Tanaka, H., Liu, D.W., Yan, D., and Yusupov, M., 2021. Low Temperature Plasma for Biology, Hygiene, and Medicine: Perspective and Roadmap. IEEE Transactions on Radiation and Plasma Medical Sciences. [https://doi.org/10.1109/TRPMS.2021.3135118 DOI: 10.1109/TRPMS.2021.3135118]  [https://ieeexplore.ieee.org/abstract/document/9650590 Open access article.]</ref>
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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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Plasma processing plays an essential role in various industrial applications such as semiconductor fabrication, polymer functionalization, chemical synthesis, agriculture and food safety, health industry, and hazardous waste management<ref name="VanVeldhuizen2002">Van Veldhuizen, E.M., and Rutgers, W.R., 2002. Pulsed Positive Corona Streamer Propagation and Branching. Journal of Physics D: Applied Physics, 35(17), p.2169.  [https://doi.org/10.1088/0022-3727/35/17/313 DOI: 10.1088/0022-3727/35/17/313]</ref><ref name="Yang">Yang, Y., Cho, Y.I. and Fridman, A., 2012. Plasma Discharge in Liquid: Water Treatment and Applications. CRC press. ISBN: 978-1-4398-6623-8  [https://doi.org/10.1201/b11650 DOI: 10.1201/b11650]</ref><ref name="Rezaei2019">Rezaei, F., Vanraes, P., Nikiforov, A., Morent, R., and De Geyter, N., 2019. Applications of Plasma-Liquid Systems: A Review. Materials, 12(17), article 2751, 69 pp.  [https://doi.org/10.3390/ma12172751 DOI: 10.3390/ma12172751]&nbsp;&nbsp;  [https://www.mdpi.com/1996-1944/12/17/2751 Open access article].</ref><ref name="Herianto2021">Herianto, S., Hou, C.Y., Lin, C.M., and Chen, H.L., 2021. Nonthermal plasma-activated water: A comprehensive review of this new tool for enhanced food safety and quality. Comprehensive Reviews in Food Science and Food Safety, 20(1), pp. 583-626. [https://doi.org/10.1111/1541-4337.12667 DOI: 10.1111/1541-4337.12667]</ref>.  Plasma is a gaseous state of matter consisting of charged particles, metastable-state molecules or atoms, and free radicals. Depending on the energy or temperature of the electrons, compared with the temperature of the background gas, plasmas can be classified as thermal or non-thermal. In thermal plasma, an example of which is an electrical arc, individual species’ temperatures typically exceed several thousand kelvins (K). Non-thermal plasmas are formed using less power with temperatures ranging from ambient to approximately 1000 K<ref name="Jiang2014">Jiang, B., Zheng, J., Qiu, S., Wu, M., Zhang, Q., Yan, Z. and Xue, Q., 2014. Review on Electrical Discharge Plasma Technology for Wastewater Remediation. Chemical Engineering Journal, 236, pp. 348–368. [https://doi.org/10.1016/j.cej.2013.09.090 DOI: 10.1016/j.cej.2013.09.090]</ref>. An example of a non-thermal plasma is a dielectric barrier discharge used for commercial ozone generation.
 
  
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Plasma that is applied in water treatment (Figure 1) is typically non-thermal, which offers high-energy process efficiency and selectivity<ref name="Jiang2014"/><ref name="Magureanu2018">Magureanu, M., Bradu, C., and Parvulescu, V.I., 2018. Plasma Processes for the Treatment of Water Contaminated with Harmful Organic Compounds. Journal of Physics D: Applied Physics, 51(31), p. 313002. [https://doi.org/10.1088/1361-6463/aacd9c DOI:    10.1088/1361-6463/aacd9c]</ref>. Since the 1980s when the first plasma reactor was utilized to oxidize a dye<ref name="Clements1987">Clements, J.S., Sato, M., and Davis, R.H., 1987. Preliminary Investigation of Prebreakdown Phenomena and Chemical Reactions Using a Pulsed High-Voltage Discharge in Water. IEEE Transactions on Industry Applications, IA-23(2), pp. 224-235.  [https://doi.org/10.1109/TIA.1987.4504897 DOI: 10.1109/TIA.1987.4504897]</ref>, over a hundred different plasma reactors have been developed to treat a range of contaminants of environmental importance including biological species. Examples include treatment of pharmaceuticals, volatile organic compounds (VOCs), 1,4-dioxane, herbicides, pesticides, warfare agents, bacteria, yeasts and viruses using direct-in-liquid discharges with and without bubbles and discharges in a gas over and contacting the surface of a liquid. Different excitation sources including AC, nanosecond pulsed and DC voltages have been utilized to produce pulsed corona, corona-like, spark, arc, and glow discharges, among other discharge types. Many reviews of plasma processing for water treatment applications have recently been published<ref name="Zeghioud2020">Zeghioud, H., Nguyen-Tri, P., Khezami, L., Amrane, A., and Assadi, A.A., 2020. Review on Discharge Plasma for Water Treatment: Mechanism, Reactor Geometries, Active Species and Combined Processes. Journal of Water Process Engineering, 38, p.101664. [https://doi.org/10.1016/j.jwpe.2020.101664 DOI: 10.1016/j.jwpe.2020.101664]</ref><ref name="Murugesan2020">Murugesan, P., Evanjalin Monica, V., Moses, J.A., and Anandharamakrishnan, C., 2020. Water Decontamination Using Non-Thermal Plasma: Concepts, Applications, and Prospects. Journal of Environmental Chemical Engineering, 8(5), p. 104377. [https://doi.org/10.1016/j.jece.2020.104377 DOI: 10.1016/j.jece.2020.104377]</ref>.
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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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Plasma-based water treatment (PWT) owes its strong oxidation and disinfection capabilities to the production of reactive oxidative species (ROS), primarily OH radicals, atomic oxygen, singlet oxygen and hydrogen peroxide. The process also produces reductive species such as solvated electrons and reactive nitrogen species (RNS) when nitrogen and oxygen are present in the discharge. This process has the advantage of synergistic effects of high electric fields, UV/VUV light emissions and in some cases shockwave formation in a liquid. It requires no chemical additions, and can be optimized for batch or continuous processing.  
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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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==Fundamentals of Sediment Risk Assessment==
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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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[[File: SedRiskFig1.PNG | thumb |700px|Figure 1. Schematic of the sediment risk assessment process]]
 
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Whereas there is strong evidence of anthropogenic impacts on the benthic community at many sediment sites, the degree of toxicity (or even its presence or absence) cannot be predicted with absolute certainty using contaminant concentrations alone<ref name="Apitz2011"/>. A sediment ERA should include lines of evidence (LOEs) derived from several different investigations<ref name="Wenning2005"/>. One common approach to develop several of these LOEs in a decision framework is the triad approach. Triad-based assessment frameworks require evidence based on sediment chemistry, toxicity, and benthic community structure (possibly including evidence of bioaccumulation) to designate sediment as toxic and requiring management or control<ref name="Chapman1996">Chapman, P.M., Paine, M.D., Arthur, A.D., Taylor, L.A., 1996. A triad study of sediment quality associated with a major, relatively untreated marine sewage discharge. Marine Pollution Bulletin 32(1), pp. 47–64.  [https://doi.org/10.1016/0025-326X(95)00108-Y DOI: 10.1016/0025-326X(95)00108-Y]</ref>. In some decision frameworks, particularly those used to establish and rank risks in national or regional programs, all components of the triad are carried out simultaneously, with the various LOEs combined to support weight of evidence (WOE) decision making. In other frameworks, LOEs are tiered to minimize costs by collecting only the data required to make a decision and leaving some potential consequences and uncertainties unresolved.
 
  
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Figure 1 provides an overview of a sediment risk assessment process. The first step, and a fundamental requirement, in sediment risk assessment, involves scoping and planning prior to undertaking work. This is important for optimizing the available assessment resource and conducting an assessment at the appropriate level of detail that is transparent and free, to the extent possible, of any bias or preconceived beliefs concerning the outcome<ref name="Hill2000">Hill, R.A., Chapman, P.M., Mann, G.S. and Lawrence, G.S., 2000. Level of Detail in Ecological Risk Assessments. Marine Pollution Bulletin, 40(6), pp. 471-477. [https://doi.org/10.1016/S0025-326X(00)00036-9 DOI: 10.1016/S0025-326X(00)00036-9]</ref>.
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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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===Screening-Level Risk Assessment (SLRA)===
 
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Technical guidance in many countries strongly encourages sediment risk assessment to begin with a Screening-Level Risk Assessment (SLRA)<ref name="USEPA2005"/><ref name="Tarazona2014"/><ref name="Fletcher2008"/>. The SLRA is a simplified risk assessment conducted using limited data and often assuming certain, generally conservative and generic, sediment characteristics, sediment contaminant levels, and exposure parameters in the absence of sufficient readily available information<ref name="Hope2006">Hope, B.K., 2006. An examination of ecological risk assessment and management practices. Environment International, 32(8), pp. 983-995. [https://doi.org/10.1016/j.envint.2006.06.005 DOI: 10.1016/j.envint.2006.06.005]</ref><ref name="Weinstein2010">Weinstein, J.E., Crawford, K.D., Garner, T.R. and Flemming, A.J., 2010. Screening-level ecological and human health risk assessment of polycyclic aromatic hydrocarbons in stormwater detention pond sediments of Coastal South Carolina, USA. Journal of Hazardous Materials, 178(1-3), pp. 906-916. [https://doi.org/10.1016/j.jhazmat.2010.02.024 DOI: 10.1016/j.jhazmat.2010.02.024]</ref><ref name="Rak2008">Rak, A., Maly, M.E., Tracey, G., 2008. A Guide to Screening Level Ecological Risk Assessment, TG-090801. Tri-Services Ecological Risk Assessment Working Group (TSERAWG), U.S. Army Biological Technical Assistance Group (BTAG), Aberdeen Proving Ground, MD. 26 pp. [https://usaphcapps.amedd.army.mil/erawg/SLERA.pdf Free Download]&nbsp;&nbsp; [[Media: Rak2008.pdf | Report.pdf]]</ref><ref name="USEPA2001">US Environmental Protection Agency (USEPA), 2001. ECO Update. The Role of Screening-Level Risk Assessments and Refining Contaminants of Concern in Baseline Ecological Risk Assessments. EPA 540/F-01/014. Washington, D.C. [https://www.epa.gov/sites/default/files/2015-09/documents/slera0601.pdf  Website]&nbsp;&nbsp; [[Media: EPA 540_F-01_014.pdf | Report.pdf]]</ref>.
 
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The analysis is often semi-quantitative, and typically includes comparisons of various chemical and physical sediment conditions to threshold limits established in national or international regulations or by generally accepted scientific interpretations. US technical guidance encourages the comparison of contaminant measurements in water, sediment, or soil to National Oceanographic and Atmospheric Administration (NOAA) sediment screening quick reference tables, or SQuiRT cards, which list quality guidelines from a range of sources, based on differing narrative intent<ref name="Buchman2008">Buchman, M.F., 2008. Screening Quick Reference Tables (SQuiRTs), NOAA OR&R Report 08-1. National Oceanographic and Atmospheric Administration (NOAA), Coastal Protection and Restoration Protection Division. 34 pp. [https://repository.library.noaa.gov/view/noaa/9327  website]&nbsp;&nbsp; [[Media: SQuiRTs2008.pdf | Report.pdf]]</ref>.
 
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The screening level approach is intended to minimize the chances of concluding that there is no risk when, in fact, risk may exist. Thus, the results of an SLRA may indicate contaminants or sediments in certain locations in the original study area initially thought to be of concern are acceptable (i.e., contaminant levels are below threshold levels), or that contaminant levels are high enough to indicate immediate action without further assessment (e.g., contaminant levels are well above probable-effects guidelines). In other cases, or at other locations, SLRA may indicate the need for further examination. Further study may apply site-specific, rather than generic and conservative assumptions, to reduce uncertainty.
 
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===Detailed Risk Assessment===
 
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Detailed sediment risk assessment is conducted when SLRA results indicate one or more sediment contaminants exceed background conditions or regulatory threshold limits. For some contaminants, such as the dioxins and other persistent, bioaccumulative, and toxic substances (PBTs), technical guidance may mandate further examination, regardless of whether threshold levels are exceeded<ref name="Solomon2013">Solomon, K., Matthies, M., and Vighi, M., 2013. Assessment of PBTs in the European Union: a critical assessment of the proposed evaluation scheme with reference to plant protection products. Environmental Sciences Europe, 25(1), pp. 1-17. [https://doi.org/10.1186/2190-4715-25-10 DOI: 10.1186/2190-4715-25-10]&nbsp;&nbsp; [https://enveurope.springeropen.com/articles/10.1186/2190-4715-25-10 Open Access Article]</ref><ref name="Matthies2016">Matthies, M., Solomon, K., Vighi, M., Gilman, A. and Tarazona, J.V., 2016. The origin and evolution of assessment criteria for persistent, bioaccumulative and toxic (PBT) chemicals and persistent organic pollutants (POPs). Environmental Science: Processes and Impacts, 18(9), pp. 1114-1128. [https://doi.org/10.1039/C6EM00311G DOI: 10.1039/C6EM00311G]</ref>. Detailed sediment risk assessment typically follows a three-step framework similar to that described for ecological risk assessment - problem formulation, exposure analysis, and risk characterization<ref name="Suter2008">Suter, G.W., 2008. Ecological Risk Assessment in the United States Environmental Protection Agency: A Historical Overview. Integrated Environmental Assessment And Management, 4(3), pp. 285-289. [https://doi.org/10.1897/IEAM_2007-062.1 DOI: 10.1897/IEAM_2007-062.1]&nbsp;&nbsp; Free download from: [https://bioone.org/journals/integrated-environmental-assessment-and-management/volume-4/issue-3/IEAM_2007-062.1/Ecological-Risk-Assessment-in-the-United-States-Environmental-Protection-Agency/10.1897/IEAM_2007-062.1.pdf?casa_token=ieq3Cnc-YdIAAAAA:_MH-gpnwpJKvZSV2Qew43Y4ocdgADq1HvugpvmrblcGONMJgvIjYB52zQnXn_oAUW0gTy5GAkfY BioOne]</ref>.
 
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US sediment management guidance describes a detailed risk assessment process similar to that followed for US ecological risk assessment<ref name="USEPA2005"/>. The first step is problem formulation. It involves defining chemical and physical conditions, delineating the spatial footprint of the sediment area to be examined, and identifying the human uses and ecological features of the sediment. Historical data are included in this initial step to better understand the results of biota, sediment, and water sampling as well as laboratory toxicity testing results. The SLRA is often included as a part of problem formulation.
 
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The second step is exposure analysis. This step includes the identification of pathways by which human and aquatic organisms might directly or indirectly contact contaminants in the sediment. The exposure route (i.e., ingestion, dermal, or inhalation of particulates or gaseous emissions) and both the frequency and duration of contact (i.e., hourly, daily, or seasonally) are determined for each contaminant exposure pathway and human and ecological receptor. The environmental fate of the contaminant, factors affecting uptake, and the overall exposure dose are included in the calculation of the level of contaminant exposure. The exposure analysis also includes an effects assessment, whereby the biological response and associated level required to manifest different biological responses are determined for each contaminant.
 
  
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The third step is risk-characterization. It involves calculating the risks for each human and ecological receptor posed by each sediment contaminant, as well as the cumulative risk associated with the combined exposure to all contaminants exerting similar biological effects. An uncertainty analysis is often included in this step of the risk assessment to convey where knowledge or data are lacking regarding the presence of the contaminant in the sediment, the biological response associated with exposure to the contaminant, or the behavior of the receptor with respect to contact with the sediment. A sensitivity analysis also may be conducted to convey the range of exposures (lowest, typical, and worst-case) and risks associated with changes in key assumptions and parameter values used in the exposure calculations and effects assessment.
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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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==Key Considerations==
 
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===Stakeholder Engagement===
 
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Stakeholder involvement is widely acknowledged as an important element of [[Wikipedia: Dredging | dredged]] material management<ref name="Collier2014">Collier, Z.A., Bates, M.E., Wood, M.D. and Linkov, I., 2014. Stakeholder engagement in dredged material management decisions. Science of the Total Environment, 496, pp. 248-256.  [https://doi.org/10.1016/j.scitotenv.2014.07.044 DOI: 10.1016/j.scitotenv.2014.07.044]  Free download from: [https://www.researchgate.net/profile/Matthew-Bates-9/publication/264460412_Stakeholder_Engagement_in_Dredged_Material_Management_Decisions/links/5a9d50fbaca2721e3f32adea/Stakeholder-Engagement-in-Dredged-Material-Management-Decisions.pdf ResearchGate]</ref>, sediment remediation<ref name="Oen2010">Oen, A.M.P., Sparrevik, M., Barton, D.N., Nagothu, U.S., Ellen, G.J., Breedveld, G.D., Skei, J. and Slob, A., 2010. Sediment and society: an approach for assessing management of contaminated sediments and stakeholder involvement in Norway. Journal of Soils and Sediments, 10(2), pp. 202-208. [https://doi.org/10.1007/s11368-009-0182-x DOI: 10.1007/s11368-009-0182-x]</ref>, and other environmental and sediment related activities<ref name="Gerrits2004">Gerrits, L. and Edelenbos, J., 2004. Management of Sediments Through Stakeholder Involvement. Journal of Soils and Sediments, 4(4), pp. 239-246.  [https://doi.org/10.1007/BF02991120 DOI: 10.1007/BF02991120]</ref><ref name="Braun2019">Braun, A.B., da Silva Trentin, A.W., Visentin, C. and Thomé, A., 2019. Sustainable remediation through the risk management perspective and stakeholder involvement: A systematic and bibliometric view of the literature. Environmental Pollution, 255(1), p.113221.  [https://doi.org/10.1016/j.envpol.2019.113221 DOI: 10.1016/j.envpol.2019.113221]</ref>.
 
  
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Sediment management, particularly at the river basin scale, involves a wide variety of different environmental, governmental, and societal issues<ref name="Liu2018">Liu, C., Walling, D.E. and He, Y., 2018. The International Sediment Initiative case studies of sediment problems in river basins and their management. International Journal of Sediment Research, 33(2), pp. 216-219.  [https://doi.org/10.1016/j.ijsrc.2017.05.005 DOI: 10.1016/j.ijsrc.2017.05.005] Free download from: [https://www.researchgate.net/profile/Cheng-Liu-43/publication/317032034_Review_The_International_Sediment_Initiative_Case_Studies_of_sediment_problems_in_river_basins_and_their_management/links/5f4f37d2299bf13a319703df/Review-The-International-Sediment-Initiative-Case-Studies-of-sediment-problems-in-river-basins-and-their-management.pdf ResearchGate]</ref>. Incorporating these different views, interests, and perspectives into a form that builds consensus for whatever actions and goals are in mind (e.g., commercial ports and shipping, navigation, flood protection, or habitat restoration) necessitates a formal stakeholder engagement process<ref name="Slob2008">Slob, A.F.L., Ellen, G.J. and Gerrits, L., 2008. Sediment management and stakeholder involvement. In: Sustainable Management of Sediment Resources, Vol. 4: Sediment Management at the River Basin Scale, Owens, P.N. (ed.), pp. 199-216. Elsevier.  [https://doi.org/10.1016/S1872-1990(08)80009-8 DOI: 10.1016/S1872-1990(08)80009-8]</ref>.
+
==Peeper Designs==
 +
[[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)]]
 +
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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Results from a three-year (2008-2010) [https://www.ngi.no/eng/Projects/Sediment-and-society Sediment and Society] research project funded by the Norwegian Research Council point to three important challenges that must be resolved for successful stakeholder engagement: (1) how to include people who have important management information and local knowledge, but not much influence in the decision-making process; (2) how to secure resources to ensure participation and (3) how to engage and motivate stakeholders to participate early in the sediment remediation planning process<ref name="Oen2010"/>.
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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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===Conceptual Site Model===
+
==Peepers Preparation, Deployment and Retrieval==
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The preparation of a conceptual site model (CSM) is a fundamental component of problem formulation and the first step in detailed sediment risk assessment. The CSM is a narrative and/or illustrative representation of the physical, chemical and biological processes that control the transport, migration and actual or potential impacts of sediment contamination to human and/or ecological receptors<ref name="NJDEP2019">New Jersey Department of Environmental Protection, 2019. Technical Guidance for Preparation and Submission of a Conceptual Site Model. Version 1.1. Site Remediation and Waste Management Program, Trenton, NJ. 46 pp. [https://www.nj.gov/dep/srp/guidance/srra/csm_tech_guidance.pdf Free download].</ref><ref name="USEPA2011">US Environmental Protection Agency, 2011. Guidance for the Development of Conceptual Models for a Problem Formulation Developed for Registration Review. Environmental Fate and Effects Division, Office of Pesticide Programs, Washington, D.C. [https://www.epa.gov/pesticide-science-and-assessing-pesticide-risks/guidance-development-conceptual-models-problem Website]</ref>. The CSM should include a “food web” because the aquatic food web is an important exposure pathway by which contaminants in the sediment reach humans and pelagic aquatic life<ref name="Arnot2004">Arnot, J.A. and Gobas, F.A., 2004. A Food Web Bioaccumulation Model for Organic Chemicals in Aquatic Ecosystems. Environmental Toxicology and Chemistry, 23(10), pp. 2343-2355.  [https://doi.org/10.1897/03-438 DOI: 10.1897/03-438]</ref>.
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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)]]
 +
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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The CSM provides an early opportunity for critical examination of the interactions between sediment and the water column and the influence of groundwater inputs, surface runoff, and hydrodynamics. For example, there are situations where impacts in the aquatic food web can be driven by ongoing inputs to the water column from upstream sources, but mistakenly connected to polluted sediments. Other considerations included in a CSM can be socio-economic and include linkages to the ecosystem services provided by sediments<ref name="Broszeit2019">Broszeit, S., Beaumont, N.J., Hooper, T.L., Somerfield, P.J. and Austen, M.C., 2019. Developing conceptual models that link multiple ecosystem services to ecological research to aid management and policy, the UK marine example. Marine Pollution Bulletin, 141, pp.236-243.  [https://doi.org/10.1016/j.marpolbul.2019.02.051 DOI: 10.1016/j.marpolbul.2019.02.051]&nbsp;&nbsp; [https://www.sciencedirect.com/science/article/pii/S0025326X19301511/pdfft?md5=34993d6c3a57b6fb18a8b6329597fcb9&pid=1-s2.0-S0025326X19301511-main.pdf Open Access Article.]</ref><ref name="Wang2021">Wang, J., Lautz, L.S., Nolte, T.M., Posthuma, L., Koopman, K.R., Leuven, R.S. and Hendriks, A.J., 2021. Towards a systematic method for assessing the impact of chemical pollution on ecosystem services of water systems. Journal of Environmental Management, 281, p. 111873.  [https://doi.org/10.1016/j.jenvman.2020.111873 DOI: 10.1016/j.jenvman.2020.111873]&nbsp;&nbsp; [https://www.sciencedirect.com/science/article/pii/S0301479720317989/pdfft?md5=daff5e94f8aed44ffce6508afef2308c&pid=1-s2.0-S0301479720317989-main.pdf  Open Access Article.]</ref>, or the social, economic and environmental impacts of sediment management alternatives. In such a case, when risk assessment seeks to compare risks of various management actions (including no action), the CSM can be termed a sustainability CSM, or SustCSM<ref name="McNally2020">McNally, A.D., Fitzpatrick, A.G., Harrison, D., Busey, A., and Apitz, S.E., 2020. Tiered approach to sustainability analysis in sediment remediation decision making. Remediation Journal, 31(1), pp. 29-44.  [https://doi.org/10.1002/rem.21661 DOI: 10.1002/rem.21661]&nbsp;&nbsp; [https://onlinelibrary.wiley.com/doi/epdf/10.1002/rem.21661 Open Access Article].</ref><ref name="Holland2011">Holland, K.S., Lewis, R.E., Tipton, K., Karnis, S., Dona, C., Petrovskis, E., and Hook, C., 2011. Framework for Integrating Sustainability Into Remediation Projects. Remediation Journal, 21(3), pp. 7-38. [https://doi.org/10.1002/rem.20288 DOI: 10.1002/rem.20288].</ref>. At a minimum, however, the purpose of the CSM is to illustrate the scope of the risk assessment and guide the quantification of exposure and risk.
+
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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===Environmental Fate===
+
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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An important consideration in exposure analysis is the determination of the bioavailable fraction of the contaminant in the sediment. There are two considerations. First, the adverse condition may be buried deep enough in sediments to be below the biologically available zone; typically, conditions in sediment below a depth of 5 cm will not contact burrowing benthic organisms<ref name="Anderson2010">Anderson, R.H., Prues, A.G. and Kravitz, M.J., 2010. Determination of the biologically relevant sampling depth for terrestrial ecological risk assessments. Geoderma, 154(3-4), pp.336-339.  [https://doi.org/10.1016/j.geoderma.2009.11.004 DOI: 10.1016/j.geoderma.2009.11.004]</ref>. If there is no prospect for the adverse condition to come closer to the surface, then the risk assessment could conclude the risk of exposure is insignificant. The second consideration relates to chemistry and the factors involved in the binding to sediment particles or the chemical form of the substance in the sediment<ref name="Eggleton2004">Eggleton, J. and Thomas, K.V., 2004. A review of factors affecting the release and bioavailability of contaminants during sediment disturbance events. Environment International, 30(7), pp. 973-980.  [https://doi.org/10.1016/j.envint.2004.03.001 DOI: 10.1016/j.envint.2004.03.001]</ref>. However, these assumptions should be examined in the context of [[Climate Change Primer | climate change]], and the likelihood of more frequent and extreme events, putting burial at risk, higher temperatures and changing biogeochemical conditions, which may alter environmental fate of contaminants, compared to historical studies.  
 
  
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The above contaminant bioavailability considerations are important factors influencing assumptions in the risk assessment about contaminant exposure<ref name="Peijnenburg2020">Peijnenburg, W.J., 2020. Implementation of bioavailability in prospective and retrospective risk assessment of chemicals in soils and sediments. In: The Handbook of Environmental Chemistry, vol 100, Bioavailability of Organic Chemicals in Soil and Sediment, Ortega-Calvo, J.J., Parsons, J.R. (ed.s), pp.391-422. Springer.  [https://doi.org/10.1007/698_2020_516 DOI: 10.1007/698_2020_516]</ref><ref name="Ortega-Calvo2015">Ortega-Calvo, J.J., Harmsen, J., Parsons, J.R., Semple, K.T., Aitken, M.D., Ajao, C., Eadsforth, C., Galay-Burgos, M., Naidu, R., Oliver, R. and Peijnenburg, W.J., 2015. From Bioavailability Science to Regulation of Organic Chemicals. Environmental Science and Technology, 49, 10255−10264. [https://doi.org/10.1021/acs.est.5b02412 DOI: 10.1021/acs.est.5b02412]&nbsp;&nbsp; [https://pubs.acs.org/doi/pdf/10.1021/acs.est.5b02412 Open Access Article].</ref>. There have been recent advances in the use of sorbent amendments applied to contaminated sediments that alter sediment geochemistry, increase contaminant binding, and reduce contaminant exposure risks to people and the environment<ref name="Ghosh2011">Ghosh, U., Luthy, R.G., Cornelissen, G., Werner, D. and Menzie, C.A., 2011. In-situ sorbent amendments: a new direction in contaminated sediment management. Environmental Science and Technology, 45, 4, 1163–1168.  [https://doi.org/10.1021/es102694h DOI: 10.1021/es102694h]&nbsp;&nbsp; [https://pubs.acs.org/doi/pdf/10.1021/es102694h Open Access Article]</ref>. [[Passive Sampling of Sediments | Passive sampling techniques]] have emerged to quantify chemical binding to sediment and determine the freely dissolved concentration that is bioavailable.
+
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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===Assessment and Measurement Endpoints===
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==Equilibrium Determination (Tracers)==
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Assessment and measurement endpoints used in sediment risk assessment are comparable to those described in USEPA ecological risk assessment guidance<ref name="USEPA2005"/><ref name="USEPA1992">US Environmental Protection Agency (USEPA), 1992. Framework for Ecological Risk Assessment, EPA/630/R-92/001. Risk Assessment Forum, Washington DC.  [[Media: EPA-630-R-92-001.pdf | Report.pdf]]</ref><ref name="USEPA1996">US Environmental Protection Agency (USEPA), 1996. Eco Update: Ecological Significance and Selection of Candidate Assessment Endpoints. EPA/540/F-95/037. Office of Solid Waste and Emergency Response, Washington DC.  [[Media: EPA 540-F-95-037.pdf | Report.pdf]]</ref><ref name="USEPA1997b">US Environmental Protection Agency (USEPA), 1997. Ecological Risk Assessment Guidance for Superfund: Process for Designing and Conducting Ecological Risk Assessments - Interim Final, EPA 540/R-97/006. Office of Solid Waste and Emergency Response, Washington DC.  [[Media: EPA 540-R-97-006.pdf | Report.pdf]]</ref><ref name="USEPA1998">US Environmental Protection Agency (USEPA), 1998. Guidelines for Ecological Risk Assessment. EPA/630/R-95/002F. Risk Assessment Forum, Washington DC. [[Media: EPA 630-R-95-002F.pdf | Report.pdf]]</ref>. A sediment risk assessment, and ecological risk assessments more broadly, must have clearly defined endpoints that are socially and biologically relevant, accessible to prediction and measurement, and susceptible to the hazard being assessed<ref name="USEPA1992"/>.
+
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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Assessment endpoints for humans include both carcinogenic and noncarcinogenic effects. Due to their assumed higher levels of exposure, human receptors used in sediment risk assessment typically include recreational, commercial, and subsistence fishermen, i.e., people who might be at increased risk from eating fish or contacting the sediment or water on a regular basis such as indigenous peoples, immigrants from fishing cultures, and subsistence fishers who rely upon fish as a major source of protein. Special considerations are given to women of child-bearing age, pregnant women and young children. Assessment endpoints for ecological receptors focus on benthic organisms, resident fish, piscivorous and other predatory birds and marine mammals. Endpoints typically include mortality, reproductive success and population susceptibility to disease or similar adverse chronic conditions.
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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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Measurement endpoints are related quantitatively to each assessment endpoint. Whenever practical, multiple measurement endpoints are chosen to provide additional lines of evidence for each assessment endpoint. For example, for humans, it might be possible to measure contaminant levels in both food items and human blood or tissue. For predatory fish, birds and mammals, it might be possible to measure contaminants in both prey and predator tissues. Measurement endpoints can be selected to assess non-chemical stressors as well, such as habitat alteration and water turbidity. Typically, measurement endpoints are compared to measurements at a reference site to ascertain the degree of departure from local natural or background conditions.
+
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''):
 +
</br>
 +
{|
 +
| || '''Equation&nbsp;1:'''
 +
|&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;[[File: Equation1r.png]]
 +
|-
 +
| Where: || ||
 +
|-
 +
| || ''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>
 +
|-
 +
| || ''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)
 +
|-
 +
| || ''K'' || is the elimination rate of the target analyte
 +
|-
 +
| || ''t'' || is the deployment time (days)
 +
|}
  
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===Sediment Toxicity Testing===
+
The elimination rate of the target analyte (''K'') is calculated using Equation 2:
−
Sediment bioassays are an integral part of effects characterization when assessing the risks posed by contaminated sediments and developing sediment quality guidelines<ref name="USEPA2014">US Environmental Protection Agency (USEPA), 2014. Toxicity Testing and Ecological Risk Assessment Guidance for Benthic Invertebrates. Office of Chemical Safety and Pollution Prevention, Washington DC.  [https://www.epa.gov/pesticide-science-and-assessing-pesticide-risks/toxicity-testing-and-ecological-risk-assessment Website]&nbsp;&nbsp; [[Media: USEPA2014.pdf | Report.pdf]]</ref><ref name="Simpson2016a">Simpson, S., Campana, O., Ho, K., 2016. Chapter 7, Sediment Toxicity Testing. In: J. Blasco, P.M. Chapman, O. Campana, M. Hampel (ed.s), Marine Ecotoxicology: Current Knowledge and Future Issues. Academic Press Incorporated. pp. 199-237.  [https://doi.org/10.1016/B978-0-12-803371-5.00007-2 DOI: 10.1016/B978-0-12-803371-5.00007-2]</ref>. The selection of appropriate sediment bioassays is dependent on the questions being addressed, the physical and chemical characteristics of the sediment matrix, the nature of the contaminant(s) of concern, and preferences of the supervising regulatory authority for the test method and test organisms<ref name="Amiard-Triquet2015">Amiard-Triquet, C., Amiard, J.C. and Mouneyrac, C. (ed.s), 2015. Aquatic Ecotoxicology: Advancing Tools For Dealing With Emerging Risks. Academic Press, NY. ISBN #9780128009499.  [https://doi.org/10.1016/B978-0-12-800949-9.12001-7 DOI: 10.1016/B978-0-12-800949-9.12001-7]</ref>. Bioassay procedures have been standardized in several countries, and it is not unusual for different test methods to be required in different countries for the same sediment management purpose<ref name="DelValls2004">DelValls, T.A., Andres, A., Belzunce, M.J., Buceta, J.L., Casado-Martinez, M.C., Castro, R., Riba, I., Viguri, J.R. and Blasco, J., 2004. Chemical and ecotoxicological guidelines for managing disposal of dredged material. TrAC Trends in Analytical Chemistry, 23(10-11), pp. 819-828.  [https://doi.org/10.1016/j.trac.2004.07.014 DOI: 10.1016/j.trac.2004.07.014]&nbsp;&nbsp; Free download from: [https://d1wqtxts1xzle7.cloudfront.net/46085251/Chemical_and_Ecotoxicological_Guidelines20160530-23122-4fooj2-with-cover-page-v2.pdf?Expires=1637618385&Signature=aNsOfciO0HPhucL8S713nenRlvviD2dbLi8y63n93iGX~Cc7CHwyYQ2bfNlT6VnjuFJeVT83M01Xog6esr14gyvL9pmlo3hw5fQp5J9vA8gqXcT9kQfM1T2Q0Ig883yGMFmtgUrrU6p8c8V~8rh5DTKDD5ZsiL4zloGgF6Gs4F2ecEDqyFBZ17yYpXGVVBmpfm87sUpaPY0Ix9iWJ~5nxM~HF6XYl1sA1rgFSerT-Y5W8Ma7-XMljnYHQ7hW7eqMjyN66IDj7pwafG7Ox-Hnp07IuD-oMY1dHHrzTOmHpXpWgMYLn2zf1BSmy~tqIFHE6UjZn5ako93PgExuzEjEiw__&Key-Pair-Id=APKAJLOHF5GGSLRBV4ZA Academia.edu]</ref>. Guidance documents in Australia, Canada, Europe and the US cover the wide range of sediment bioassay procedures most often used in risk assessment<ref name="Bat2005">Bat, L., 2005. A Review of Sediment Toxicity Bioassays Using the Amphipods and Polychaetes. Turkish Journal of Fisheries and Aquatic Sciences, 5(2), pp. 119-139.  [https://dergipark.org.tr/en/pub/trjfas-ayrildi/issue/13287/160604 Free download]&nbsp;&nbsp; [[Media: Bat2005.pdf | Report.pdf]]</ref><ref name="Keddy1995">Keddy, C.J., Greene, J.C. and Bonnell, M.A., 1995. Review of Whole-Organism Bioassays: Soil, Freshwater Sediment, and Freshwater Assessment in Canada. Ecotoxicology and Environmental Safety, 30(3), pp. 221-251.  [https://doi.org/10.1006/eesa.1995.1027 DOI: 10.1006/eesa.1995.1027]</ref><ref name="Giesy1990">Giesy, J.P., Rosiu, C.J., Graney, R.L. and Henry, M.G., 1990. Benthic invertebrate bioassays with toxic sediment and pore water. Environmental Toxicology and Chemistry, 9(2), pp. 233-248.  [https://doi.org/10.1002/etc.5620090214 DOI: 10.1002/etc.5620090214]</ref><ref name="Simpson2016b">Simpson, S. and Batley, G. (ed.s), 2016. Sediment Quality Assessment: A Practical Guide, Second Edition. 358 pp. CSIRO Publishing, Australia. ISBN # 9781486303847.</ref><ref name="Moore2019">Moore, D.W., Farrar, D., Altman, S. and Bridges, T.S., 2019. Comparison of Acute and Chronic Toxicity Laboratory Bioassay Endpoints with Benthic Community Responses in Field‐Exposed Contaminated Sediments. Environmental Toxicology and Chemistry, 38(8), pp. 1784-1802.  [https://doi.org/10.1002/etc.4454 DOI: 10.1002/etc.4454]</ref>.
+
</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)
 +
|}
  
−
In general, sediment toxicity tests focus on either (acute) lethality in whole organisms (typically benthic infaunal species such as amphipods and polychaetes) following short-term or acute exposures (<14 days) or (chronic) sublethal responses (e.g., reduced growth or reproduction or both) following longer-term exposures<ref name="Simpson2016a"/>. It is not unusual in sediment risk assessment to rely on more than one sediment bioassay. Both acute and chronic tests involving either solid-phase or pore-water sediment fractions can be useful to discern the contributions of different contaminants in whole sediment by examining the response of different endpoints in different test organisms<ref name="Keddy1995"/><ref name="Giesy1990"/>. The application of more specialized techniques such as toxicity identification evaluations (TIEs) have also proved useful to help identify contaminants or contaminant classes most likely responsible for toxicity and to exclude potentially confounding factors such as ammonia<ref name="Ho2013">Ho, K.T. and Burgess, R.M., 2013. What's causing toxicity in sediments? Results of 20 years of toxicity identification and evaluations. Environmental Toxicology and Chemistry, 32(11), pp. 2424-2432.  [https://doi.org/10.1002/etc.2359 DOI: 10.1002/etc.2359]</ref><ref name="Bailey2016">Bailey, H.C., Curran, C.A., Arth, P., Lo, B.P. and Gossett, R., 2016. Application of sediment toxicity identification evaluation techniques to a site with multiple contaminants. Environmental Toxicology and Chemistry, 35(10), pp. 2456-2465.  [https://doi.org/10.1002/etc.3488 DOI: 10.1002/etc.3488]</ref>.
+
The elimination rate of the tracer (''K<small><sub>tracer</sub></small>'') is calculated using Equation 3:
 +
</br>
 +
{|
 +
| || '''Equation&nbsp;3:'''  
 +
|&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;[[File: Equation3r2.png]]
 +
|-
 +
| Where: || ||
 +
|-
 +
| || ''K<small><sub>tracer</sub></small>'' || is the elimination rate of the tracer
 +
|-
 +
| || ''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)
 +
|-
 +
| || ''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)
 +
|-
 +
| || ''t'' || is the deployment time (days)
 +
|}
  
−
===Uncertainty===
+
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"/>.
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As part of the overall analysis of risk from exposure to certain sediment conditions, it is generally understood there is a moderate degree of uncertainty associated with sampling and the environmental fate of contaminants; an order of magnitude of uncertainty associated with ecological exposure and dose-response; and greater than an order of magnitude of uncertainty associated with the quantification of potential human health effects<ref name="DiGuardo2018">Di Guardo, A., Gouin, T., MacLeod, M. and Scheringer, M., 2018. Environmental fate and exposure models: advances and challenges in 21st century chemical risk assessment. Environmental Science: Processes and Impacts, 20(1), pp. 58-71.  [https://doi.org/10.1039/C7EM00568G DOI: 10.1039/C7EM00568G]&nbsp;&nbsp;  [https://pubs.rsc.org/en/content/articlehtml/2018/em/c7em00568g  Open access article]</ref>. The sources of uncertainty and significance to sediment risk assessment can vary widely, thereby affecting confidence in the decisions made based on risk assessment<ref name="Reckhow1994">Reckhow, K.H., 1994. Water quality simulation modeling and uncertainty analysis for risk assessment and decision making. Ecological Modelling, 72(1-2), pp.1-20.  [https://doi.org/10.1016/0304-3800(94)90143-0 DOI: 10.1016/0304-3800(94)90143-0]</ref><ref name="Chapman2002">Chapman, P.M., Ho, K.T., Munns Jr, W.R., Solomon, K. and Weinstein, M.P., 2002. Issues in sediment toxicity and ecological risk assessment. Marine Pollution Bulletin, 44(4), pp. 271-278.  [https://doi.org/10.1016/S0025-326X(01)00329-0 DOI: 10.1016/S0025-326X(01)00329-0]</ref>.
 
  
−
Consequently, technical guidance in several countries encourages including a quantitative uncertainty analysis in sediment risk assessment<ref name="USEPA2005"/><ref name="Tarazona2014"/><ref name="Apitz2005a"/><ref name="Apitz2005b"/>. The aim of uncertainty analysis is to express either quantitatively or qualitatively the limitations inherent in predicting exposures and effects and, ultimately, the level of overall risk posed by sediment conditions<ref name="Batley2002">Batley, G.E., Burton, G.A., Chapman, P.M. and Forbes, V.E., 2002. Uncertainties in Sediment Quality Weight-of-Evidence (WOE) Assessments. Human and Ecological Risk Assessment, 8(7), pp. 1517-1547.  [https://doi.org/10.1080/20028091057466 DOI: 10.1080/20028091057466]</ref>. Sediment risk assessment increasingly relies on a weight-of-evidence process to improve the certainty of conclusions about whether or not impairment exists due to sediment contamination, and, if so, which stressors and biological species (or ecological responses) are of greatest concern<ref name="Burton2002">Burton, G.A., Batley, G.E., Chapman, P.M., Forbes, V.E., Smith, E.P., Reynoldson, T., Schlekat, C.E., Besten, P.J.D., Bailer, A.J., Green, A.S. and Dwyer, R.L., 2002. A Weight-of-Evidence Framework for Assessing Sediment (or Other) Contamination: Improving Certainty in the Decision-Making Process. Human and Ecological Risk Assessment, 8(7), pp. 1675-1696.  [https://doi.org/10.1080/20028091056854 DOI: 10.1080/20028091056854]</ref>. Recent advancements, including the use of Bayesian networks and geographic information systems, also help capture the range of variability in both measured and predicted exposures and responses<ref name="Holsman2017">Holsman, K., Samhouri, J., Cook, G., Hazen, E., Olsen, E., Dillard, M., Kasperski, S., Gaichas, S., Kelble, C.R., Fogarty, M. and Andrews, K., 2017. An ecosystem‐based approach to marine risk assessment. Ecosystem Health and Sustainability, 3(1), p. e01256.  [https://doi.org/10.1002/ehs2.1256 DOI: 10.1002/ehs2.1256]&nbsp;&nbsp; [https://www.tandfonline.com/doi/full/10.1002/ehs2.1256 Open access article]</ref><ref name="Marcot2019">Marcot, B.G. and Penman, T.D., 2019. Advances in Bayesian network modelling: Integration of modelling technologies. Environmental Modelling and Software, 111, pp. 386-393.  [https://doi.org/10.1016/j.envsoft.2018.09.016 DOI: 10.1016/j.envsoft.2018.09.016]</ref><ref name="Men2019">Men, C., Liu, R., Wang, Q., Guo, L., Miao, Y. and Shen, Z., 2019. Uncertainty analysis in source apportionment of heavy metals in road dust based on positive matrix factorization model and geographic information system. Science of The Total Environment, 652, pp. 27-39.  [https://doi.org/10.1016/j.scitotenv.2018.10.212 DOI: 10.1016/j.scitotenv.2018.10.212]</ref>. The level of sophistication applied to the uncertainty analysis is a subjective consideration and often decided by regulatory pressures, public perceptions and the likely cost (not only economic, but also social and environmental) of mitigating or removing the contamination.
+
==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.
  
−
==Role in Sediment Management==
+
'''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.
−
Whether or not remediation of contaminated sediments is warranted depends on the magnitude of direct or indirect health risks to humans, ecological threats to aquatic biota, and the extent of risk reduction that can be achieved by removal or containment of the contamination<ref name="Kvasnicka2020">Kvasnicka, J., Burton Jr, G.A., Semrau, J. and Jolliet, O., 2020. Dredging Contaminated Sediments: Is it Worth the Risks? Environmental Toxicology and Chemistry, 39(3), pp. 515-516.  [https://setac.onlinelibrary.wiley.com/doi/pdfdirect/10.1002/etc.4679 DOI: 10.1002/etc.4679]&nbsp;&nbsp; [https://setac.onlinelibrary.wiley.com/doi/pdfdirect/10.1002/etc.4679 Open access article]</ref>. As all sediment management also introduces risk pathways, such as sediment re-suspension leading to contaminant release, possible impacts due to land, water and energy usage, and risk to workers, remedial decision-making should also consider the risks posed by the remedial process. There are two types of remediation risks inherent in sediment remediation - engineering and biological. Sediment remedy implementation risks are predominantly short-term engineering issues associated with applying the remedy such as worker and community health and safety, equipment failures, and accident rates<ref name="Wenning2006">Wenning, R.J., Sorensen, M. and Magar, V.S., 2006. Importance of Implementation and Residual Risk Analyses in Sediment Remediation. Integrated Environmental Assessment and Management, 2(1), pp. 59-65.  [https://doi.org/10.1002/ieam.5630020111 DOI: 10.1002/ieam.5630020111]&nbsp;&nbsp; [https://setac.onlinelibrary.wiley.com/doi/full/10.1002/ieam.5630020111 Open access article]</ref>. Sediment residual risks are predominantly longer-term changes in exposure and effects to humans, aquatic biota, and wildlife after the remedy has been implemented<ref name="Wenning2006"/>.
 
  
−
In addition to evaluating sediment conditions prior to remediation, sediment risk assessment can be useful to understand how the engineering risks, the contaminant exposure pathways, and which human and wildlife populations are at risk might change with different remediation options<ref name="NRC2001">National Research Council (NRC), 2001. A Risk‐Management Strategy For PCB Contaminated Sediments. Committee On Remediation Of PCB‐Contaminated Sediments, Board On Environmental Studies And Toxicology. National Academies Press, Washington DC. 452 pp. ISBN: 0-309-58873-1 [https://doi.org/10.17226/10041 DOI: 10.17226/10041]&nbsp;&nbsp; Free download from: [https://www.nap.edu/catalog/10041/a-risk-management-strategy-for-pcb-contaminated-sediments The National Academies Press]</ref>. Decision tools such as multi-criteria decision analysis (MCDA), or sustainability assessment<ref name="Apitz2018">Apitz, S.E., Fitzpatrick, A., McNally, A., Harrison, D., Coughlin, C., and Edwards, D.A., 2018. Stakeholder Value-Linked Sustainability Assessment: Evaluating Remedial Alternatives for the Portland Harbor Superfund Site, Portland, Oregon, USA. Integrated Environmental Assessment and Management, 14(1), pp. 43-62. [https://doi.org/10.1002/ieam.1998 DOI: 10.1002/ieam.1998]&nbsp;&nbsp; [https://setac.onlinelibrary.wiley.com/doi/full/10.1002/ieam.1998 Open access article]</ref><ref name="Fitzpatrick2018">Fitzpatrick, A., Apitz, S.E., Harrison, D., Ruffle, B., and Edwards, D.A., 2018. The Portland Harbor Superfund Site Sustainability Project:  Introduction. Integrated Environmental Assessment and Management, 14(1), pp. 17-21.  [https://doi.org/10.1002/ieam.1997 DOI: 10.1002/ieam.197]&nbsp;&nbsp; [https://setac.onlinelibrary.wiley.com/doi/full/10.1002/ieam.1997 Open access article]</ref>, for example, incorporate elements from sediment risk assessment to support remediation decision making<ref name="Linkov2006a">Linkov, I., Satterstrom, F.K., Kiker, G., Seager, T.P., Bridges, T., Gardner, K.H., Rogers, S.H., Belluck, D.A. and Meyer, A., 2006. Multicriteria Decision Analysis: A Comprehensive Decision Approach for Management of Contaminated Sediments. Risk Analysis, 26(1), pp. 61-78.  [https://doi.org/10.1111/j.1539-6924.2006.00713.x DOI: 10.1111/j.1539-6924.2006.00713.x]&nbsp;&nbsp; Free download from: [https://digitalcommons.unl.edu/cgi/viewcontent.cgi?article=1164&context=usarmyceomaha US Army Corps of Engineers]</ref>. Sediment risk assessment also plays an important role in the implementation of monitored natural recovery (MNR) as a remediation strategy<ref name="Magar2006">Magar, V.S. and Wenning, R.J., 2006. The role of monitored natural recovery in sediment remediation. Integrated Environmental Assessment and Management, 2(1), pp. 66-74.  [https://doi.org/10.1002/ieam.5630020112 DOI: 10.1002/ieam.5630020112]&nbsp;&nbsp; [https://setac.onlinelibrary.wiley.com/doi/full/10.1002/ieam.5630020112 Open access article]</ref>. Insofar as ecological recovery is affected by surface‐sediment‐contaminant concentrations, the primary recovery processes for MNR are natural sediment burial and transformation of the contaminant to less toxic forms by biological or chemical processes<ref name="Magar2009">Magar, V.S., Chadwick, D.B., Bridges, T.S., Fuchsman, P.C., Conder, J.M., Dekker, T.J., Steevens, J.A., Gustavson, K.E. and Mills, M.A., 2009. Technical Guide: Monitored Natural Recovery at Contaminated Sediment Sites. Environmental Security Technology Certification Program (ESTCP) Project ER-0622. 277 pp.  [https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/Contaminated-Sediments/In-place-Remediation/ER-200622/(language)/eng-US Website]&nbsp;&nbsp; [https://apps.dtic.mil/sti/pdfs/ADA512822.pdf Free download]</ref>.
+
'''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.
  
−
Since risk reduction is the long‐term goal of contaminated sediment management<ref name="Apitz2002">Apitz, S.E. and Power, E.A., 2002. From Risk Assessment to Sediment Management: An International Perspective. Journal of Soils and Sediments, 2(2), pp. 61-66.  [https://doi.org/10.1007/BF02987872 DOI: 10.1007/BF02987872]&nbsp;&nbsp; Free download from: [https://www.researchgate.net/profile/Sabine-Apitz/publication/225649107_From_risk_assessment_to_sediment_management_An_international_perspective/links/09e4150cb2df7c6331000000/From-risk-assessment-to-sediment-management-An-international-perspective.pdf ResearchGate]</ref>, predicting the rate at which contaminant exposures and risks are mitigated by sedimentation and degradation over time can be aided by including parameters in the risk assessment that calculate the rate of contaminant removal or decay in the sediment. Evaluating sediment management options in terms of risk reduction involves assessing risks under the diverse set of conditions that include the current state of the site as well as the conditions that would occur both during the implementation work and long after the work is complete and the ecosystem stabilizes<ref name="Linkov2006b">Linkov, I., Satterstrom, F.K., Kiker, G.A., Bridges, T.S., Benjamin, S.L. and Belluck, D.A., 2006. From Optimization to Adaptation: Shifting Paradigms in Environmental Management and Their Application to Remedial Decisions. Integrated Environmental Assessment and Management, 2(1), pp. 92-98. [https://doi.org/10.1002/ieam.5630020116 DOI: 10.1002/ieam.5630020116]&nbsp;&nbsp; [https://setac.onlinelibrary.wiley.com/doi/epdf/10.1002/ieam.5630020116 Open access article]</ref><ref name="Reible2003">Reible, D., Hayes, D., Lue-Hing, C., Patterson, J., Bhowmik, N., Johnson, M. and Teal, J., 2003. Comparison of the Long-Term Risks of Removal and In Situ Management of Contaminated Sediments in the Fox River. Soil and Sediment Contamination, 12(3), pp. 325-344.  [https://doi.org/10.1080/713610975 DOI: 10.1080/713610975]</ref>.
+
'''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.
  
−
==Summary==
+
'''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.
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Effective sediment risk assessment begins with an initial scoping and planning exercise. The work proceeds to a SLRA and, if warranted, detailed risk assessment using a process comparable to ecological risk assessment. The key elements of sediment risk assessment must include a well‐designed and site‐specific CSM; a transparent and well‐thought‐out biological and chemical data collection and analysis plan; carefully selected reference sites and decision criteria; and an explicit discussion of uncertainty. If the risk assessment concludes that unacceptable risks exist, risk‐management strategies must be evaluated, selected, implemented, and their success evaluated.
 
  
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Sediment risk assessments are designed to simulate and predict plausible interactions between contaminants or other stressors and both ecological and human receptors. The intent is to derive meaningful insights that provide conclusions that are both rational and protective, in that they err on the side of over-estimating the likely environmental risks. Although conservative assumptions should always be used early in the sediment risk assessment process, final decisions should be supported by refined, realistic estimates of risk provided by site‐specific data and sound analytical approaches. It is increasingly evident after nearly 50 years of application that sediment risk assessment is most useful when supported by a well‐designed, site‐specific, and tiered assessment process<ref name="Bridges2005">Bridges, T., Berry, W., Della Sala, S., Dorn, P., Ells, S., Gries, T., Ireland, S., Maher, E., Menzie, C., Porebski, L., and Stronkhorst, J., 2005. Chapter 6: A framework for assessing and managing risks from contaminated sediments. In: Use of sediment quality guidelines and related tools for the assessment of contaminated sediments. Wenning, Batley, Ingersoll, and Moore, editors. Society of Environmental Toxicology and Chemistry (SETAC), pp. 227–266. ISBN: 1-880611-71-6</ref>.
+
'''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==
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==See Also==
 
==See Also==
 +
*[https://vimeo.com/809180171/c276c1873a Peeper Deployment Video]
 +
*[https://vimeo.com/811073634/303edf2693 Peeper Retrieval Video]
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*[https://vimeo.com/811328715/aea3073540 Peeper Processing Video]
 +
*[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]

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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