Long-term dynamics of the atrazine mineralization potential in surface and subsurface soil in an agricultural field as a response to atrazine applications

The dynamics of the atrazine mineralization potential in agricultural soil was studied in two soil layers (topsoil and at 35-45 cm depth) in a 3 years field trial to examine the long term response of atrazine mineralizing soil populations to atrazine application and intermittent periods without atrazine and the effect of manure treatment on those processes. In topsoil samples, ¹⁴C-atrazine mineralization lag times decreased after atrazine application and increased with increasing time after atrazine application, suggesting that atrazine application resulted into the proliferation of atrazine mineralizing microbial populations which decayed when atrazine application stopped. Decay rates appeared however much slower than growth rates. Atrazine application also resulted into the increase of the atrazine mineralization potential in deeper layers which was explained by the growth on leached atrazine as measured in soil leachates recovered from that depth. However, no decay was observed during intermittent periods without atrazine application in the deeper soil layer. atzA and trzN gene quantification confirmed partly the growth and decay of the atrazine degrading populations in the soil and suggested that especially trzN bearing populations are the dominant atrazine degrading populations in both topsoil and deeper soil. Manure treatment only improved the atrazine mineralization rate in deeper soil layers. Our results point to the importance of the atrazine application history on a field and suggests that the long term survival of atrazine degrading populations after atrazine application enables them to rapidly proliferate once atrazine is again applied.     

生物质炭对污染土壤中的镉生物有效性及阿特拉津消解的影响

通过室内土培实验,研究添加1%在300℃和700℃制备的甘蔗叶生物质炭(BCst-300、BCst-700)和蚕沙生物质炭(BCse-300、BCse-700)对复合污染土壤中镉生物有效性和阿特拉津消解的影响;从土壤pH值、阳离子交换量、有机碳和微生物生物量碳、氮的变化初步探讨添加生物质炭影响土壤镉生物有效性和阿特拉津消解的机理.研究表明,添加生物质炭显著降低了土壤镉的生物有效性,同时加快了阿特拉津的生物降解,培养结束(60 d)时,添加BCst-300、BCst-700、BCse-300和BCse-700土壤中有效镉含量分别比对照降低了23.03%、31.43%、47.84%和38.69%,阿特拉津消解率分别比对照提高了12.45%、7.85%、49.10%和40.76%,其中蚕沙生物质炭对降低土壤镉的有效性以及促进阿特拉津生物降解效果优于甘蔗叶生物质炭,且BCse-300的效果最为显著.相关性分析结果表明,土壤镉的生物有效性与土壤pH值和阳离子交换量呈极显著负相关性,说明提高土壤pH值和阳离子交换量是外源生物质炭降低土壤镉的生物有效性的重要机制;阿特拉津残留量与土壤pH值、阳离子交换量、微生物生物量碳、氮均呈极显著负相关性,表明生物质炭可以通过改变土壤pH值、阳离子交换量、微生物生物量碳、氮从而促进土壤中阿特拉津的降解.     

Effect of soil properties on bioavailability and extractability of phenanthrene and atrazine sequestered in soil

Sixteen soils with markedly different properties were analyzed to determine their porosity in the range of 7 nm-10 microm, cation-exchange capacity (CEC), surface area and clay mineralogy. The extent of sequestration of phenanthrene and atrazine has been shown to differ markedly among these soils. Correlations were sought between soil characteristics and four methods of measuring sequestration. Simple correlation analysis showed that some but not all measures of phenanthrene and atrazine sequestration were highly correlated with organic C content, nanoporosity or CEC but not other properties of the soils. Multiple linear-regression analysis suggested an interaction of organic C content with soil texture, CEC or surface area in determining the extent of atrazine or phenanthrene sequestration. We conclude that organic C content, CEC and other properties of soil may be useful predictors of sequestration of some compounds.     

Temporal variability in dynamic and colloidal metal fractions determined by high resolution in situ measurements in a UK estuary

In recent environmental legislation, such as the Water Framework Directive in the European Union (WFD, 2000/60/EC), the importance of metal speciation and biological availability is acknowledged, although analytical challenges remain. In this study, the Voltammetric In situ Profiler (VIP) was used for high temporal resolution in situ metal speciation measurements in estuarine waters. This instrument simultaneously determines Cd, Cu and Pb species within a size range (ca. <4 nm) that is highly relevant for uptake by organisms. The colloidal metal fraction can be quantified through a combination of VIP measurements and analyses of total dissolved metal concentrations.VIP systems were deployed over tidal cycles in a seasonal study of metal speciation in the Fal Estuary, southwest England. Total dissolved concentrations were 4.97-315 nM Cu, 0.13-8.53 nM Cd and 0.35-5.75 nM Pb. High proportions of Pb (77 ± 17%) and Cu (60 ± 25%) were present as colloids, which constituted a less important fraction for Cd (37 ± 30%). The study elucidated variations in the potentially toxic metal fraction related to river flow, complexation by organic ligands and exchanges between dissolved and colloidal phases and the sediment. Based on published toxicity data, the bioavailable Cu concentrations (1.7-190 nM) in this estuary are likely to severely compromise the ecosystem structure and functioning with respect to species diversity and recruitment of juveniles. The study illustrates the importance of in situ speciation studies at high resolution in pursuit of a better understanding of metal (bio)geochemistry in dynamic coastal systems.     

Accumulation of heavy metals from contaminated soil to plants and evaluation of soil remediation by vermiculite

We evaluated the distribution of 15 metal ions, namely Al, Cd, Cu, Cr, Fe, La, Mn, Ni, Pb, Sc, Ti, V, Y, Zn and Zr, in the soil of a contaminated site in Piedmont (Italy). This area was found to be heavily contaminated with Cu, Cr and Ni. The availability of these metal ions was studied using Tessier’s sequential extraction procedure: the fraction of mobile species, which potentially is the most harmful for the environment, was much higher than that normally present in unpolluted soils. This soil was hence used to evaluate the effectiveness of treatment with vermiculite to reduce the availability of the pollutants to two plants, Lactuca sativa and Spinacia oleracea, by pot experiments. The results indicated that the addition of vermiculite significantly reduces the uptake of metal pollutants by plants, confirming the possibility of using this clay in amendment treatments of metal-contaminated soils. The effect of plant growth on metal fractionation in soils was investigated. Finally, the sum of the metal percentages extracted into the first two fractions of Tessier’s protocol was found to be suitable in predicting the phytoavailability of most of the pollutants present in the investigated soil.     

Assessment of aided phytostabilization of copper-contaminated soil by X-ray absorption spectroscopy and chemical extractions

Field plots were established at a timber treatment site to evaluate remediation of Cu contaminated topsoils with aided phytostabilization. Soil containing 2600 mg kg⁻¹ Cu was amended with a combination of 5 wt% compost and 2 wt% iron grit, and vegetated. Sequential extraction was combined with extended X-ray absorption fine structure (EXAFS) spectroscopy to correlate changes in Cu distribution across five fractions with changes in the predominant Cu compounds two years after treatment in parallel treated and untreated field plots. Exchangeable Cu dominated untreated soil, most likely as Cu(II) species non-specifically bound to natural organic matter. The EXAFS spectroscopic results are consistent with the sequential extraction results, which show a major shift in Cu distribution as a result of soil treatment to the fraction bound to poorly crystalline Fe oxyhydroxides forming binuclear inner-sphere complexes.     

Migration of heavy metals in soil as influenced by compost amendments

Soils contaminated with heavy metals can pose a major risk to freshwaters and food chains. In this study, the success of organic and inorganic intervention strategies to alleviate toxicity in a highly acidic soil heavily contaminated with As, Cu, Pb, and Zn was evaluated over 112 d in a mesocosm trial. Amelioration of metal toxicity was assessed by measuring changes in soil solution chemistry, metal leaching, plant growth, and foliar metal accumulation. Either green waste- or MSW-derived composts increased plant yield and rooting depth, reduced plant metal uptake, and raised the pH and nutrient status of the soil. We conclude that composts are well suited for promoting the re-vegetation of contaminated sites; however, care must be taken to ensure that very short-term leaching pulses of heavy metals induced by compost amendment are not of sufficient magnitude to cause contamination of the wider environment.     

Application of phosphate-solubilizing bacteria for enhancing bioavailability and phytoextraction of cadmium (Cd) from polluted soil

In this study, phosphate-solubilizing bacteria (PSB), Bacillus megaterium, were used to enhance Cd bioavailability and phytoextractability of Cd from contaminated soils. This strain showed a potential for directly solubilizing phosphorous from soils more than 10 folds greater than the control without inoculation. The results of pot experiments revealed that inoculation with B. megaterium significantly increased the extent of Cd accumulation in Brassica juncea and Abutilon theophrasti by two folds relative to the uninoculated control. The maximum Cd concentrations due to inoculation were 1.6 and 1.8 mg Cd g⁻¹ plant for B. juncea and A. theophrasti after 10 wk, respectively. The total biomass of A. theophrasti was not significantly promoted by the inoculation treatment, yet the total biomass of B. juncea increased from 0.087 to 0.448 g. It is also worth to mention that B. juncea predominantly accumulates Cd in its stems (39%) whereas A. theophrasti accumulates it in its leaves (68%) after 10 wk. The change of the Cd speciation indicated that inoculation of B. megaterium as PSB increased the bioavailabilty of Cd and consequently enhanced its uptake by plants. The present study may provide a new insight for improving phytoremediation using PSB in the Cd-contaminated soils.     

Influence of environmental factors on the response of a natural population of Daphnia magna (Crustacea: Cladocera) to spinosad and Bacillus thuringiensis israelensis in Mediterranean coastal wetlands

The present study was undertaken to assess the impact of a candidate mosquito larvicide, spinosad (8, 17 and 33 μg L⁻¹) on a field population of Daphnia magna under natural variations of water temperature and salinity, using Bti (0.16 and 0.50 μL L⁻¹) as the reference larvicide. Microcosms (125 L) were placed in a shallow temporary marsh where D. magna was naturally present. The peak of salinity observed during the 21-day observation period may have been partly responsible for the decrease of daphnid population density in all the microcosms. It is also probably responsible for the absence of recovery in the microcosms treated with spinosad which caused a sharp decrease of D. magna abundance within the first two days following treatment whereas Bti had no effect. These results suggest that it may be difficult for a field population of daphnids to cope simultaneously with natural (water salinity and temperature) and anthropogenic (larvicides) stressors.     

Lactate oxidation in pyrite suspension: a Fenton-like process in situ generating H2O2

Pyrite is a common mineral at many mining sites. In this study, the mineral pyrite was studied as a Fenton-like reagent for environmental concerns. We selected lactate as a model target molecule to evaluate the Fenton-like catalytic efficiency of pyrite upon organic oxidation. A complete set of control experiments in both aerobic and anaerobic atmospheres unequivocally established that the pyrite in aqueous solution could spontaneously in situ generate OH and H₂O₂, serving as a Fenton-like reagent to catalyze the oxidation of lactate to pyruvate with no need for additional H₂O₂. We called it the pyrite-only Fenton-like (PF) reagent. Monitoring concentration changes of lactate and pyruvate with the time indicated that the pyrite mediated the favorable pyruvate formation at pH 4.5, 60 °C, under air atmosphere. The PF reaction could be stimulated by visible light illumination. Under the optimum conditions, up to 50% of lactate was degraded within 10 d. The results suggest that pyrite and its Fenton-like processes may be potentially practical in wastewater treatment.     

Fungal degradation of an acetolactate synthase (ALS) inhibitor pyrazosulfuron-ethyl in soil

Owing to reported phytotoxicity of some sulfonylurea class of herbicides in number of sensitive crops and higher persistence in soil, present study was conducted to isolate and identify pyrazosulfuron-ethyl degrading fungi from soil of rice field. Penicillium chrysogenum and Aspergillus niger, were isolated and identified from rhizospere soil of rice field, as potent pyrazosulfuron-ethyl degrading fungi. Degradation of pyrazosulfuron-ethyl by P. chrysogenum and A. niger, yielded transformation products/metabolites which were identified and characterized by LC/MS/MS. The rate of dissipation of pyrazosulfuron-ethyl was found higher in soil of rice field and soil inoculated with P. chrysogenum. This showed important route of degradation of pyrazosulfuron-ethyl by microbes apart from chemical degradation.     

Disposition of fipronil in rats

In the scientific literature, little attention has been paid to the disposition of fipronil, a phenyl pyrazole insecticide. In this study, the tissue distribution, the metabolic fate, and the elimination of fipronil was investigated in rats using radiolabeled fipronil. When a single oral dose of ¹⁴C-fipronil (10 mg kg⁻¹ b.w.) was given to rats, the proportion of dose eliminated in urine and feces 72 h after dosing was ca 4% for each route. At the end of the experiment the highest levels of radioactivity were found in adipose tissue and adrenals.     

The exposition of a calcareous Mediterranean soil to toxic concentrations of Cr, Cd and Pb produces changes in the microbiota mainly related to differential metal bioavailability

The involvement of the bacterial community of an agricultural Mediterranean calcareous soil in relation to several heavy metals has been studied in microcosms under controlled laboratory conditions. Soil samples were artificially polluted with Cr(VI), Cd(II) and Pb(II) at concentrations ranging from 0.1 to 5000 mg kg⁻¹ and incubated along 28 d. The lowest concentrations with significant effects in soil respirometry were 10 mg kg⁻¹ Cr and 1000 mg kg⁻¹ Cd and Pb. However, only treatments showing more than 40% inhibition of respirometric activity led to significant changes in bacterial composition, as indicated by PCR-DGGE analyses. Presumable Cr- and Cd-resistant bacteria were detected in polluted microcosms, but development of the microbiota was severely impaired at the highest amendments of both metals. Results also showed that bioavailability is an important factor determining the impact of the heavy metals assayed, and even an inverted potential toxicity ranking could be achieved if their soluble fraction is considered instead of the total concentration. Moreover, multiresistant bacteria were isolated from Cr-polluted soil microcosms, some of them showing the capacity to reduce Cr(VI) concentrations between 26% and 84% of the initial value. Potentially useful strains for bioremediation were related to Arthrobacter crystallopoietes, Stenotrophomonas maltophilia and several species of Bacillus.     

Bioremediation of tributyltin contaminated sediment: degradation enhancement and improvement of bioavailability to promote treatment processes

Bioremediation of tributyltin (TBT) contaminated sediment was studied and degradation enhancement and improvement of bioavailability were also investigated. In TBT spiked sediment, the half-life of TBT in the control sample, representing natural attenuation, was 578 d indicating its persistence. In the stimulated sample (pH 7.5, aeration and incubated at 28 °C), the half-life was significantly reduced to 11 d. Further stimulation by nutrient addition (succinate, glycerol and l-arginine) or inoculation with Enterobacter cloacae (∼10⁷ viable cells g⁻¹ of sediment) resulted in half-life reduction to 9 and 10 d, respectively. In non-spiked sediment, the indigenous microorganisms were able to degrade aged TBT, but the extended period of contamination decreased the degradation efficiency. To improve bioavailability, addition of surfactant, adjustment of salinity and sonication were studied. The highest percentage solubilisation of TBT in water was obtained by adjusting salinity to 20 psu, which increased the solubility of TBT from 13% to 33%. Half-lives after bioavailability was improved were 5, 4 and 4 d for stimulation, stimulation w/nutrient addition and stimulation w/inoculation, respectively. However, natural attenuation in the control sample was not enhanced. The results show that providing suitable conditions is important in enhancing TBT biodegradation, and bioavailability improvement additionally increased the rate and degraded amount of TBT. Unfortunately, nutrient addition and inoculation of the degrader did not enhance the degradation appreciably.     

农药在土壤上吸着/解吸及其对生物利用率影响的研究进展

正确预测有机污染物在环境中的归宿 ,在很大程度上依赖对它们的吸着 -解吸动力学行为的认识。自 2 0世纪 80年代起 ,吸着 -解吸动力学逐渐受到重视。本文介绍了国内外有关农药在土壤 /沉积物上的吸着 -解吸动力学和吸着 -解吸对土壤有机污染物的生物利用率的影响等方面的近期研究成果 ,着重从实验方法、模型、机理等方面进行了详细的综述     

人工纳米颗粒输入对稻田土壤Cd形态转化及生物有效性的影响

进入农田土壤的人工纳米颗粒对土壤中重金属迁移转化及毒性的影响仍不明确。通过模拟稻田淹水-落干过程,研究了二氧化钛（TiO2-NPs）、氧化锌（ZnO-NPs）和多壁碳纳米管（MWCNTs）3种典型人工纳米颗粒对水稻土中重金属Cd赋存形态及生物有效性的影响。结果表明,3种纳米颗粒的添加均引起了土壤pH的增加;TiO2-NPs和ZnO-NPs添加能够显著降低土壤中酸可提取态Cd含量;ZnO-NPs的添加对土壤中铁锰氧化物结合态和有机结合态Cd的含量也有明显降低,但不同浓度处理间Cd含量并无显著差异;MWCNTs对土壤Cd形态转化无显著影响。与对照处理相比,添加TiO2-NPs的处理土壤中,CaCl2和DTPA提取态Cd含量分别降低了13.9%~17.5%和5.4%~8.9%,降幅均与TiO2-NPs添加浓度成正比。添加ZnO-NPs的土壤中,DTPA提取态Cd的含量降幅在8.4%~18.7%之间,降低幅度与ZnO-NPs添加浓度成反比。     

Isonychia spp. and macroinvertebrate community responses to stressors in streams utilizing the benthic in situ toxicity identification evaluation (BiTIE) method

Exposures of caged organisms in situ have proven to be a useful way to improve exposure realism and link to stressor effects in aquatic assessments of hazard or risk. A novel cage system, the benthic in situ toxicity identification evaluation (BiTIE), was developed for benthic macroinvertebrates (surrogate species, resident populations and communities) to separate low and high flow effects, and major chemical classes of stressors in streams. Three resin types were used to separate the chemical stressors in the streams Honey Creek and Little Beavercreek, Ohio, USA: Dowex Optipore (non-polar organics), zeolite (ammonia), and polywool (control). Isonychia spp. sensitivity was compared to Chironomus tentans, and no significant differences were found (p>0.05). Isonychia spp. growth (length) showed a stressor response in the zeolite treatments, and community testing revealed improved metric responses in the Dowex treatments. The BiTIE chamber system demonstrated stressor-response relationships using sublethal and multimetric endpoints.     

Copper availability and bioavailability are controlled by rhizosphere pH in rape grown in an acidic Cu-contaminated soil

We evaluated how root-induced changes in rhizosphere pH varied and interacted with Cu availability and bioavailability in an acidic soil. Rape was grown on a Cu-contaminated acidic soil, which had been limed at 10 rates. Soil Cu bioavailability was not influenced by liming. However, liming significantly decreased CaCl₂-extracted Cu for pH between 3.7 and 5.1. Little effect was found for pH above 5.1. For soil pH < 4.4, CaCl₂-Cu contents were smaller in rhizosphere than uncropped soil. Rhizosphere alkalisation occurred at pH < 4.8, while acidification occurred at greater pH. This explained the changes of CaCl₂-Cu in the rhizosphere at low pH and the absence of pH dependency of Cu bioavailability to rape. In addition, apoplastic Cu in roots increased with increasing soil pH, most probably as a result of increased dissociation and affinity of cell wall compounds for Cu.     

Deltamethrin degradation and effects on soil microbial activity

Deltamethrin [(S)-cyano-3-phenoxybenzyl-cis-(1R,3R)-2,2-dimethyl) cyclo–propane carboxylate),1] labelled at gem-dimethyl groups of the cyclopropane ring was applied on two Egyptian soils at a level of 10 mg/kg soil for a laboratory incubation experiment under aerobic and anaerobic conditions. A steady decrease of soil extractable¹⁴C-residues, accompanied by a corresponding increase of non- extractable bound ¹⁴C-residues was observed over a 90-day incubation period. The percentage of evolved ¹⁴CO₂ increased with time under aerobic and anaerobic conditions in both soils. The effect of deltamethrin on soil microorganisms as well as the counter effect of microorganisms on the insecticide was also investigated. As the incubation period increased, the inhibitory effect of the insecticide on the microorganisms decreased and the evolution of carbon dioxide depended on the applied dose. The nature of soil methanol soluble residues was determined by chromatographic analysis which revealed the presence of the parent insecticide as the main product in addition to four metabolites: 3-(2′,2′-dibromovinyl)-2,2-dimethylcyclopropane carboxylic acid (II); 3-phenoxybenzaldehyde (III); 3-phenoxybenzoic acid (IV); 3-phenoxybenzyl alcohol (V).