The photochemical degradation of two widely used organophosphorothioate insecticides, fenitrothion and diazinon, was investigated in aqueous solutions containing three separate dissolved constituents commonly found in natural waters (NO 3 − , CO 3 2− and dissolved organic matter (DOC)). The effect of these constituents on pesticide photodegradation was compared to degradation in “constituent-free” pure water. Solutions were irradiated in an Atlas solar simulator fitted with a UV-filtered Xenon arc lamp with light irradiances (500 W m−2) measured using a spectral radiometer to allow derivation of quantum yields of degradation. Fenitrothion absorbs light within the solar UV range (λ, 295–400 nm) and underwent direct photolysis in pure water whereas diazinon (λ max ∼250 nm) showed no observable loss over the experimental period. However, photodegradation conforming to pseudo-first-order kinetics was observed for both chemicals in the presence of the dissolved constituents (at concentrations typically observed in natural waters), with the rates of photodecay observed in the order of NO 3 − > CO 3 2− ≅ DOC, with the highest rates observed in the 3 mM NO 3 − solutions (k Fen = 0.155 ± 0.041 h−1; k Dia = 0.084 ± 0.0007 h−1). For diazinon this rate was comparable to fenitrothion photolysis in pure water (k fen 0.072 ± 0.0078 h−1), highlighting the importance of NO 3 − on a non-photolabile pesticide, with indirect photodegradation probably attributable to the light-induced release of aqueous hydroxyl radicals (·OH) from NO 3 − . Suwannee river fulvic acid (serving as DOC) did not statistically affect the rate of photodecay for fenitrothion relative to its photolysis in MilliQ water, although measured rates in DOC solutions were slightly lower. However, measurable rates of photodecay were apparent for diazinon in the DOC solutions, indicating that fulvic acid, possibly in the form of “excited” triplet-state-DOC plays a role in diazinon transformation. Hydrolysis was not apparent for fenitrothion (in buffered solutions of pH 5–9) but was notable for diazinon at the lower pHs of 5 and 3 (k Dia-hyd 0.3414 h−1 at pH 3 and 0.228 h−1 at pH 5), resulting in the formation of the degradate, 2-isopropyl–6-methyl–4-pyrimidinol. This work highlights the importance of dissolved constituents on abiotic photodegradation of pesticides and it is recommended that these constituents be incorporated into laboratory-based fate-testing regimes.

PURPOSE: Isoproturon, a herbicide belonging to the phenylurea family, is widely used to kill weeds in soils. Recent study indicated that isoproturon has become a contaminant in ecosystems due to its intensive use, thus bringing environmental risks to crop production safety. Salicylic acid (SA) is one of the components in plant defense signaling pathways and regulates diverse physiological responses to biotic and environmental stresses. The purpose of the study is to help to understand how SA mediates the biological process in wheat under isoproturon stress. METHODS: Wheat seeds (Triticum aestivum, cv. Yangmai 13) were surface-sterilized and placed on moist filter paper for germination. After 24 h, the germinating seeds were placed on a plastic pot (1 L) containing 1,120 g soil mixed with isoproturon at 4 mg kg−1 soil. After 4 days, wheat leaves were sprayed with 5 mg L−1 SA. The SA treatment was undertaken once a day and lasted for 6 days, when the third true leaf was well developed. For control seedlings, only water was sprayed. Seedlings were grown under a light intensity of 300 µmol m−2 s−1 with a light/dark cycle of 12/12 h at 25°C, and watered to keep 70% relative water content in soils. RESULTS AND DISCUSSION: We investigated the role of SA in alleviating isoproturon-induced toxicity in the food crop wheat (T. aestivum). Plants exposed to 4 mg kg−1 isoproturon showed growth stunt and oxidative damage, but concomitant treatment with 5 mg L−1 SA was able to attenuate the toxic effect. Isoproturon in soils was readily accumulated by wheat, but such accumulation can be blocked significantly by SA application. Treatment with SA decreased the abundance of O2 .− and H2O2, as well as activities of antioxidant enzymes, and increased activities of catalase in isoproturon-exposed plants. The enzyme activities were confirmed by the native polyacrylamide gel electrophoresis. Further, an RT-PCR-based assay was performed to show that several transcripts coding antioxidant enzymes were increased with isoproturon but decreased by SA. CONCLUSION: The present results indicate that exogenous SA is able to improve the wheat tolerance to isoproturon toxicity.

BACKGROUND, AIM, AND SCOPE: 2,2-bis(chlorophenyl)-1,1,1-trichloroethane (DDT) metabolites, other than those routinely measured [i.e., 2,2-bis(chlorophenyl)-1,1-dichloroethylene (DDE) and 2,2-bis(chlorophenyl)-1,1-dichloroethane (DDD)], have recently been detected in elevated concentrations not only in the surface water of Teltow Canal, Berlin, but also in sediment samples from Elbe tributaries (e.g., Mulde and Havel/Spree). This was paralleled by recent reports that multiple other metabolites could emerge from the degradation of parent DDT by naturally occurring organisms or by interaction with some heavy metals. Nevertheless, only very few data on the biological activities of these metabolites are available to date. The objective of this communication is to evaluate, for the first time, the cytotoxicity, dioxin-like activity, and estrogenicity of the least-studied DDT metabolites. METHODS: Four DDT metabolites, p,p′-2,2-bis(chlorophenyl)-1-chloroethylene (DDMU), p,p′-2,2-bis(chlorophenyl)-1-chloroethane (DDMS), p,p′-2,2-bis(4-ch1oropheny1)acetonitrile (DDCN), and p,p′-2,2-bis(chlorophenyl)acetic acid (DDA), were selected based on their presence in environmental samples in Germany such as in sediments from the Mulde River and Teltow Canal. O,p′-DDT was used as reference in all assays. Cytotoxicity was measured by neutral red retention with the permanent cell line RTG-2 of rainbow trout (Oncorhynchus mykiss). Dioxin-like activity was determined using the 7-ethoxyresorufin-O-deetylase assay. The estrogenic potential was tested in a dot blot/RNAse protection-assay with primary hepatocytes from male rainbow trout (O. mykiss) and in a yeast estrogen screen (YES) assay. RESULTS: All DDT metabolites tested revealed a clear dose–response relationship for cytotoxicity in RTG-2 cells, but no dioxin-like activities with RTL-W1 cells. The dot blot/RNAse protection-assay demonstrated that the highest non-toxic concentrations of these DDT metabolites (50 μM) had vitellogenin-induction potentials comparable to the positive control (1 nM 17β-estradiol). The estrogenic activities could be ranked as o,p′-DDT > p,p′-DDMS > p,p′-DDMU > p,p′-DDCN. In contrast, p,p′-DDA showed a moderate anti-estrogenic effect. In the YES assay, besides the reference o,p′-DDT, p,p′-DDMS and p,p′-DDMU displayed dose-dependent estrogenic potentials, whereas p,p′-DDCN and p,p′-DDA did not show any estrogenic potential. DISCUSSION: The reference toxicant o,p′-DDT displayed a similar spectrum of estrogenic activities similar to 17β-estradiol, however, with a lower potency. Both p,p′-DDMS and p,p′-DDMU were also shown to have dose-dependent estrogenic potentials, which were much lower than the reference o,p′-DDT, in both the vitellogenin and YES bioassays. Interestingly, p,p′-DDA did not show estrogenic activity but rather displayed a tendency towards anti-estrogenic activity by inhibiting the estrogenic effect of 17β-estradiol. The results also showed that the p,p′-metabolites DDMU, DDMS, DDCN, and DDA do not show any dioxin-like activities in RTL-W1 cells, thus resembling the major DDT metabolites DDD and DDE. CONCLUSIONS: All the DDT metabolites tested did not exhibit dioxin-like activities in RTL-W1 cells, but show cytotoxic and estrogenic activities. Based on the results of the in vitro assays used in our study and on the reported concentrations of DDT metabolites in contaminated sediments, such substances could, in the future, pose interference with the normal reproductive and endocrine functions in various organisms exposed to these chemicals. Consequently, there is an urgent need to examine more comprehensively the risk of environmental concentrations of the investigated DDT metabolites using in vivo studies. However, this should be paralleled also by periodic evaluation and monitoring of the current levels of the DDT metabolites in environmental matrices. RECOMMENDATIONS AND PERSPECTIVES: Our results clearly point out the need to integrate the potential ecotoxicological risks associated with the “neglected” p,p′-DDT metabolites. For instance, these DDT metabolites should be integrated into sediment risk assessment initiatives in contaminated areas. One major challenge would be the identification of baseline data for such risk assessment. Further studies are also warranted to determine possible additive, synergistic, or antagonistic effects that may interfere with the fundamental cytotoxicity and endocrine activities of these metabolites. For a more conclusive assessment of the spectrum of DDT metabolites, additional bioassays are needed to identify potential anti-estrogenic, androgenic, and/or anti-androgenic effects.

TiO2:Nb nanopowders within a dopant concentration in the range of 0.1–15 at.% were prepared by one-step flame spray synthesis. Effect of niobium doping on structural, optical and photocatalytic properties of titanium dioxide nanopowders was studied. Morphology and structure were investigated by means of Brunauer–Emmett–Teller isotherm, X-ray diffraction and transmission electron microscopy. Diffuse reflectance and the resulting band gap energy were determined by diffuse reflectance spectroscopy. Photocatalytic activity of the investigated nanopowders was revised for the photodecomposition of methylene blue (MB), methyl orange (MO) and 4-chlorophenol under UVA and VIS light irradiation. Commercial TiO2-P25 nanopowder was used as a reference. The specific surface area of the powders was ranging from 42.9 m2/g for TiO2:0.1 at.% Nb to 90.0 m2/g for TiO2:15 at.% Nb. TiO2:Nb particles were nanosized, spherically shaped and polycrystalline. Anatase was the predominant phase in all samples. The anatase-related transition was at 3.31 eV and rutile-related one at 3.14 eV. TiO2:Nb nanopowders exhibited additional absorption in the visible range. In comparison to TiO2-P25, improved photocatalytic activity of TiO2:Nb was observed for the degradation of MB and MO under both UVA and VIS irradiation, where low doping level (Nb < 1 at.%) was the most effective. Niobium doping affected structural, optical and photocatalytic properties of TiO2. Low dopant level enhanced photocatalytic performance under UVA and VIS irradiation. Therefore, TiO2:Nb (Nb < 1 at.%) can be proposed as an efficient selective solar light photocatalyst.

PURPOSE: Malachite Green (MG) is used for a variety of applications but is also known to be carcinogenic and mutagenic. In this study, a novel Micrococcus sp. (strain BD15) was observed to efficiently decolorize MG. The purposes of this study were to explore the optimal conditions for decolorization and to evaluate the potential use of this strain for MG decolorization. METHODS: Optical microscope and UV–visible analyses were carried out to determine whether the decolorization was due to biosorption or biodegradation. A Plackett–Burman design was employed to investigate the effect of various parameters on decolorization, and response surface methodology was then used to explore the optimal decolorization conditions. Kinetics analysis and antimicrobial activity tests were also performed. RESULTS: The results indicated that the decolorization by the strain was mainly due to biodegradation. Concentrations of MG, urea, and yeast extract and inoculum size had significantly positive effects on MG decolorization, while concentrations of CuCl₂ and MgCl₂, and temperature had significantly negative effects. The interaction between different parameters could significantly affect decolorization, and the optimal conditions for decolorization were 1.0 g/L urea, 0.9 g/L yeast extract, 100 mg/L MG, 0.1 g/L inoculums (dry weight), and incubation at 25.2°C. Under the optimal conditions, 96.9% of MG was removed by the strain within 1 h, which represents highly efficient microbial decolorization. Moreover, the kinetic data for decolorization fit a second-order model well, and the strain showed a good MG detoxification capability. CONCLUSION: Based on the results of this study, we propose Micrococcus sp. strain BD15 as an excellent candidate strain for MG removal from wastewater.

INTRODUCTION: Canola, which is genetically modified (GM) for tolerance to glyphosate, has the potential to become established as a new glyphosate resistant weed, thus reducing the effectiveness of glyphosate. METHODS: Volunteer from dormant canola seeds produced thousands of plants per hectare in the fourth year (2011) following a 2007 crop harvest. This occurred with no additional canola seed production since the 2007 harvest. RESULTS: Volunteer plants following harvests of annual crops are typically only a problem for the first year after harvest. In California, glyphosate is the core herbicide on over a million hectares of high value row, tree, and vine crops and new glyphosate resistant weeds reduce the effectiveness of glyphosate. CONCLUSIONS: The combination of dormant seed and herbicide resistance makes GM glyphosate-resistant canola a new and difficult California weed which was first observed in the winter of 2009.

PURPOSE: Phytoremediation is the exploitation of plants and their rhizospheric microorganisms for pollutants treatment like textile dyes, which are toxic, carcinogenic and mutagenic from the effluent. The purpose of this work was to explore a naturally found plant and bacterial synergism to achieve an enhanced degradation of Remazol Black B dye (RBB). METHODS: In vitro cultures of Zinnia angustifolia were obtained by seed culture method. Enzymatic analysis of the plant roots and Exiguobacterium aestuarii strain ZaK cells was performed before and after decolorization of RBB. Metabolites of RBB formed after its degradation were analyzed using UV–Vis spectroscopy, high-performance liquid chromatography (HPLC), Fourier transform infrared (FTIR) and gas chromatography–mass spectrometry (GC-MS). Phytotoxicity studies were performed. RESULTS: The consortium ZE was found to be more efficient than individual plant and bacteria. Z. angustifolia roots showed significant induction in the activities of lignin peroxidase, laccase, DCIP reductase and tyrosinase during dye decolorization. E. aestuarii showed significant induction in the activities of veratryl alcohol oxidase, azo reductase and DCIP reductase. Analysis of metabolites revealed differential metabolism of RBB by plant, bacteria and consortium ZE. E. aestuarii and Z. angustifolia led to the formation of 3,6-diamino-4-hydroxynaphthalene-2-sulfonic acid, (ethylsulfonyl)benzene, and 3,4,6-trihydroxynaphthalene-2-sulfonic acid and propane-1-sulfonic acid, respectively, whereas consortium ZE produced 4-hydroxynaphthalene-2-sulfonic acid, naphthalene-2-sulfonic acid and 4-(methylsulfonyl)phenol. The phytotoxicity study revealed the nontoxic nature of the metabolites formed after dye degradation. CONCLUSION: Consortium ZE was found to be more efficient and faster in the degradation of RBB when compared to degradation by Z. angustifoila and E. aestuarii individually.

INTRODUCTION: Titanium dioxide (TiO2) nanoparticle powders have been extensively studied to quickly photodegrade some organic pollutants; however, the effect of the particle size of TiO2 nanoparticle aggregates on degradation remains unclear because microscale aggregates form once the nanoparticle powders enter into water. METHODS: The degradation of azo dye by different particle sizes of TiO2 nanoparticle aggregates controlled by NaCl concentrations was investigated to evaluate the particle size effect. Removal reactions of reactive black 5 (RB5) with TiO2 nanoparticles followed pseudo-first-order kinetics. RESULTS: The increase of TiO2 dosage from 40 to 70 mg/L enhanced the degradation. At doses around 100 mg/L TiO2, degradation rates decreased which could be the result of poor UV light transmittance at high-particle concentrations. At average particle sizes of TiO2 nanopowders less than around 500 nm, the degradation rates increased with decreasing particle size. As the average particle size exceeded 500 nm, the degradation rates were not significantly changed. CONCLUSIONS: For the complete degradation experiments, the mineralization rates of total organic carbon disappearance are generally following the RB5 decolorization kinetic trend. These findings can facilitate the application of TiO2 nanoparticles to the design of photodegradation treatments for wastewater.

INTRODUCTION: This paper is in response to criticism of our article “The human sex odds at birth after the atmospheric atomic bomb tests, after Chernobyl, and in the vicinity of nuclear facilities” published in Environ Sci Pollut Res 18(5):697–707, 2011. METHODS: Our findings and methods concerning the disturbed human sex odds at birth have been criticized in this journal for being artifacts of data mining, that the concept of statistical significance was misunderstood, and that confounding factors have not been accounted for. Here, we show that this criticism has no basis. We applied well-established statistical methods to large official data sets, and confounding is less important at the level of secular sex odds trends in aggregated annual figures from countries or continents. RESULTS AND CONCLUSIONS: Moreover, our results are strengthened by recent findings concerning increased infant death sex odds in Germany and increased Down syndrome prevalence at birth across Europe after Chernobyl. Prompted by our studies, an official investigation in Lower Saxony, Germany, by the “Niedersächsisches Landesgesundheitsamt (NLGA)” confirmed our observation of severely escalated sex odds within 40 km distance from the nuclear storage site in Gorleben, Germany.

BACKGROUND, AIM, AND SCOPE: The start-up pattern of biofilm remediation system affects the biofilm characteristics and operating performances. The objective of this study was to evaluate the performances of the contaminated source water remediation systems with different start-up patterns in view of the pollutants removal performances and microbial community succession. METHODS: The operating performances of four lab-scale simulated river biofilm reactors were examined which employed different start-up methods (natural enrichment and artificial enhancement viadischarging sediment with influent velocity gradient increase) and different bio-fillers (Elastic filler and AquaMats® ecobase). At the same time, the microbial communities of the bioreactors in different phases were analyzed by polymerase chain reaction, denaturing gradient gel electrophoresis, and sequencing. RESULTS AND DISCUSSION: The pollutants removal performances became stable in the four reactors after 2 months’ operation, with ammonia nitrogen and permanganate index (CODMn) removal efficiencies of 84.41–94.21% and 69.66–76.60%, respectively. The biomass of mature biofilm was higher in the bioreactors by artificial enhancement than that by natural enrichment. Microbial community analysis indicated that elastic filler could enrich mature biofilm faster than AquaMats®. The heterotrophic bacteria diversity of biofilm decreased by artificial enhancement, which favored the ammonia-oxidizing bacteria (AOB) developing on the bio-fillers. Furthermore, Nitrosomonas- and Nitrosospira-like AOB coexisted in the biofilm, and Pseudomonas sp., Sphaerotilus sp., Janthinobacterium sp., Corynebacterium aurimucosum were dominant in the oligotrophic niche. CONCLUSION: Artificial enhancement via the combination of sediment discharging and influent velocity gradient increasing could enhance the biofilm formation and autotrophic AOB enrichment in oligotrophic niche.