Background, aim, and scope Soil contamination with heavy metals occurs as a result of both anthropogenic and natural activities. Heavy metals could have long-term hazardous impacts on the health of soil ecosystems and adverse influences on soil biological processes. Soil enzymatic activities are recognized as sensors towards any natural and anthropogenic disturbance occurring in the soil ecosystem. Similarly, microbial biomass carbon (MBC) is also considered as one of the important soil biological activities frequently influenced by heavy metal contamination. The polymerase chain reaction-denaturing gradient gel electrophoresis (DGGE) has recently been used to investigate changes in soil microbial community composition in response to environmental stresses. Soil microbial community structure and activities are difficult to elucidate using single monitoring approach; therefore, for a better insight and complete depiction of the soil microbial situation, different approaches need to be used. This study was conducted in a greenhouse for a period of 12 weeks to evaluate the changes in indigenous microbial community structure and activities in the soil amended with different application rates of Cd, Pb, and Cd/Pb mix. In a field environment, soil is contaminated with single or mixed heavy metals; so that, in this research, we used the selected metals in both single and mixed forms at different application rates and investigated their toxic effects on microbial community structure and activities, using soil enzyme assays, plate counting, and advanced molecular DGGE technique. Soil microbial activities, including acid phosphatase (ACP), urease (URE), and MBC, and microbial community structure were studied. Materials and methods A soil sample (0-20 cm) with an unknown history of heavy metal contamination was collected and amended with Cd, Pb, and Cd/Pb mix using the CdSO₄ and Pb(NO₃)₂ solutions at different application rates. The amended soils were incubated in the greenhouse at 25 ± 4°C and 60% water-holding capacity for 12 weeks. During the incubation period, samples were collected from each pot at 0, 2, 9, and 12 weeks for enzyme assays, MBC, numeration of microbes, and DNA extraction. Fumigation-extraction method was used to measure the MBC, while plate counting techniques were used to numerate viable heterotrophic bacteria, fungi, and actinomycetes. Soil DNAs were extracted from the samples and used for DGGE analysis. Results ACP, URE, and MBC activities of microbial community were significantly lower (p < 0.05) in the metal-amended samples than those in the control. The enzyme inhibition extent was obvious between different incubation periods and varied as the incubation proceeded, and the highest rate was detected in the samples after 2 weeks. However, the lowest values of ACP and URE activities (35.6% and 36.6% of the control, respectively) were found in the Cd₃/Pb₃-treated sample after 2 weeks. Similarly, MBC was strongly decreased in both Cd/Pb-amended samples and highest reduction (52.4%) was detected for Cd₃/Pb₃ treatment. The number of bacteria and actinomycetes were significantly decreased in the heavy metal-amended samples compared to the control, while fungal cells were not significantly different (from 2.3% to 23.87%). In this study, the DGGE profile indicated that the high dose of metal amendment caused a greater change in the number of bands. DGGE banding patterns confirmed that the addition of metals had a significant impact on microbial community structure. Discussion In soil ecosystem, heavy metals exhibit toxicological effects on soil microbes which may lead to the decrease of their numbers and activities. This study demonstrated that toxicological effects of heavy metals on soil microbial community structure and activities depend largely on the type and concentration of metal and incubation time. The inhibition extent varied widely among different incubation periods for these enzymes. Furthermore, the rapid inhibition in microbial activities such as ACP, URE, and MBC were observed in the 2 weeks, which should be related to the fact that the microbes were suddenly exposed to heavy metals. The increased inhibition of soil microbial activities is likely to be related to tolerance and adaptation of the microbial community, concentration of pollutants, and mechanisms of heavy metals. The DGGE profile has shown that the structure of the bacterial community changed in amended heavy metal samples. In this research, the microbial community structure was highly affected, consistent with the lower microbial activities in different levels of heavy metals. Furthermore, a great community change in this study, particularly at a high level of contamination, was probably a result of metal toxicity and also unavailability of nutrients because no nutrients were supplied during the whole incubation period. Conclusions The added concentrations of heavy metals have changed the soil microbial community structure and activities. The highest inhibitory effects on soil microbial activities were observed at 2 weeks of incubation. The bacteria were more sensitive than actinomycetes and fungi. The DGGE profile indicated that bacterial community structure was changed in the Cd/Pb-amended samples, particularly at high concentrations. Recommendations and perspectives The investigation of soil microbial community structure and activities together could give more reliable and accurate information about the toxic effects of heavy metals on soil health.

Background, aim, and scope Riverine retention decreases loads of nitrogen (N) and phosphorus (P) in running water. It is an important process in nutrient cycling in watersheds. However, temporal riverine nutrient retention capacity varies due to changes in hydrological, ecological, and nutrient inputs into the watershed. Quantitative information of seasonal riverine N and P retention is critical for developing strategies to combat diffuse source pollution and eutrophication in riverine and coastal systems. This study examined seasonal variation of riverine total N (TN) and total P (TP) retention in the ChangLe River, an agricultural drainage river in east China. Methods Water quality, hydrological parameters, and hydrophyte coverage were monitored along the ChangLe River monthly during 2004-2006. Nutrient export loads (including chemical fertilizer, livestock, and domestic sources) entering the river from the catchment area were computed using an export coefficient model based on estimated nutrient sources. Riverine TN and TP retention loads (RNRL and RPRL) were estimated using mass balance calculations. Temporal variations in riverine nutrient retention were analyzed statistically. Results and discussion Estimated annual riverine retention loads ranged from 1,538 to 2,127 t year⁻¹ for RNRL and from 79.4 to 90.4 t year⁻¹ for RPRL. Monthly retention loads varied from 6.4 to 300.8 t month⁻¹ for RNRL and from 1.4 to 15.3 t month⁻¹ for RPRL. Both RNRL and RPRL increased with river flow, water temperature, hydrophyte coverage, monthly sunshine hours, and total TN and TP inputs. Dissolved oxygen concentration and the pH level of the river water decreased with RNRL and RPRL. Riverine nutrient retention ratios (retention as a percentage of total input) were only related to hydrophyte coverage and monthly sunshine hours. Monthly variations in RNRL and RPRL were functions of TN and TP loads. Conclusions Riverine nutrient retention capacity varied with environmental conditions. Annual RNRL and RPRL accounted for 30.3-48.3% and 52.5-71.2%, respectively, of total input TN and TP loads in the ChangLe River. Monthly riverine retention ratios were 3.5-88.7% for TN and 20.5-92.6% for TP. Hydrophyte growth and coverage on the river bed is the main cause for seasonal variation in riverine nutrient retention capacity. The total input TN and TP loads were the best indicators of RNRL and RPRL, respectively. Recommendations and perspectives High riverine nutrient retention capacity during summer due to hydrophytic growth is favorable to the avoidance of algal bloom in both river systems and coastal water in southeast China. Policies should be developed to strictly control nutrient applications on agricultural lands. Strategies for promoting hydrophyte growth in rivers are desirable for water quality management.

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.

Background, aim and scope The importance of groundwater for human life cannot be overemphasised. Besides fulfilling essential ecological functions, it is a major source of drinking water. However, in the industrial area of Bitterfeld, it is contaminated with a multitude of harmful chemicals, including genotoxicants. Therefore, recently developed methodologies including preparative capillary gas chromatography (pcGC), MOLGEN-MS structure generation and mutagenicity prediction were applied within effect-directed analysis (EDA) to reduce sample complexity and to identify candidate mutagens in the samples. A major focus was put on the added value of these tools compared to conventional EDA combining reversed-phase liquid chromatography (RP-LC) followed by GC/MS analysis and MS library search. Materials and methods We combined genotoxicity testing with umuC and RP-LC with pcGC fractionation to isolate genotoxic compounds from a contaminated groundwater sample. Spectral library information from the NIST05 database was combined with a computer-based structure generation tool called MOLGEN-MS for structure elucidation of unknowns. Finally, we applied a computer model for mutagenicity prediction (ChemProp) to identify candidate mutagens and genotoxicants. Results and discussion A total of 62 components were tentatively identified in genotoxic fractions. Ten of these components were predicted to be potentially mutagenic, whilst 2,4,6-trichlorophenol, 2,4-dichloro-6-methylphenol and 4-chlorobenzoic acid were confirmed as genotoxicants. Conclusions and perspectives The results suggest pcGC as a high-resolution fractionation tool and MOLGEN-MS to improve structure elucidation, whilst mutagenicity prediction failed in our study to predict identified genotoxicants. Genotoxicity, mutagenicity and carcinogenicity caused by chemicals are complex processes, and prediction from chemical structure still appears to be quite difficult. Progress in this field would significantly support EDA and risk assessment of environmental mixtures.

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.

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 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.

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.

Introduction Isotope ratios of lead (²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb) in Japanese women's hair of the twentieth century were measured to evaluate lead contamination of human proximate environment of those days. Materials and Methods The historic hair samples (n = 40) were collected in 1980s by staffs of Department of Human Ecology, University of Tokyo, from Japanese women who cut their hair in 1910s to 1968 by themselves for hair piece or needle pad and who had stored it by the time of collection. Additional five contemporary hair samples (one from male and four from females) were also included. The hair samples were digested with HNO₃, diluted with water to Pb concentration of 10 µg/kg, and isotope ratios were measured by inductively coupled plasma mass spectrometry. Results and Discussion Isotope ratios as well as Pb concentration in the hair samples of the twentieth century varied to a considerable extent depending on the period of hair cut. The oldest hair samples (1910-1920s) had the highest concentration and the most distinct isotope ratios from those of Japanese domestic Pb indicating serious contamination of proximate environment of people of those days with Pb originated from mines in other regions of the world, probably through the usage of Pb-containing face powder. The concentration and isotope ratios of Pb decreased thereafter indicating less serious contamination of proximate environment of Japanese which, in turn, should have affected by environmental contamination of mid-twentieth century due to industrial activities and leaded gasoline. Contemporary Pb level was quite low (<1 mg/kg); however, isotope ratios were close to those in 1960s when hair concentration was assumed to be strongly affected by leaded gasoline.

Purpose China's freshwater subtropical shallow lakes are increasingly eutrophic and susceptible to production of heavy growths or water blooms of cyanobacteria. One example was the heavy water bloom that occurred for the first time in Lake Xuanwu, in 2005, an urban lake located in Nanjing city. The aim of the present study was to determine dynamics of water bloom dominating Microcystis in this lake. Meanwhile, the relationship between environmental factors and Microcystis populations was also analyzed. Materials and methods Molecular detection, using quantitative polymerase chain reaction, was used in this lake to study the dynamics of the cyanobacterial community, its Microcystis populations, and the microcystin-producing Microcystis genotypes from August 2005 to November 2006. Results It was shown that Microcystis wesenbergii and Microcystis aeruginosa were the main components of the cyanobacterial blooms in Lake Xuanwu, and they coexisted with species of the filamentous cyanobacterial genera Anabaena, Planktothrix, and Anabaenopsis. Microcystis cells were detected during the entire survey period and in all sample sites. The cell abundance of Microcystis ranged from 3.6 × 10² cells ml⁻¹ to a peak of 3.8 × 10⁶ cells ml⁻¹. The ratio of mcyB-containing Microcystis subpopulations to the total Microcystis varied, ranging from 0.1% to 12.8%. The abundance of Microcystis containing the mcyB microcystin gene was shown to be significantly correlated with concentrations of total phosphorus and phosphate. Conclusions Water temperature was the primary factor affecting Microcystis abundance in the lake, and phosphorus loading was shown to be a main factor in governing the growth of both microcystin-producing genotype and total Microcystis population. Higher Microcystis cell counts at the bottom of the water column before and after appearance of water blooms in Lake Xuanwu suggested that Microcystis numbers in the water column, especially at the bottom of the water column, play an important role in forming the next water bloom.