Sediments

Valence state: The combining capacity of an atom or radical determined by the number of electrons that it will lose, add, or share when it reacts with other atoms.

Source: The American Heritage™ Dictionary of the English Language, Fourth Edition
Copyright © 2000 by Houghton Mifflin Company.

free product: A NAPL found in the subsurface in sufficient quantity that it can be partially recovered by pumping or gravity drain.

aerobic: Direct aerobic metabolism involves microbial reactions that require oxygen to go forward. The bacteria uses a carbon substrate as the electron donor and oxygen as the electron acceptor. Degradation of contaminants that are susceptible to aerobic degradation but not anaerobic often ceases in the vicinity of the source zone because of oxygen depletion. This can sometimes be reversed by adding oxygen in the form of air (air sparging, bioventing), ozone, or slow oxygen release compound (e.g., ORC(r)).

Aerobic dechlorination may also occur via cometabolism where the dechlorination is incidental to the metabolic activities of the organisms. In this case, contaminants are degraded by microbial enzymes that are metabolizing other organic substrates. Cometabolic dechlorination does not appear to produce energy for the organism. At pilot- or full-scale treatment, cometabolic and direct dechlorination may be indistinguishable, and both processes may contribute to contaminant removal. For aerobic cometabolism to occur there must be sufficient oxygen and a suitable substrate which allows the microbe to produce the appropriate enzyme. These conditions may be present naturally but often in the presence of a source area oxygen and a substrate such as methane or propane will need to be introduced.

Adapted from US. EPA 2006 Engineering Issue: In Situ and Ex Situ Biodegradation Technologies for Remediation of Contaminated Sites

anaerobic: Direct anaerobic metabolism involves microbial reactions occurring in the absence of oxygen and encompasses many processes, including fermentation, methanogenesis, reductive dechlorination, sulfate-reducing activities, and denitrification. Depending on the contaminant of concern, a subset of these activities may be cultivated. In anaerobic metabolism, nitrate, sulfate, carbon dioxide, oxidized metals, or organic compounds may replace oxygen as the electron acceptor.

Anaerobic dechlorination also may occur via cometabolism where the dechlorination is incidental to the metabolic activities of the organisms. In this case, contaminants are degraded by microbial enzymes that are metabolizing other organic substrates. Cometabolic dechlorination does not appear to produce energy for the organism. At pilot- or full-scale treatment, cometabolic and direct dechlorination may be indistinguishable, and both processes may contribute to contaminant removal.

Quoted from US. EPA 2006 Engineering Issue: In Situ and Ex Situ Biodegradation Technologies for Remediation of Contaminated Sites

architecture: "Architecture" refers to the physical distribution of the contaminant in the subsurface. Residuals that take the form of long thin ganglia or small dispersed globules provide a larger surface area that will dissolve much faster than if the same amount of liquid were concentrated in a competent pool.

Sources: For purposes of this discussion, a DNAPL source zone includes the zone that encompasses the entire subsurface volume in which DNAPL is present either at residual saturation or as "pools" of accumulation above confining units. In addition, the DNAPL source zone includes regions that have come into contact with DNAPL that may be storing contaminant mass as a result of diffusion of DNAPL into the soil or rock matrix.

source zone: For purposes of this discussion, a DNAPL source zone includes the zone that encompasses the entire subsurface volume in which DNAPL is present either at residual saturation or as "pools" of accumulation above confining units. In addition, the DNAPL source zone includes regions that have come into contact with DNAPL that may be storing contaminant mass as a result of diffusion of DNAPL into the soil or rock matrix.

focal ulceration: The process or fact of a localized area being eroded away.

metaplasia of the glandular stomach: A change of cells to a form that does not normally occur in the tissue in which it is found.

hyperplasia of the glandular stomach: A condition in which there is an increase in the number of normal cells in a tissue or organ.

histiocytic: Degenerative.

duodenum: First part of the small intestine.

microcytic: Any abnormally small cell.

squamous cell papillomas: A small solid benign tumor with a clear-cut border that projects above the surrounding tissue.

squamous cell carcinomas: Cancer that begins in squamous cells-thin, flat cells that look under the microscope like fish scales. Squamous cells are found in the tissue that forms the surface of the skin, the lining of hollow organs of the body, and the passages of the respiratory and digestive tracts. Squamous cell carcinomas may arise in any of these tissues.

jejunum: The middle portion of the small intestine, between duodenum and ileum. It represents about 2/5 of the remaining portion of the small intestine below duodenum.

ileum: The distal and narrowest portion of the small intestine.

squamous: Flat cells that look like fish scales.

metaplasia: A condition in which there is a change of one adult cell type to another similar adult cell type.

ossification: The process of creating bone, that is of transforming cartilage (or fibrous tissue) into bone.

clastogenesis: Any process resulting in the breakage of chromosomes.

neoplastic: Abnormal and uncontrolled growth of cells.

ulceration: The process or fact of being eroded away.

leucocytosis: An elevation of the total number of white cells in blood.

neutrophils: A type of white blood cell.

chromodulin: A small protein that binds four trivalent chromium ions.

biomagnification: The increased accumulation and concentration of a contaminant at higher levels of the food chain; organisms higher on the food chain will have larger amounts of contaminants than those lower on the food chain, because the contaminants are not eliminated or broken down into other chemicals within the organisms.

exencephaly: Cerebral tissue herniation through a congenital or acquired defect in the skull.

everted viscera: Rotated body organs in the chest cavity.

To Be Considered: Documents, such as federal or state guidances, that are not legally binding but may be relevant to the topic in question.

gaining: A gaining surface water body is one where groundwater flows into it.

losing: A surface water body is losing when there is a permeable sediment bed that is not in contact with the groundwater allowing the surface water to seep through it.

fluvial: Of or pertaining to flow in rivers and streams.

lacustrine: Of or pertaining to a lake as in lacustrine sediments—sediments at the bottom of a lake.

lipid: Any class of fats that are insoluble in water.

lipophilic: Able to dissolve in lipids—in this case fatty tissue.

organelles: A part of a cell such as mitochondrion, vacuole, or chloroplast that plays a specific role in how the cell functions and membranes.

RfD: The RfD is an estimate of a daily exposure of the human population (including sensitive sub-groups) to a substance that is likely to be without "the appreciable risk of deleterious effects during a lifetime." An RfD is expressed in units of mg/kg-day.

autonomic: That part of the nervous system that controls non-conscious actions such as heart rate, perspiration and digestion.

ataxia: Lack of muscle coordination.

funnel-and-gate configuration: A system where low-permeability walls (the funnel) placed in the saturated zone direct contaminated ground-water toward a permeable treatment zone (the gate)

References: ATSDR (Agency for Toxic Substances and Disease Registry). 2015. Draft Toxicological Profile for Perfluoroalkyls. 574 pp.

EFSA (European Food Safety Authority). 2008. Opinion of the scientific panel on contaminants in the food chain on perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) and their salts. EFSA Journal 653:1-131.

Hekster, F.M., R.W.P.M. Laane, and P. de Voogt. 2003. Environmental and toxicity effects of perfluoroalkylated substances. Reviews of Environmental Contamination and Toxicology 179:99-121.

Higgins, C. and R. Luthy. 2006. Sorption of perfluorinated surfactants on sediments. Environmental Science & Technology 40(23):7251-7256.

HSDB (Hazardous Substances Data Bank). 2012 Update. Perfluorooctanoic acid.

Kaiser, M.A., B.S. Larsen, C-P.C. Kao, and R.C. Buck. 2005. Vapor pressures of perfluorooctanoic, -nonanoic, -decanoic, -undecanoic, and -dodecanoic acids. Journal of Chemical and Engineering Data 50(6):1841-1843.

Kauck, E.A. and A.R. Diesslin. 1951. Some properties of perfluorocarboxylic acids. Industrial and Engineering Chemical Research 43(10):2332-2334.

Lewis, R.J., Sr., ed. 2004. Sax's Dangerous Properties of Industrial Materials. 11th ed. Wiley-Interscience, Hoboken, NJ. V3:2860.

Lide, D.R. 2007. CRC Handbook of Chemistry and Physics. 88th ed. CRC Press, Boca Raton, FL. 3-412.

SRC (Syracuse Research Corporation). 2016. PHYSPROP Database. SRC Scientific Databases, Accessed May 2016.

UNEP (United Nations Environmental Program). 2015. Proposal to List Pentadecafluorooctanoic Acid (CAS No: 335-67-1, PFOA, Perfluorooctanoic Acid), Its Salts and PFOA-Related Compounds in Annexes A, B and/or C to the Stockholm Convention on Persistent Organic Pollutants. UNEP/POPS/POPRC.11/5.

USEPA (U.S. Environmental Protection Agency). 2016. Drinking Water Health Advisory for Perfluorooctanoic Acid (PFOA).#pdfsmall# Office of Water, EPA 822-R-16-005, 103 pp

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• Site Characterization
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Sampling

This sampling section is divided into four subsections. The first subsection is a general overview of sampling plan development. The second subsection identifies documents that address sediment sampling and the measurement of contaminant flux at the sediment surface water interface. The third subsection identifies documents on biota sampling techniques. The last subsection identifies documents that discuss sediment pore water sampling methods.

Sampling Plan Development

EPA requires that a sediment sampling plan contain a quality assurance project plan that is developed through a systematic planning process. The proper development and execution of the plan ensures that the samples collected are representative of the media sampled and of a known quality. Guidance documents on how to develop sampling plans are available on the EPA quality webpage.

VSP is an EPA-approved software tool that supports the development of a defensible sampling plan based on statistical sampling theory and the statistical analysis of sample results to support confident decision making. VSP couples site, building, and sample location visualization capabilities with optimal sampling design and statistical analysis strategies.

Also available for use in sampling design is the Decision Error Feasibility Trials software (DEFT). DEFT is a program that allows users to evaluate the financial feasibility of incorporating selected data quality objective (DQO) constraints into a statistical sampling design before developing a final plan. The program assists with the 7-step DQO process, which is used to develop statistical sampling design plans. DQO constraints are determined in steps 1 through 6 and all the DQO outputs are incorporated into a sampling design during step 7. Before implementing step 7, it is efficient and cost effective to ensure that all DQO constraints are appropriate and feasible. The user can test the proposed constraints on several simple sampling designs (e.g., simple random sampling, composite sampling, stratified sampling). DEFT allows users to enter, verify, and adjust DQO outputs. More information can be found on the EPA quality webpage (under QA/G-4D).

Sediment Sampling for Physical/Chemical Properties

Cost and Performance Report: Quantifying In Situ Metal Contaminant Mobility in Marine Sediments
Environmental Security Technology Certification Program, CU9712, 37 pp, 2000

This report describes a benthic flux sampling device.

Cross Validation of Two Partitioning-Based Sampling Approaches in Mesocosms Containing PCB Contaminated Field Sediment, Biota, and Activated Carbon Amendment
Schmidt, S., A. Wang, P. Gidley, A. Wooley, G. Lotufo, R. Burgess, U. Ghosh, L. Fernandez, and P. Mayer. Environmental Science & Technology 51(17):9996-10004(2017) [Abstract]

This study compared two passive sampling-based approaches—(1) ex situ equilibrium sampling with multiple thicknesses of silicone and (2) in situ pre-equilibrium sampling with LDPE loaded with performance reference compounds—for measuring the bioavailable concentrations of PCBs in contaminated sediments. The study demonstrated that the two methods generated similar results. This information provides environmental managers with the ability to select between these two methods (depending on the circumstances) and know that the results will be comparable.

Development of a Passive Multisampling Method to Measure Dioxins/Furans and Other Contaminant Bioavailability in Aquatic Sediments
Lohmann, R. and M. Khairy.
SERDP Project ER-2538, 72 pp, 2016

A passive sampling method utilizing polyethylene samplers was developed for in situ sampling of dioxins/furans and a wide range of other hydrophobic organic contaminants in sediment and the overlying water column. Contaminant concentrations resulting from multi-sampler deployments at several sites along the Passaic River (New Jersey) were compared with those in benthic invertebrates to demonstrate the ability to predict tissue concentrations. Good agreement was generally observed between pore water concentrations obtained in the lab and the in situ sampler for dioxins/furans and PCBs. Lipid-normalized PCDD/Fs were better estimated from pore water and river water for the majority of the congeners.

A Guide to the Proper Selection and Use of Federally Approved Sediment and Water-Quality Samplers
Davis, B.E.
USGS, Open File Report 2005-1087, 26 pp, 2005

This report provides a general understanding of sediment sampling equipment and technology, guidance for the selection of appropriate equipment, and an introduction to new FISP-approved sampling equipment. It primarily addresses suspended and bedload sediment samplers and surface water samplers.

High Resolution In-Situ Monitoring of Hyporheic Zone Biogeochemistry
Environment Agency, UK, Science Report SC030155/SR3, 51 pp, 2005

Improved Methods for Correlating Turbidity and Suspended Solids for Monitoring
USACE, ERDC TN-DOER-E8, 12 pp, 2000

In Situ Catchment Scale Sampling Of Emerging Contaminants Using Diffusive Gradients In Thin Films (DGT) And Traditional Grab Sampling: A Case Study Of The River Thames, UK
Wang, R., E. Biles, Y. Li, M.D. Juergens, M.J. Bowes, K.C. Jones, and H. Zhang.
Environmental Science & Technology 54(18):11155-11164(2020) [Abstract]

DGT and grab sampling were compared for their suitability to screen and monitor emerging contaminants (ECs) at the catchment scale in the River Thames system. The study also explored their sources and environmental fate. Triethyl phosphate (summer 13-160 ng/L and winter 18-46 ng/L) and tris(chloropropyl) phosphate (summer 242-4282 ng/L and winter 215-854 ng/L) were the main organophosphate esters (OPEs) in the study area. DGT and grab sampling were in good agreement for chemicals that were relatively stable in the rivers. DGT provided a better integral of loadings and exposure than grab sampling for chemicals that showed high water body variation. DGT was not as sensitive as grab sampling under the procedures employed here, but there are several options to improve it to give comparable/better performance.

Integrating Passive Sampling Methods into Management of Contaminated Sediment Sites: A Guide for Department of Defense Remedial Project Managers
Thompson, T., C. Menzie, and S.K. Driscoll.
ESTCP Project ER-201216, 62 pp, 2016

This document discusses how to integrate passive sampling methods into the management of contaminated sediment sites, with a focus on the passive sampling devices most commonly used to measure non-polar organic chemicals, such as PCBs and PAHs.

Methods for Collection, Storage and Manipulation of Sediments for Chemical and Toxicological Analyses: Technical Manual
USEPA, Office of Water, EPA-823-B-01-002, 208 pp, 2001

Passive Sampling for Contaminated Sediment Sites
Naval Facilities Engineering Command, ESTS N39430-16-D-1802, 8 pp, 2018

The most commonly used types of passive samplers—polyethylene devices, polyoxymethylene, polydimethylsiloxane-coated solid-phase microextraction, polar organic chemical integrative samplers, and diffusive gradient in thin film (DGT^®)—are described and accompanied by preparation and deployment considerations. Key data analysis steps are highlighted for extraction and analysis and the interpretation of results related to the calculation of water concentrations, mass transfer models, QA/QC, and bioaccumulation prediction.

Proceedings of the Federal Interagency Sediment Monitoring Instrument and Analysis Research Workshop, September 9-11, 2003, Flagstaff, Arizona
Gray, J., ed.
USGS Circular 1276, 50 pp, 2005

This document discusses data needs, uncertainty, and new technologies related to suspended-sediment measurement, bedload-transport measurement, and bed-material and bed-topography measurement. It also covers the management of sediment-flux computations and estimates from new technologies on sediment data.

Quantifying In Situ Metal Contaminant Mobility in Marine Sediments
Hampton, T.W. and D.B. Chadwick
SPAWAR Systems Center, Technical Report 1826, 142 pp, 2000

This report contains a complete description of the equipment, processes, and methods used to demonstrate and validate the Benthic Flux Sampling Device for quantifying in situ metal contaminant mobility in marine sediments. Test and demonstration results, an analysis and interpretation of the results, and performance and cost information are also included in the report.

Sediment Sampling Guide and Methodologies (second edition)
State of Ohio, Environmental Protection Agency, 35 pp, 2001

Sampling for Contaminants in Sediments and Sediment Pore Water
Hazardous Waste Clean-Up Information (CLU-IN) Web Site

This Web page provides short descriptions and pictures of sediment and pore water sampling equipment and a list of references.

Special Series: Passive Sampling Methods for Contaminated Sediments
Integrated Environmental Assessment and Management 10(2):163-236(2014)

A special series of six Open Access papers was generated from the SETAC Technical Workshop, "Guidance on Passive Sampling Methods to Improve Management of Contaminated Sediments," held November 2012 in Costa Mesa, CA, in which 45 experts convened to review the state of science to gain consensus on PSM applications in assessing management actions on contaminated sediments.

Using Passive Polyethylene Samplers to Evaluate Chemical Activities Controlling Fluxes and Bioaccumulation of Organic Contaminants in Bed Sediments
Gschwend, P.M.
SERDP, Project ER-1496, 45 pp, 2010

This project demonstrated the efficacy of using polyethylene (PE) strips to assess the availability of C-13-labeled forms of PAHs and PCBs in sediment beds in moving to other locations (e.g., overlying waters). This movement is relevant to receptors (e.g., shellfish and fish) and to microorganisms that might facilitate degradation. The method involves insertion of PE strips, pre-loaded with internal standards, across the bed-water interface at sites of concern, leaving the PE to absorb the HOC, and then retrieving the samplers and measuring HOC accumulated in the PE by solvent extraction and GCMS. Additional information: Final Report (2015)

Biota Sampling

Concepts and Approaches for the Bioassessment of Non-Wadeable Streams and Rivers
Flotemersch, J.E., J.B. Stribling, and M.J. Paul.
USEPA, EPA 600-R-06-127, 245 pp, 2006

The document assists users who are establishing or refining bioassessment protocols. It includes specific methods related to field sampling; laboratory sample processing; taxonomy; data entry, management, and analysis; and final assessment and reporting.

Environmental Monitoring and Assessment Program-Surface Waters: Field Operations and Methods for Measuring the Ecological Condition of Non-Wadeable Rivers and Streams
Lazorchak, J.M., B.H. Hill, D.K. Averill, D.V. Peck, and D.J. Klemm (eds).
USEPA, 204 pp, 2000

This document describes procedures for collecting data, samples, and information about biotic assemblages, environmental measures, or attributes of indicators of non-wadeable stream ecosystem conditions.

Great River Ecosystems Field Operations Manual
Angradi, T.R. (ed.)
USEPA, Office of Research and Development, EPA/620/R-06/002, 227 pp, 2006

This manual describes procedures for collecting samples and field measurements for biotic assemblages and abiotic characteristics of the Great Rivers of the Central Basin of the United States: the Missouri, Upper Mississippi, and Ohio Rivers.

National Coastal Assessment: Field Operations Manual
USEPA, National Health and Environmental Effects Research Laboratory, EPA 620/R-01/003, 72 pp, 2001

This manual covers benthic sampling in estuarine systems.

Revised Protocols for Sampling Algal, Invertebrate, and Fish Communities as Part of the National Water-Quality Assessment Program
Moulton II, S.R., J.G. Kennen, R.M. Goldstein, and J.A. Hambrook
USGS, Open-File Report 02-150, 87 pp. 2002

This report revises and unifies into a single document the algal, invertebrate, and fish community sampling protocols used in the National Water-Quality Assessment Program.

Pore Water Sampling

Approaches For Managing Contaminated Sediments
Michalsen, M. and G. Rosen | SERDP & ESTCP Webinar Series, Webinar #124, December 2020

Two webinars presented as part of the SERDP and ESTCP series focused on DoD-funded research efforts to measure and manage contaminated sediments. The first presentation discussed an approach to develop and validate a standardized polymeric sampler method to quantify freely-dissolved organic contaminant concentrations of PAHs and PCBs in sediment porewater. The second discussed research results following long-term monitoring of AquaGate+PAC™ to reduce PCB availability in surface sediment at Pier 7 of the Puget Sound Naval Shipyard. Additional information on the Puget Sound Naval Shipyard Pier 7 project

Chemical Techniques for Assessing Bioavailability of Sediment-Associated Contaminants: SPME versus Tenax Extraction
You, J., A.D. Harwood, H. Li, and M.J. Lydy.
Journal of Environmental Monitoring 13(4):792-800(2011)

This review summarizes studies using matrix-SPME or Tenax extraction to estimate hydrophobic organic contaminant bioavailability and toxicity, and evaluates the strengths and weakness of the two techniques. The advantages of SPME fibers are their applicability for use in situ and their potentially greater range of compound selection by selection of appropriate coatings. Tenax extraction requires only a single time-point treatment, which decreases time and labor and is more effective for compounds with short environmental half-lives. Tenax extraction also has lower detection limits, making it more applicable for highly toxic contaminants.

Evaluation of Pore-Water Samplers at a Drainage Ditch, Installation Restoration Site 4, Naval Air Station Corpus Christi, Corpus Christi, Texas, 2005-06
Vroblesky, D.A. and C.C. Casey
USGS, Scientific Investigations Report 2007-5154, 16 pp, 2007

The report compares the results of pore-water samples taken with two different variations of six newly developed pore-water samplers (as well as three standard water-filled passive diffusion samplers) that were installed at a drainage ditch.

Ex Situ Determination of Freely Dissolved Concentrations of Hydrophobic Organic Chemicals in Sediments and Soils: Basis for Interpreting Toxicity and Assessing Bioavailability, Risks and Remediation Necessity
Jonker, M.T.O., R.M. Burgess, U. Ghosh, P.M. Gschwend, S.E. Hale, R. Lohmann, et al.
Nature Protocols 151800-1828(2020)

A passive sampling protocol was developed to determine the freely dissolved concentration (C_free) of hydrophobic organic chemicals in sediment and soil samples. The protocol describes the selection and preconditioning of the passive sampling polymer, critical incubation system component dimensions, equilibration and equilibrium condition confirmation, quantitative sampler extraction, quality assurance/control issues, and final calculations of C_free. The full procedure requires several weeks, depending on the sampler used, due to prolonged equilibration times. However, hands-on time, excluding chemical analysis, is approximately 3 days for a set of ~15 replicated samples.

Field Tests of Nylon-Screen Diffusion Samplers and Pushpoint Samplers for Detection of Metals in Sediment Pore Water, Ashland and Clinton, Massachusetts, 2003
Zimmerman, M.J., D.A. Vroblesky, K.W. Campo, A.J. Massey, and W. Scheible
USGS. Scientific Investigations Report 2005-5155, 56 pp, 2005

Guidance on the Use of Passive-Vapor-Diffusion Samplers to Detect Volatile Organic Compounds in Ground-Water-Discharge Areas, and Example Applications in New England
Church, P.E., D.A. Vroblesky, F.P. Lyford, and R.E. Willey
USGS, Water-Resources Investigations Report 02-4186, 90 pp, 2002

Nanofiber-Enabled, Multi-Target Passive Sampling Device for Determination of the Freely-Dissolved Sediment Pore Water Concentrations of Organic Contaminants
Martinez, A. and D.M. Cwiertny.
SERDP Project ER-2543, 63 pp, 2016

A suite of electrospun nanofiber mats (ENMs) was fabricated as next-generation multi-target passive samplers to test their sorption capacities for a set of hydrophilic (aniline and nitrobenzene) and hydrophobic compounds (PCBs and dioxin). The average diameter of the ENMs ranged from 70 (PET) to 1,000 (EVA) nm, with a relative standard deviation of less than 50% for each material. In water the ENMs yielded a fast equilibration time (<3 days) for the tested compounds. The ENM-water partition coefficient (KENM-w) for the hydrophilic compounds ranged from 0.72 to 2.8 log units. The KENM-w for hydrophobic compounds ranged from 3.2 to 6.4 log units. Collectively, the rates and KENM-w measured for the best performing ENMs often exceeded partition coefficients achieved with commercially available passive sampling materials (e.g., low-density polyethylene and PDMS glass fiber), particularly for hydrophilic compounds.

Pore Water Sampling
Lewis, R.
USEPA, Region 4, Standard Operating Procedure SESDPROC 513-R0, 16 pp, 2007

This SOP is for a push point sampler.

Pushpoint Sampling for Defining Spatial and Temporal Variations in Contaminant Concentrations in Sediment Pore Water near the Ground-Water/Surface-Water Interface
Zimmerman, M.J., A.J. Massey, and K.W. Campo
USGS, Scientific Investigations Report 2005-5036, 75 pp, 2005

Sampling for Contaminants in Sediments and Sediment Pore Water
Hazardous Waste Clean-Up Information (CLU-IN) Web Site

This site provides short descriptions and pictures of sediment and pore water sampling equipment and a list of references.

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