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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.

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 (C_p,t), the elimination rate of the target analyte (K) and the deployment time (t):

	Equation 1:
Where:
	C₀	is the freely dissolved concentration of the analyte in the sediment (mg/L or μg/L), sometimes referred to as C_free
	C_p,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:
Where:
	K	is the elimination rate of the target analyte
	K_tracer	is the elimination rate of the tracer
	D	is the free water diffusivity of the analyte (cm²/s)
	D_tracer	is the free water diffusivity of the tracer (cm²/s)

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

	Equation 3:
Where:
	K_tracer	is the elimination rate of the tracer
	C_tracer,i	is the measured initial concentration of the tracer in the peeper prior to deployment (mg/L or μg/L)
	C_tracer,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

^ 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
^ ^2.0 ^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
^ 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
^ ^4.0 ^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
^ ^5.0 ^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
^ 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
^ ^7.0 ^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
^ 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
^ 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
^ ^10.0 ^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
^ 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
^ ^12.0 ^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
^ 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
^ 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
^ ^15.0 ^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
^ 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

@@ Line 1: / Line 1: @@
-==Supercritical Water Oxidation (SCWO)==
+==Sediment Porewater Dialysis Passive Samplers for Inorganics (Peepers)==
-Supercritical water oxidation (SCWO) is a single step [[Wikipedia: Wet oxidation | wet oxidation]] process that transforms organic matter into water, carbon dioxide and, depending on the waste undergoing treatment, an inert mineral solid residue. The process is highly effective and can treat a variety of wet wastes without dewatering. The SCWO technology allows for the complete destruction of persistent and toxic organic contaminants such as [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | perfluoroalkyl and polyfluoroalkyl substances (PFAS)]], [[1,4-Dioxane | 1,4-dioxane]], and many more.
+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.
 <div style="float:right;margin:0 0 2em 2em;">__TOC__</div>
 '''Related Article(s):'''
-* [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)]]
+*[[Contaminated Sediments - Introduction]]
-* [[PFAS Transport and Fate]]
+*[[Contaminated Sediment Risk Assessment]]
-* [[Chlorinated Solvents]]
+*[[In Situ Treatment of Contaminated Sediments with Activated Carbon]]
+*[[Passive Sampling of Munitions Constituents]]
+*[[Sediment Capping]]
+*[[Mercury in Sediments]]
+*[[Passive Sampling of Sediments]]
-'''Contributor(s):''' [[Kobe Nagar]] and [[Dr. Marc Deshusses]]
-'''Key Resource(s):'''
+'''Contributor(s):'''
-*Treatment of municipal sewage sludge in supercritical water: A review<ref name="Qian2016">Qian, L., Wang, S., Xu, D., Guo, Y., Tang, X., and Wang, L., 2016. Treatment of municipal sewage sludge in supercritical water: A review. Water Research, 89, pp. 118-131.  [https://doi.org/10.1016/j.watres.2015.11.047 DOI: 10.1016/j.watres.2015.11.047]&nbsp;&nbsp; Free download from: [https://www.researchgate.net/profile/Shuzhong-Wang/publication/284563832_Treatment_of_Municipal_Sewage_Sludge_in_Supercritical_Water_a_Review/links/5d9b63b6299bf1c363fef63e/Treatment-of-Municipal-Sewage-Sludge-in-Supercritical-Water-a-Review.pdf ResearchGate]</ref>.
+*Florent Risacher, M.Sc.
+*Jason Conder, Ph.D.
-*Supercritical Water Oxidation – Current Status of Full-scale Commercial Activity for Waste Destruction<ref name="Marrone2013">Marrone, P.A., 2013. Supercritical Water Oxidation – Current Status of Full-scale Commercial Activity for Waste Destruction. Journal of Supercritical Fluids, 79, pp. 283-288. [https://doi.org/10.1016/j.supflu.2012.12.020 DOI: 10.1016/j.supflu.2012.12.020]&nbsp;&nbsp; Author’s manuscript available from: [https://semspub.epa.gov/work/06/9545963.pdf US EPA]</ref>.
+'''Key Resource(s):'''
-==Introduction==
+*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>
-Supercritical water oxidation (SCWO) is an [[Wikipedia: Advanced oxidation process | advanced oxidation process]] that holds enormous potential for the treatment of a wide range of organic wastes, in particular concentrated wet wastes in slurries such as biosolids, sludges, agricultural wastes, chemical wastes with recalcitrant chemicals such as [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)| perfluoroalkyl and polyfluoroalkyl substances (PFAS)]], and many more. SCWO relies on the unique reactivity and transport properties that occur when an aqueous waste stream is brought above the critical point of water (374&deg;C and 218 atm, or 704&deg;F and 3200 psi, see phase diagram in Figure 1). [[Wikipedia: Supercritical fluid |  Supercritical water]] is a dense single phase with transport properties similar to those of a gas, and solvent properties comparable to those of a non-polar solvent<ref name="Tassaing2002">Tassaing, T., Danten, Y., and Besnard, M., 2002. Infrared spectroscopic study of hydrogen bonding in water at high temperature and pressure, Journal of Molecular Liquids, 101(1-3), pp. 149-158.  [https://doi.org/10.1016/S0167-7322(02)00089-2 DOI: 10.1016/S0167-7322(02)00089-2]</ref>. Oxygen is fully soluble in supercritical water, resulting in extremely rapid and complete oxidation of all organics to carbon dioxide, clean water (that can be reused), and some non-leachable inorganic salts.
-For SCWO to be economical, the heat from the oxidation reaction is recovered and used in part to heat the influent stream, while the excess heat can be converted to electricity. Depending on the concentration of waste in the feedstock, SCWO reactors can be operated autothermally, i.e., no outside input of heat is required. Typical reaction times are in the order of 2-10 seconds, resulting in SCWO systems that are quite compact compared to other technologies (see Table 1). The process does not generate harmful by-products such as nitrogen oxides (NOx) or Sulfur oxides (SOx), carbon monoxide (CO), or odors<ref Name="Bermejo">Bermejo, M.D. and Cocero, M.J., 2006. Supercritical water oxidation: A technical review. AIChE Journal, 52(11) pp. 3933-3951.  [https://doi.org/10.1002/aic.10993 DOI: 10.1002/aic.10993]</ref>. Typically, if present, ammonia and organic nitrogen in the waste undergoing treatment are converted to nitrogen gas, while phosphorous precipitates as phosphates and can be recovered. When [[Wikipedia: Halogen | halogen]] containing contaminants are treated (e.g., [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)| PFAS]]), halogen-carbon bonds are generally broken and [[Wikipedia: Halide | halide]] anions are released in solution (e.g., F- when treating PFAS or Cl- when treating [[Wikipedia: Trichloroethylene | trichloroethene (TCE)]] and [[Wikipedia: Tetrachloroethylene | tetrachloroethene (PCE)]]).
+*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>
-==Advantages and Disadvantages==
+*[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]
-There are many advantages to SCWO treatment. SCWO is a destructive treatment in that the compounds treated are mineralized to simple elements or harmless molecules (e.g., water and carbon dioxide) rather than just being transferred to another medium. Another advantage is the absence of reaction by-products, incompletely oxidized contaminants or unreacted harmful oxidants (e.g., ozone). SCWO is an extremely rapid and effective reaction (typical reaction times are in the order of 5-10 seconds) making it possible to build systems that are very compact and have a high throughput. SCWO is also a very clean process. The highly oxidizing environment makes it possible to effectively treat all sorts of organic contaminants, often recalcitrant to other processes, with very high (>99%) destruction efficiencies. This includes treatment of trace contaminants, slurries of biosolids, waste oil, food wastes, plastics, or emerging contaminants such as PFAS or 1,4-dioxane. Also, the relatively moderate temperatures (380-600&deg;C) compared to other destructive technologies such as incineration, combined with the presence of supercritical water prevent the formation of NOx and SOx compounds. Lastly, SCWO treatment does not require drying of the waste, and both liquids and slurries can be treated using SCWO.
-There are several disadvantages to SCWO treatment. First, a significant amount of energy needs to be expended to bring the oxidant and the waste undergoing treatment to the critical point of water. Although a large fraction of this energy can be efficiently recovered in heat exchangers, compensating for heat losses constrains SCWO to the treatment of concentrated wastes with sufficient organic content for the exothermic oxidation reaction to provide the necessary heat. Typically, a minimum calorific content of around 2 MJ/kg (which generally corresponds to a chemical oxygen demand of about 120-150 g/L) is needed for autothermal operation. For more dilute streams, external heating or supplementation of fuel (diesel, alcohol, waste oil, etc.) can be implemented, but it can rapidly become cost prohibitive. Thus, SCWO is currently not economical for very large volumes (>50,000 gallon/day) of very dilute waste streams. A second limitation is related to the pumping of the waste. Because the process is conducted at high pressure (240 bars or 3500 psi), positive displacement pumps are required. This limits SCWO to liquids and slurries that can be pumped. Waste streams that contain excessive grit or abrasive materials, and soils cannot currently be processed using SCWO.
+==Introduction==
+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"/>.
-The many appealing benefits of supercritical water processing have stimulated engineers and entrepreneurs to invest significant efforts and resources in the development of the technology. Today, after roughly 30 years of development, commercial deployment is on the horizon<ref name="Marrone2013"/>. Technical challenges that have slowed down commercial deployment of SCWO are linked to the complex nature of a high-pressure, high-temperature process. Critical issues include reactor materials selection to resist corrosion (typically high nickel alloys are used), reactor designs and construction to withstand the corrosive nature of the reactive mass, dealing with highly exothermic reactions at high pressure and high temperature, plugging of the reactor by minerals deposits, and energy recovery for autothermal operation. Another challenge was the unrealistic goal of some companies entering the SCWO market to produce power from waste streams (often wastewater sludge) at a competitive cost (3-5 cents/kWh). This was not feasible with the available technology, which led to several business failures.
+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.
-The value proposition of treating recalcitrant wastes using SCWO is markedly different, especially in today’s context of increasing liability for trace levels of emerging contaminants such as PFAS. SCWO may prove to be the optimal treatment technology for many highly concentrated aqueous waste streams.
+==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]]
+[[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]]]
+[[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.
-==State of the Art==
+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).
-Relatively few large scale SCWO systems exist. Researchers at Duke University ([http://sanitation.pratt.duke.edu/community-treatment/about-community-treatment-project Deshusses lab]) have designed and built a prototype pilot-scale SCWO system housed in a standard 20-foot shipping container (Figure 2). This project was funded by the Reinvent the Toilet program of the [https://www.gatesfoundation.org/ Bill and Melinda Gates Foundation]. The pilot system is a continuous process designed to treat 1 ton of sludge per day at 10-20% dry solids content. The unit has been undergoing testing at Duke since early 2015. The design includes moderate preheating of the waste slurry, followed by mixing with supercritical water (~600&deg;C) and air, which serves as the oxidant. This internal mixing rapidly brings the waste undergoing treatment to supercritical conditions thereby minimizing corrosion and the risks of waste charring and associated reactor plugging. The organics in the sludge are rapidly oxidized to CO<sub>2</sub>, while the heat of oxidation is recovered to heat the influent waste. The reactor is a single tubular reactor. The high supercritical fluid velocity in the system helps with controlling mineral salts deposition in the reactor. The system is well instrumented, and operation is controlled using a supervisory control and data acquisition (SCADA) system with historian software for trends analysis and reporting of key performance indicators (e.g., temperatures and pressures, pollutant destruction). Experiments conducted with this pilot plant have shown effective treatment of a wide variety of otherwise problematic wastes such as primary, secondary and digested sludge slurries, landfill leachate (see Figure 3), animal waste, and co-contaminants including waste oil, food wastes, and plastics. The results are consistent with other SCWO studies and show very rapid treatment of all wastes with near complete conversion (often >99.9%) of organics to CO<sub>2</sub>. Total nitrogen and phosphorous removal are generally over 95% and 98%, respectively. Emerging contaminants such as pharmaceuticals, [[Perfluoroakyl and Polyfluoroalkyl Substances (PFAS) |PFAS]], [[1,4-Dioxane | 1,4-dioxane]] and [[Wikipedia: Microplastics | microplastics]] are also treated with destruction generally exceeding 99%.
-Early projections for treatment costs (Capital Expenditures + Operating Expenditures) for slurries are in the range of $12 to $90 per ton (or $0.04 to $0.37 per gallon) depending on system scale and contaminant concentration, with a majority of the cost coming from amortizing the equipment. These cost projections make SCWO treatment very competitive compared to other treatment technologies for high-strength wastes. When treating large volumes of water, combining SCWO with another technology (e.g., nanofiltration, reverse osmosis, or adsorption onto GAC) should be considered so that only the concentrated brines or spent sorbent are treated using SCWO, thereby increasing the cost effectiveness of the overall treatment.
+==Peepers Preparation, Deployment and Retrieval==
+[[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.
-==SCWO for the Treatment of PFAS and AFFF==
+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.
-Several reports have indicated that PFAS can be treated using SCWO<ref name="Kucharzyk2017">Kucharzyk, K.H., Darlington, R., Benotti, M., Deeb, R. and Hawley, E., 2017. Novel treatment technologies for PFAS compounds: A critical review. Journal of Environmental Management, 204(2), pp. 757-764.  [https://doi.org/10.1016/j.jenvman.2017.08.016 DOI: 10.1016/j.jenvman.2017.08.016]&nbsp;&nbsp; Manuscript available from: [https://www.researchgate.net/profile/Katarzyna_kate_Kucharzyk/publication/319125507_Novel_treatment_technologies_for_PFAS_compounds_A_critical_review/links/5a06590b4585157013a3be77/Novel-treatment-technologies-for-PFAS-compounds-A-critical-review.pdf ResearchGate]</ref>. Several runs treating biosolids known to contain PFAS as well as dilutions of pure [[Wikipedia: Firefighting foam | aqueous film forming foam (AFFF)]] have also been conducted with the Duke SCWO system. Typical results are shown in Table 2. They indicate very effective treatment performance, with for example 110,000 ng/L PFOS in the feed reduced to 0.79 ng/L in the effluent, and many other PFAS reduced to below their detection limits. No HF was found in the effluent gas, and all the fluorine from the destroyed PFAS was accounted for as fluoride in the effluent water. These results show the ability of the SCWO process to destroy PFAS to levels well below the EPA health advisory levels of 70 ng/L for PFOS and PFOA. The ESTCP project [https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/ER20-5350/ER20-5350 ER20-5350]<ref name="Deshusses2020">Deshusses, M.A., 2020. Supercritical Water Oxidation (SCWO) for Complete PFAS Destruction. ER20-5350. [https://www.serdp-estcp.org/Program-Areas/Environmental-Restoration/ER20-5350/ER20-5350 Project website]</ref> launched in June 2020 will assess the technical feasibility of using supercritical water oxidation (SCWO) for the complete destruction of PFAS in a variety of relevant waste streams and will evaluate the cost effectiveness of the treatment.
+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<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.
-Three technologies are well demonstrated for removal of [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | PFAS]] from drinking water and non-potable groundwater (as described below):
+==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<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>.
-* membrane filtration including [[wikipedia: Reverse osmosis | reverse osmosis (RO)]] and [[Wikipedia: Nanofiltration | nanofiltration (NF)]]
-* granular [[Wikipedia: Activated carbon | activated carbon]] (GAC) and powdered activated carbon (PAC) adsorption
-* [[wikipedia: Ion_exchange | anion exchange (IX)]]
-However, these technologies are less demonstrated for removal of PFAS from more complex matrices such as wastewater and leachate.
+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.
-Site-specific considerations that affect the selection of optimum treatment technologies for a given site include water chemistry, required flow rate, treatment criteria, waste residual generation, residual disposal options, and operational complexity.  Treatability studies with site water are highly recommended because every site has different factors that may affect engineering design for these technologies.
-===Membrane Filtration===
+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''):
-[[File: revOsmosisPlant.png | thumb | 500px | Figure 1.  A RO municipal drinking water plant in Arizona]]
+</br>
-Given their ability to remove dissolved contaminants at a molecular size level, RO and some NF membranes can be highly effective for PFAS removal. For RO systems (Figure 1), several studies have demonstrated effective removal of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) (see [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | PFAS]] for nomenclature) from drinking water with removal rates well above 90%<ref name="Tang2006">Tang, C.Y., Fu, Q.S., Robertson, A.P., Criddle, C.S., and Leckie, J.O., 2006. Use of Reverse Osmosis Membranes to Remove Perfluorooctane Sulfonate (PFOS) from Semiconductor Wastewater. Environmental Science and Technology, 40(23), pp. 7343-7349.   [https://doi.org/10.1021/es060831q DOI: 10.1021/es060831q]</ref><ref name="Flores2013">Flores, C., Ventura, F., Martin-Alonso, J., and Caixach, J., 2013. Occurrence of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) in NE Spanish surface waters and their removal in a drinking water treatment plant that combines conventional and advanced treatments in parallel lines. Science of the Total environment, 461, 618-626.  [https://doi.org/10.1016/j.scitotenv.2013.05.026 DOI: 10.1016/j.scitotenv.2013.05.026]</ref><ref name="Appleman2014">Appleman, T.D., Higgins, C.P., Quiñones, O., Vanderford, B.J., Kolstad, C., Zeigler-Holady, J.C., and Dickenson, E.R., 2014. Treatment of poly- and perfluoroalkyl substances in US full-scale water treatment systems. Water Research, 51, pp. 246-255.  [https://doi.org/10.1016/j.watres.2013.10.067 DOI: 10.1016/j.watres.2013.10.067]</ref>. RO potable water reuse treatment systems implemented in California have also demonstrated effective PFOS and PFOA removal as reported by the Water Research Foundation (WRF)<ref name="Dickenson2016"/>. Analysis of permeate at both sites referenced by the WRF confirmed that short and long chain PFAS concentrations in the treated water were reduced to levels below test method reporting limits.
+{|
+| || '''Equation&nbsp;1:'''
-Full-scale studies using larger effective pore size NF membranes for PFAS removal are limited in number but are promising since NF systems are somewhat less costly than RO and may be nearly as effective in removing PFAS.  Recent laboratory or pilot studies have shown good performance of NF membranes<ref name="Steinle-Darling2008">Steinle-Darling, E., and Reinhard, M., 2008. Nanofiltration for Trace Organic Contaminant Removal: Structure, Solution, and Membrane Fouling Effects on the Rejection of Perfluorochemicals. Environmental Science and Technology, 42(14), pp. 5292-5297.  [https://doi.org/10.1021/es703207s DOI: 10.1021/es703207s]&nbsp;&nbsp; Free download from: [https://d1wqtxts1xzle7.cloudfront.net/48926882/es703207s20160918-21142-1xmqco5.pdf?1474189169=&response-content-disposition=inline%3B+filename%3DNanofiltration_for_Trace_Organic_Contami.pdf&Expires=1613000850&Signature=N-ZvvjOJX3TSOQzg7od3Q0LulNSZOqqjfummVEUfmiYlC3VasS4FuBHOgY52Xy~7FrKbOLhx0xx8QHdUsR~fbRTMQNXhiqbEslnU2gda2EcZHMMJj0mf-01wIA3jFIywA7IIabmTd3uMUGsIfT1D0PrGY00RmprYIQBoG3Dg~KjoizdfxYfvEgdZw2C~7D47pPiwMSnavZiGuvO0~dbRF8nawL7Prg91xt5BFTNUQQiIrIlMWc4PhVjzE5Su2CUZqnNlYdAW5Ck7B9lKmmVMPiOgz07vFnyp7m-q4UK3woa~aBFW9Wp~hjqN6vfohn8Hocv5oMpZNamhu8vBbPilKw__&Key-Pair-Id=APKAJLOHF5GGSLRBV4ZA Academia].</ref><ref name="Appleman2013">Appleman, T.D., Dickenson, E.R., Bellona, C., and Higgins, C.P., 2013. Nanofiltration and granular activated carbon treatment of perfluoroalkyl acids. Journal of Hazardous Materials, 260, 740-746.  [https://doi.org/10.1016/j.jhazmat.2013.06.033 DOI: 10.1016/j.jhazmat.2013.06.033]</ref><ref name="Soriano2017">Soriano, Á., Gorri, D., and Urtiaga, A., 2017. Efficient treatment of perfluorohexanoic acid by nanofiltration followed by electrochemical degradation of the NF concentrate. Water Research, 112, 147-156.  [https://doi.org/10.1016/j.watres.2017.01.043 DOI: 10.1016/j.watres.2017.01.043]&nbsp;&nbsp; [[Media: Soriano2017.pdf | Author’s Manuscript.]]</ref><ref name="Zeng2017">Zeng, C., Tanaka, S., Suzuki, Y., Yukioka, S., and Fujii, S., 2017. Rejection of Trace Level Perfluorohexanoic Acid (PFHxA) in Pure Water by Loose Nanofiltration Membrane. Journal of Water and Environment Technology, 15(3), pp. 120-127.  [https://doi.org/10.2965/jwet.16-072 DOI: 10.2965/jwet.16-072]&nbsp;&nbsp; Free download from: [https://www.jstage.jst.go.jp/article/jwet/15/3/15_16-072/_pdf J-STAGE]</ref><ref name="Wang2018">Wang, J., Wang, L., Xu, C., Zhi, R., Miao, R., Liang, T., Yue, X., Lv, Y. and Liu, T., 2018. Perfluorooctane sulfonate and perfluorobutane sulfonate removal from water by nanofiltration membrane: The roles of solute concentration, ionic strength, and macromolecular organic foulants. Chemical Engineering Journal, 332, pp. 787-797.  [https://doi.org/10.1016/j.cej.2017.09.061 DOI: 10.1016/j.cej.2017.09.061]</ref>.
+|&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)
+|}
-Although membrane RO and NF processes are generally capable of providing uniform removal rates relative to short and long chain PFAS compounds (see [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | PFAS]] for nomenclature), other aspects of these treatment technologies are more challenging:
+The elimination rate of the target analyte (''K'') is calculated using Equation 2:
+</br>
+{|
+| || '''Equation&nbsp;2:'''
+|&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;[[File: Equation2r.png]]
+|-
+| Where: || ||
+|-
+| || ''K''|| is the elimination rate of the target analyte
+|-
+| || ''K<small><sub>tracer</sub></small>'' || is the elimination rate of the tracer
+|-
+| || ''D'' || is the free water diffusivity of the analyte (cm<sup>2</sup>/s)
+|-
+| || ''D<small><sub>tracer</sub></small>'' || is the free water diffusivity of the tracer (cm<sup>2</sup>/s)
+|}
-* Membranes must be flushed and cleaned periodically, such that overall water recovery rates (process water volumes consumed, wasted, and lost vs. treated water volumes produced) are much lower than those for GAC and IX processes. Membrane fouling can be slowed or avoided depending on operating conditions, membrane modifications, and feed modifications<ref name="LeRoux2005">Le Roux, I., Krieg, H.M., Yeates, C.A. and Breytenbach, J.C., 2005. Use of chitosan as an antifouling agent in a membrane bioreactor. Journal of Membrane Science, 248(1-2), pp. 127-136.  [https://doi.org/10.1016/j.memsci.2004.10.005 DOI: 10.1016/j.memsci.2004.10.005]</ref>. Typically, 70-90% of the water supplied into a membrane RO process is recoverable as treated water. The remaining 10-30% is reject containing approximately 4 to 8 times the initial PFAS concentration (depending on recovery rate).
+The elimination rate of the tracer (''K<small><sub>tracer</sub></small>'') is calculated using Equation 3:
+</br>
-* These cleaning and flushing processes create a continuous liquid waste stream, which periodically includes harsh membrane cleaning chemicals as well as a continuous flow of concentrated membrane reject chemicals (i.e., PFAS) that must be properly managed and disposed of.  Management often includes further treatment to remove PFAS from the liquid waste.
+{|
+| || '''Equation&nbsp;3:'''
-* RO and NF systems are inherently more expensive and complicated systems to implement, operate, and maintain compared to adsorption processes. Treatment system operator certification and process monitoring requirements are correspondingly markedly higher for RO and NF than they are for GAC and IX.
+|&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;[[File: Equation3r2.png]]
+|-
-* Water feed pressures required to drive flow through membrane RO and NF processes are considerably higher than those involved with GAC and IX processes. This results in reduced process efficiency and higher pumping and electrical operating costs.
+| Where: || ||
+|-
-* Membrane systems can also be subject to issues with irreversible membrane fouling, clogging, and scaling or other physical membrane damage and failures. Additional water pretreatment and higher levels of monitoring and maintenance are then required, further adding to the higher costs of such systems.
+| || ''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)
+|}
-===Activated Carbon Adsorption===
+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"/>.
-[[File: GAChouse.JPG | thumb| 500px | Figure 2.  Typical private water supply well GAC installation for removal PFAS. Pressure gages and sample ports located before the first (or lead) vessel, at the midpoint, and after the second (or lag) vessel allow monitoring for pressure drop due to fouling and for contaminant breakthrough.]]
-Activated carbon is a form of carbon processed to have small pores that increase the surface area available for adsorption of constituents from water. Activated carbon is derived from many source materials, including coconut shells, wood, lignite, and bituminous coal. Different types of activated carbon base materials have varied adsorption characteristics such that some may be better suited to removing certain contaminant compounds than others.  Results from laboratory testing, pilot evaluations, and full-scale system operations suggest that bituminous coal-based GAC is generally the best performing carbon for PFAS removal<ref name="McNamara2018">McNamara, J.D., Franco, R., Mimna, R., and Zappa, L., 2018. Comparison of Activated Carbons for Removal of Perfluorinated Compounds from Drinking Water. Journal‐American Water Works Association, 110(1), pp. E2-E14.  [https://doi.org/10.5942/jawwa.2018.110.0003 DOI: 10.5942/jawwa.2018.110.0003]</ref><ref name="Westreich2018">Westreich, P., Mimna, R., Brewer, J., and Forrester, F., 2018. The removal of short‐chain and long‐chain perfluoroalkyl acids and sulfonates via granular activated carbons: A comparative column study. Remediation Journal, 29(1), pp. 19-26.  [https://doi.org/10.1002/rem.21579 DOI: 10.1002/rem.21579]</ref>.
-The removal efficiency of individual PFAS compounds using GAC is a function of both the PFAS functional group (carboxylic acid versus sulfonic acid) and also the perfluoro-carbon chain length<ref name="McCleaf2017">McCleaf, P., Englund, S., Östlund, A., Lindegren, K., Wiberg, K., and Ahrens, L., 2017. Removal efficiency of multiple poly-and perfluoroalkyl substances (PFASs) in drinking water using granular activated carbon (GAC) and anion exchange (AE) column tests. Water Research, 120, pp. 77-87.  [https://doi.org/10.1016/j.watres.2017.04.057 DOI: 10.1016/j.watres.2017.04.057]</ref><ref name="Eschauzier2012">Eschauzier, C., Beerendonk, E., Scholte-Veenendaal, P., and De Voogt, P., 2012. Impact of Treatment Processes on the Removal of Perfluoroalkyl Acids from the Drinking Water Production Chain. Environmental Science and Technology, 46(3), pp. 1708-1715.  [https://doi.org/10.1021/es201662b DOI: 10.1021/es201662b]</ref>(see [[Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) | PFAS]] for nomenclature):
+==Using Peeper Data at a Sediment Site==
-* perfluoro-sulfonate acids (PFSAs) are more efficiently removed than perfluoro-carboxylic acids (PFCAs) of the same chain length
+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.
-* long chain compounds of the same functional group are removed better than the shorter chains
-Activated carbon may be applied in drinking water systems as GAC or PAC<ref name="Dudley">Dudley, L.A., Arevalo, E.C., and Knappe, D.R., 2015. Removal of Perfluoroalkyl Substances by PAC Adsorption and Anion Exchange. Water Research Foundation Project #4344.  Free  download of Executive Summary from: [https://www.waterrf.org/system/files/resource/2019-04/4344_ProjectSummary.pdf Water Research Foundation (Public Plus account)]</ref><ref name="Qian2017">Qian, J., Shen, M., Wang, P., Wang, C., Li, K., Liu, J., Lu, B. and Tian, X., 2017. Perfluorooctane sulfonate adsorption on powder activated carbon: Effect of phosphate (P) competition, pH, and temperature. Chemosphere, 182, pp. 215-222.  [https://doi.org/10.1016/j.chemosphere.2017.05.033 DOI: 10.1016/j.chemosphere.2017.05.033]</ref>. GAC has larger granules and is reusable, while PAC has much smaller granules and is not typically reused.  PAC has most often been used as a temporary treatment because costs associated with disposal and replacement of the used PAC tend to preclude using it for long-term treatment. A typical GAC installation for a private drinking water well is shown in Figure 2. Contrary to PAC, GAC used to treat PFAS can be reactivated by the manufacturer, driving the PFAS from the GAC and into off-gas. The extracted gas is then treated with thermal oxidation (temperatures often 1200&deg;C to 1400&deg;C).  The reactivated GAC is then brought back to the site and reused.  Thus, GAC can ultimately be a destructive treatment technology.
-[[File: IXcycle.png | thumb | 400px | left | Figure 3.  Operational cycle of a packed bed reactor with anion exchange resin beads]]
+'''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.
-===Anion Exchange===
+'''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.
-Anion exchange has also been demonstrated for the adsorption of PFAS, and published results note higher sorption per pound than GAC<ref name="McCleaf2017"/><ref name=" Senevirathna2010">Senevirathna, S.T.M.L.D., Tanaka, S., Fujii, S., Kunacheva, C., Harada, H., Shivakoti, B.R., and Okamoto, R., 2010. A comparative study of adsorption of perfluorooctane sulfonate (PFOS) onto granular activated carbon, ion-exchange polymers and non-ion-exchange polymers. Chemosphere, 80(6), pp. 647-651.  [https://doi.org/10.1016/j.chemosphere.2010.04.053 DOI: 10.1016/j.chemosphere.2010.04.053]&nbsp;&nbsp; Free download from: [https://www.researchgate.net/profile/Chinagarn_Kunacheva/publication/44672056_A_comparative_study_of_adsorption_of_perfluorooctane_sulfonate_PFOS_onto_granular_activated_carbon_ion-exchange_polymers_and_non-ion-exchange_polymers/links/5a3380510f7e9b2a288a2b21/A-comparative-study-of-adsorption-of-perfluorooctane-sulfonate-PFOS-onto-granular-activated-carbon-ion-exchange-polymers-and-non-ion-exchange-polymers.pdf ResearchGate]</ref><ref name="Woodard2017">Woodard, S., Berry, J., and Newman, B., 2017. Ion exchange resin for PFAS removal and pilot test comparison to GAC. Remediation Journal, 27(3), pp. 19-27.  [https://doi.org/10.1002/rem.21515 DOI: 10.1002/rem.21515]</ref>. The higher capacity is believed to be due to combined hydrophobic and ion exchange adsorption mechanisms, whereas GAC mainly relies on hydrophobic attraction. Anion exchange resins can be highly selective, or they can also remove other contaminants based on design requirements and water chemistry. Resins have greater affinity for PFAS subgroup PFSA than for PFCA, and affinity increases with carbon chain length.
-[[Wikipedia: Ion-exchange resin | Anion exchange resins]] are a viable alternative to GAC for ''ex situ'' treatment of PFAS anions, and several venders sell resins capable of removing PFAS. Resins available for treating PFAS include regenerable resins that can be used multiple times (Figure 3) and single-use resins that must be disposed or destroyed after use<ref name=" Senevirathna2010"/>. Regenerable resins generate a solvent and brine solution, which is distilled to recover the solvent prior to the brine being adsorbed onto a small quantity of GAC or resin for ultimate disposal. This use of one treatment technology (GAC, IX) to support another (RO) is sometimes referred to as a “treatment train” approach. Single-use resins can be more fully exhausted than regenerable resins can and may be a more cost-effective solution for low concentration PFAS contamination, while regenerable resins may be more cost effective for higher concentration contamination.
-==Developing PFAS Treatment Technologies==
+'''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.
-{| class="wikitable" style="float:right; margin-left:10px;"
-|+ Table 1.  Developmental Technologies
-|-
-! Stage
-! Separation/Transfer
-! Destructive*
-|-
-| Developing
-|
-* Biochar<ref name="Guo2017">Guo, W., Huo, S., Feng, J., and Lu, X., 2017. Adsorption of perfluorooctane sulfonate (PFOS) on corn straw-derived biochar prepared at different pyrolytic temperatures. Journal of the Taiwan Institute of Chemical Engineers, 78, pp. 265-271.  [https://doi.org/10.1016/j.jtice.2017.06.013 DOI: 10.1016/j.jtice.2017.06.013]</ref><ref name="Kupryianchyk2016">Kupryianchyk, D., Hale, S.E., Breedveld, G.D., and Cornelissen, G., 2016. Treatment of sites contaminated with perfluorinated compounds using biochar amendment. Chemosphere, 142, pp. 35-40.  [https://doi.org/10.1016/j.chemosphere.2015.04.085 DOI: 10.1016/j.chemosphere.2015.04.085]&nbsp;&nbsp; Free download from: [https://www.researchgate.net/profile/Sarah_Hale3/publication/276067521_Treatment_of_sites_contaminated_with_perfluorinated_compounds_using_biochar_amendment/links/5cdbe03b299bf14d959895d9/Treatment-of-sites-contaminated-with-perfluorinated-compounds-using-biochar-amendment.pdf ResearchGate]</ref><ref name="Inyang2017">Inyang, M., and Dickenson, E.R., 2017. The use of carbon adsorbents for the removal of perfluoroalkyl acids from potable reuse systems. Chemosphere, 184, pp. 168-175.  [https://doi.org/10.1016/j.chemosphere.2017.05.161 DOI: 10.1016/j.chemosphere.2017.05.161]</ref>
-* Modified Zeolites<ref name="Espana2015">Espana, V.A.A., Mallavarapu, M., and Naidu, R., 2015. Treatment technologies for aqueous perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA): A critical review with an emphasis on field testing. Environmental Technology and Innovation, 4, pp. 168-181.  [https://doi.org/10.1016/j.eti.2015.06.001 DOI: 10.1016/j.eti.2015.06.001]&nbsp;&nbsp; Free download from: [https://www.researchgate.net/profile/Ravi_Naidu2/publication/341241612_Recent_advances_in_the_analysis_of_per-and_polyfluoroalkyl_substances_PFAS-A_review/links/5eb9e3d892851cd50dab441c/Recent-advances-in-the-analysis-of-per-and-polyfluoroalkyl-substances-PFAS-A-review.pdf ResearchGate]</ref><ref name="CETCO2019">CETCO, 2019. FLUORO-SORB&reg; Adsorbent (product sales brochure).  [https://www.mineralstech.com/docs/default-source/performance-materials-documents/cetco/environmental-products/brochures/ps_fluorosorb_am_en_201905_v1.pdf Free download]&nbsp;&nbsp; [[Media:  FluoroSorb2019.pdf | Fluoro-Sorb.pdf]]</ref>
-* Specialty adsorbents<ref name="Zhang2011">Zhang, Q., Deng, S., Yu, G., and Huang, J., 2011. Removal of perfluorooctane sulfonate from aqueous solution by crosslinked chitosan beads: sorption kinetics and uptake mechanism. Bioresource Technology, 102(3), pp. 2265-2271.  [https://doi.org/10.1016/j.biortech.2010.10.040 DOI: 10.1016/j.biortech.2010.10.040]</ref><ref name="Cao2016">Cao, F., Wang, L., Ren, X., and Sun, H., 2016. Synthesis of a perfluorooctanoic acid molecularly imprinted polymer for the selective removal of perfluorooctanoic acid in an aqueous environment. Journal of Applied Polymer Science, 133(15).  [https://doi.org/10.1002/app.43192 DOI: 10.1002/app.43192]</ref><ref name="Hu2016">Hu, L., Li, Y., and Zhang, W., 2016. Characterization and application of surface-molecular-imprinted-polymer modified TiO2 nanotubes for removal of perfluorinated chemicals. Water Science and Technology, 74(6), pp. 1417-1425.  [https://doi.org/10.2166/wst.2016.321 DOI: 10.2166/wst.2016.321]&nbsp;&nbsp; [[Media: Hu2016.pdf | Free access article.]]</ref>
-|
-* Electro-oxidation<ref name="Zhang2016">Zhang, C., Tang, J., Peng, C., and Jin, M., 2016. Degradation of perfluorinated compounds in wastewater treatment plant effluents by electrochemical oxidation with Nano-ZnO coated electrodes. Journal of Molecular Liquids, 221, pp. 1145-1150.  [https://doi.org/10.1016/j.molliq.2016.06.093 DOI: 10.1016/j.molliq.2016.06.093]</ref><ref name="Urtiaga2015">Urtiaga, A., Fernández-González, C., Gómez-Lavín, S., and Ortiz, I., 2015. Kinetics of the electrochemical mineralization of perfluorooctanoic acid on ultrananocrystalline boron doped conductive diamond electrodes. Chemosphere, 129, pp. 20-26.  [https://doi.org/10.1016/j.chemosphere.2014.05.090 DOI: 10.1016/j.chemosphere.2014.05.090]&nbsp;&nbsp; Free download from: [https://d1wqtxts1xzle7.cloudfront.net/39233145/00b7d53b67db54fca5000000.pdf?1445006282=&response-content-disposition=inline%3B+filename%3DKinetics_of_the_electrochemical_minerali.pdf&Expires=1613074964&Signature=Bfvds3n9udSs5F9J00Embf8MRJxumQVJoaj5jEni5mqPnmo2QFGGN3fUvWISkRD1yKfoIhNEDQ0a-ISxfZ9vW9jBTkTjN7ud7aSC3rBelIFdtFasfpEXgPvnqsLfKRTWI5S~QRsHbvK5XbwnKo2VyFAmUcuJUjVFP1PK1kEY9-gB2d-8FwSJWbCAAd83fNWm3zHzbOvdchJ~fjAqlydgq7Pu~AwEeH4Zl1LhcYxajzcenTSiBWmMStfOUpTyETSCpSwF7XKuhKMYGePsit8fAWpxH4dleYWmvOi9Gc9YyTB32qBziOTfeqjhTsA-uqECz9bxyD65voHUW7sEchkrKw__&Key-Pair-Id=APKAJLOHF5GGSLRBV4ZA Academia.edu]</ref><ref name="Schaefer2018">Schaefer, C.E., Choyke, S., Ferguson, P.L., Andaya, C., Burant, A., Maizel, A., Strathmann, T.J. and Higgins, C.P., 2018. Electrochemical Transformations of Perfluoroalkyl Acid (PFAA) Precursors and PFAAs in Groundwater Impacted with Aqueous Film Forming Foams. Environmental Science and Technology, 52(18), pp. 10689-10697.  [https://doi.org/10.1021/acs.est.8b02726 DOI: 10.1021/acs.est.8b02726]</ref>
-* Heat activated persulfate<ref name="Park2016">Park, S., Lee, L.S., Medina, V. F., Zull, A., and Waisner, S., 2016. Heat-activated persulfate oxidation of PFOA, 6: 2 fluorotelomer sulfonate, and PFOS under conditions suitable for in-situ groundwater remediation. Chemosphere, 145, pp. 376-383.  [https://doi.org/10.1016/j.chemosphere.2015.11.097 DOI: 10.1016/j.chemosphere.2015.11.097]</ref>
-* Alkaline perozone<ref name="Lin2012">Lin, A.Y.C., Panchangam, S.C., Chang, C.Y., Hong, P.A., and Hsueh, H.F., 2012. Removal of perfluorooctanoic acid and perfluorooctane sulfonate via ozonation under alkaline condition. Journal of Hazardous Materials, 243, pp. 272-277.  [https://doi.org/10.1016/j.jhazmat.2012.10.029 DOI: 10.1016/j.jhazmat.2012.10.029]</ref>
-* Sonolysis<ref name="Campbell2015">Campbell, T., Hoffmann, M.R., 2015. Sonochemical degradation of perfluorinated surfactants: Power and multiple frequency effects. Separation and Purification Technology, 156(3), pp. 1019-1027.  [https://doi.org/10.1016/j.seppur.2015.09.053 DOI: 10.1016/j.seppur.2015.09.053]&nbsp;&nbsp; Free download from: [https://www.researchgate.net/profile/Tammy_Campbell5/publication/282583363_Sonochemical_Degradation_of_Perfluorinated_Surfactants_Power_and_Multiple_Frequency_Effects/links/5bfc40bd92851cbcdd74449b/Sonochemical-Degradation-of-Perfluorinated-Surfactants-Power-and-Multiple-Frequency-Effects.pdf ResearchGate]</ref><ref name="Cheng2010">Cheng, J., Vecitis, C.D., Park, H., Mader, B.T., Hoffmann, M.R., 2010. Sonochemical Degradation of Perfluorooctane Sulfonate (PFOS) and Perfluorooctanoate (PFOA) in Groundwater: Kinetic Effects of Matrix Inorganics. Environmental Science and Technology, 44(1), pp. 445-450.  [https://doi.org/10.1021/es902651g DOI: 10.1021/es902651g]</ref><ref name="Gole2018a">Gole, V.L., Sierra-Alvarez, R., Peng, H., Giesy, J.P., Deymier, P., Keswani, M., 2018. Sono-chemical treatment of per- and poly-fluoroalkyl compounds in aqueous film-forming foams by use of a large-scale multi-transducer dual-frequency based acoustic reactor. Ultrasonics Sonochemistry, 45, pp. 213-222.  [https://doi.org/10.1016/j.ultsonch.2018.02.014 DOI: 10.1016/j.ultsonch.2018.02.014]&nbsp;&nbsp; [https://www.sciencedirect.com/science/article/pii/S1350417718301937 Open access article.]&nbsp;&nbsp; [[Media: Gole2018a.pdf | Report.pdf]]</ref><ref name="Gole2018b">Gole, V.L., Fishgold, A., Sierra-Alvarez, R., Deymier, P., Keswani, M., 2018. Treatment of perfluorooctane sulfonic acid (PFOS) using a large-scale sonochemical reactor. Separation and Purification Technology, 194, pp. 104-110.  [https://doi.org/10.1016/j.seppur.2017.11.009 DOI: 10.1016/j.seppur.2017.11.009]</ref>
-* Super Critical Water Oxidation
-|-
-| Maturing and</br>Demonstrated
-|
-* Chemical coagulation<ref name="Cornelsen2015">Cornelsen Ltd., 2015. PerfluorAd, PFC Water Treatment Solution (product sales site). [http://www.cornelsen.co.uk/perfluorad-pfc-treatment/ Website]</ref>
-* Electrocoagulation<ref name="Wang2016">Wang, Y., Lin, H., Jin, F., Niu, J., Zhao, J., Bi, Y., and Li, Y., 2016. Electrocoagulation mechanism of perfluorooctanoate (PFOA) on a zinc anode: Influence of cathodes and anions. Science of the Total Environment, 557, pp. 542-550.  [https://doi.org/10.1016/j.scitotenv.2016.03.114 DOI: 10.1016/j.scitotenv.2016.03.114]</ref>
-* Foam fractionation<ref name="Horst2018">Horst, J., McDonough, J., Ross, I., Dickson, M., Miles, J., Hurst, J., and Storch, P., 2018. Water Treatment Technologies for PFAS: The Next Generation. Groundwater Monitoring and Remediation, 38(2), pp. 13-23.  [https://doi.org/10.1111/gwmr.12281 DOI: 10.1111/gwmr.12281]</ref><ref name="EPC2017">EPC Media Group Pty Ltd., 2017. OPEC systems delivers PFAS contamination breakthrough. Waste + Water Management Australia, 44(3), 26-27.  [https://search.informit.org/doi/10.3316/informit.253699294687114 DOI: 10.3316/informit.253699294687114]   ISSN: 1838-7098</ref>
-|
-* Low temperature plasma<ref name="Stratton2017">Stratton, G.R., Dai, F., Bellona, C.L., Holsen, T.M., Dickenson, E.R., and Mededovic Thagard, S., 2017. Plasma-Based Water Treatment: Efficient Transformation of Perfluoroalkyl Substances in Prepared Solutions and Contaminated Groundwater. Environmental Science and Technology, 51(3), pp. 1643-1648.  [https://doi.org/10.1021/acs.est.6b04215 DOI: 10.1021/acs.est.6b04215]</ref><ref name="Singh2019">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>
-|-
-| colspan="3" style="background:white;" | * There are several other destructive technologies such as alternative oxidants, and activation</br>methods of oxidants, but for the purpose of this article, the main categories are presented here.
-|}
-Numerous&nbsp;separation&nbsp;and destructive technologies are in the developmental stages of bench-scale testing or limited field-scale demonstrations.  Some of these are listed in Table&nbsp;1:
-==Conclusions==
+'''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.
-The well established processes for removing PFAS from water all produce residuals that require management, and it is likely that newer processes under development will also produce some residuals.  Often, it is the residuals that limit the usefulness of the process.  For instance, RO and NF may currently provide the most complete treatment of water, but the production of a relatively high volume of PFAS-containing liquid reject (the portion of the liquid that retains the contaminants and is “rejected” from the process) limits their application.  Often, a second treatment technology such as an adsorbent is required to support the main technology by concentrating or treating the residuals.
-As more testing and operational data on adsorbents are generated, it is becoming evident that no adsorbent technology outperforms the others in all cases.  Whether GAC, ion exchange or another technology is the most technically efficient and cost effective long term option for a given site depends on influent water geochemistry and contaminant concentrations, treatment standards, co-contaminants, duration of treatment, and required flow rates. New generation adsorbents are rapidly being introduced into the market at “evaluation scale” which may provide advantages over commercially available adsorbents.
-Several newer technologies are being evaluated in the lab and in the field which include electro-oxidation, heat-activated persulfate, sonolysis, electrocoagulation, low temperature plasma, super critical water oxidation, and foam fractionation. These and other potential treatments for PFAS are still largely in the developmental stage. Several technologies show promise for improved management of PFAS sites. However, it is unlikely that a single technology will be adequate for full remediation at many sites. A multi-technology treatment train approach may be necessary for effective treatment of this complicated group of compounds.
-<br clear="left" />
+'''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 />
 ==See Also==
+*[https://vimeo.com/809180171/c276c1873a Peeper Deployment Video]
+*[https://vimeo.com/811073634/303edf2693 Peeper Retrieval Video]
+*[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]

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Latest revision as of 21:47, 14 October 2024

Sediment Porewater Dialysis Passive Samplers for Inorganics (Peepers)

Contents

Introduction

Peeper Designs

Peepers Preparation, Deployment and Retrieval

Equilibrium Determination (Tracers)

Using Peeper Data at a Sediment Site

References

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