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

• Overview
• Policy and Guidance
• Conceptual Site Models
• Fate and Transport of Contaminants
• Site Characterization
  • Sampling
  • Analytical Methods
• Risk Assessment
• Remediation
• Additional Resources

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Analytical Methods

Generally, the analyses of sediment and water samples conform to standard laboratory procedures, such those found in SW-846 or the Contract Laboratory Statement of Work. A list of methods that are specific to many of the contaminants of concern in sediments can be found in the detection and characterization sections of Contaminant Focus. Some sediment characteristics, such as marine salinity, may require modification of the analytical or preparation methods.

A comprehensive list of laboratory methods, many of which pertain to sediment and biota analysis, can be found at the US Fish and Wildlife Analytical Control Facility Web site.

Sediment Testing for Physical/Chemical Properties

Evaluation of Dredged Material Proposed For Discharge in Waters of the U.S. - Testing Manual. Inland Testing Manual
USACE/USEPA, Office of Water, EPA-823/B-98/004, 571 pp, 1998

This manual describes laboratory techniques, test species, procedures, detection limits, and evaluation protocols representing the state of knowledge at publication. The document has a tiered approach to testing that is designed to provide the information needed to determine the potential for contaminant related impacts of proposed dredging discharges without necessitating unnecessary testing and evaluation.

Biota Analysis

Standard laboratory methods, such as those found in SW 846, may be used to analyze biota tissues for the presence of contaminants. Sample preparation procedures for biota tissues differ from those used for water and sediment sample analysis.

Extraction, Cleanup, and Gas Chromatography/Mass Spectrometry Analysis of Sediments and Tissues for Organic Contaminants
Sloan, C.A., D.W. Brown, R.W. Pearce, R.H. Boyer, J.L. Bolton, D.G. Burrows, D.P. Herman, and M.M. Krahn.
NOAA Tech. Memo. NMFS-NWFSC-59, 47 p, 2004.

Review of Field Validation Studies of Sediment Bioassays for the Regulatory Evaluation of Dredged Material
U.S. Army Corps of Engineers, ERDC TN-DOER-C23, 19 pp, 2001

Chemical Analysis

Field

An In Situ Laser-Induced Fluorescence System for Polycylic Aromatic Hydrocarbon-Contaminated Sediments
Aldstadt, J., R.S. Germain, T. Grundl, and R. Schweitzer
USEPA, Great Lakes National Program Office, 54 pp, 2002

Integrated Field-Screening for Rapid Sediment Characterization
ESTCP, Space and Naval Warfare Systems Center, San Diego, ESTCP Project #9717, 122 pp, 2000

This document provides an evaluation of the use of field portable X-ray fluorescence, UV fluorescence spectroscopy, and Quiksed for evaluating metals, the presence of PAHs, and sediment toxicity, respectively.

Laboratory

Determination of Polychlorinated Biphenyls (PCBs) in Sediment and Biota
Webster, L., P. Roose, P. Bersuder, M. Kotterman, M. Haarich, and K. Vorkamp.
ICES Techniques in Marine Environmental Sciences, No. 53, 23 pp, 2013

The determination of PCBs in sediment and biota generally involves extraction with organic solvents, cleanup, and gas chromatographic separation with electron capture detection or mass spectrometry. Due to the low concentrations of non-ortho-substituted PCBs compared to those of other PCBs, their determination may require an additional separation step. All stages of the procedure are susceptible to insufficient recovery and/or contamination; therefore, quality control procedures are important in order to check method performance.

Passive PE Sampling in Support of In Situ Remediation of Contaminated Sediments: Standard Operating Procedure for PE Analysis
Gschwend, P., J. MacFarlane, K. Palaia, S. Reichenbacher, and D. Gouveia.
ESTCP Project ER-200915, 7 pp, 2012

This method describes procedures for chemical analysis of contaminants contained in polyethylene (PE) as deployed in polyethylene devices (PEDs) to sample hydrophobic organic compounds in aquatic and sediment environments. The procedure generates extracts suitable for high-resolution GC/MS analysis and is applicable to lab- or field-exposed PEDs.

PCB Method Comparison of High and Low Resolution Sediment Analysis
Coots, R.
Washington Dept. of Ecology, Publication 14-03-009 , 72 pp, 2014

Ten archived marine and freshwater sediment samples from cleanup projects with known PCB concentrations were split three ways and analyzed by congeners (high resolution), homologs (low resolution), and Aroclor methods. Detection limits varied between methods, with estimated sample detection limits for congeners averaging about 50 times lower than those reported for homologs and over 400 times lower than Aroclors. A strong statistical relationship was noted for total PCBs determined by congener analysis compared to either the homolog analysis or the same dataset Kaplan and Meier adjusted to account for nondetects. When total PCB Aroclors were compared to high resolution congeners, a weaker yet still strong relationship was reported.

SW 846 Method 4430 Screening for Polychlorinated Dibenzo-P-Dioxins and Furans (PCDD/Fs) by Aryl Hydrocarbon-Receptor PCR Assay
USEPA, Office of Solid Waste, SW 846 Method 4430, 21 pp, 2007

SW-846 Method 8261A: Volatile Organic Compounds by Vacuum Distillation in Combination with Gas Chromatography/Mass Spectrometry (VD/GC/MS)
USEPA, Office of Solid Waste, 99 pp, 2006

This recommended version, which reflects an update of a previous version of this method, incorporates the latest available vacuum distillation equipment and is consistent with Method 8260C. The revised method is based on a vacuum distillation and cryogenic trapping procedure (Method 5032) and gas chromatography/mass spectrometry. It incorporates an internal standard-based matrix correction, involving the analysis of multiple internal standards to predict matrix effects. Normalization of the matrix effects makes Method 8261 analyses matrix independent and allows multiple matrices to be analyzed within a sample batch. As a result, the calculations involved are specific to this method and may not be used with data generated by another method. The method includes all of the necessary steps from sample preparation through instrumental analysis.

This method is used to determine the concentrations of volatile organic compounds, and some low-boiling semivolatile organic compounds, in nearly all matrices, including water, soil, sediment, sludge, oil, and animal tissue. Unlike Method 5032/8260, this method uses internal standards to measure matrix effects and compensates analyte responses for matrix effects. This method should be considered for samples where matrix effects are anticipated to severely impact analytical results.

SW-846 Method 8272: Parent and Alkyl Polycyclic Aromatics in Sediment Pore Water by Solid-Phase Microextraction and Gas Chromatography/Mass Spectrometry in Selected Ion Monitoring Mode
USEPA, Office of Solid Waste, 34 pp, 2007

EPA's narcosis model for benthic organisms in sediments contaminated with PAHs is based on the concentrations of dissolved PAHs in the interstitial water or pore water of the sediment. Method 8272 covers the separation of pore water from PAH-impacted sediment samples, the removal of colloids, and the subsequent measurement of dissolved concentrations of the 10-parent PAHs and two alkylated daughter PAHs in the pore water samples. This method directly determines the concentrations of dissolved PAHs in environmental sediment pore water, groundwater, and other water samples using solid-phase microextraction for static sample collection followed by desorption into a gas chromatograph equipped with a mass spectrometric detector operated in the selected ion monitoring mode for analyte identification and quantitation.

Toxicity Analyses

Field

Integrated Field-Screening for Rapid Sediment Characterization
ESTCP, Space and Naval Warfare Systems Center, San Diego, ESTCP Project #9717, 122 pp, 2000

This document evaluates the use of field portable X-ray fluorescence, UV fluorescence spectroscopy, and Quiksed for evaluating metals, the presence of PAHs, and sediment toxicity, respectively.

Use of Sediment Quality Guidelines and Related Tools for the Assessment of Contaminated Sediments Executive Summary Booklet of a SETAC Pellston Workshop
Wenning, R.J. and C.G. Ingersoll (eds.)
SETAC, 48 pp, 2002

This workshop focused on the evaluation of the scientific foundations supporting different chemically-based numeric sediment quality guidelines (SQGs) and methods to improve the integration of SQGs into different sediment quality assessment frameworks that include information derived from multiple chemical and biological lines of evidence.

Laboratory

Confounding Factors in Sediment Toxicology
Lapota, D., D. Duckworth, and J.Q. Word
SPAWAR, 19 pp, 2000

Bioassays, which are often required as part of an ecological risk assessment, often demonstrate toxicity that could lead to inaccurate conclusions and subsequently expensive remedial actions. Evidence of toxicity in sediments can often be caused by natural factors termed "false positives" or "confounding factors," such as ammonia, sulfide, or grain size, rather than actual contaminants of concern. The objective of this issue paper is to evaluate the natural factors that cause toxicity or false positives; identify, discuss, and optimize methods to measure or eliminate these factors; and identify and discuss standard and new cost-effective sediment toxicity bioassays.

The Determination of Sediment Polycyclic Aromatic Hydrocarbon (PAH) Bioavailability Using Direct Pore Water Analysis by Solid-Phase Microextraction (SPME)
Geiger, S.C.
ESTCP Project ER-200709, 483 pp, 2010

Direct determination of PAH concentrations in dissolved sediment pore water using EPA method SW-8272 and ASTM provisional method D-7363-07 utilizes SPME on a very small sample of sediment (20 ml to <40 ml) to provide PAH concentration data. PAHs in sediments at the Washington Navy Yard, Washington, DC, were targeted for a demonstration of the SPME analytical method and the developed PAHs bioavailability assessment protocol.

Development of Sediment Extracts for Rapid Assessment of Organic Contaminant Bioavailability
Price, C., et al.
USACE, ERDC/TN EEDP 02-31, 10 pp, 2003

This technical note describes the development of sediment extraction procedures for evaluating the bioaccumulation potential of non-polar organic contaminants from dredged material.

Development of Marine Sediment Toxicity for Ordnance Compounds and Toxicity Identification Evaluation Studies at Select Naval Facilities
NAVFAC, NFESC Contract Report CR 01-002-ENV, 205 pp, 2000

Development of a Rapid, Inexpensive Bioassay for Screening Contaminant Bioavailability in Sediment Using mRNA Profiling
Perkins, E., H. Fredrickson, and G. Lotufo
USACE, ERDC/TN EEDP-04-35, 8 pp, 2002

Dredged Material Analysis Tools; Performance of Acute and Chronic Sediment Toxicity Methods
Steevens, Jeffery, Alan Kennedy, Daniel Farrar, Cory McNemar, Mark R. Reiss, Kropp, R.K., J. Doi, and T. Bridges
USACE, ERDC/EL TR-08-16, 73 pp, 2008

Method for Assessing the Chronic Toxicity of Marine and Estuarine Sediment-associated Contaminants with Amphipod Leptocheirus plumulosus
USEPA and USACE, EPA/600/R-01/020, 130 pp, 2001

Methods for Measuring the Toxicity and Bioaccumulation of Sediment-Associated Contaminants with Freshwater Invertebrates, Second Edition
USEPA, Office of Research and Development and Office of Water, EPA/600/R-99/064, 212 pp, 2000

SW 846 Method 4435: Method for Toxic Equivalents (TEQS) Determinations for Dioxin-Like Chemical Activity with the CALUX® Bioassay
USEPA, Office of Solid Waste, 58 pp

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