Fate of glutaraldehyde in hospital wastewater and combined effects of glutaraldehyde and surfactants on aquatic organisms

Glutaraldehyde (GA), an aliphatic dialdehyde disinfectant, and surfactants, one of the major components of detergents, are widely used in hospitals in order to eliminate pathogenic organisms causing nosocomial infectious diseases. After their use, disinfectants and surfactants reach the wastewater network together. The discharge of chemical compounds from hospital activities into wastewater is also a well-known problem, causing pollution of water resources and constituting an ecological risk for aquatic organisms. In this study, the chemistry and toxicology of GA and surfactant mixtures were reviewed in order to estimate their fate in aquatic ecosystems. Furthermore, their joint effects on aquatic organisms were experimentally assessed in the laboratory. A simple model of the additive joint action of toxicants was used to determine combined acute toxicity effects on the bacteria luminescence and Daphnia mobility of three mixtures containing GA at 1.5 x EC50 24 h [in mg/L] on Daphnia and anionic, cationic and nonionic surfactants at twice their critical micellar concentration (CMC). The mixture of GA and a cationic surfactant gave an EC50 30 min on Vibrio fischeri of 0.158%, with a concentration of 0.04 mg GA/L and 1.04 mg CTAB/L, which provided an additive action. The interaction between GA and an anionic surfactant on V. fischeri produced an antagonistic joint action with an EC50 30 min of 3.95%, containing 1.06 mg GA/L and 33.2 mg SDS/L. A synergistic action with an EC50 30 min of 8.4% on V. fischeri was observed for the mixture containing GA and a nonionic surfactant. Antagonistic interactions were observed for the joint action between GA and the surfactants studied on Daphnia. The mixture of GA and CTAB was more toxic (EC50 24 h=0.02%) than the two other mixtures (EC50 24 h GA+SDS=6%; EC50 24 h GA+TX 100=10%). This study provides new data on the toxicity of certain hospital pollutants entering the aquatic environment and detected in surface and groundwaters. It is necessary to study the joint effects of GA and surfactant mixtures following chronic and sublethal standard bioassays in order to estimate the contribution of the additive joint action models in assessing the environmental risk of hospital wastewater (HW).     

Determination of pharmaceutical compounds in hospital effluents and their contribution to wastewater treatment works

A method was developed for the simultaneous determination of almost 40 pharmaceuticals; including antidepressants, non-steroidal anti-inflammatories, analgesics, hypolipidemics, α- and β-blockers, an anti cancer drug, anti-fungal agents, an opiate, an antibiotic, an anti-coagulant, a diuretic, an anti-anginal and an anti-diabetic compound. This was used to assess the contribution of pharmaceuticals originating from hospital effluents to one of Oslo city's wastewater treatment works. Some pharmaceuticals were found to contribute to more of the wastewater loading than others. 11% of the propranolol entering the wastewater treatment works stems from hospital effluent, approximately 2% of the atenolol, carbemazepine, metaprolol and atorvastatin, and for several other compounds the contribution is less than 1%.This assessment shows that point sources discharges from hospitals typically make a small contribution to the overall pharmaceutical load when compared to municipal areas, however this varies from substance to substance and is not the case when a drug's use is primarily hospital based.     

Review of pollutants in petroleum refinery wastewaters and effect upon aquatic organisms

In the past decade, the number of organic chemical contaminants identified in oil refinery wastewaters has risen from less than 20 to over 300. This increase in knowledge was made possible by advances in gas chromatography-mass spectrometry instrumentation and new techniques to maximize resolution of capillary chromatography. The types of compounds identified in refinery wastewaters are similar to those identified in crude oils; i.e., aliphatic, aromatic, alkyl aromatic, polynuclear aromatic hydrocarbons, and some hydrocarbons containing nitrogen, sulfur, and oxygen. The contaminants in oil refinery wastewaters acutely lethal to aquatic organisms can be removed by biological treatment systems. However, biological treatment systems may not be capable of removing all deleterious contaminants. Long-term fathead minnow bioassays of biologically treated refinery wastewaters resulted in 10%–50% mortality after 14–16 days of exposure. The lethal effects were eliminated by sequential treatment with dual media filtration-activated carbon adsorption.     

Polycyclic aromatic hydrocarbons and effects on marine organisms in the Istanbul Strait

Surficial sediments and mussels (Mytilus galloprovincialis) from the Istanbul Strait and Marmara Sea were analysed for sixteen parent polycyclic aromatic hydrocarbon (PAH) contents by gas chromatography-mass spectrometry (GC-MS) employing isotope dilution technique. Microalgae toxicity testing was applied to sediment elutriates and biological responses in terms of filtration rate and lysosomal stability were measured in mussels. Total PAH concentrations ranged from 2.1 to 3152 ng g^? 1 dry wt in sediments and from 43–601 ng g^? 1 wet weight in mussels. Molecular indices of phenanthrene/ anthracene, fluoranthene/pyrene and benzo(a)anthracene/chrysene were used to differentiate between pyrolytic and petroleum origin. Results showed that most of the contamination originates from high temperature pyrolytic inputs with some slight contribution of petrogenic PAH. PAH in sediments were frequently lower than the National Oceanic and Atmospheric Administration (NOAA)–ERM (Effects Range Medium) index. Results of sediment elutriate toxicity testing and biomarkers indicate that the cause of negative effects in sediments may result from different classes of pollutants and does not only relate with PAH contamination. Mussels from most of the stations showed both reduced lysosomal membrane stability and filtration rate indicating disturbed health although the two biomarker results did not always complement each other. The effect studies showed that the pollutants in the strait ecosystem have more pronounced effects in the middle parts than those at the Black Sea entrance.     

The effects of atrazine on dissolved oxygen and nitrate concentrations in aquatic systems

The effects of the herbicide atrazine, on nitrate-nitrogen (nitrate-N) and dissolved oxygen concentrations in aquatic microcosms were determined. Treatment levels consisted of a control, 50, 100, and 150 μg/1 atrazine with four replicates per treatment. From a stock atrazine solution serial dilutions were prepared for each treatment level. The serial dilutions were added as single daily doses in 150 mL increments to the appropriate treatment. Dissolved oxygen was measured twice daily for each ssytem. Nitrate-N concentrations were measured twice weekly for the duration of the experiment.Dissolved oxygen was not resistant to the atrazine perturbation and decreased to concentrations approximating 0.0 mg/L for all atrazine concentrations. However, dissolved oxygen concentrations were resilient to perturbation and recovered to pretreatment levels within 48 h following cessation of toxicant input. Nitrate-N concentrations also were not resistant to the atrazine perturbation and decreased to more than 90% of the pretreatment concentrations following atrazine introduction. Nitrate-N concentrations for atrazine treatments exhibited high resilience to the perturbation. Nitrate-N concentrations recovered to approximately 90% of the preperturbation nitrate-N concentrations 48 h after cessation of the toxicant.Although small amounts of atrazine may have a significant impact upon aquatic systems by reducing levels of dissolved oxygen and nitrate, there appears to be no permanent ecosystem damage since these systems recover rapidly when atrazine levels return to zero.     

Fate and effects of amphoteric surfactants in the aquatic environment

Amphoteric surfactants form part of specialty surfactants available for formulators to improve or design new formulations in response to environmental, toxicity, safety and performance demands. Nevertheless, limited information on the ecological properties of amphoterics is available. In the present work, the aerobic and anaerobic biodegradability and the aquatic toxicity of different types of amphoteric surfactants (three alkyl betaines, one alkylamido betaine and three alkyl imidazoline derivatives) were studied. The amphoteric surfactants tested were readily biodegradable under aerobic conditions (CO(2) headspace test) and alkylamido betaines and alkyl imidazoline derivatives were also easily biodegradable under anaerobic conditions (test based on the ECETOC method). Toxicity to Photobacterium phosphoreum and Daphnia magna increased with the fatty chain length of the surfactant. The EC(50) toxicity values of the amphoterics tested were higher than 5 mg/L, and alkyl imidazoline derivatives, with EC(50) values from 20 to >200 mg/L, showed the lowest aquatic toxicity.     

Effects of ranitidine and its photoderivatives in the aquatic environment

This study was designed to assess the overall ecotoxicity of ranitidine, a histamine H₂-receptor antagonist that inhibits stomach acid production. Hence, in addition to ranitidine, its main two photoderivatives, obtained by solar simulator irradiation in water, were investigated. The photoproducts were identified by their physical features. Bioassays were performed on rotifers and microcrustaceans to assess acute and chronic toxicity, while SOS Chromotest and Ames test were utilized to detect the genotoxic potential of the investigated compounds. The results showed that ranitidine did not show any acute toxicity at the highest concentration tested (100 mg/L) for all the organisms utilized in the bioassays. Chronic exposure to these compounds caused inhibition of growth population on rotifers and crustaceans. Genotoxic and mutagenic effects were especially found for one photoproduct suggesting that transformation products, as frequently demonstrated, may show effects higher than the respective parental compound.     

Variations of 210Po and 210Pb in various marine organisms from Western English Channel: contribution of 210Po to the radiation dose

Measurements of (210)Po were carried out in various marine matrices (mussels, oysters, seaweed, fish, and abalones) and in seawater at several points along the French coast, over a period of 2 years (2003-2005). These measurements contribute to a better knowledge of this element, since few recent data exist for the French coast. Marked seasonal variations have been revealed in some species and there are differences according to the way of life of these species. Activities in mussels (Mytilus edulis) and oysters (Crassostrea gigas) are similar and varying between 90 and 600 Bq kg(-1) (d.w.). Activities in macroalgae (Fucus serratus) are lowest, between 4 and 16 Bq kg(-1) (d.w.). In oyster, abalone (Haliotis tuberculata) and fish (Solea solea, Sparus sp.), the strongest activities are measured in the digestive glands, the gills and the gonads. (210)Po/(210)Pb ratios in all cases have values of more than one for all species. From a significant number of measurements, CFs were calculated for seaweed (between 4.6 x 10(3) and 5.0 x 10(3)) and for molluscs, with highest CFs (>10(5)) found for the digestive gland and gills of the oysters, the digestive gland of the abalones and the liver of fish. Finally, the activities measured have made it possible to estimate the internal dose from chronic exposure due to (210)Po received by the marine organisms (0.05 microGh(-1) for macroalgae, between 0.70 and 1.5 microGh(-1) for mussels and oyster), and the contribution of seafood to the dose received by humans (46-129 microSvy(-1)).     

Field observations of the effects of protracted low levels of ionizing radiation on natural aquatic population by using a cytogenetic tool

In the present study, an effort is attempted to record the impact of chronic radiation on natural aquatic populations exposed to protracted doses (lower if compared to intervention levels but higher if compared to typical background) and to chemical pollution. The methodology is based on the analyses of chromosome aberrations observed in cells. Therefore, some preliminary research results on the cytogenetic effects on aquatic organisms of various taxa, in coastal ecosystems are presented, considering some selective regions of elevated natural gamma radiation and conventional pollution. These areas are the geothermal spring areas in the island of Ikaria-Eastern Aegean Sea and the port of Pireus, in Greece. The data are compared to the findings recorded in some organisms collected from the North Aegean Sea the early period after the Chernobyl accident. With regard to the different species examined, a first evaluation of the results is made using the reported field findings for the wide area of Chernobyl. The environmental assessment of the studied areas in terms of radiation impact is based on the cytogenetic injuries observed, and evidence of ecosystem disturbance is also pointed out. The final environmental assessment based on the quantified effects observed in the organisms from the studied areas takes into account a published conceptual model of zones of radiation dose rates and the resulting organism responses in a step function scale.     

Occurrence,fate and effects of azoxystrobin in aquatic ecosystems: A review

The use of pesticides for crop protection may result in the presence of toxic residues in environmental matrices. In the aquatic environment, pesticides might freely dissolve in the water or bind to suspended matter and to the sediments, and might be transferred to the organisms' tissues during bioaccumulation processes, resulting in adverse consequences to non-target species. One such group of synthetic organic pesticides widely used worldwide to combat pathogenic fungi affecting plants is the strobilurin chemical group. Whereas they are designed to control fungal pathogens, their general modes of action are not specific to fungi. Consequently, they can be potentially toxic to a wide range of non-target organisms. The present work had the intent to conduct an extensive literature review to find relevant research on the occurrence, fate and effects of azoxystrobin, the first patent of the strobilurin compounds, in aquatic ecosystems in order to identify strengths and gaps in the scientific database. Analytical procedures and existing legislation and regulations were also assessed. Data gathered in the present review revealed that analytical reference standards for the most relevant environmental metabolites of azoxystrobin are needed. Validated confirmatory methods for complex matrices, like sediment and aquatic organisms' tissues, are very limited. Important knowledge of base-line values of azoxystrobin and its metabolites in natural tropical and estuarine/marine ecosystems is lacking. Moreover, some environmental concentrations of azoxystrobin found in the present review are above the Regulatory Acceptable Concentration (RAC) in what concerns risk to aquatic invertebrates and the No Observed Ecologically Adverse Effect Concentration (NOEAEC) reported for freshwater communities. The present review also showed that there are very few data on azoxystrobin toxicity to different aquatic organisms, especially in what concerns estuarine/marine organisms. Besides, toxicity studies mostly address azoxystrobin and usually neglect the more relevant environmental metabolites. Further work is also required in what concerns effects of exposure to multi-stressors, e.g. pesticide mixtures. Even though Log K_ow for azoxystrobin and R234886, the main metabolite of azoxystrobin in water, are below 3, the bio-concentration factor and the bioaccumulation potential for azoxystrobin are absent in the literature. Moreover, no single study on bioaccumulation and biomagnification processes was found in the present review.     

Atmospheric versus lithogenic contribution to the composition of first- and second-order stream waters in Seoul and its vicinity

The spatial variations in the chemistry of first- and second-order stream waters (N = 65) were investigated in the easterly bound of Seoul in order to assess the effects of urban air pollution on surface water chemistry. The sulfate (SO4(2-)) was high (range 3.9-17.8 mg l(-1), mean 11.8 mg l(-1)) within 30 km away from the center of Seoul, compared to the levels (range 1.1-7.7 mg l(-1), mean 4.3 mg l(-1)) observed in remote areas (30-70 km away). Both graphical examination and statistical evaluation (variogram) of sulfate concentration data consistently showed the decrease of sulfate concentration with increasing distance. The results of mass balance modeling also indicate that the concentrations of SO4(2-), Cl- and Na+ may be affected mainly by dry/wet deposition. However, the spatial variations of major cations such as Ca2+ and Na+ are well explained by the reaction of rainwater with diverse rocks in the watercourse. The water type was found to change from Ca(-Na)-SO4) type to Ca(-a)-HCO3 type with the increasing distance. It is thus inferred that the pollutants like SO2 emitted from strong man-made source areas of Seoul are transported to the considerable distance (at least 30 km away) by westerlies and that such mechanism may lead to the changes of the anion composition in surface water. In the remote area (> 30 km away from Seoul), the stream water chemistry appears to be influenced more effectively by the weathering of rock-forming minerals.     

Distribution of leeches in aquatic ecosystems of the city of Yekaterinburg and its vicinity

Ecological features and species composition of leeches were studied in 25 water bodies located in the city of Yekaterinburg and its vicinity. Specific features of their occurrence and distribution in water bodies of various types were analyzed. Dominant, mass, common, and rare species were distinguished.     

Ecological effects of various toxic agents on the aquatic microcosm in comparison with acute ionizing radiation

The purpose of this study was an evaluation of the effect levels of various toxic agents compared with acute doses of ionizing radiation for the experimental model ecosystem, i.e., microcosm mimicking aquatic microbial communities. For this purpose, the authors used the microcosm consisting of populations of the flagellate alga Euglena gracilis as a producer, the ciliate protozoan Tetrahymena thermophila as a consumer and the bacterium Escherichia coli as a decomposer. Effects of aluminum and copper on the microcosm were investigated in this study, while effects of gamma-rays, ultraviolet radiation, acidification, manganese, nickel and gadolinium were reported in previous studies. The microcosm could detect not only the direct effects of these agents but also the community-level effects due to the interspecies interactions or the interactions between organisms and toxic agents. The authors evaluated doses or concentrations of each toxic agent which had the following effects on the microcosm: (1) no effects; (2) recognizable effects, i.e., decrease or increase in the cell densities of at least one species; (3) severe effects, i.e., extinction of one or two species; and (4) destructive effects, i.e., extinction of all species. The resulting effects data will contribute to an ecological risk assessment of the toxic agents compared with acute doses of ionizing radiation.     

Ecological and toxicological effects of inorganic nitrogen pollution in aquatic ecosystems: A global assessment

We provide a global assessment, with detailed multi-scale data, of the ecological and toxicological effects generated by inorganic nitrogen pollution in aquatic ecosystems. Our synthesis of the published scientific literature shows three major environmental problems: (1) it can increase the concentration of hydrogen ions in freshwater ecosystems without much acid-neutralizing capacity, resulting in acidification of those systems; (2) it can stimulate or enhance the development, maintenance and proliferation of primary producers, resulting in eutrophication of aquatic ecosystems; (3) it can reach toxic levels that impair the ability of aquatic animals to survive, grow and reproduce. Inorganic nitrogen pollution of ground and surface waters can also induce adverse effects on human health and economy. Because reductions in SO2 emissions have reduced the atmospheric deposition of H2SO4 across large portions of North America and Europe, while emissions of NOx have gone unchecked, HNO3 is now playing an increasing role in the acidification of freshwater ecosystems. This acidification process has caused several adverse effects on primary and secondary producers, with significant biotic impoverishments, particularly concerning invertebrates and fishes, in many atmospherically acidified lakes and streams. The cultural eutrophication of freshwater, estuarine, and coastal marine ecosystems can cause ecological and toxicological effects that are either directly or indirectly related to the proliferation of primary producers. Extensive kills of both invertebrates and fishes are probably the most dramatic manifestation of hypoxia (or anoxia) in eutrophic and hypereutrophic aquatic ecosystems with low water turnover rates. The decline in dissolved oxygen concentrations can also promote the formation of reduced compounds, such as hydrogen sulphide, resulting in higher adverse (toxic) effects on aquatic animals. Additionally, the occurrence of toxic algae can significantly contribute to the extensive kills of aquatic animals. Cyanobacteria, dinoflagellates and diatoms appear to be major responsible that may be stimulated by inorganic nitrogen pollution. Among the different inorganic nitrogenous compounds (NH4+, NH3, NO2-, HNO2NO3-) that aquatic animals can take up directly from the ambient water, unionized ammonia is the most toxic, while ammonium and nitrate ions are the least toxic. In general, seawater animals seem to be more tolerant to the toxicity of inorganic nitrogenous compounds than freshwater animals, probably because of the ameliorating effect of water salinity (sodium, chloride, calcium and other ions) on the tolerance of aquatic animals. Ingested nitrites and nitrates from polluted drinking waters can induce methemoglobinemia in humans, particularly in young infants, by blocking the oxygen-carrying capacity of hemoglobin. Ingested nitrites and nitrates also have a potential role in developing cancers of the digestive tract through their contribution to the formation of nitrosamines. In addition, some scientific evidences suggest that ingested nitrites and nitrates might result in mutagenicity, teratogenicity and birth defects, contribute to the risks of non-Hodgkin's lymphoma and bladder and ovarian cancers, play a role in the etiology of insulin-dependent diabetes mellitus and in the development of thyroid hypertrophy, or cause spontaneous abortions and respiratory tract infections. Indirect health hazards can occur as a consequence of algal toxins, causing nausea, vomiting, diarrhoea, pneumonia, gastroenteritis, hepatoenteritis, muscular cramps, and several poisoning syndromes (paralytic shellfish poisoning, neurotoxic shellfish poisoning, amnesic shellfish poisoning). Other indirect health hazards can also come from the potential relationship between inorganic nitrogen pollution and human infectious diseases (malaria, cholera). Human sickness and death, extensive kills of aquatic animals, and other negative effects, can have elevated costs on human economy, with the recreation and tourism industry suffering the most important economic impacts, at least locally. It is concluded that levels of total nitrogen lower than 0.5-1.0 mg TN/L could prevent aquatic ecosystems (excluding those ecosystems with naturally high N levels) from developing acidification and eutrophication, at least by inorganic nitrogen pollution. Those relatively low TN levels could also protect aquatic animals against the toxicity of inorganic nitrogenous compounds since, in the absence of eutrophication, surface waters usually present relatively high concentrations of dissolved oxygen, most inorganic reactive nitrogen being in the form of nitrate. Additionally, human health and economy would be safer from the adverse effects of inorganic nitrogen pollution.     

Worldwide occurrence and effects of antifouling paint booster biocides in the aquatic environment: a review

Organic booster biocides were recently introduced as alternatives to organotin compounds in antifouling products, after restrictions imposed on the use of tributyltin (TBT) in 1987. Replacement products are generally based on copper metal oxides and organic biocides. This ban has led to an increase in alternative coating products containing the above biocides. The most commonly used biocides in antifouling paints are: Irgarol 1051, diuron, Sea-nine 211, dichlofluanid, chlorothalonil, zinc pyrithione, TCMS (2,3,3,6-tetrachloro-4-methylsulfonyl) pyridine, TCMTB [2-(thiocyanomethylthio) benzothiazole], and zineb. Since 1993, several studies have demonstrated the presence of these biocides in European coastal environment as a result of their increased use. More recently, the presence of these biocides was also revealed in waters from Japan, United States, Singapore, Australia and Bermuda. This paper reviews the currently available data on the occurrence of these biocides in the aquatic environment. Some data dealing with the environmental fate, partitioning, behaviour and risk assessment of antifouling paint booster biocides are also reported in order to discuss the detected levels of contamination.     

Acute and sublethal toxicity tests to monitor the impact of leachate on an aquatic environment

In this study, a specific landfill leachate (1200 mg l(-1) COD and 600 mg l(-1) BOD(5)) was used to develop a standardised short-term acute and longer-term sublethal ex-situ toxicity testing programme, in order to determine the potential ecological implications of leaching contaminants reaching the water table. Bioassays were undertaken with juvenile Gammarus pulex and Asellus aquaticus macro-invertebrates. Preliminary acute test variables included static and static renewed flow rates for 96-h, starved and fed specimens, and aerobic and oxygen depleting conditions. However, regardless of any test variable, the lethal concentration (LC(50)) for A. aquaticus remained at 12.3% v/v leachate in deionized water, whilst that for G. pulex was only 1%. Sublethal toxicity was judged on the basis of frequency of births and the growth rate of newly born individuals. Tests showed that even a dilution as high as 1:66- would influence the fecundity of a Gammarus population, whilst a dilution of 1:20 would affect the size of an Asellus breeding colony.     

A novel approach to the sequential extraction of plutonium from oxic and anoxic sediment using sodium citrate to inhibit post-extraction resorption

Sequential extraction has been used extensively to study the solid partitioning of radionuclides in soils and sediments. A difficulty with sequential extraction is that radionuclides released by a particular extractant can be resorbed and artificially redistributed amongst the remaining solid phases. Here, we describe experiments (on selected model phase and natural materials), which were designed to determine whether the inclusion of a chelating agent (sodium citrate) in an established sequential extraction protocol (a) inhibits post-extraction resorption of plutonium, (b) increases non-targeted dissolution of sediment phases, and (c) gives rise to unwanted ligand competition for plutonium. The results clearly demonstrate the capacity of citrate to inhibit the resorption of plutonium from the various extractants, and confirm that there is no discernible increase in non-targeted phase dissolution, but indicate significant ligand competition with the carbonate phase. The merits of using citrate are discussed and an optimised sequential extraction protocol that includes citrate is proposed. Finally, the protocol is applied to oxic and anoxic sediments sampled in the NE Irish Sea and the Roads of Cherbourg, and it is shown that the bulk of the plutonium on these sediments is associated with the more labile geochemical fractions.