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.

Background, aim, and scope Transport of bacteria through natural porous media is an issue of increasing concern arising in several very important environmental processes. These include the percolation of bacteria from fecal waste to drinking water reservoirs, thus leading to a risk for human health, or the bioremediation of contaminated soils in which the bacteria are expected to travel long distances underground in order to reach contaminated areas and degrade chemicals originating from accidental spills. An understanding of bacterial retention and transport mechanisms in porous media would be of great help in the development of models able to predict the distance covered by bacterial suspensions in these situations. Materials and methods Experiments were carried out preparing columns filled of soil and sand, introducing bacteria culture (Escherichia coli, Pseudomona putida, and Listeria innocua) solutions by the top of the column. Breakthrough curves were obtained to see the transport of the bacteria in the column. Results The transport of different bacteria in the two soils aimed at establishing the relative importance of straining in different conditions. This has enabled us to obtain certain parameters, such as the sticking coefficients derived from the filtration theory or bacterial recoveries after multi-step elution, which aid our understanding of how bacteria are retained by mechanisms different to those usually included in the physico-chemical filtration theory. Discussion Several indicators may be used to determine the degree of relevance of straining as a mechanism acting during bacterial transport through porous media. Usually, in natural media, neither straining nor physico-chemical filtration is the sole mechanism contributing to bacterial retention. The retention of bacteria by straining mechanisms can be assessed by means of elution profiles under varying conditions. The inversion of flow in our experiments gave rise to secondary elution peaks, probably originating from bacteria retained in narrow pores Conclusions According to experimental observations, straining was shown to contribute highly to bacterial retention in all the soils tested, in particular in the soils with a broader grain size distribution and more irregular shape. In both media, an increase in ionic strength did not lead to significant differences in bacterial retention, possibly due to the lack of relevance of ionic repulsion as a barrier to physico-chemical attachment of particles Recommendation and perspectives The study of bacteria transport in natural soil is an important step in the development of decontamination processes. The importance of the straining in the transport process has been revealed in the work carried out in this paper.

Background, aim, and scope Atmospheric pollution is a worldwide problem. Exposure to atmospheric pollutants causes toxic cellular effects. One of the mechanisms of toxicity by these pollutants is the promotion of oxidative stress. Several signaling pathways control cellular redox homeostasis. In this respect, nuclear factor erythroid 2-related factor 2 (Nrf2) is a crucial transcription factor in the cell's response to oxidative stress. Main features In cellular animal models, exposure to atmospheric pollutants activates Nrf2, attenuating its toxic and even its carcinogenic effects. Therefore, we have reviewed the scientific literature in order to indicate that air pollutants, such as particulate matter, polycyclic aromatic hydrocarbons, and gaseous matter, are Nrf2 pathway inductors, triggering self-defense through the establishment of proinflammatory and antioxidant responses. Results and discussion Exposure to reactive molecules as atmospheric pollutants causes the activation of Nrf2 and the subsequent regulation of the expression of cytoprotective and detoxifying enzymes, as well as antioxidants. Moreover, induction of Nrf2 prior to exposure reduces the harmful effects of pollutants. The present article discusses the protective role of the Nrf2 pathway against different atmospheric pollutant insults. Conclusions Nrf2 regulates the expression of numerous cytoprotective genes that function to detoxify reactive species produced during atmospheric pollutant metabolic reactions. From the papers highlighted in this review, we conclude that Nrf2 has an important role in the defense against atmospheric pollutant-induced toxicity. Perspectives Further studies are needed to understand the signaling events that turn on the system in response to atmospheric pollutant stress. This could allow for the possibility of targeting the pathway for prevention benefits in the near future.

Background, aim and scope A new method using sedimentary metals and geographic information system as indicators for assessing temporal and spatial anthropogenic change in estuaries has been applied to a large coastal lake (Lake Macquarie) in New South Wales, Australia. Materials, methods and results Two vintages of data (1975 and 2003) on surficial sediment metal (Cd, Cu, Pb and Zn) concentrations combined with ²¹⁰Pb core profiles were used to determine past changes in sediment quality and to predict possible future relaxation rates for the entire lake area in response to change in anthropogenic pressure. Sediment cores showed distinct vertical profiles; sedimentation rates in the northern part of the lake were consistent (14 mm year⁻¹) over the 55-year period investigated. Discussion and conclusions Surficial metal concentrations were highest in the 1975 sediment than in the 2003 samples, with the northern part of Lake Macquarie having much greater metal concentrations than the rest of the lake. Past and future declining sedimentary metal concentrations in the northern part of the lake were expected due to the closure of a nearby Pb-Zn smelter; however, possible increases in Cu in the south of the lake to the year 2020 were surprising. The new method presented in this study can assist estuary managers by providing data on past, present and future conditions, which are essential in making informed decisions for the improvement of estuarine systems.

Introduction Arsenic is a well known water contaminant that causes toxicological and carcinogenic effects. In this work magnetite nanoparticles were examined as possible arsenic sorbents. The objective of this work was to develop a sorption kinetics model, which could be used to predict the amount of arsenic adsorbed by magnetite nanoparticles in the presence of naturally occurring species using a first-order rate equation, modified to include adsorption, described by a Langmuir isotherm. Discussion Arsenate and arsenite adsorption to magnetite nanoparticles was studied, including the effect of naturally occurring species (sulfate, silica, calcium magnesium, dissolved organic matter, bicarbonate, iron, and phosphate) on adsorption. Conclusion The model accurately predicts adsorption to magnetite nanoparticles used in a batch process to remove arsenic from spiked Houston, TX tap water, and contaminated Brownsville, TX groundwater.

Background, aim and scope For reliable environmental risk assessment of pollutants, knowledge on the effects at different levels of biological organisation is needed. During the early days of biomarker research in environmental studies approximately two decades ago, biochemical biomarkers were considered as the most promising tool for such purposes. Among these, three enzymes have often been studied: catalase (CAT), glutathione S-transferase (GST) and cholinesterase (ChE). However, despite their intensive research, their measurements in invertebrates have not been commonly applied in environmental risk assessment (ERA) or for regulatory purposes. Main features In the present review, we summarise our past experiences in biochemical biomarker research in two crustacean species: water flea Daphnia magna and terrestrial isopod Porcellio scaber. This is to orientate their use and to provide recommendations for the use of novel biomarkers in environmental studies, such as proteomic or genomic responses. Results and discussion We assessed the intrinsic properties of biochemical biomarkers CAT, GST and ChE in the D. magna and the isopod P. scaber. It was found that they are not in agreement with the expectations that were previously given for their use in environmental studies. To advance their use in environmental risk assessment, we suggest that based on their properties, their role should be more specifically defined. ERA includes several distinct steps, among them hazard identification, effect assessment and finally risk characterisation, each of which requires a different type of toxicity data. We recommend that the use of biochemical markers is most appropriate for hazard identification because this is a procedure whose purpose is to characterise the potential hazard of the substance in question and is more flexible in terms of using different tools. Furthermore, our results imply that biochemical markers are not always more sensitive than whole-organism responses, as was anticipated. Their sensitivity depends on the mode of action, duration of exposure and test species. Therefore, we suggest that combining both a battery of biomarkers from different levels of biological organisation and an array of biomarkers within a single level could identify hazard adequately. Conclusions The lesson learnt from biochemical biomarkers in environmental studies utilizing crustacean model species is that, for successful application of each group of biomarkers, their intrinsic properties are needed to be known before an (eco)toxicity study is designed. We suggest that a substantial body of experience obtained with biochemical biomarkers should be exploited to new emerging biomarkers in environmental studies in order to facilitate their application. Recommendations and perspectives The future of biomarkers lies in a combination of traditional biochemical and new-generation biomarkers. The latter are not only a potential replacement for existing biomarkers but will also provide new knowledge which might encourage renewed research and development of traditional biomarkers. For research purposes, complete ecotoxicity information should include contributions from molecular fingerprint of an organism, as well as whole organism, population and ecosystem responses. Still, the type of biomarkers used for routine purposes will depend on their reproducibility, their ease of use, robustness, affordability of the methodology and the type of chemicals, organisms and ecosystem of interest.

Background, aim, and scope Experimental data on partition coefficients and environmental half-lives of sulfur analogs of polychlorinated organic compounds are scarce. Consequently, little is known about their overall persistence and long-range transport potential, which are the most vital measures in the environmental exposure assessment. We performed Multimedia Modeling of environmental fate and transport to complement this paucity of scientific data. The main aim of our study was to investigate whether the sulfur analogs of polychlorinated dibenzo-p-dioxins, -dibenzofurans, and -diphenylethers are as environmentally persistent and/or mobile as their oxygen counterparts and to propose the environmental exposure-related classification of the examined sulfur compounds. Materials and methods Our study included all possible congeners of the sulfur analogs generated in a combinatorial approach. We predicted (1) lacking data on partition coefficients (log K OW, log K OA and log K AW) for oxygen- and sulfur analogs using Quantitative Structure-Property Relationship (QSPR) modeling and (2) their half-lives in air, water, and soil using US EPA tool ‘The PBT Profiler, v. 1.203 2006'. Subsequently, we introduced these results into multimedia mass balance model ‘The OECD POV and LRTP Screening Tool, v. 2.2'. Results Our study revealed that log K OW and log K OA are increasing by constant values of 0.60 and 1.07, respectively, and the values of log K AW are decreasing by 0.90, whenever one oxygen atom in the carbon skeleton is replaced by sulfur. The persistence ranking performed by the PBT Profiler showed that PCDDs, PCDFs, PCDEs, and their sulfur analogs belong to one half-life class. Discussion The Multimedia Modeling by the means of ‘The OECD POV and LRTP Screening Tool, v. 2.2' suggested that the long-range transport potential depends on the presence/absence of oxygen/sulfur atoms in particular molecules, their substitution pattern and the parent carbon skeleton. Sulfur analogs are generally less mobile than their oxygen analogs, but have similar overall persistence and much higher bioaccumulation potential. Thus, according to the classification of chemicals proposed by Klasmeier et al. (Environ Sci Technol 40:53-60, 2006), some of them show POP-like POV and LRTP characteristics while the rest shows POP-like POV characteristics. Conclusions The sulfur analogs of PCDDs, PCDFs, or PCDEs bring environmental mobility comparable with the risk related to the oxygen ones; they belong to the pollutants of ‘highest' or ‘intermediate' priority. Recommendations and perspectives Further studies that would verify the necessity to include the studied sulfur molecules in the international lists of high-priority environmental pollutants are recommended.

Purpose The purpose of this paper is to assess fatal cancer risk after external and internal (inhalation and ingestion) exposure from natural radionuclides in soil like ²³⁸U, ²³²Th, ⁴⁰K, and ²²⁶Ra on the territory of Bela Crkva, Serbia. Although receiving doses are low from sources like natural radionuclides in soil, because of stochastic effects of ionizing radiation, risk for developing cancer exists and can be quantified. Methods Concentrations of radionuclides from 80 soil samples are measured using HPGe detector. Fatal cancer risk is assessed from calculated ambient dose rate in the target organs of body due to external and internal exposure. Monte Carlo simulations are used to obtain conversion factors which are required to calculate absorbed dose rate in target organs. Results and discussion Assessed cancer risk for ²³⁸U in the case of both inhalation and ingestion exposure is from 1.11 × 10⁻⁶ to 24 × 10⁻⁶ for minimal and maximal activity in soil samples, from 1.02 × 10⁻⁶ to 23.3 × 10⁻⁶ for exposure to ²²⁶Ra, from 1.89 × 10⁻⁶ to 50.3 × 10⁻⁶ for exposure to ²³²Th, and from 0.265 × 10⁻⁶ to 9.83 × 10⁻⁶ for exposure to ⁴⁰K. Overall risk from ⁴⁰K as external and internal source is from 0.8 × 10⁻⁶ to 31.9 × 10⁻⁶. Calculated cancer risks from both inhalation and ingestion exposure could be related to all tissues that are on the way of distribution of particles within the body but especially to deposition sites in the body. Conclusion Assessed risks for fatal cancer development from inhaled and ingested natural radionuclides originating in soil are not increased.

Background, aim, and scope Building up a comprehensive accurate monitoring program requires the knowledge on the contamination in principal, complemented by detailed information on individual contaminants. The selection of pollutants to be considered in monitoring actions is based dominantly on the information available about their environmental relevance (e.g., persistence, bioaccumulation potential, toxicological and ecotoxicological properties) and their occurrence within the affected environmental system. Therefore, this study focused on the identification of organic contaminants in selected German and European rivers to demonstrate the usefulness of a screening approach as complementary base for the compound selection process within monitoring activities. Materials and methods Gas chromatography-mass spectrometry-based screening analyses were performed on five and six samples from German and European rivers, respectively. Identification of individual contaminants was based on the investigation of mass spectral and gas chromatographic properties compared with databases and reference materials. Results This study summarized the results of non-target screening analyses applied to river water samples and focused dominantly on, so far, unnoticed organic contaminants. Numerous compounds have been identified belonging to the groups of pharmaceuticals, technical additives, pesticides, personal care products, and oxygen-, nitrogen-, and sulfur-containing compounds of obviously anthropogenic origin. They are discussed in terms of their structural properties, their possible application or usage, and the environmental information available so far. Discussion Generally, two different groups of compounds have been differentiated that might contribute to potential monitoring programs. Firstly, more specific contaminants characterizing the individual riverine systems have been depicted (e.g., 4-chloro-2-(trifluoromethyl)aniline, di-iso-propylurea). The consideration of these substances in monitoring analyses to be applied to the corresponding catchment areas is recommended in order to monitor the real state of pollution. Secondly, contaminants have been introduced that appeared with higher multiplicity throughout the different river systems (e.g., TMDD, TXIB). Since these compounds tend to obviously have an elevated environmental stability accompanied by a widespread distribution, it is recommended to consider them in international high-scale monitoring programs. Conclusions For monitoring purposes, a fundamental knowledge on the diversity of pollutants is an important precondition, which can be supported by screening analyses. Obviously, numerous organic contaminants have been neglected so far in environmental studies on river water, comprising also investigation on potential harmful effects and, therefore, their implementation in monitoring activities has been hindered. Recommendations and perspectives Therefore, based on the results of this study, screening analyses should be established as principle tools to improve and complement the substance spectra for monitoring purposes. Secondly, scientific efforts should be strengthened to expand our knowledge on actually appearing organic contaminants in riverine systems.