Organic contaminants in the aquatic environment II. Behaviour and fate in the hydrological cycle

The literature concerning the behaviour and fate of organic compounds in natural aquatic systems and in water and waste-water-treatment processes is reviewed. The factors governing the transport of organic compounds in water bodies are considered and the physical, chemical and biological processes which may bring about their transformation are also reviewed.The behaviour and removal of individual classes of organic micropollutants in conventional unit waste-water-treatment processes are assessed, together with an evaluation of the effectiveness of both tertiary and advanced waste-water-treatment procedures in the exclusion of organic contaminants from waste waters. Consideration is also given to the behaviour of organics in sewage-sludge treatment.The role of water-treatment processes in the removal of organic pollutants from raw and recycled waters and the production of potentially harmful organics during chlorination or other disinfection procedures is evaluated.The fate of organic micropollutants in the hydrological cycle and the effects of the disposal of sewage sludges contaminated with organic substances of concern are discussed.     

Indirect effects of contaminants in aquatic ecosystems

Contaminants such as petroleum hydrocarbons, heavy metals and pesticides can cause direct toxic effects when released into aquatic environments. Sensitive species may be impaired by sublethal effects or decimated by lethality, and this ecological alteration may initiate a trophic cascade or a release from competition that secondarily leads to responses in tolerant species. Contaminants may exert direct effects on keystone facilitator and foundation species, and contaminant-induced changes in nutrient and oxygen dynamics may alter ecosystem function. Thus, populations and communities in nature may be directly and/or indirectly affected by exposure to pollutants. While the direct effects of toxicants usually reduce organism abundance, indirect effects may lead to increased or decreased abundance. Here we review 150 papers that reference indirect toxicant effects in aquatic environments. Studies of accidental contaminant release, chronic contamination and experimental manipulations have identified indirect contaminant effects in pelagic and benthic communities caused by many types of pollutants. Contaminant-induced changes in behavior, competition and predation/grazing rate can alter species abundances or community composition, and enhance, mask or spuriously indicate direct contaminant effects. Trophic cascades were found in 60% of the manipulative studies and, most commonly, primary producers increased in abundance when grazers were selectively eliminated by contaminants. Competitive release may also be common, but is difficult to distinguish from trophic cascades because few experiments are designed to isolate the mechanism(s) causing indirect effects. Indirect contaminant effects may have profound implications in environments with strong trophic cascades such as the freshwater pelagic. In spite of their undesirable environmental influence, contaminants can be useful manipulative tools for the study of trophic and competitive interactions in natural communities.     

Foam in the aquatic environment

Foams are ubiquitous in the environment, commonly seen as discoloured patches on streams, rivers, lakes and sea water. They often are assumed to be anthropogenic in origin as they are aesthetically unpleasant, yet they frequently appear in pristine environments indicating a natural origin. In contrast to “hidden” chemical pollution, e.g. heavy metals, pesticides etc. the visibility of foam alarms the public.To derive more information on foam in freshwaters and marine ecosystems, a literature review was performed. Alongside with some basic considerations on the formation of foam, on methods to measure foam formation and on the legal aspects of foam on surface waters, the ecological importance of foam in the aquatic environment is discussed in this paper.     

Evaluation of selected ubiquitous contaminants in the aquatic environment and their transformation products. A pilot study of their removal from a sewage treatment plant

A simple method using direct sample injection combined with liquid chromatography tandem mass spectrometry has been developed for the simultaneous analysis of six alkaloid compounds in environmental samples. The target list includes two psychostimulants (nicotine and caffeine), three metabolites (cotinine, nicotinic acid and paraxanthine) and a coffee chemical (trigonelline). The analytical method was evaluated in three different matrices (surface water, influent and effluent wastewater). The method developed showed an adequate sensitivity, below 0.6 μg L⁻¹ for wastewater and 0.1 μg L⁻¹ for river matrices, without any prior treatment of the samples. Finally, the methodology was applied to real samples for evaluation of their removal from a sewage treatment plant and their persistence/fate in the aquatic environment. All compounds studied in this work were detected at all sampling points collected along the Henares River. However, nicotinic acid was only detected three times in treated sewage samples at levels above its detection limit.     

Biological contaminants in the built environment and their health implications

The building environment provides ecological niches for the development of biological agents. Dr Singh describes how investigations can provide a better understanding of building-related sickness and comments on how non-destructive environmental control strategies can be effective.     

Persistence of Diquat in the aquatic environment

Diquat (a commonly-used aquatic herbicide) added to a weed-infested simulated lake impoundment was sorbed initially by the weeds. Following rapid weedkill, profuse proliferation of microorganisms occurred, promoting degradation of the herbicide sorbed on the decomposing weeds. Within 22 days, Diquat was degraded extensively to water-soluble products (32%) and only minimal sediment adsorption occurred (19%).In weed-free sediment-water incubation systems. Diquat in water was adsorbed rapidly by Lakes Mendota and Tomahawk sediments, and the major portion of the herbicide persisted in its intact form throughout the experiment (up to 180 days). Slow microbial degradation occurred in the Lake Mendota system, as indicated by ¹⁴CO₂ evolution which was favored by aerobic conditions and a small volume of overlying water. Microbial degradation in the Lake Tomahawk system was negligible.     

Occurrence of antibiotics in the aquatic environment

The recent monitoring of drug residues in the aquatic environment has gained much interest as many pharmaceutical compounds can frequently be found in sewage treatment plant (STP) effluents and river water at concentrations up to several microgram/l. This article describes the analysis of various water samples for 18 antibiotic substances, from the classes of macrolid antibiotics, sulfonamides, penicillins and tetracyclines. Samples were preconcentrated via lyophilization and quantified using HPLC-electrospray-tandem-mass spectrometry. The investigated STP effluents and surface water samples showed frequent appearance of an erythromycin degradation product, roxithromycin and sulfamethoxazole with concentrations up to 6 micrograms/l. Neither tetracyclines nor penicillins could be detected at concentration levels above 50 and 20 ng/l, respectively. From the large number of ground water samples that were taken from agricultural areas in Germany, no contamination by antibiotics was detected except for two sites. This indicates that intake from veterinary applications to the aquatic environment is of minor importance.     

Levels and trends of radioactive contaminants in the Greenland environment

Levels of radioactive contaminants in various Greenland environments have been assessed during 1999-2001. The source of 137Cs, 90Sr and (239,240)Pu in terrestrial and fresh water environments is mainly global fallout. In addition, the Chernobyl accident gave a small contribution of 137Cs. Reindeer and lamb contain the largest observed 137Cs concentrations in the terrestrial environment--up to 80 Bq kg(-1) fresh weight have been observed in reindeer. Due to special environmental conditions, 137Cs is transferred to landlocked Arctic char with extremely high efficiency in South Greenland leading to concentrations up to 100 Bq kg(-1) fresh weight. In these cases very long ecological half-lives are seen. Concentrations of 99Tc, 137Cs and 90Sr in seawater and in marine biota decrease in the order North-East Greenland and the coastal East Greenland current > South-West Greenland > Central West Greenland and North-West Greenland > Irmiger Sea-Faroe Islands. The general large-scale oceanic circulation combined with European coastal discharges and previous contamination of the Arctic Ocean causes this. As the same tendency is seen for the persistent organic pollutants (POPs) DDT and PCB in marine biota, it is suggested that long-distance oceanic transport by coastal currents is a significant pathway also for POPs in the Greenland marine environment. The peak 99Tc discharge from Sellafield 1994-1995 has only been slightly visible in the present survey year 2000. The concentrations are expected to increase in the future, especially in East Greenland. The Bylot Sound at the Thule Airbase (Pituffik) in North-West Greenland was contaminated with plutonium and enriched uranium in a weapons accident in 1968. Biological activity has mixed accident plutonium efficiently into the new sediments resulting in continued high surface sediment concentrations three decades after the accident. Transfer of plutonium to benthic biota is low--and lower than observed in the Irish Sea. This is supposed to be caused by the physico-chemical form of the accident plutonium. A recent study indicates that 'hot particles' hold considerably more plutonium than previously anticipated and that the Bylot Sound sediments may account for the major part of the un-recovered plutonium after the accident, i.e. approximately 3 kg.     

Sources and behavior of technetium in the environment

Technetium is a man-made element produced in increasing amounts during the last decades. The chemical and physical properties of some technetium compounds are considered, and a discussion of possible source terms is included. Literature on the environmental behavior of technetium is reviewed to evaluate its transfer and equilibrium distribution in aquatic and terrestrial ecosystems. Considerable effort has been expended in the last years in order to understand the biogeochemical processes responsible for the long-term behavior of technetium in the environment and its transfer through food chains as well as to identify critical pathways of the long-lived radioisotope Tc-99 from the environment to man.     

Abiotic methylation of mercury in the aquatic environment

Methylation of inorganic mercury in the aquatic environment has been considered to be largely the result of biological processes, primarily involving sulfate-reducing bacteria. However, these processes cannot account for all of the methylmercury that is formed naturally. A growing body of evidence suggests that chemical reactions represent another possible pathway for mercury methylation in the aquatic environment. In order to assess the abiotic contribution to mercury methylation in the water column, and specifically the conditions under which this contribution may be significant, the current state of knowledge about environmentally significant methylation reactions is reviewed. Results of our laboratory-based investigations of aqueous mercury reactions with some potential methyl donors, including MeCo(dmg)(2)(H2O), a simple model for methylcobalamin, various methyltin compounds and methyl iodide, are presented. In each reaction, the yield of methylmercury and the rate of methylation depend strongly on environmental factors such as pH, temperature, and the presence of complexing agents, especially chloride.     

Sources and transformations of chlorophenols in the natural environment

The present review updates our knowledge about chlorophenols, their chemical reactions and transformations in the natural environment, as well as factors affecting kinetics and mechanisms of these processes. Effects of pH of the environment and structure of molecules (also the number of chlorine atoms and their position in the molecule) on the behaviour of these compounds in the natural environment are also discussed. In addition, ways of propagation of chlorophenols in the natural environment are presented and discussed on the background of their physical and chemical properties, which influence the propagation rate in the ecosystems.     

Fate of oil dispersants in aquatic environment

Chemical oil dispersants have been used throughout most of the world to combat oil spills. However, their fate in aquatic environment remains uncertain. This study was conducted to investigate the persistence of five oil dispersants in the aquatic environment. The results indicate that petroleum utilizing bacteria possess high potential for the biodegradation of oil dispersants. The order of biodegradability for the five oil dispersants was as follows: Magnus 101 > BP1100X>BP1100>Linco No. 4>Corexit 8666. From the results of this study and a review of the literature data, it can be concluded that treatment of oil spills with chemical dispersants is unlikely to cause any build-up of organic contaminants in the aquatic environment.     

A preliminary survey of organochlorine contaminants in Nigerian environment

Random samples of imported fish, vegetables, blood, mother's milk and urine have been screened for organochlorine pesticide residues. The main contaminants detected were DDT group (DDT, DDD and DDE), HCH complex and HCB. Some of the samples contained heptachlor epoxide and oxychlordane. Pentachlorophenol was determined in blood and urine samples.     

Cholinesterase activities in the scallop Pecten jacobaeus: characterization and effects of exposure to aquatic contaminants

Nearshore marine environments of industrialized countries are increasingly threatened by anthropogenic pollution. It is therefore a priority task to investigate the sensitivity of new ecotoxicological warning signals of the occurrence and effects of aquatic pollutants. The main aims of the present study were: 1) to characterize the biochemical properties of ChEs in tissues of the bivalve Pecten jacobaeus, using different specific substrates and selective inhibitors; 2) to measure sensitivity of ChE activities to in vitro exposure to the OPs azamethiphos and DFP and to the heavy metals cadmium and zinc. Our final aim was to carry out a preliminary evaluation of the suitability of ChEs measurement in tissues of the scallop for monitoring marine environmental quality and neurotoxic compounds contamination in the Mediterranean Sea. Responses to specific inhibitors have suggested that ChEs in adductor muscle share many characteristics with vertebrate acetylcholinesterase. Dose-dependent inhibition of ChE was observed in response to in vitro exposure to environmental contaminants such as cadmium and azamethiphos. Sensitivity to zinc and DFP was lower. ChEs in P. jacobaeus might therefore have potential as a sensitive biomarker for monitoring marine pollution. Results of the present study will be useful to focus further experiment of exposure to pollutants under in vivo conditions. CAPSULE: Cholinesterase activities in scallop Pecten jacobaeus were observed to be sensitive to contaminants in vitro and may therefore have potential as biomarkers for monitoring water pollution.     

Biological fate of organic priority pollutants in the aquatic environment

This is a review of the literature on the fate of the organic priority pollutants in the aquatic environment including biological wastewater treatment systems. Included is a brief discussion of the biological processes—mineralization, cometabolism, bioaccumulation and polymerization—and conditions under which biodegradation occurs. Observed biodegradation data from laboratory studies and biological treatment systems are summarized.     

Occurrence of triiodinated X-ray contrast agents in the aquatic environment

High concentrations of adsorbable organic iodine (AOI) are found in municipal treatment plant effluents and surface waters by specific organic halogen determination. The high AOI is caused by widely used triiodinated X-ray contrast agents, which are very stable and hydrophilic. We have analysed specifically surface water influenced by a municipal treatment plant effluent, the surface water after bank filtration and raw drinking water. The X-ray contrast agents were determined by liquid chromatography-mass spectrometry with positive electrospray ionization after enrichment by solid phase extraction. Diatrizoate and iopromide, two triiodinated contrast agents are detectable in all samples, whereby the less polar component iopromide seems to be reduced during bank filtration. Just a trace of iopromide is identified in surface water after bank filtration and in the raw drinking water. Approximately 60% of the initial AOI is extractable and approximately 25% of the extractable AOI can be identified as specific triiodinated contrast agents.     

The fate of wastewater-derived NDMA precursors in the aquatic environment

To assess the stability of precursors of the chloramine disinfection byproduct N-nitrosodimethylamine (NDMA) under conditions expected in effluent-dominated surface waters, effluent samples from four municipal wastewater treatment plants were subjected to chlorination and chloramination followed by incubation in the presence of inocula derived from activated sludge. Samples subjected to free chlorine disinfection showed lower initial concentrations of NDMA precursors than those that were not chlorinated or were disinfected with pre-formed chloramines. For chloraminated and control (unchlorinated) treatments, the concentration of NDMA precursors decreased by an average of 24% over the 30-day incubation in samples from three of the four facilities. At the fourth facility, where samples were collected on three different days, NDMA precursor concentrations decreased by approximately 80% in one sample and decreased by less than 20% in the other two samples. In contrast to the low reactivity of the NDMA precursors, NDMA disappeared within 30 days under the conditions employed in these experiments. These results and measurements made in an effluent-dominated river suggest that although NDMA may be removed after wastewater effluent is discharged, wastewater-derived NDMA precursors could persist long enough to form significant concentrations of NDMA in drinking water treatment plants that use water originating from sources that are subjected to wastewater effluent discharges.