Organic Contaminant Analytical Methods of the National Status and Trends Program: 2000-2006

This document describes the analytical methods used to quantify core organic chemicals in tissue and sediment collected as part of NOAA’s National Status and Trends Program (NS&T) for the years 2000-2006. Organic contaminat analytical methods used during the early years of the program are described in NOAA Technical Memoranda NOS ORCA 71 and 130 (Lauenstein and Cantillo, 1993; Lauenstein and Cantillo, 1998) for the years 1984-1992 and 1993-1996, respectively. These reports are available from our website (http://www.ccma.nos.gov) The methods detailed in this document were utilized by the Mussel Watch Project and Bioeffects Project, which are both part of the NS&T program. The Mussel Watch Project has been monitoring contaminants in bivalves and sediments since 1986 and is the longest active national contaminant monitoring program operating in U.S. costal waters. Approximately 280 Mussel Watch sites are sampled on a biennial and decadal timescale for bivalve tissue and sediment respectively. Similarly, the Bioeffects Assessment Project began in 1986 to characterize estuaries and near coastal environs. Using the sediment quality triad approach that measures; (1) levels of contaminants in sediments, (2) incidence and severity of toxicity, and (3) benthic macrofaunal conmmunities, the Bioeffects Project describes the spatial extent of sediment toxicity. Contaminant assessment is a core function of both projects. These methods, while discussed here in the context of sediment and bivalve tissue, were also used with other matricies including: fish fillet, fish liver, nepheloid layer, and suspended particulate matter. The methods described herein are for the core organic contaminants monitored in the NS&T Program and include polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), butyltins, and organochlorines that have been analyzed consistently over the past 15-20 years. Organic contaminants such as dioxins, perfluoro compounds and polybrominated biphenyl ethers (PBDEs) were analyzed periodically in special studies of the NS&T Program and will be described in another document. All of the analytical techniques described in this document were used by B&B Laboratories, Inc, an affiliate of TDI-Brook International, Inc. in College Station, Texas under contract to NOAA. The NS&T Program uses a performance-based system approach to obtain the best possible data quality and comparability, and requires laboratories to demonstrate precision, accuracy, and sensitivity to ensure results-based performance goals and measures. (PDF contains 75 pages)

Long-Term Monitoring of Ecological Conditions In Gray’s Reef National Marine Sanctuary: Comparison of soft-bottom benthic assemblages and contaminant levels in sediments and biota in Spring 2000 and 2005

As part of an ongoing program of benthic sampling and related assessments of sediment quality at Gray’s Reef National Marine Sanctuary (GRNMS) off the coast of Georgia, a survey of soft-bottom benthic habitats was conducted in spring 2005 to characterize condition of macroinfaunal assemblages and levels of chemical contaminants in sediments and biota relative to a baseline survey carried out in spring 2000. Distribution and abundance of macrobenthos were related foremost to sediment type (median particle size, % gravel), which in turn varied according to bottom-habitat mesoscale features (e.g., association with live bottom versus flat or rippled sand areas). Overall abundance and diversity of soft-bottom benthic communities were similar between the two years, though dominance patterns and relative abundances of component species were less repeatable. Seasonal summer pulses of a few taxa (e.g., the bivalve Ervilia sp. A) observed in 2000 were not observed in 2005. Concentrations of chemical contaminants in sediments and biota, though detectable in both years, were consistently at low, background levels and no exceedances of sediment probable bioeffect levels or FDA action levels for edible fish or shellfish were observed. Near-bottom dissolved oxygen levels and organic-matter content of sediments also have remained within normal ranges. Highly diverse benthic assemblages were found in both years, supporting the premise that GRNMS serves as an important reservoir of marine biodiversity. A total of 353 taxa (219 identified to species) were collected during the spring 2005 survey. Cumulatively, 588 taxa (371 identified to species) have been recorded in the sanctuary from surveys in 2000, 2001, 2002, and 2005. Species Accumulation Curves indicate that the theoretical maximum should be in excess of 600 species. Results of this study will be of value in advancing strategic science and management goals for GRNMS, including characterization and long-term monitoring of sanctuary resources and processes, as well as supporting evolving interests in ecosystem-based management of the surrounding South Atlantic Bight (SAB) ecosystem. (PDF contains 46 pages)

Contaminant trends in US National Estuarine Research Reserves

Inputs of toxic chemicals provide one of the major types of anthropogenic stress threatening our Nation's coastal and estuarine waters. To assess this threat, the National Oceanic and Atmospheric Administration's (NOAA’s) National Status and Trends (NS&T) Program Mussel Watch Project monitors the concentrations of more than 70 toxic chemicals in sediments and on the whole soft-parts of mussels and oysters at over 300 sites around the U.S. Twenty of the 25 designated areas that comprise NOAA's National Estuarine Research Reserve System (NERRS) have one or more Mussel Watch monitoring sites. Trace elements and organic contaminants were quantified including As, Ag, Cd, Cu, Hg, Ni, Pb, Zn, ΣPCBs, ΣPAHs, DDT and its metabolites, and butyltins. The Mussel Watch sites located in or near the 20 Reserves provide for both status and trends. Generally the Reserves have trace element and organic contaminant concentrations that are at or below the median concentration determined for all NS&T Mussel Watch monitoring data. Trends were derived using the Spearman-rank correlation coefficient. It was possible to determine if trends exist for sites at which six or more years of data are available. Generally no trends were found for trace elements but when trends were found they were usually decreasing. The same general conclusion holds for organic contaminants but more decreasing trends were found than for trace elements. The greatest number of decreasing trends were found for tributyltin and its metabolites. (PDF contains 203 pages)

An assessment of two decades of contaminant monitoring in the Nation’s Coastal Zone.

Executive Summary: Information found in this report covers the years 1986 through 2005. Mussel Watch began monitoring a suite of trace metals and organic contaminants such as DDT, PCBs and PAHs. Through time additional chemicals were added, and today approximately 140 analytes are monitored. The Mussel Watch Program is the longest running estuarine and coastal pollutant monitoring effort conducted in the United States that is national in scope each year. Hundreds of scientific journal articles and technical reports based on Mussel Watch data have been written; however, this report is the first that presents local, regional and national findings across all years in a Quick Reference format, suitable for use by policy makers, scientists, resource managers and the general public. Pollution often starts at the local scale where high concentrations point to a specific source of contamination, yet some contaminants such as PCBs are atmospherically transported across regional and national scales, resulting in contamination far from their origin. Findings presented here showed few national trends for trace metals and decreasing trends for most organic contaminants; however, a wide variety of trends, both increasing and decreasing, emerge at regional and local levels. For most organic contaminants, trends have resulted from state and federal regulation. The highest concentrations for both metal and organic contaminants are found near urban and industrial areas. In addition to monitoring throughout the nation’s coastal shores and Great Lakes, Mussel Watch samples are stored in a specimen bank so that trends can be determined retrospectively for new and emerging contaminants of concern. For example, there is heightened awareness of a group of flame retardants that are finding their way into the marine environment. These compounds, known as polybrominated diphenyl ethers (PBDEs), are now being studied using historic samples from the specimen bank and current samples to determine their spatial distribution. We will continue to use this kind of investigation to assess new contaminant threats. We hope you find this document to be valuable, and that you continue to look towards the Mussel Watch Program for information on the condition of your coastal waters. (PDF contains 118 pages)

Potential Application of Adsorptive Media to Enhance Phosphorus Uptake in Stormwater Basins and Wetlands at Lake Tahoe : literature review. Report to the University of California Davis Tahoe Research Group

Phosphorus removal by wetlands and basins in Lake Tahoe may be improved through designing these systems to filter storm water through media having higher phosphorus removal capabilities than local parent material. Substrates rich in iron, aluminum and calcium oftentimes have enhanced phosphorus removal. These substrates can be naturally occurring, byproducts of industrial or water treatment processes, or engineered. Phosphorus removal fundamentally occurs through chemical adsorption and/or precipitation and much of the phosphorus can be irreversibly bound. In addition to these standard media, other engineered substrates are available to enhance P removal. One such substrate is locally available in Reno and uses lanthanum coated diatomaceous earth for arsenate removal. This material, which has a high positive surface charge, can also irreversibly remove phosphorus. Physical factors also affect P removal. Specifically, specific surface area and particle shape affect filtration capacity, contact area between water and the surface area, and likelihood of clogging and blinding. A number of substrates have been shown to effectively remove P in case studies. Based upon these studies, promising substrates include WTRs, blast furnace slag, steel furnace slag, OPC, calcite, marble Utelite and other LWAs, zeolite and shale. However, other nonperformance factors such as environmental considerations, application logistics, costs, and potential for cementification narrow the list of possible media for application at Tahoe. Industrial byproducts such as slags risk possible leaching of heavy metals and this potential cannot be easily predicted. Fly ash and other fine particle substrates would be more difficult to apply because they would need to be blended, making them less desirable and more costly to apply than larger diameter media. High transportation costs rule out non-local products. Finally, amorphous calcium products will eventually cementify reducing their effectiveness in filtration systems. Based upon these considerations, bauxite, LWAs and expanded shales/clays, iron-rich sands, activated alumina, marble and dolomite, and natural and lanthanum activated diatomaceous earth are the products most likely to be tested for application at Tahoe. These materials are typically iron, calcium or aluminum based; many have a high specific surface area; and all have low transportation costs. (PDF contains 21 pages)

Pathways for the uptake of dissolved organic matter (DOM) by aquatic animals

In this article, pathways from freshwater and marine environments are described. DOM is defined operationally as all the organic compounds which pass through a filter of pore size 0.45 microm., those retained on the surface of the filter being particulate organic matter (POM). DOM can be taken up directly by animals by transfer across the body wall, but more commonly DOM is obtained from ingested food. Once ingested POM from food particles are broken down in the gut, small molecules of DOM are released for transfer across the gut wall. Some ingested particles are attacked by micro-organisms living in the gut, thereby making the DOM available to the host animal. The importance of the microbial loop is discussed, as well as aggregation processes between the fractions of DOM which are more obviously particulate in nature. (DBO)

Different patterns of uptake and depuration of cadmium by periphyton community and a grazer species (Physa sp.): A mesocosm evalution

Widespread pollution by heavy metals generated by various industries has serious adverse effects on human health and the environment. Cadmium is a heavy metal recognised as one of the most hazardous environmental pollutants. It is a non-essential and non-beneficial element to organisms, causing toxicity and other deleterious effects on various components of the aquatic environment. The ability of algal periphyton to concentrate cadmium from fresh water is well known. Moreover, periphyton communities are able to accumulate large amounts of cadmium despite its low concentration in fresh water. Many researchers use algal periphyton as an indicator of water quality in aquatic environments. In the present study, the authors ask two basic questions: Does cadmium accumulate along a food chain consisting of the periphyton community and a grazer species (Physa sp.) under semi-natural conditions provided by artificial streams? If not, which one can better indicate the water quality?

Assessment of contaminant body burdens and histopathology of fish and shellfish species frequently used for subsistence food by Alaskan Native communities

Subsistence food items can be a health concern in rural Alaska because community members often rely on fish and wildlife resources not routinely monitored for persistent bioaccumulative contaminants and pathogens. Subsistence activities are a large part of the traditional culture, as well as a means of providing protein in the diets for Tribal members. In response to the growing concerns among Native communities, contaminant body burden and histopathological condition of chum and sockeye salmon (Oncorhynchus keta and Oncorhynchus nerka) and the shellfish cockles and softshell clams (Clinocardium nuttallii and Mya arenaria) were assessed. In the Spring of 2010, the fish and shellfish were collected from traditional subsistence harvest areas in the vicinity of Nanwalek, Port Graham, and Seldovia, AK, and were analyzed for trace metals and residues of organic contaminants routinely monitored by the NOAA National Status & Trends Program (NS&T). Additionally, the fish and shellfish were histologically characterized for the presence, prevalence and severity of tissue pathology, disease, and parasite infection. The fish and shellfish sampled showed low tissue contamination, and pathologic effects of the parasites and diseases were absent or minimal. Taken together, the results showed that the fish and shellfish were healthy and pose no safety concern for consumption. This study provides reliable chemistry and histopathology information for local resource managers and Alaska Native people regarding subsistence fish and shellfish use and management needs.

Sediment quality triad assessment in Kachemak Bay: characterization of soft bottom benthic habitats and contaminant bioeffects assessment condensed. A NOAA/NOS/NCCOS/CCMA Special Report

A baseline environmental characterization of the inner Kachemak Bay, Alaska was conducted using standardized National Status and Trends Bioeffects Program methods. Three sites near the village of Port Graham were also sampled for comparison. Concentrations of over 120 organic and metallic contaminants were analyzed. Ambient toxicity was assessed using two bioassays. A detailed benthic community condition assessment was performed. Habitat parameters (e.g. depth, salinity, temperature, dissolved oxygen, sediment grain size, and organic carbon content) that influence species and contaminant distribution were also measured at each sampling site. The following is the synopsis of findings • Sediments were mostly mixed silt and sand with pockets of muddy zones. Organic compounds (PAHs, DDTs, PCBs, chlorinated pesticides) were detected throughout the bay but at relatively low concentrations. With some exceptions, metals concentrations were relatively low and probably reflect the input of glacial runoff. • Homer Harbor had elevated concentrations of metallic and organic contaminants. Concentrations of organic contaminants measured were five to ten times higher in the harbor sites than in the open bay sites. Tributyltin was elevated in Homer Harbor relative to the other areas. • There was no evidence of residual PAHs attributable to oil spills, outside of local input in the confines of the harbor. • The benthic community is very diverse. Specific community assemblages were distributed based on depth and water clarity. Species richness and diversity was lower in the eastern end of the bay in the vicinity of the Fox River input. Abundance was also generally lower in the eastern portion of the study area, and in the intertidal areas near Homer. The eastern portions of the bay are stressed by the sediment load from glacial meltwater. • Significant toxicity was virtually absent. • The benthic fauna at Port Graham contained a significant number of species not found in Kachemak Bay. • Selected metal concentrations were elevated at Port Graham relative to Kachemak Bay, probably due to local geology. Organic contaminants were elevated at a site south of the village.

Sediment Quality Triad assessment in Kachemak Bay: characterization of soft bottom benthic habitats and contaminant bioeffects assessment

A baseline environmental characterization of the inner Kachemak Bay, Alaska was conducted using the sediment quality triad approach based on sediment chemistry, sediment toxicity, and benthic invertebrate community structure. The study area was subdivided into 5 strata based on geophysical and hydrodynamic patterns in the bay (eastern and western intertidal mud flats, eastern and western subtidal, and Homer Harbor). Three to seven locations were synoptically sampled within each stratum using a stratified random statistical design approach. Three sites near the village of Port Graham and two sites in the footprint of a proposed Homer Harbor expansion were also collected for comparison. Concentrations of over 120 organic and metallic contaminants were analyzed. Ambient toxicity was assessed using two amphipod bioassays. A detailed benthic community condition assessment was performed. Habitat parameters (depth, salinity, temperature, dissolved oxygen, sediment grain size, and organic carbon content) that influence species and contaminant distribution were also measured at each sampling site. Sediments were mostly mixed silt and sand; characteristic of high energy habitats, with pockets of muddy zones. Organic compounds (PAHs, DDTs, PCBs, cyclodienes, cyclohexanes) were detected throughout the bay but at relatively low concentrations. Tributyltin was elevated in Homer Harbor relative to the other strata. With a few exceptions, metals concentrations were relatively low and probably reflect the input of glacial runoff. Relative to other sites, Homer Harbor sites were shown to have elevated concentrations of metallic and organic contaminants. The Homer Harbor stratum however, is a deep, low energy depositional environment with fine grained sediment. Concentrations of organic contaminants measured were five to ten times higher in the harbor sites than in the open bay sites. Concentration of PAHs is of a particular interest because of the legacy of oil spills in the region. There was no evidence of residual PAHs attributable to oil spills, outside of local input, beyond the confines of the harbor. Concentrations were one to ten times below NOAA sediment quality guidelines. Selected metal concentrations were found to be relatively elevated compared to other data collected in the region. However, levels are still very low in the scale of NOAA’s sediment quality guidelines, and therefore appear to pose little or no ecotoxicity threat to biota. Infaunal assessment showed a diverse assemblage with more than 240 taxa recorded and abundances greater than 3,000 animals m-22 in all but a few locations. Annelid worms, crustaceans, snails, and clams were the dominant taxa accounting for 63 %, 19%, 5%, and 7 % respectively of total individuals. Specific benthic community assemblages were identified that were distributed based on depth and water clarity. Species richness and diversity was lower in the eastern end of the bay in the vicinity of the Fox River input. Abundance was also generally lower in the eastern portion of the study area, and in the intertidal areas near Homer. The eastern portions of the bay are stressed by the sediment load from glacial meltwater. Significant toxicity was virtually absent. Conditions at the sites immediately outside the existing Homer Harbor facility did not differ significantly from other subtidal locations in the open Kachemak Bay. The benthic fauna at Port Graham contained a significant number of species not found in Kachemak Bay. Contaminant conditions were variable depending on specific location. Selected metal concentrations were elevated at Port Graham and some were lower relative to Kachemak Bay, probably due to local geology. Some organic contaminants were accumulating at a depositional site.

Effect of sublethal concentration of artificial seawater on oxygen uptake and opercular frequency in an Indian major carp, Labeo rohita (Ham.)

The present study reports the effect of artificial seawater on oxygen uptake and opercular frequency in an Indian major carp, Labeo rohita. Whereas a control fish of 7.34 g average body weight consumed 1.538 ml O sub(2.) hˉ¹, the 24h and 96h exposed fish of the same body weight consumed 1.07 4 and 0.897 ml O sub(2.) hˉ¹, respectively. The oxygen uptake per unit body weight under controlled condition was 0.219 ml. gˉ¹. hˉ¹, whereas in 24h and 96h exposed fish, it was 0.152 and 0.124 ml. gˉ¹, hˉ¹, respectively. The change in opercular movement in 24h exposed fish was 7.67% higher, whereas in 96h exposed fish, it was 22.43% higher as compared to the control one. All changes are highly significant (p<0.001).