BACKGROUND: Soil samples from remote Alpine areas were analyzed for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans and polychlorinated biphenyls by high-resolution gas chromatography/high-resolution gas spectrometry. Additionally, the EROD micro-assay and a genetically modified yeast estrogen bioassay were carried out to determine persistent aryl hydrocarbon receptors (AhR) and estrogen receptors (ER) agonists, respectively. Regarding the AhR agonists, the toxicity equivalents of analytical and EROD determined values were compared, targeting both altitude of samples and their soil organic content. The ratio between bioassay derived equivalents and analytical determinations suggested no significant contribution of unknown AhR inducers in these sampling sites and some antagonism in soils with relatively high PCB loading. More CYP1A1 expression was induced at the highest sites or about 1400–1500 m a.s.l. along the altitude profiles. Surprisingly, no clear tendencies with the soil organic content were found for dioxin-like compounds. Mean values obtained in the present study were for ER agonists, 0.37 ± 0.12 pg 17ß-estradiol EQ g⁻¹ dry soil and 6.1 ± 4.2 pg TCDD-EQ g⁻¹ dry soil for AhR agonists. CONCLUSION: Low bioassay responses with a higher relative amount of AhR inducers than ER disrupters were detected, indicating the higher abundance of persistent dioxin-like than estrogen-like compounds in these forested mountainous areas.

BACKGROUND, AIM, AND SCOPE: Ferro-cyanide is one of the commonly found species at cyanide-contaminated soils and groundwater. Unlike botanical metabolism of KCN via the β-cyanoalanine pathway, processes involved in the plant-mediated assimilation of ferro-cyanide are still unclear. The objective of this study was to investigate a possible mechanism involved in uptake and assimilation of ferro-cyanide by plants. MATERIALS AND METHODS: Detached roots of plants were exposed to ferro-cyanide in a closed-dark hydroponic system amended with HgCl2, AgNO3, LaCl3, tetraethylammonium chloride (TEACl), or Na3VO4, respectively, at 25 ± 0.5°C for 24 h. Total CN, free CN-, and dissolved Fe2+ were analyzed spectrophotometrically. Activity of β-cyanoalanine synthase involved in cyanide assimilation was also assayed using detached roots of plants in vivo. RESULTS: Dissociation of ferro-cyanide [FeII(CN)6]-4 to free CN- and Fe2+ in solution was negligible. The applied inhibitors did not show any significant impact on the uptake of ferro-cyanide by soybean (Glycine max L. cv. JD 1) and hybrid willows (Salix matsudana Koidz × alba L.; p > 0.05), but rice (Oryza sativa L. cv. JY 98) was more susceptible to the inhibitors compared with the controls (p < 0.05). However, TEACl had the most severe effect on the assimilation of ferro-cyanide by soybean, hybrid willows, and maize (Zea mays L. cv. PA 78; p < 0.01), whereas AgNO3 was the most sensitive inhibitor to rice (p < 0.01). No measurable difference in β-cyanoalanine synthase activity of roots exposed to ferro-cyanide was observed compared with the control without any cyanides (p > 0.05), whereas roots exposed to KCN showed a considerable increase in enzyme activity (p < 0.05). CONCLUSIONS: Plants take up Fe2+ and CN- as a whole complex, and in vivo dissociation to free CN- is not prerequisite during the botanical assimilation of ferro-cyanide. Ferro-cyanide is likely metabolized by plants directly through an unknown pathway rather than the β-cyanoalanine pathway.

Introduction Chlorimuron-ethyl has been widely used for the soybean production of China, but less information is available on the possible risk of long-term application of this herbicide. Materials and methods In this paper, soil samples were collected from the plots having been received 30 g active component of chlorimuron-ethyl/ha per year for 5 and 10 years in a continuously cropped soybean field of Northeast China, with their microbial community analyzed by plate counting, PCR-DGGE, and cloning library. Chlorimuron-ethyl had a higher accumulation in test soils, and the accumulation decreased the CFU of soil bacteria and increased the CFU of soil fungi significantly. The CFU of soil actinomycetes only had a significant decrease in the plot having been received chlorimuron-ethyl for 10 years. Results and discussion Under the long-term stress of chlorimuron-ethyl, the diversity and evenness of soil microbial community decreased, and more importantly, some bacterial and fungal species that possibly benefited soybean's growth, e.g., Acidobacteria, γ-proteobacteria, Cortinarius violaceu, Acarospora smaragdula, and Xerocomus chrysenteron decreased or demised, while some species that could induce the obstacle of soybean's continuous cropping, e.g., Fusarium oxysporum, Rhizoctonia solani, and Phytophthora sojae, increased or appeared. Some actinomycetes were inhibited having negative effects on the antagonism between soil microbes. It is considered that due to the longer half-life of chlorimuron-ethyl in soil and the resistance and resilience of soil microbes to short-term environmental stress, long-term in situ investigation rather than laboratory microcosm test or short-term field experiment would be more appropriate to the accurate assessment of the ecological risk of long-term chlorimuron-ethyl application. Further studies should be made on the application mode and duration of chlorimuron-ethyl to reduce the possible ecological risk of applying this herbicide on continuously cropped soybean field.

PURPOSE: The aim of this work was to determine some microbial characteristics of Mytilus galloprovincialis harvested from four stations, located in Izmir coastal area (Eastern Aegean Sea, Turkey). The area along the Izmir coast is densely populated, and it includes extensive agricultural lands, industrial and domestic discharge. Shellfish contamination from sewage-polluted waters is very important for public health. MATERIALS AND METHODS: Mussel samples were collected by SCUBA equipment. While, counts of culturable heterotrophic bacteria (aerobic, mesophilic) in samples were determined by the spread plate method, fecal coliforms were enumerated by the most probable number (MPN) method using the standard five-tube method. Additionally, samples were evaluated with the presence of Salmonella spp. RESULTS AND DISCUSSION: The results showed that levels of fecal coliforms determined were higher than the allowed limit (>300 MPN/100 g) in all the stations during the study period. Maximum fecal coliform count was observed in all of the stations in March, May and November as 2.4 × 105 MPN/100 g. The mean number of culturable heterotrophic bacteria varied between 1.7 × 105 and 6.7 × 106 CFU/100g, and maximum heterotrophic bacteria level was recorded in March 2006. In addition, the presence of Salmonella spp. was positive in one or more stations in all periods except for January. CONCLUSION: The results obtained from this study can be of use to prevent potentially harmful adverse effects of microorganisms from polluted waters and shellfish. Necessary hygienic measurements should be regularly taken and shellfish products should certainly not be consumed raw or undercooked.

Purpose Adsorption of metals (Pb, Cd, Cu, Ni, Zn) to TiO₂ nanoparticles and bulk particles was examined for use as a contaminant removal substrate as a function of particle size, sorbent concentration, and exhaustion. Methods Adsorption experiments were conducted with 0.01, 0.1, and 0.5 g/L nanoparticles in a pH 8 solution and in spiked San Antonio tap water. Results When results were normalized by mass, nanoparticles adsorbed more than the bulk particles but when results were surface-area normalized, the opposite was observed. The adsorption data shows the ability of the TiO₂ nanoparticles to remove Pb, Cd, and Ni from solution with similar adsorption at 0.1 and 0.5 g/L. Adsorption kinetics for all metals tested was described by a modified first order rate equation with the nanoparticles having a faster rate of adsorption than the bulk particles. The nanoparticles were able to simultaneously removal multiple metals (Zn, Cd, Pb, Ni, Cu) from both pH 8 solution and spiked San Antonio tap water. Exhaustion experiments showed that both the nanoparticles and bulk particles were exhausted at pH 6 but at pH 8, exhaustion did not occur for the nanoparticles. Conclusion Comparison of K d, distribution coefficient, with other literature showed that the nanoparticles were better sorbents than other metal oxide nanoparticles and a commercial activated carbon.

Background, aim, and scope Biowaste contains compounds of agricultural value such as organic carbon, nutrients, and trace elements and can partially replace mineral fertilizer (MIN) and improve the physical properties of the soil. However, the obvious benefits of land spreading need to be carefully evaluated against potential adverse effects on the environment and human health. Environmental contamination resulting from biowaste application is one of the key variables when assessing cost/benefits. This study provides data on the resulting concentration of polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in the soil column as a result of the different types of fertilizers. Materials and methods In a long-term field experiment established in 1962, we investigated the influence of the application of biowaste-derived fertilizers such as sewage sludge (SSL), compost (COM), and farmyard manure (FYM) to a luvisol derived from loess on the contents of PCDD/Fs and DL-PCBs. Control plots amended only with MIN served as a basis to compare the biowaste-amended soils with soils affected only by atmospheric deposition, thus experimentally separating the two pathways of soil contamination. Samples of the soil column down to a depth of 90 cm were taken in 2001 and analyzed for PCDD/Fs and dioxin-like PCBs according to US-EPA methods 1613 and 1668, respectively. Results Thirty-nine years of experimental SSL and COM applications exceeding four times the maximal amount as laid down in German legislation resulted in a doubling of the international toxicity equivalent (I-TEQ) budget for PCDD/Fs and a threefold increase for DL-PCBs as compared to test plots amended with MIN only. As compared to MIN, the application of FYM had no effect on the PCDD/F and PCB content in soil. The average contribution of the DL-PCBs to the WHO-TEQ was 19% in the MIN and FYM plots and somewhat higher in the COM (23%) and in the SSL (27%) plots. Discussion Although the test plots received four times the maximum application of SSL as laid down in the German SSL ordinance and the investigated region represents the upper end of the topsoil concentrations typically found in Germany, the soils treated with SSL and COM were still a factor of 4 below the German guideline value of PCDD/Fs for arable land. No enhancement of translocation of PCDD/Fs and PCBs into the corresponding subsoils due to the presence of dissolved humic matter or other surfactants potentially present in the biowaste was observed. The similarity of congener patterns in all soils, irrespective of the type of fertilizer applied, points towards atmospheric deposition of PCDD/Fs and DL-PCBs as the main intake route in the soils. The higher levels in the SSL- and COM-amended soils can be explained by the fact that both biowastes are subject to atmospheric deposition occurring at their origin. In the case of COM, it is accumulation in the foliage, while in the case of SSL, atmospheric particulate from wet and dry deposition is collected in the wastewater treatment system via urban runoff. Conclusions It appears that the common practice of SSL applications in Germany does not pose a current threat to the agro-environment with regard to PCDD/Fs and DL-PCBs. However, time trend data on PCDD/Fs in SSL-amended soils will be needed to obtain a prognosis about the long-term effect of biowaste applications on soil quality.

INTRODUCTION: Effluent organic matter from biological wastewater treatment plants is composed of degradation products and soluble microbial products (SMP). Protein, polysaccharide, humic acid, and DNA were major biomolecules of SMP. Little is known about the effects of SMP as microbially derived precursors on disinfection byproduct formation and speciation in biologically treated wastewater. In addition, there has never been any attempt to directly chlorinate the major biomolecules of SMP. MATERIALS AND METHODS: In this study, model compounds (bovine serum albumin, starch, DNA, and humic acid) and SMP collected from a sequencing batch reactor (SBR) were chlorinated to verify the trihalomethane and haloacetic acid species that were produced from them. RESULTS AND DISCUSSION: The results showed that chloroform, dichlorobromomethane, dichloroacetic acid, and trichloroacetic acid were generated from the chlorination of SMP in the SBR, and there was a close relationship between the species predicted from the model chemical compounds and those obtained from the SMP.

INTRODUCTION: Through leaching experiments and simulated rainfall experiments, characteristics of vertical leaching of exogenous rare earth elements (REEs) and phosphorus (P) and their losses with surface runoff during simulated rainfall in different types of soils (terra nera soil, cinnamon soil, red soil, loess soil, and purple soil) were investigated. RESULTS AND ANALYSES: Results of the leaching experiments showed that vertical transports of REEs and P were relatively low, with transport depths less than 6 cm. The vertical leaching rates of REEs and P in the different soils followed the order of purple soil > terra nera soil > red soil > cinnamon soil > loess soil. Results of the simulated rainfall experiments (83 mm h⁻¹) revealed that more than 92% of REEs and P transported with soil particles in runoff. CONCLUSION: The loss rates of REEs and P in surface runoff in the different soil types were in the order of loess soil > terra nera soil > cinnamon soil > red soil > purple soil. The total amounts of losses of REEs and P in runoff were significantly correlated.

The potential RDX contamination of food chain from polluted soil is a significant concern in regards to both human health and environment. Using a hydroponic system and selected soils spiked with RDX, this study disclosed that four crop plant species maize (Zea mays), sorghum (Sorghum sudanese), wheat (Triticum aestivum), and soybean (Glycine max) were capable of RDX uptake with more in aerial parts than roots. The accumulation of RDX in the plant tissue is concentration-dependent up to 21 mg RDX/L solution or 100 mg RDX/kg soil but not proportionally at higher RDX levels from 220 to 903 mg/kg soil. While wheat plant tissue harbored the highest RDX concentration of 2,800 μg per gram dry biomass, maize was able to remove a maximum of 3,267 μg RDX from soil per pot by five 4-week plants at 100 mg/kg of soil. Although RDX is toxic to plants, maize, sorghum, and wheat showed reasonable growth in the presence of the chemical, whereas soybeans were more sensitive to RDX. Results of this study facilitate assessment of the potential invasion of food chain by RDX-contaminated soils.

Introduction and aims The Chilean Altiplano ecosystem is conserved free from contaminants and pollutants because of the absence of major local human activities such as agriculture or other industries. We studied the effects of paraoxon on proliferation and apoptosis of testicular cells during active spermatogenesis in Dugesia gonocephala collected from a pristine river (Guacollo) in the Altiplano region nearby Visviri town, Chile. Materials and methods Adult planarians were incubated in varying concentrations of paraoxon (0.8, 0.4, 0.04, 0.004, and 0.0004 mM) for 4 h. After 3 h of incubation, bromodeoxyuridine (BrdU) was added. Effects on cell proliferation (BrdU) and apoptosis (Apaf-1) were determined by immunohistochemistry. Results Paraoxon concentrations of 0.4 and 0.8 mM caused 100% mortality in the respective treatment groups. The lowest tested concentration (0.0004 mM) caused a significant increase on cell proliferation in the seminiferous tubules, as well as an increase in the number of apoptotic cells. All other tested concentrations significantly inhibited cell proliferation and induced apoptosis. Conclusions Paraoxon inhibits DNA synthesis and induces apoptosis during spermatogenesis in adult planarians from a high-altitude, pollution-free environment. This could suggest its use as a biosensor or biomarker for contamination with agro pesticides.