Background, aim, and scope Aquatic microcontaminants (MCs) comprise diverse chemical classes, such as pesticides, biocides, pharmaceuticals, consumer products, and industrial chemicals. For water pollution control and the evaluation of water protection measures, it is crucial to screen for MCs. However, the selection and prioritization of which MCs to screen for is rather difficult and complex. Existing methods usually are strongly limited because of a lack of screening regulations or unavailability of required data. Method and models Here, we present a simple exposure-based methodology that provides a systematic overview of a broad range of MCs according to their potential to occur in the water phase of surface waters. The method requires input of publicly available data only. Missing data are estimated with quantitative structure-property relationships. The presented substance categorization methodology is based on the chemicals' distribution behavior between different environmental media, degradation data, and input dynamics. Results Seven different exposure categories are distinguished based on different compound properties and input dynamics. Ranking the defined exposure categories based on a chemical's potential to occur in the water phase of surface waters, exposure categories I and II contain chemicals with a very high potential, categories III and IV contain chemicals with a high potential, and categories V and VI contain chemicals with a moderate to low potential. Chemicals in category VII are not evaluated because of a lack of data. We illustrate and evaluate the methodology on the example of MCs in Swiss surface waters. Furthermore, a categorized list containing potentially water-relevant chemicals is provided. Discussion Chemicals of categories I and III continuously enter surface waters and are thus likely to show relatively steady concentrations. Therefore, they are best suited for water monitoring programs requiring a relatively low sampling effort. Chemicals in categories II and IV have complex input dynamics. They are consequently more difficult to monitor. However, they should be considered if an overall picture is needed that includes contaminants from diffuse sources. Conclusions The presented methodology supports compound selection for (a) water quality guidance, (b) monitoring programs, and (c) further research on the chemical's ecotoxicology. The results from the developed categorization procedure are supported by data on consumption and observed concentrations in Swiss surface waters. The presented methodology is a tool to preselect potential hazardous substances based on exposure-based criteria for policy guidance and monitoring programs and a first important step for a detailed risk assessment for potential microcontaminants.

Background, aim, and scope Freshwater reservoirs can be impacted by several hazardous substances through inputs from agricultural activity, sewage discharges, and groundwater leaching and runoff. The water quality assessment is very important for implementation of the monitoring and remediation programs to minimize the risk promoted by hazardous substances in aquatic ecosystems. Evaluation of the degree of contamination of aquatic environments must not take in account only its chemical characterization but it must be complemented with biological assays, which determine potential toxic effects and allows an integrated evaluation of its effects in populations and aquatic ecosystem communities. The application of this type of strategy has clear advantages allowing a general evaluation of the effects from all the water components, including those due to unknown substances and synergic, antagonistic, or additive effects. There are only a few studies that reported ecotoxicological acute end points, for the assessment of surface water quality, and the relationship among toxicity results and the anthropogenic pollution sources and the seasonal period. The aim of this study was to assess the ecotoxicological characterization of the surface water from Alqueva reservoir (South of Portugal) and to evaluate the influence of anthropogenic sources of pollution and their seasonal variation in its toxicity. The construction of Alqueva reservoir was recently finished (2002) and, to our knowledge, an ecotoxicological assessment of its surface water has not been performed. Because of that, no information is available on the possible impact of pollutants on the biota. The surface water toxicity was assessed using acute and chronic bioassays. The results are to be used for developing a monitoring program, including biological methods. Materials and methods Water samples were collected during 2006-2007, at each of the nine sampling sites selected in Alqueva reservoir. These sampling points allow an assessment at the upstream (Sra. Ajuda, Alcarrache, Álamos-Captação), at the middle (Alqueva-Montante, Alqueva-Mourão, Lucefecit), and at the downstream of the water line (Alqueva-Jusante; Ardila-confluência; Moinho das Barcas). The campaigns occurred in February, March, May, July, September, and November of 2006 and February, March, and May of 2007. The rainy season comprised November, February, and March, and the dry season included May, July, and September. A total of 81 samples were collected during the study period. The physical-chemical parameters were analyzed following standard and recommended methods of analysis (APHA et al. 1998). The pesticide analyses were performed using gas chromatography according to DIN EN ISO 6468 (1996). Surface water ecotoxicity was evaluated using the following bioassays: Vibrio fischeri luminescence inhibition, Thamnocephalus platyurus mortality, and Daphnia magna immobilization and reproduction assay. The Spearman rank correlation coefficients were used to evaluate the associations between the water sample physicochemical properties (from each sampling station in each season) and the acute and chronic toxicological effects, with a level of significance p < 0.05. Results In the acute toxicity study, the species that was found to be the most sensitive was T. platyurus. T. platyurus detected a higher number of toxic water samples during the dry season. Concerning the luminescent inhibition of V. fischeri, the results showed that this organism detected a great number of toxic water samples in rainy seasons. The water samples, which promoted higher toxic effects towards this species, were from the north and from the middle of the reservoir. The correlation analysis showed that V. fischeri luminescent inhibition (%) was positively correlated with total phosphorus, chlorpyrifos, iron, and arsenic. T. platyurus mortality (%) was positively correlated with the water pH, 5-day biochemical oxygen demand (BOD₅), chlorides, atrazine, simazine, terbuthylazine, and endosulfan sulfate contents. Although the surface waters did not promote acute toxicity to the crustacean D. magna, in the chronic exposure, a significant decrease in the number of juveniles per female was observed, mainly at the dry period. The number of juveniles per female, in the reproduction test of D. magna, was negatively correlated with pH, temperature, BOD₅, chloride, atrazine, simazine, terbuthylazine, and endosulfan sulfate. The water toxicity of the Alqueva water might be due principally to the intensive agriculture activities surrounding the reservoir and to the municipal wastewater discharges. Discussion The physicochemical parameters and the pesticide concentrations indicated that the water quality was worse in the north part of the reservoir system. These results are characteristic of the majority of reservoirs, once the construction of the dam promoted, by itself, the impounding of water flow and the increase of compound residence time. The toxicity tests corroborate with the chemical characterization. Acute toxicity of Alqueva water may be a result of the effect promoted by chlorpyrifos, endosulfan sulfate, phosphorus, and iron. Chronic toxicity may be a result of the effect of herbicides, arsenic, organic matter, endosulfan sulfate in mixture. Hence, the water toxicity of the Alqueva might be due principally to the intensive agriculture activities surrounding the reservoir and to the municipal wastewater discharges. Conclusions This study has shown that a large number of samples from different sites of the Alqueva reservoir contained potentially toxic contaminants. The sites with impaired water quality were those located at the north of the reservoir and in the surrounding areas of intensive agricultural activity. The results demonstrated that the use of a screening of acute and chronic toxicity tests with organisms from different trophic levels and with distinct sensibilities allowed the detections of several patterns of toxicity from spatial and temporal variability promoted by natural or anthropogenic sources. The chronic responses showed, especially in the dry season, that some of the species belonging to this aquatic ecosystem might be at risk. Recommendations and perspectives The V. fischeri and T. platyurus are two species that should be used in the acute bioassays for the ecotoxicological monitoring programs of this reservoir. It is recommended that other species, such as a productive organism (algae), be included in the next study, once the water reservoir had high levels of herbicides. Ecotoxicological assessment of surface water must integrate initial screening based on acute tests followed always by chronic bioassays. The results implicitly suggest that the implementation of processes of remediation by reducing pollutant input into the reservoir and by the implementation of water treatment processes is important and necessary.

PURPOSES AND AIMS: Economically efficient methods for removing arsenic from the drinking water supply are urgently needed in many parts of the world. Iron oxides are known to have a strong affinity for arsenic in water. However, they are commonly present in the forms of fine powder or floc, which limits their utility in water treatment. In this study, a novel granular adsorbent, iron-oxide-coated diatomite (IOCD), was developed and examined for its adsorption of arsenic from water. MATERIALS AND METHODS: An industrial-grade diatomite was used as the iron oxide support. The diatomite was first acidified and dried and then coated with iron oxide up to five times. The prepared IOCD samples were characterized for their morphology, composition, elemental content, and crystal properties by various instruments. Experiments of equilibrium and kinetic adsorption of As(V) on IOCD were conducted using 0.1- and 2-L polyethylene bottles, respectively, at different pH and temperatures. RESULTS: Iron oxide (α-Fe₂O₃ hematite) coated onto diatomite greatly improves (by about 30 times) the adsorption of As(V) from water by IOCD as compared to using raw diatomite. This improvement was attributed to increases in both surface affinity and surface area of the IOCD. The surface area of IOCD increased to an optimal value. However, as the IOCD surface area (93 m²/g) was only 45% higher than that of raw diatomite (51 m²/g), the enhanced As(V) adsorption resulted primarily from the enhanced association of negatively charged As(V) ions with the partial positive surface charge of the iron oxide. The As(V) adsorption decreased when the solution pH was increased from 3.5 to 9.5, as expected from the partial charge interaction between As(V) and IOCD. The adsorption data at pH 5.5 and 7.5 could be well fitted to the Freundlich equation. A moderately high exothermic heat was observed for the As(V) adsorption, with the calculated molar isosteric heat ranging from −4 to −9 kcal/mol. The observed heats fall between those for physical adsorption and chemisorption and are indicative of the formation of a series of ion-pair complexes of As(V) ions with iron oxide surface groups. CONCLUSIONS: This study demonstrated that the granular IOCD was successfully developed and employed to remove the As(V) in aqueous solution. The Freundlich isotherm well fitted the equilibrium adsorption data of As(V) onto IOCD, and both the pseudo-second-order model and the pore diffusion model simulated well the adsorption kinetics. Compared to other iron-oxide-based adsorbents reported in the literatures, the adsorption capacity of IOCD is relatively high and its kinetics is fast.

Purposes Very few data for polybrominated diphenyl ethers (PBDEs) were available in the Yangtze River Delta (YRD), one of the most developed and urbanized region in China. In this study, Chongming Island, located at the estuary of the Yangtze River, was selected as background area to investigate the occurrence, sources, and inventory of PBDEs. Methods Forty-two PBDE congeners were determined in surface soils from farmland, woodland, grassland, tideland, and road collected in Chongming Island. Results The mean concentrations of Σ₂₆PBDE (not including BDE-209) and BDE-209 in soils were 0.76 and 12 ng/g dry weight, respectively. BDE-209 contributed more than 90% of the total of 27 frequently detected BDE congeners, followed by BDE-99 and BDE-47. Weak correlations were found between total organic carbon content and PBDE congeners concentrations in surface soils. PBDE levels varied with land use. Farmland and woodland soils contained higher Σ₂₆PBDE concentrations. BDE-209 levels were the highest in road soils. The mass inventories of PBDEs in soils of Chongming Island were estimated at 3.1 and 310 kg for Σ₂₆PBDEs and BDE-209, respectively. Conclusions The PBDE levels in Chongming Island were similar to those in European background soils, suggesting minimum influence of pollutants from the YRD via air, and wastewater inputs or few PBDE products were used herein. From the standpoint of eco-inland, more studies are needed to explore the reasons of PBDE difference by land use and to assess people intake PBDEs via agriculture products consumption in this region.

Background, aim, and scope Many pollutants have received significant attention due to their potential estrogenic effect and are classified as endocrine disrupting compounds (EDCs). Because of possible ecological effects and increased attention for water reuse schemes, it is important to increase our understanding of the EDC removal capacities of various wastewater treatment systems. However, there has so far been little research on the fate and behavior of EDCs in stabilization pond systems for wastewater treatment, which represent an important class of wastewater treatment systems in developing countries because of their cost-effectiveness. The aim of this work is to study the fate and behavior of EDCs in algae and duckweed ponds. Because the synthetic hormone 17α-ethinylestradiol (EE2) and the natural hormones estrone (E1), as well as 17β-estradiol (E2), have been detected in effluents of sewage treatment plants and been suggested as the major compounds responsible for endocrine disruption in domestic sewage; E1, E2, and EE2 were therefore chosen as target chemicals in this current work. Materials and methods Both batch tests and continuous-flow tests were carried out to investigate the sorption and biodegradation of estrogens in algae and duckweed pond systems. The applied duckweed was a Lemna species. The applied algae was a mixture of pure cultures of six different algae genera, i.e., Anabaena cylindrica, Chlorococcus, Spirulina platensis, Chlorella, Scenedesmus quadricauda, and Anaebena var. Synthetic wastewater were used in all tests. The concentrations of estrogens were measured with three different enzyme-linked immunosorbent assay kits specific for E1, E2, or EE2. When the concentrations of estrogens in water samples were below the lowest quantitative analysis range (0.05 µg/l), preconcentration of the water samples were performed by means of solid phase extraction (SPE) with C18 cartridges. Results The 6-day batch tests show that the presence of algae or duckweed accelerated the removal of the three estrogens from the synthetic wastewater. More estrogens were removed in the tests with duckweed than in tests with algae or with wastewater. In the sorption tests, a swift sorption of the three estrogens was observed when the estrogens were contacted with duckweed or algae, while the estrogen concentrations in tap water kept unchanged during the 3-h sorption tests. The mass balances indicated that only about 5% of the estrogens were bound to the algae sediment or duckweed at the end of the 6-day tests. Results of the continuous-flow tests revealed that the algae and duckweed ponds effectively removed E1, E2, and EE2 even at nanograms per liter level. Interconversion of E1 and E2 occurred both in batch and continuous-flow tests. E2 could be readily transformed to E1, especially in the tests with algae. Discussion Different processes like sorption, biodegradation and photolytic degradation might play an important role in the removal of estrogens from the aquatic phase. The 3-h sorption tests support the importance of sorption for estrogen removal, in which a rapid initial sorption was observed over the first 2 min for E1/E2/EE2 to both duckweed and algae. In the 6-day batch tests, estrogens were sorbed by algae or duckweed during the early stage when algae and duckweed were contacted with the synthetic wastewater and the sorbed estrogens were further biodegraded by the microorganisms developed in the wastewater. The persistent estrogen concentrations in tap water, however, implied that no sorption, biodegradation, or photolytic degradation occurred in tap water under the specific experimental conditions. Under aerobic or anoxic conditions, E2 could be first oxidized to E1, which is further oxidized to unknown metabolites and finally to CO₂ and water. Under anaerobic conditions, E1 can also be reduced to E2. However, the interconversion might be much more complex especially in the tests with algae because both aerobic and anaerobic conditions occurred in these tests due to the variation of the dissolved oxygen concentration induced by the light regime. Conclusions This study shows that estrogens, E1, E2, and EE2, can be effectively removed from the continuous-flow algae and duckweed ponds even when their concentrations are at nanograms per liter level. The presence of algae and duckweed accelerate the removal of estrogens from the synthetic wastewater because estrogens can be quickly sorbed on duckweed or algae. The sorbed estrogens are subsequently degraded by microorganisms, algae, or duckweed in the wastewater treatment system. E1 and E2 are interconvertible in both duckweed and algae pond systems. E2 can be readily transformed to E1, especially in the tests with algae. Recommendation and perspectives Based on the tests performed so far, one can conclude that both sorption and biodegradation are important to the estrogens removal from stabilization pond systems for wastewater treatment. Further research using, e.g., radioimmunoassay is needed to investigate the biodegradation pathway of estrogens in algae and duckweed ponds.

Background and purpose In Pakistan, almost 70% of the population lives in rural areas. Ninety-four percent of households in rural areas and 58% in urban areas depend on biomass fuels (wood, dung, and agricultural waste). These solid fuels have poor combustion efficiency. Due to incomplete combustion of the biomass fuels, the resulting smoke contains a range of health-deteriorating substances that, at varying concentrations, can pose a serious threat to human health. Indoor air pollution accounts for 28,000 deaths a year and 40 million cases of acute respiratory illness. It places a significant economic burden on Pakistan with an annual cost of 1% of GDP. Despite the mounting evidence of an association between indoor air pollution and ill health, policy makers have paid little attention to it. This review analyzes the existing information on levels of indoor air pollution in Pakistan and suggests suitable intervention methods. Methods This review is focused on studies of indoor air pollution, due to biomass fuels, in Pakistan published in both scientific journals and by the Government and international organizations. In addition, the importance of environmental tobacco smoke as an indoor pollutant is highlighted. Results Unlike many other developing countries, there are no long-term studies on the levels of indoor air pollution. The limited studies that have been undertaken indicate that indoor air pollution should be a public health concern. High levels of particulate matter and carbon monoxide have been reported, and generally, women and children are subject to the maximum exposure. There have been a few interventions, with improved stoves, in some areas since 1990. However, the effectiveness of these interventions has not been fully evaluated. Conclusion Indoor air pollution has a significant impact on the health of the population in Pakistan. The use of biomass fuel as an energy source is the biggest contributor to poor indoor air quality followed by smoking. In order to arrest the increasing levels of indoor pollution, there is a dire need to recognize it as a major health hazard and formulate a national policy to combat it. An integrated effort, with involvement of all stakeholders, could yield promising results. A countrywide public awareness campaign, on the association of indoor air pollution with ill health, followed by practical intervention would be an appropriate approach. Due to the current socioeconomic conditions in the country, development and adoption of improved cooking stoves for the population at large would be the most suitable choice. However, the potential of biogas as a fuel should be explored further, and modern fuels (natural gas and LPG) need to be accessible and economical. Smoking in closed public spaces should be banned, and knowledge of the effect of smoking on indoor air quality needs to be quantified.

Purpose In this study, seasonal variations in the concentration profile of four analgesics and one lipid regulator were monitored on their way from a wastewater treatment plant (WWTP) effluent, along a river, and into a lake. Methods From December 2007 to December 2008, water samples were collected monthly (n = 12) from an upstream point, the effluent, four downstream points of the WWTP, and at the point where the river merges with the lake, and the concentrations of ibuprofen, naproxen, bezafibrate, diclofenac, and ketoprofen were determined. The analytical methodology involved solid-phase extraction of the target compounds from water samples followed by liquid chromatography coupled with tandem mass spectrometry for compound separation and detection. Results The studied pharmaceuticals were found in the effluent at concentrations ranging from 31 to 1,852 ng l⁻¹ depending on the season. In the river and lake, the concentrations were much lower (6-400 ng l⁻¹) mainly due to dilution but also to a season-dependent contribution from natural transformation processes. The mean mass flow of all analgesics was highest during winter while the highest mean mass flow of the lipid regulator bezafibrate was observed in spring. Conclusions The WWTP is the main source of the target compounds in the aquatic environment. The observed winter accumulation signifies the importance of natural transformation processes, which can only be estimated based on mass flow data, on the fate of pharmaceuticals in the environment.

Background, aim and scope Polychlorinated biphenyls (PCB) and dichlorodiphenyltrichloroethane (DDT) concentrations were determined in the liver of two deep sea fish species, Mediterranean slimehead and blackfin sorcerer, from the Adriatic Sea (southeastern Mediterranean Sea). Results and discussion The examination of congener profiles showed that hexachlorinated molecules were dominant (hexa-CBs, 55.3-56.2%), followed by penta-CBs (21.5-21.8%) and hepta-PCB 180 (14.9-16.0%). PCB 138, 153 and 180 were the prominent congeners accounting for 69.3% of the total PCBs. Among the compounds of DDT, p,p′-DDE was the most dominant molecule (Mediterranean slimehead, 86.6%; blackfin sorcerer, 92.8%), demonstrating the old age of these compounds in the environment. In both species, PCB contents were higher than those of DDTs. Contaminant load was higher in Mediterranean slimehead (PCBs, 1,086 ng g⁻¹ lipid weight; DDTs, 799 ng g⁻¹ lipid weight) than in blackfin sorcerer (PCBs, 561 ng g⁻¹ lipid weight; DDTs, 224 ng g⁻¹ lipid weight). Conclusion The high ratios ΣPCBs/ΣDDTs indicated predominantly industrial versus agrarian activities in the area. Dioxins toxic equivalent (TEQ) concentrations (8.1-18.7 pg TEQ per gram wet weight) reached those encountered in marine organisms at higher levels in the trophic chain, revealing the onerous status of contamination by PCBs in Mediterranean deep sea biota.

PURPOSE: Chlor-alkali plants are one of the most important point sources of mercury to aquatic environment. The problem of Hg contamination has been studied in a region, Rm Valcea (Romania), impacted by the wastewater discharge of a chlor-alkali plant. The purpose of the present study is to evaluate the current status of mercury pollution in the Babeni reservoir (Olt River) and the exposure of local population via fish consumption to mercury originating from the chlor-alkali plant. METHODS: Sediments were collected from Valcea, Govora and Babeni reservoirs. Grain size distribution, organic content and total mercury (THg) concentrations were analysed in sediments. Fish were purchased from local anglers, and the scalp hair was collected from volunteers. THg in sediment, fish and hair samples was determined using an atomic absorption spectrophotometer for Hg determination. Monomethylmercury (MMHg) was analysed in the muscle and liver tissues by species-specific isotope dilution and capillary gas chromatography hyphenated to inductively coupled plasma mass spectrometer. RESULTS: High mercury concentrations were found in the sediments and in fish from Babeni reservoir, with a median of 2.1 mg/kg (IQR = 3.2) in sediments and a mean value of 1.8 ± 0.8 mg/kg_ww in fish muscle. MMHg concentrations in fish were well above the WHO guidelines for fish consumption. Local population consuming fish from the Babeni reservoir had THg concentrations in hair significantly higher than those consuming fish from upstream reservoirs and/or from the shops and reached a median value of 2.5 mg/kg (IQR = 3.6). CONCLUSIONS: The remnant pollution in the fish of this reservoir, and probably many other lakes and reservoirs receiving Hg polluted wastewater, represents a considerable health risk for the local fish consumers.

Background, aim and scope Australia is the largest producer of bauxite in the world, with an annual output of approximately 62 million metric dry tons in 2007. For every tonne of alumina, about 2 tonnes of highly alkaline and highly saline bauxite-processing residue are produced. In Western Australia, Alcoa World Alumina, Australia (Alcoa) produces approximately 15 MT of residue annually from its refineries (Kwinana, Pinjarra and Wagerup). The bauxite-processing residue sand (BRS) fraction represents the primary material for rehabilitating Alcoa's residue disposal areas (RDAs). However, the inherently hostile characteristics (high alkalinity, high salinity and poor nutrient availability) of BRS pose severe limitations for establishing sustainable plant cover systems. Alcoa currently applies 2.7 t ha⁻¹ of di-ammonium phosphate ((NH₄)₂HPO₄; DAP)-based fertiliser as a part of rehabilitation of the outer residue sand embankments of its RDAs. Limited information on the behaviour of the dominant components of this inorganic fertiliser in highly alkaline BRS is currently available, despite the known effects of pH on ammonium (NH₄) and phosphorus (P) behaviour. The aim of this study was to quantify the effects of pH on NH₃ volatilisation and residual nitrogen (N) in BRS following DAP applications. Methods The sponge-trapping and KCl-extraction method was used for determining NH₃ volatilisation from surface-applied DAP in samples of BRS collected from each of Alcoa's three Western Australia Refineries (Kwinana, Pinjarra, Wagerup) under various pH conditions (pH 4, 7, 9 and 11). Following cessation of volatilisation, the residual N was extracted from BRS using 2 M KCl and concentrations of NH ₄ ⁺ -N and NO ₃ ⁻ -N were determined by flow injection analysis. Results The quantities of NH₃ volatilised increased dramatically as the pH increased from 4 to 11. Much of the N lost as NH₃ (up to 95.2%) occurred within a short period (24 h to 7 days), particularly for the pH 9 and 11 treatments. Concentrations of residual NH ₄ ⁺ -N recovered in DAP-treated BRS at the end of the experiment decreased with increasing pH. This finding was consistent with increasing loss of N via volatilisation as pH increased. The concentration of NO ₃ ⁻ -N was very low due to no nitrification in BRS. Discussion The pH was a key driver for NH₃ volatilisation from DAP-treated BRS and primarily controlled N dynamics in BRS. Results indicate that NH₄ not adsorbed by BRS was highly susceptible to volatilisation. The likely lack of nitrifying bacteria did not allow conversion of ammonium to nitrate, thereby further exacerbating the potential for loss via volatilisation Conclusions It was demonstrated that the pH is the key factor controlling the loss of inorganic N from BRS. Although volatilisation was considerably lower at pH 4, achieving this pH reduction in the field is not possible at present. Findings from this study highlight the need to better understand which forms of N fertiliser are most suitable for use in highly alkaline BRS. Recommendation and perspectives Although pH reduction is the most likely means of stopping NH₃ volatilisation in BRS, it is economically and operationally unfeasible to add sufficient acidity for adequately lowering pH in the BRS for revegetation. More attention on forms of fertilisers more suitable to highly alkaline, microbially inert soil conditions appears to be warranted.