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)

Extreme events and ecological forecasting

Almost all extreme events lasting less than several weeks that significantly impact ecosystems are weather related. This review examines the response of estuarine systems to intense short-term perturbations caused by major weather events such as hurricanes. Current knowledge concerning these effects is limited to relatively few studies where hurricanes and storms impacted estuaries with established environmental monitoring programs. Freshwater inputs associated with these storms were found to initially result in increased primary productivity. When hydrographic conditions are favorable, bacterial consumption of organic matter produced by the phytoplankton blooms and deposited during the initial runoff event can contribute to significant oxygen deficits during subsequent warmer periods. Salinity stress and habitat destruction associated with freshwater inputs, as well as anoxia, adversely affect benthic populations and fish. In contrast, mobile invertebrate species such as shrimp, which have a short life cycle and the ability to migrate during the runoff event, initially benefit from the increased primary productivity and decreased abundance of fish predators. Events studied so far indicate that estuaries rebound in one to three years following major short-term perturbations. However, repeated storm events without sufficient recovery time may cause a fundamental shift in ecosystem structure (Scavia et al. 2002). This is a scenario consistent with the predicted increase in hurricanes for the east coast of the United States. More work on the response of individual species to these stresses is needed so management of commercial resources can be adjusted to allow sufficient recovery time for affected populations.

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)

Endocrine disruption in fish: An assessment of recent research and results

This report provides an assessment of recent investigations into endocrine disruption in fresh and saltwater species of fish. Most work to date has concen-trated on reproductive endocrine disruption. Laboratory studies have shown a variety of synthetic and natural chemicals including certain industrial intermediates, PAHs, PCBs, pesticides, dioxins, trace elements and plant sterols can interfere with the endocrine system in fish. The potency of most of these chemicals, however, is typically hundreds to thousands of times less than that of endog-enous hormones. Evidence of environmental endocrine disruption ranges from the presence of female egg proteins in males and reduced levels of endogenous hormones in both males and females, to gonadal histopathologies and intersex (presence of ovotestes) fish. Overt endocrine disruption in fish does not appear to be a ubiquitous environmental phenomenon, but rather more likely to occur near sewage treatment plants, pulp and paper mills, and in areas of high organic chemical contamination. However, more wide-spread endocrine disruption can occur in rivers with smaller flows and correspondingly large or numerous wastewater inputs. Some of the most severe examples of endocrine disruption in fish have been found adjacent to sewage treatment plants. Effects are thought to be caused prima-rily by natural and synthetic estrogens and to a lesser extent by the degradation products of alkylphenol poly-ethoxylate surfactants. Effects found in fish near pulp and paper mills include reduced levels of estrogens and androgens as well as masculinization of females, and has been linked to the presence of β-sitosterol, a plant sterol. Effects seen in areas of heavy industrial activity typically include depressed levels of estrogens and androgens as well as reduced gonadal growth, and may be linked to the presence of PAHs, PCBs, and possibly dioxins. At this time, however, there is no clear indication that large populations of fish are being seriously impacted as a result of endocrine disruption, although additional work is needed to address this possibility. (PDF contains 63 pages)

Evaluating approaches and technologies for monitoring organic contaminants in the aquatic environment, Ann Arbor, MI, July 21-23, 2006: workshop proceedings

The Alliance for Coastal Technologies (ACT) convened a workshop on Evaluating Approaches and Technologies for Monitoring Organic Contaminants in the Aquatic Environment in Ann Arbor, MI on July 21-23, 2006. The primary objectives of this workshop were to: 1) identify the priority management information needs relative to organic contaminant loading; 2) explore the most appropriate approaches to estimating mass loading; and 3) evaluate the current status of the sensor technology. To meet these objectives, a mixture of leading research scientists, resource managers, and industry representatives were brought together for a focused two-day workshop. The workshop featured four plenary talks followed by breakout sessions in which arranged groups of participants where charged to respond to a series of focused discussion questions. At present, there are major concerns about the inadequacies in approaches and technologies for quantifying mass emissions and detection of organic contaminants for protecting municipal water supplies and receiving waters. Managers use estimates of land-based contaminant loadings to rivers, lakes, and oceans to assess relative risk among various contaminant sources, determine compliance with regulatory standards, and define progress in source reduction. However, accurately quantifying contaminant loading remains a major challenge. Loading occurs over a range of hydrologic conditions, requiring measurement technologies that can accommodate a broad range of ambient conditions. In addition, in situ chemical sensors that provide a means for acquiring continuous concentration measurements are still under development, particularly for organic contaminants that typically occur at low concentrations. Better approaches and strategies for estimating contaminant loading, including evaluations of both sampling design and sensor technologies, need to be identified. The following general recommendations were made in an effort to advance future organic contaminant monitoring: 1. Improve the understanding of material balance in aquatic systems and the relationship between potential surrogate measures (e.g., DOC, chlorophyll, particle size distribution) and target constituents. 2. Develop continuous real-time sensors to be used by managers as screening measures and triggers for more intensive monitoring. 3. Pursue surrogate measures and indicators of organic pollutant contamination, such as CDOM, turbidity, or non-equilibrium partitioning. 4. Develop continuous field-deployable sensors for PCBs, PAHs, pyrethroids, and emerging contaminants of concern and develop strategies that couple sampling approaches with tools that incorporate sensor synergy (i.e., measure appropriate surrogates along with the dissolved organics to allow full mass emission estimation).[PDF contains 20 pages]

Growth response of Clarias gariepinus fry to organic and inorganic fertilizers

The growth response of Clarias gariepinus was investigated in various types of fertilizers. Fertilizer type was found to influence plankton abundance which in turn determine the growth and well being of C. gariepinus. The best weight increase recorded was in cow dung /NPK (1.37~c1.01g) followed by poultry (0.49~c0.31g), NPK/poultry (0.05~c0.25g) and NPK(0.03~c0.57g) The survival rate in these treatments were cow dung/NPK (100%), poultry (100%), NPK/cow/poultry (33%) and NPK (8%)

The assessment of physico-chemical parameters of Shiroro Lake and its major tributaries

The physico-chemical parameters of the surface water of Shiroro Lake and its major tributaries at their entry point to the reservoir were assessed over a period of eighteen months. As in other African inland water bodies there were seasonal variations in the parameters measured. The hydrological regime of the lake, precipitation chemistry, bedrock chemistry and hydro-electric power generation influence and determine the inputs of dissolved organic carbon, nutrient levels and water quality of the lake. The added nutrients to the lake by means of the major tributary rivers and inundation of surrounding areas also influence the water quality of the lake. The wet season mean values for water and air temperature were significantly (P <0.05) higher than dry season mean values in all stations. However, for pH, Dissolved oxygen and Phosphate-phosphorus the dry season mean values were higher than wet season mean values

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)

Temperature, organic matter and the sustainability of aquatic systems

Changes in sustainability of aquatic ecosystems are likely to be brought about by the global warming that has been widely predicted. In this article, the effects of water temperature on water-bodies (lakes, oceans and rivers) are reviewed followed by the effects of temperature on aquatic organisms. Almost all aquatic organisms require exogenous heat before they can metabolise efficiently. An organism that is adapted to warm temperatures will have a higher rate of metabolism of food organisms and this increases feeding rate. In addition, an increase in temperature raises the metabolism of food organisms, so food quality can be altered. Where populations have a different tolerance to temperature the result is habitat partitioning. One effect of prolonged high temperature is that it causes water to evaporate readily. In the marine littoral this is not an important problem as tides will replenish water in pools. Small rain pools are found in many tropical countries during the rainy season and these become incompletely dried at intervals. The biota of such pools must have resistant stages within the life cycle that enable them to cope with periods of drying. The most important potential effects of global warming include (i) the alteration of existing coastlines, (ii) the development of more deserts on some land masses, (iii) higher productivity producing higher crop production but a greater threat of algal blooms and (iv) the processing of organic matter at surface microlayers.

The importance of organic detritus in lotic ecosystems: Aspects of trophic interactions

Very little research has been carried out on detrital energetics and pathways in lotic ecosystems. Most investigations have concentrated on the degradation of allochthonous plant litter by fungi, with a glance at heterotrophic bacteria associated with decaying litter. In this short review, the author describes what is known of the detrition of plant litter in lotic waters, which results from the degradative activities of colonising saprophytic fungi and bacteria, and goes on to relate this process to those invertebrates that consume coarse and/or fine particulate detritus, or dissolved organic matter that aggregates into colloidal exopolymer particles. It is clear that many of the key processes involved in the relationships between the physical, chemical, biotic and biochemical elements present in running waters are very complex and poorly understood. Those few aspects for which there are reliable models with predictive power have resulted from data collections made over periods of 20 years or more. Comprehensive research of single catchments would provide a fine opportunity to collect data over a long period.

The content of organic matter in some waters in the Moscow region [Translation from: C.R. Acad. Soc. URSS, 61, 293-296, 1948]

There is at the moment no direct method of determining the organic matter content of natural waters. In 1940/41 8 different water bodies in central Russia were studied and their organic matter identified. The author concludes that there is currently no easy method to determine organic matter in water. A number methods need to be applied.

Some data on the content of organic carbon in rivers in the winter months. [Translation from: Gidrochim. Mat. 23, 36-38, 1955]

Observations are reported on the content of organic matter in the Moscow region in 1941. Some data is given on alkalinity, oxygen content and colourisation of the rivers.

Optical properties of the organic substances from aqueous humus surface waters. [Translation from: Gidrochim. Mat. 23, 31-35, 1955]

Dissolved organic matter, especially turf and peat, is repsonsible for the colouration of water. The reported study tried to determine the nature of the colouring agent or organic matter by the establishment of a relationship between the intensity of colouration and the total organic matter content. 44 waters from different sources were examined.

Organic detritus and its role as a food source in chalk streams

This review deals with the variation in populations of invertebrates and the relationships between invertebrate production and detrital food material in chalk streams. The total quantity of detrital material processed by invertebrate consumers is many times greater than the production of these consumers. The amount of detritus ingested each year by chalk stream invertebrates may well be similar to the annual input of autochthonous primary production plus that from allochthonous tree cover.

Nitrates in surface waters, inputs and seasonality: Progress report for the period April - December 1987

The objective of this short project progress report is to investigate, in a catchment on which earlier nitrate data are available for comparison, seasonality and budgets, in relation to land use, of nitrate inputs, concentrations and loads. Sampling was undertaken from 1984-87 in the River Frome catchment and data on nitrate concentrations analysed.