BACKGROUND: The state of the art of passive water sampling of (nonpolar) organic contaminants is presented. Its suitability for regulatory monitoring is discussed, with an emphasis on the information yielded by passive sampling devices (PSDs), their relevance and associated uncertainties. Almost all persistent organic pollutants (POPs) targeted by the Stockholm Convention are nonpolar or weakly polar, hydrophobic substances, making them ideal targets for sampling in water using PSDs. Widely used nonpolar PSDs include semi-permeable membrane devices, low-density polyethylene and silicone rubber. RESULTS AND DISCUSSION: The inter-laboratory variation of equilibrium partition constants between PSD and water is mostly 0.2–0.5 log units, depending on the exact matrix used. The sampling rate of PSDs is best determined by using performance reference compounds during field deployment. The major advantage of PSDs over alternative matrices applicable in trend monitoring (e.g. sediments or biota) is that the various sources of variance including analytical variance and natural environmental variance can be much better controlled, which in turn results in a reduction of the number of analysed samples required to obtain results with comparable statistical power. CONCLUSION: Compliance checking with regulatory limits and analysis of temporal and spatial contaminant trends are two possible fields of application. In contrast to the established use of nonpolar PSDs, polar samplers are insufficiently understood, but research is in progress to develop PSDs for the quantitative assessment of polar waterborne contaminants. In summary, PSD-based monitoring is a mature technique for the measurement of aqueous concentrations of apolar POPs, with a well-defined accuracy and precision.

PURPOSE: In the reservoir created in the reclaimed land in Isahaya Bay, Japan, Microcystis aeruginosa, which produces microcystins (MCs), bloomed every year, and the water with high levels of MCs in the reservoir has been often drained to Isahaya Bay to adjust the water level. The principal aims of this study are to clarify the water conditions suitable for blooming of M. aeruginosa in the reservoir, to follow the amount of distribution of MCs inside and outside the reservoir, and to discuss how blooming of M. aeruginosa is controlled in the reservoir and how MCs produced by Microcystis spread or accumulate in the aquatic environment. METHOD: We monitored the water quality (temperature, salinity, dissolved inorganic nitrogen (DIN), and dissolved inorganic phosphorus) in the reservoir with seasonal blooming of microalgae including phytoplankton and M. aeruginosa using the concentrations of chlorophyll α and MCs, respectively, and collected the surface sediment in the reservoir and the bay to determine the MC content using the ELISA method. RESULT: M. aeruginosa bloomed in extremely low DIN conditions of the water in warm seasons (spring and late summer to autumn). The year-mean standing stock of MCs was approximately 34.5 kg in the water and 8.4 kg in the surface sediment in the reservoir. Approximately 64.5 kg of MCs was discharged with the effluent to the bay in a year. CONCLUSION: Since a large amount of MCs always suspends in the water in the reservoir and it has been discharged to the bay, suspension-feeding animals are exposed most seriously to the high levels of MCs occurring in these areas. We need to pay attention to the danger of widespread dispersal of MCs and biological concentration of MCs by fish and clam inside and outside the reservoir.

INTRODUCTION: Two emergent macrophytes, Arundo donax and Phragmites australis, were established in experimental subsurface flow, gravel-based constructed wetlands (CWs) receiving untreated recirculating aquaculture system wastewater. MATERIALS AND METHODS: The hydraulic loading rate was 3.75 cm day−1. Many of the monitored water quality parameters (biological oxygen demand [BOD], total suspended solids [TSS], total phosphorus [TP], total nitrogen [TN], total ammoniacal nitrogen [TAN], nitrate nitrogen [NO3], and Escherichia coli) were removed efficiently by the CWs, to the extent that the CW effluent was suitable for use on human food crops grown for raw produce consumption under Victorian state regulations and also suitable for reuse within aquaculture systems. RESULTS AND DISCUSSION: The BOD, TSS, TP, TN, TAN, and E. coli removal in the A. donax and P. australis beds was 94%, 67%, 96%, 97%, 99.6%, and effectively 100% and 95%, 87%, 95%, 98%, 99.7%, and effectively 100%, respectively, with no significant difference (p > 0.007) in performance between the A. donax and P. australis CWs. In this study, as expected, the aboveground yield of A. donax top growth (stems + leaves) (15.0 ± 3.4 kg wet weight) was considerably more than the P. australis beds (7.4 ± 2.8 kg wet weight). The standing crop produced in this short (14-week) trial equates to an estimated 125 and 77 t ha−1 year−1 biomass (dry weight) for A. donax and P. australis, respectively (assuming that plant growth is similar across a 250-day (September–April) growing season and a single-cut, annual harvest). CONCLUSION: The similarity of the performance of the A. donax- and P. australis-planted beds indicates that either may be used in horizontal subsurface flow wetlands treating aquaculture wastewater, although the planting of A. donax provides additional opportunities for secondary income streams through utilization of the energy-rich biomass produced.

Perfluorinated compounds (PFCs) are persistent and bioaccumulative organic compounds used as additives in many industrial products. After use, these compounds enter wastewater treatment plants (WWTP) and long-chain PFCs are primarily accumulated in sludge. The aim of this study was to determine the occurrence and behavior of five PFCs in sludge from 15 WWTP from Spain and Germany that receive both urban and industrial wastes. The PFCs studied were perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHxS), perfluorobutanesulfonate (PFBS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA). One gram of freeze-dried, sieved, and homogenized sludge was extracted using an ultrasonic bath with methanol and glacial acetic acid. After that, the extract was recovered and evaporated to dryness with a TurboVap and then 1 mL of acetonitrile was added and the extract was cleaned up with black carbon. Liquid chromatography coupled to mass spectrometry operated in selected reaction monitoring was used to determine target compounds. Quality parameters are provided for the set of compounds studied. PFCs were detected in all samples. In Spanish sludge, ∑PFC ranged from 0.28 to 5.20 ng/g dry weight (dw) with prevalence of PFOS, while in German sludge, ∑PFC ranged from 20.7 to 38.6 ng/g dw and PFBS was the dominant compound. As a next step, the evolution of PFC concentrations within the sludge treatment steps (primary sludge, anaerobic digested sludge, and centrifuged sludge) was evaluated and differences among levels and patterns were observed and were attributed to the influent water quality and treatment used. Finally, we estimated the amount of PFCs discharged via sludge in order to determine the potential impact to the environment according to different sludge usage practices in the two regions investigated. This manuscript provided an intra-European overview of PFC distribution in sludge. Levels and compound distribution depend on the WWTP sampled. This study demonstrates that PFCs are persistent to sludge treatment and the loads in sludge may pose a future environmental risk, if not controlled.

Mining activities represent a major source of environment contamination. The aim of this study was to evaluate the use of bees and ants as bioindicators to detect the heavy metal impact in post-mining areas. A biomonitoring programme involving a combination of honeybee hive matrices analysis and ant biodiversity survey was conducted over a 3-year period. The experimental design involved three monitoring stations where repeated sampling activities focused on chemical detection of cadmium (Cd), chrome (Cr) and lead (Pb) from different matrices, both from hosted beehives (foraging bees, honey and pollen) and from the surrounding environment (stream water and soil). At the same time, ant biodiversity (number and abundance of species) was determined through a monitoring programme based on the use of pitfall traps placed in different habitats inside each mining site. The heavy metal content detected in stream water from the control station was always below the analytical limit of quantification. In the case of soil, the content of Cd and Pb from the control was lower than that of mining sites. The mean heavy metal concentrations in beehive matrices from mining sites were mainly higher than the control, and as a result of regression and discriminant analysis, forager bee sampling was an efficient environmental pollution bioindicator. Ant collection and identification highlighted a wide species variety with differences among habitats mostly associated with vegetation features. A lower variability was observed in the polluted landfill characterised by lack of vegetation. Combined biomonitoring with forager bees and ants represents a reliable tool for heavy metal environmental impact studies.

INTRODUCTION: On August 2006, a cargo ship illegally dumped 500 t of toxic waste containing high concentrations of hydrogen sulphide in numerous sites across Abidjan. Thousands of people became ill. Seventeen deaths were associated with toxic waste exposure. MATERIALS AND METHODS: This study reports on environmental and health problems associated with the incident. A cross-sectional transect study was conducted in five waste dumping site areas. RESULTS: Of the households, 62.1% (n = 502) were exposed to the effects of the pollutants and 51.1% of the interviewed people (n = 2,368) in these households showed signs of poisoning. Most important symptoms were cough (37.1%), asthenia (33.1%), pruritus (29.9%) and nausea (29.1%). DISCUSSION: The health effects showed different frequencies in the five waste impact sites. Among the poisoned persons, 21.1% (n = 532) presented symptoms on the survey day (i.e., 4 months after incident). Transect sampling allowed to determine a radius of vulnerability to exposure of up to 3 km from the point of toxic waste disposal. CONCLUSION: The area of higher vulnerability is influenced by various environmental factors, such as size and severity of pollution site, duration of toxic waste pollution on the impact site and locally climatic conditions. The surveillance of effects on environment and human health is warranted to monitor the development.

This study presents oxidative transformation of carbamazepine by synthetic manganese oxide (δ-MnO2) as well as impact of variables including initial MnO2 loading, pH, coexisting metal ions, and humic acid (HA) on transformation. Manganese oxide (δ-MnO2) was synthesized and stored in the form of suspension. The oxidative reactions were conducted in 50 mL polyethylene (PE) centrifuge tubes with constant pH maintained by buffers. The kinetic experiment was carried out in the solution of pH 2.72 containing 5.0 mg/L of carbamazepine and 130.5 mg/L of MnO2. Effects of initial MnO2 loading (0–130.5 mg/L), pH (2.72–8.58) and 0.01 M of coexisting solutes (metal ions and HA) on carbamazepine oxidation were also determined. Reaction kinetics indicated that carbamazepine was rapidly degraded in the first 5 min, and approximately 95 % of carbamazepine was eliminated within 60 min. The reaction exhibited pronounced pH dependence and increased with decreasing pH values. The transformation of carbamazepine was also accelerated with increasing MnO2 loadings. Coexisting metal ions competed with carbamazepine for reactive sites leading to reduced carbamazepine removal, and the inhibitive capacity followed the order of Mn2+ > Fe3+ > Ca2+ ≈ Mg2+. Presence of HA in aqueous solution caused a significant reduction on the magnitude of carbamazepine transformation. This study indicated that carbamazepine can be effectively degraded by δ-MnO2, and transformation efficiency was strongly dependent on reaction conditions. It suggests that amendment of soil with MnO2 be a potential alternative to solve carbamazepine pollution.

INTRODUCTION: Five liver samples of two different ray species (Gymnura altavela and Zapteryx brevirostris) off the coast of Rio de Janeiro, Brazil, were analyzed for their pollution with anthropogenic and naturally occurring organohalogen compounds. MATERIAL AND METHODS: The samples were extracted with accelerated solvent extraction, and after a clean-up procedure, organohalogen compounds were separated by a modified group separation on activated silica. Subsequent analyses were done by targeted and non-targeted gas chromatography–mass spectrometry in the electron capture negative ion mode. RESULTS AND DISCUSSION: “Classic” organohalogen compounds such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and technical 1,1,1-trichloro-2,2-di(4-chlorophenyl)ethane (DDT) were detected and quantified. PCBs generally exceeded the parts per million level and represented up to 90% of the total contamination of the ray livers. High concentrations were also detected for p,p′-DDE. Non-targeted full scan investigations lead to the detection of an abundant trichlorinated compound which was identified as a new DDT metabolite in biota. Different PBDE congeners and several halogenated natural products were quantified as well. In addition, polychlorinated terphenyls were identified and analyzed in the two species. Moreover, both ray species showed different fatty acid patterns and stable carbon isotope signatures. CONCLUSIONS: The two ray species showed high concentrations of organohalogen compounds in their liver tissue. Varied δ 13C values by up to 3.1‰ indicated that the two ray species were living in different habitats.

BACKGROUND: A climate-controlled pot experiment was conducted to investigate the effects of planting alfalfa and applying organic fertilizer on the dissipation of benzo[a]pyrene from an aged contaminated agricultural soil. RESULTS: Short-term planting of alfalfa inhibited the dissipation of benzo[a]pyrene from the soil by 8.9%, and organic fertilizer enhanced benzo[a]pyrene removal from the soil by 11.6% compared with the unplanted and unfertilized treatments, respectively. No significant interaction was observed between alfalfa and organic fertilizer on benzo[a]pyrene dissipation. Sterilization completely inhibited the removal of benzo[a]pyrene from the soil indicating that its degradation by indigenous microorganisms may have been the main mechanism of dissipation. Furthermore, significant positive relationships were observed between benzo[a]pyrene removal and the contents of soil ammonium nitrogen, nitrate nitrogen, and total mineral nitrogen at the end of the experiment, suggesting that competition between plants and microorganisms for nitrogen may have inhibited benzo[a]pyrene dissipation in the rhizosphere of alfalfa and the addition of organic fertilizer may facilitate microbial degradation of benzo[a]pyrene in the soil.

BACKGROUND, AIM, AND SCOPE: According to the high incidence of cancer worldwide, the amount of cytostatic drugs administered to patients has increased. These compounds are excreted to wastewaters, and therefore become potential water contaminants. At this stage, very little is known on the presence and elimination of cytostatic compounds in wastewater treatment plants (WWTP). The aim of this study was to develop a liquid chromatography–high-resolution mass spectrometry (LC–Orbitrap–MS) method for the determination of cyclophosphamide and epirubicin in wastewaters. These compounds represent two outmost used cytostatic agents. MATERIALS AND METHODS: Extraction and analytical conditions were optimized for cyclophosphamide and epirubicin in wastewater. Both solid-phase extraction using Oasis 200 mg hydrophilic–lipophilic balanced (HLB) cartridges and direct injection analysis were evaluated. Mass spectral characterization and fragmentation conditions were optimized at 50,000 resolving power (full width at half maximum, m/z 200) to obtain maximum sensitivity and identification performance. Quality parameters (recoveries, limits of detection, and repetitivity) of the methods developed were determined, and best performance was obtained with direct water analysis of the centrifuged wastewater. Finally, this method was applied to determine the presence of cyclophosphamide and epirubicin in wastewaters from a hospital effluent, an urban effluent, and influents and effluents from three WWTP. RESULTS AND DISCUSSION: Cyclophosphamide and epirubicin were recovered after 50 mL preconcentration on solid-phase extraction 200 mg Oasis HLB cartridges (87% and 37%, respectively), and no breakthrough was observed by extracting 500 mL of water. Limits of detection were of 0.35 and 2.77 ng/L for cyclophosphamide and epirubicin, respectively. On the other hand, direct injection of water spiked at 1 μg/L provided recoveries of 107% for cyclophosphamide and 44% for epirubicin and limits of detection from 3.1 to 85 ng L−1, respectively. The analysis of wastewaters using direct injection analysis revealed the presence of cyclophosphamide and epirubicin in WWTP influents and hospital and urban effluents at levels ranging from 5.73 to 24.8 μg L−1. CONCLUSIONS: The results obtained in this study demonstrate the capability of LC–Orbitrap–MS for accurate trace analysis of these very polar contaminants. This method permitted to identify cyclophosphamide and epirubicin in wastewaters and influents of WWTP, but no traces were detected in WWTP effluents. The methodology herein developed is sensitive and robust and applicable for screening of a large number of samples since no preconcentration is needed.