Background, aim and scope Toxicity testing has become a suitable tool for wastewater evaluation included in several reference documents on best available techniques of the Integrated Pollution Prevention and Control (IPPC) Directive. The IPPC Directive requires that for direct dischargers as well as for indirect dischargers, the same best available techniques should be applied. Within the study, the whole effluent assessment approach of OSPAR has been applied for determining persistent toxicity of indirectly discharged wastewater from the metal surface treatment industry. Materials and methods Twenty wastewater samples from the printed circuit board and electroplating industries which indirectly discharged their wastewater to municipal wastewater treatment plants (WWTP) have been considered in the study. In all factories, the wastewater partial flows were separated in collecting tanks and physicochemically treated in-house. For assessing the behaviour of the wastewater samples in WWTPs, all samples were biologically pretreated for 7 days in the Zahn-Wellens test before ecotoxicity testing. Thus, persistent toxicity could be discriminated from non-persistent toxicity caused, e.g. by ammonium or readily biodegradable compounds. The fish egg test with Danio rerio, the Daphnia magna acute toxicity test, the algae test with Desmodesmus subspicatus, the Vibrio fischeri assay and the plant growth test with Lemna minor have been applied. All tests have been carried out according to well-established DIN or ISO standards and the lowest ineffective dilution (LID) concept. Additionally, genotoxicity was tested in the umu assay. The potential bioaccumulating substances (PBS) were determined by solid-phase micro-extraction and referred to the reference compound 2,3-dimethylnaphthalene. Results The chemical oxygen demand (COD) and total organic carbon (TOC) values of the effluents were in the range of 30-2,850 mg L⁻¹ (COD) and 2-614 mg L⁻¹ (TOC). With respect to the metal concentrations, all samples were not heavily polluted. The maximum conductivity of the samples was 43,700 µS cm⁻¹ and indicates that salts might contribute to the overall toxicity. Half of the wastewater samples proved to be biologically well treatable in the Zahn-Wellens test with COD elimination above 80%, whilst the others were insufficiently biodegraded (COD elimination 28-74%). After the pretreatment in the Zahn-Wellens test, wastewater samples from four (out of ten) companies were extremely ecotoxic especially to algae (maximum LIDA = 16,384). Three wastewater samples were genotoxic in the umu test. Applying the rules for salt correction of test results as allowed in the German Wastewater Ordinance, only a small part of toxicity could be attributed to salts. Considering the PBS, wastewater from the metal surface treatment industry exhibited very low levels of PBS. In one factory, the origin of ecotoxicity has been attributed to the organosulphide dimethyldithiocarbamate (DMDTC) used as a water treatment chemical for metal precipitation. The assumption based on rough calculation of input of the organosulphide into the wastewater was confirmed in practice by testing its ecotoxicity at the corresponding dilution ratio after pretreatment in the Zahn-Wellens test. Whilst the COD elimination of DMDTC was only 32% in 7 days, the pretreated sample exhibited a high ecotoxicity to algae (LIDA = 1,536) and luminescent bacteria (LIDlb = 256). Discussion Comparative data from wastewater surveillance by authorities (data from 1993 to 2007) confirmed the range of ecotoxicity observed in the study. Whilst wastewater from the metal surface treatment industry usually did not exhibit ecotoxicity (median LID 1-2), the maximum LID values reported for the algae, daphnia and luminescent bacteria tests were very high (LIDA up to 3,072, LIDD up to 512 and LIDlb up to 2,048). DMDTC was found to be one important source of ecotoxicity in galvanic wastewater. DMDTC is added in surplus, and according to the supplier, the amount in excess should be detoxified with ferric chloride or iron sulphate. The operator of one electroplating company had not envisaged a separate treatment of the organosulphide wastewater but was assuming that excess organosulphide would be bound by other heavy metals in the sewer. DMDTC degrades via hydrolysis to carbon disulfide (which is also toxic to animals and aquatic organisms), carbonyl sulphide, hydrogen sulphide and dimethylamine, but forms complexes with metals which stabilise the compound with respect to transformation. Although no impact on the WWTP is expected, the question arises whether the organosulphide is completely degraded during the passage of the WWTP. Conclusions and recommendations The results show that the organic load of wastewater from the electroplating industry has been underestimated by focussing on inorganic parameters such heavy metals, sulphide, cyanide, etc. Bioassays are a suitable tool for assessing the ecotoxicological relevance of these complex organic mixtures. The proof of biodegradability of the organic load (and its toxicity) can be provided by the Zahn-Wellens test. The environmental safety of water treatment chemicals should be better considered. The combination of the Zahn-Wellens test followed by the performance of ecotoxicity tests turned out to be a cost-efficient suitable instrument for the evaluation of indirect dischargers and considers the requirements of the IPPC Directive.

Background, aim, and scope Chemical oxygen demand (COD) is used as a discharge standard parameter in wastewater treatment plant design, environmental modelling and many other applications. Chloride interference is an important problem of COD measurement for wastewaters containing low organic matter and high chloride concentrations. In case of chloride concentrations up to 2,000 mg/L, mercury sulphate addition at a ratio of 10:1 (HgSO₄:Cl⁻) can adequately mask the interference. When chloride concentration exceeds 2,000 mg/L, this ratio becomes ineffective to hinder the interference. At this point, it is proposed to use a greater and constant ratio of mercury sulphate addition. However, this application sometimes results in extra mercury sulphate addition which is not necessary. Even in some cases, greater addition of mercury sulphate alone is not a solution to erroneous measurement results. The purpose of the study is to determine optimum HgSO₄:Cl⁻ ratios according to the chloride concentrations of the samples and to show the importance of the strength of the digestion solution for the correct determination of the COD parameter. Materials and methods CODs of the synthetic samples containing varying COD and chloride concentrations were measured by closed reflux colorimetric method using three digestion solutions having different strengths. Results It is indicated in this study that a constant ratio of mercury sulphate can only prevent chloride interference up to a specific chloride concentration. Conclusions Achieving high precision results in case of low organic matter and high chloride concentration can only be possible by both decreasing the concentration of oxidant and adding mercury sulphate.

Background In the present study, we report the analytical results of pp′DDT, pp′DDE and pp′DDD determination in lake water, plankton and zooplanktivorous fish of Lake Maggiore (Northern Italy), rather recently polluted by DDT of industrial origin, in order to understand the bottom-up pollution transfer among the abiotic and biotic components of the lake ecosystem. Materials and methods Fourteen water sampling campaigns were carried out from March 2003 to January 2009 in the water column of the deepest point (Ghiffa) of Lake Maggiore. Suspended and dissolved pollutants were determined separately. Three sampling campaigns were carried out from July 2008 to January 2009 for zooplankton and pelagic fish, and DDT residues were analysed by HRGC coupled with ECD and MS. Moreover, food items were detected in fish stomachs. Results and discussion Starting from 2007, the DDT contamination along the water column became rather homogeneous, probably because no flooding or other relevant hydrological events occurred; although steady-state condition should be expected, lipid normalised concentrations of pp′DDE and pp′DDD in zooplankton exceeded the levels of the same compounds in zooplanktivorous fishes. Conclusion As this finding represents a thermodynamic paradox since bioaccumulative pollutant concentrations are expected to increase along the trophic chain, it was supposed that the abiotic and biotic lake components were not in a steady-state condition in Lake Maggiore.

Background, aim, and scope Due to the active production and transport of crude oil in the Arabian Gulf region, the Arabian Gulf coasts are routinely polluted with oil. Therefore, such coasts have been subject of studies aiming at assessing the roles of indigenous microbial consortia in cleaning these environments. In the present study, epilithic microbial communities along Kuwait coasts were studied for their oil degradation potential. Materials and methods Gravel particles coated with deep green biofilms were collected from four coastal sites in autumn, winter, and spring. Phototrophs in these consortia were determined in terms of their chlorophyll a contents and identified by their morphological characteristics. Total bacteria were counted microscopically and cultivable bacteria by the dilution plating method on nutrient agar as well as on inorganic medium containing oil as a sole source of carbon and energy. The bacterial community structures were also characterized and compared by denaturing gradient gel electrophoresis (DGGE). Results Epilithic biomass samples from the four sites in the three seasons were rich in diatoms and picocyanobacteria as well as total bacteria. Direct counting gave bacterial numbers per square centimeter gravel surface of 2 to 6 × 10⁷ cells depending on the sampling site and season. Cultivable bacterial numbers on nutrient agar and crude oil as a sole source of carbon were 3 × 10³ to 8 × 10⁴ and 1 × 10³ to 7 × 10³ cells/cm² gravel surface, respectively. The DGGE profiles of epilithon biomass samples revealed major 16S rDNA bands that matched bands of pure oil-utilizing bacterial isolates. Discussion The microbial communities showed a degree of consistency in all sites and seasons. Conclusions The microbial consortia coating gravel particles are potentially suitable tools for self-cleaning of oily Gulf coasts. They are rich in oil-utilizing bacteria whose activities are probably enhanced by oxygen produced by the phototrophic partners in the consortia. Recommendations and perspectives The combination of conventional microbiological analysis with molecular approaches gives an enhanced idea about natural microbial communities especially those with environmental application potential.

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 For many years, highly concentrated wastewater generated from the pulp and paper industry has become the focus of much concern worldwide. The objectives of this study were to determine the treatment efficiency of the alkaline peroxide mechanical pulp (APMP) process wastewater using a sequencing batch reactor (SBR) and analyze the microbial dynamics of the wastewater treatment system using the random amplified polymorphic DNA (RAPD) method. Materials and methods An SBR was applied to the treatment of APMP pulp and paper process wastewater. The wastewater characteristics and many physicochemical operator indicators in the wastewater treatment process were analyzed and determined according to standard methods. Microbial 16 S rDNA in active sludge was extracted, amplified, and analyzed using the RAPD method for the microbial dynamics of the wastewater treatment system. Results and discussion Ten kinds of natural organic compounds of plants such as monoterpene were detected in the APMP pulp and paper process wastewater. With an influent chemical oxygen demand (COD) that varied in the range of 685.7 to 907.5 mg/L, the corresponding effluent COD was 176.5 to 266.1 mg/L and the removal efficiency was 70.3% to 79.8%. An optimal strain (S308: CAGGGGTGGA) was selected to study the population dynamics and diversity of the bacterial community. The RAPD-polymerase chain reaction (PCR) fingerprints showed very high polymorphism of the genetic bands (78-100%). Four groups of species were clustered using the unweighted pair group method with arithmetic (UPGMA) analysis, and the genetic distance was close between the species within each group. The Shannon-Weaver index was high and varied over time with the COD removal. Conclusions The RAPD-PCR technique can be used to study microbial dynamics, which was shown to vary over time with the removal efficiency of SBR treating APMP pulp and paper process wastewater.

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.

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.

Background, aim, and scope This study developed an integrated approach to identify pollutant sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) of workers based on their blood contents. Materials and methods We first measured blood PCDD/F contents of sinter plant workers and residents living near the plant. By comparing those blood indicatory PCDD/Fs found for residents with those for sinter plant workers, exposure-related blood indicatory PCDD/Fs were identified for each selected worker. We then measured PCDD/F concentrations of four different sinter plant workplaces and three different ambient environments of the background. By comparing those airborne indicatory PCDD/Fs found for ambient environments with those for sinter plant workplaces, exposure-related airborne indicatory PCDD/Fs for each workplace were obtained. Finally, by matching exposure-related blood indicatory PCDD/Fs with exposure-related airborne indicatory PCDD/Fs, all suspected pollutant sources were identified for each selected worker. Results Poor Pearson correlations were found between workers' blood contents and their corresponding PCDD/F exposures. Significant differences were found in the top three blood indicatory PCDD/Fs among the selected workers. By matching exposure-related blood indicatory PCDD/Fs with exposure-related airborne indicatory PCDD/Fs, two to three suspected pollutant sources were identified for each selected worker. Discussion The poor Pearson correlation found between workers' airborne PCDD/Fs exposures and their blood contents was because workers' blood PCDD/Fs contents were contributed not only by workers' occupational exposures, but also by other exposure sources and exposure routes. The difference in blood indicatory PCDD/Fs among the selected workers were obviously due to the intrinsic differences in their time/activity patterns in the involved workplaces. While workers used a dust respirator to perform their jobs, gas phase exposure-related airborne indicatory PCDD/Fs played an important role on identifying suspected pollutant sources. But if a dust respirator was not used, the gas + particle phase exposure-related airborne indicatory PCDD/Fs would become the key factor for identifying suspected pollutant sources. Conclusions The developed integrated approach could identify all suspected pollutant sources effectively for selected workers based on their blood contents. The identified pollutant sources were theoretically plausible since they could be verified by examining workers' time/activity patterns, their status in using dust respirators, and the concentrations of PCDD/Fs found in the selected workplace atmospheres. Recommendations and perspectives The developed technique can be used to identify possible pollutant sources not only for workers but also for many other exposure groups associated with various emission sources and exposure routes in the future.

Background, aim, and scope Zinc is an essential micronutrient element but its concentrations found in contaminated soils frequently exceed those required by the plant and soil organisms, and thus create danger to animal and human health. Phytoremediation is a technique, often employed in remediation of contaminated soils, which aims to remove heavy metals or other contaminants from soils or waters using plants. Arabidopsis (A.) halleri ssp. gemmifera is a plant recently found to be grown vigorously in heavy metal contaminated areas of Japan and it contained remarkably high amount of heavy metals in its shoots. However, the magnitude of Zn accumulation and tolerance in A. halleri ssp. gemmifera need to be investigated for its use as a phytoremediation plant. Materials and methods A. halleri ssp. gemmifera was grown for 3 weeks into half-strength nutrient solution with Zn (as ZnSO₄) levels ranging from 0.2 to 2,000 µM. The harvested plants were separated into shoots and roots, dried in the oven, and ground. The plant tissue was digested with nitric-perchloric acid, and the Zn concentration in the digested solution was measured by atomic absorption spectrophotometer. Results and discussion The results showed no reduction in shoot and root dry weight when plants were grown at 0.2 to 2,000 µM Zn in the solution. The highest Zn concentration measured in the shoots was 26,400 mg kg⁻¹ at 1,000 µM Zn, while in the roots, it was 71,000 mg kg⁻¹ at 2,000 µM Zn treatment. Similar to the Zn concentration in plant parts, maximum Zn accumulation of 62 mg plant⁻¹ in the shoots and 22 mg plant⁻¹ in the roots was obtained at 1,000 and 2,000 µM Zn in the solution. The percentage of Zn translocation in shoot varied from 69% to 90% of the total Zn, indicating that the shoot was the major sink of Zn accumulation in this plant. Conclusions The results of this study indicate that the growth of A. halleri ssp. gemmifera was not affected by the Zn level of up to 2,000 µM in the nutrient solution. The concentration of Zn found in shoot indicated that A. halleri ssp. gemmifera has an extraordinary ability to tolerate and accumulate Zn and hence a good candidate for the phytoremediation of Zn-polluted soil. Recommendations and outlook Based on the results presented in this study and earlier hydroponics, and field study, A. halleri ssp. gemmifera seems to be a potential heavy metals hyperaccumulator, and could be recommended to use for phytoremediation of Cd- and Zn-contaminated soils.