A correlation between the fate and non-extractable residue formation of 14C-metalaxyl and enzymatic activities in soil

Extracellular, oxidative soil enzymes like monophenol oxidases and peroxidases play an important role in transformation of xenobiotics and the formation of organic matter in soil. Additionally, these enzymes may be involved in the formation of non-extractable residues (NERs) of xenobiotics during humification processes. To examine this correlation, the fate of the fungicide ¹⁴C metalaxyl in soil samples from Ultuna (Sweden) was studied. Using different soil sterilization techniques, it was possible to differentiate between free, immobilized, and abiotic (“pseudoenzyme”-like) oxidative activities. A correlation between the formation of metalaxyl NER and soil organic matter content, biotic activities, as well as extracellular phenoloxidase and peroxidase activities in the bulk soil and its particle size fractions was determined. Extracellular soil-bound enzymes were involved in NER formation (up to 8% of applied radioactivity after 92 days) of the fungicide independently from the presence of living microbes and different distributions of the NER in the soil humic subfractions.     

小氮肥厂的三废及其治理

论述了小氮肥厂生产中废水、废气和废渣和产生及其废水，废气的治理方法与效果。介绍了利用废渣制砖和水泥的技术。     

Biomethanation of plant materials and agricultural residues using dung samples as wild population of microbes and also with isolated methanogens

Recycling of plant materials and agricultural residues for biomethanation was attempted in vials. The methanogenic activities of certain sewage samples have also been tested. Both sterilized and non-sterilized biomasses were used. Biomethanation was carried out with dung samples (cow, goat, buffalo, piggery wastes and poultry wash) as wild populations of microbes and in combination with other microbial isolates (isolated in the laboratory).Biomethanation had been observed to be good in most cases and particularly with the sterilized biomass. Mixed inoculum (dung samples and poultry wash) was found to be best for biomethanation. Of the microbe isolates, isolates from buffalo, pig and paper mill wastes appear to be most effective. Pretreated sawdust and rice straw were found to be good subtrates for biomethanation. Of the different plant biomass used Spirogyra (algae), Ipomea and water hyacinth were most effective whereas Jatropa gossypifolia and Parthenium sp. were the least effective. Biomethanation of Spirogyra was carried out both in anoxic and oxic conditions. Though methane production decreased enormously under oxic conditions, definite methane production continued indicating that the biomethanation process is not exclusively anoxic. Similarly, biomethanation of sewage samples from different sewage treatment plants were carried out with and without isolated methanogens and methane production was found to be moderate.     

Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in soil

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (CfP) was studied for 28 days in lab assays using a soil from Germany (A_p horizon, silt loam, and cambisol). Mineralization amounted to 12.40% of applied ¹⁴C after 28 days showing a distinct lag phase until day 7 of incubation. Portions of radioactivity extractable by means of 0.01 M CaCl₂ solution (bioavailable fraction) decreased rapidly and were 4.41% after 28 days. Even immediately after application, only 57.31% were extracted with the aqueous solvent. Subsequent extraction using accelerated solvent extraction (ASE; acetonitrile/water 4:1, v/v) released 39.91% of applied ¹⁴C with day 0 and 26.16% with day 28 of incubation from the samples. Non-extractable portions of radioactivity thus, increased with time amounting to 11.99% (day 0) and 65.00% (day 28). A remarkable increase was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with general microbial activity as determined by DMSO reduction. Analysis of the CaCl₂ and ASE extracts by radio-TLC, radio-HPLC and GC/MS revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed; DT₅₀ values (based on radio-TLC detection of the parent compound) were far below 1 day (CfP) and about 7 days (Cf). TLC analysis pointed to 2-(4-hydroxyphenoxy)-propionic acid as further metabolite. Due to fractionation of non-extractable residues, most of the ¹⁴C was associated with fulvic and humic acids, portions in humin fractions and non-humics were moderate and low, respectively. Using a special strategy, which included pre-incubation of the soil with CfP and then mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the soil examined. The microorganism grew using CfP as sole carbon source with concomitant evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and by 16S rDNA sequence analysis. The sequence exhibited high similarity with that of Rhodococcus wratislaviensis (99.56%; DSM 44107, NCIMB 13082).     

Fate and availability of glyphosate and AMPA in agricultural soil

The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT₅₀ values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, ¹⁴C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 ± 0.002% and 0.005 ± 0.001% of the applied radioactivity was measured in rape and barley, respectively.     

Validation of QuEChERS-based method for determination of flusilazole residues in grape by high-performance liquid chromatography with photodiode array detector

A high-performance liquid chromatography with photodiode array detector analytical method was developed to determine the residue levels of flusilazole in grape and investigate the dissipation pattern and safety. The results showed that the mean recoveries were in the range of 86%–90%. Limits of detection and quantification were 0.008 and 0.02 mg/kg, respectively. The residue levels of flusilazole were best described by first-order rate kinetics and with half-lives ranging from 4.2 days (recommended dose) to 4.6 days (double the recommended dose). In conclusion, flusilazole at the recommended or even at double the recommended doses does not pose any apparent hazards to consumers.     

Experimental investigation of the efficiency of triple rinsing of agricultural containers regarding their characterization as non-hazardous wastes

The efficiency of water rinsing for removing fenthion from non-combustible used pesticide containers was investigated. Four hundred empty containers from four olive oil producing areas in Greece were studied. Following triple rinsing cleaning procedures, the amount of fenthion retained in the container ranged from 0.01% to 0.1% w/w of its initial concentration. Extraction was accomplished with acetone, and the extracts were analyzed with a capillary gas chromatographic system coupled with flame ionization detector. The results obtained showed that triple rinsing is an effective procedure for removing fenthion from used pesticide containers, since the remaining pesticide concentration was below the legislated threshold value. Consequently, the containers can be handled as non-hazardous solid wastes.     

湘潭锰矿重金属环境安全及植物耐性研究

采集了湘潭锰矿红旗分矿开采区、沙圹村恢复区的代表性当季蔬菜(莴笋叶Fruticicolidae、小白菜Brassica chinensis、香葱Allium schoenoprasum、空心菜Ipomoea aquatica)、废弃区的优势植物(商陆Phytolacca acinosa、野茼蒿Crassocephalum crepidioides、苍耳Xanthium sibiricum)和3个研究区的土壤,通过原子吸收分光光度法分析了Mn、Pb、Zn含量。结果表明:开采区蔬菜Mn含量(8.3~84.5 mg/kg)明显高于恢复区(2.7~55.6 mg/kg),开采区和恢复区蔬菜都明显受到Pb污染(0.6~33mg/kg),蔬菜Zn含量范围为1.9~6.5mg/kg;3个研究区域土壤重金属均明显超标,最严重的是Pb污染(1 993.5~2 213.5mg/kg)。商陆、野茼蒿和苍耳中重金属含量差异较大,对重金属的耐性强,其中商陆表现出最好的耐性与长势。研究结论对锰矿土地合理利用以及矿区土壤重金属治理提供一定的科学依据。     

设施菜地土壤重金属累积及影响因素研究

为了解设施菜地土壤重金属累积规律及影响因,通过在全国8个省具有代表性的设施蔬菜产区采集土壤和肥料样品,系统研究了设施栽培年限、肥料施用、土壤性质对设施菜地土壤重金属Cu、Zn、Cd累积量及活度的影响.结果表明:与露天栽培相比,设施条件下随着栽培年限的延长,土壤Cu、Zn和Cd的全量和有效态浓度均呈明显的累积趋势,栽培年限>15a时的设施土壤Cu、Zn和Cd的全量和有效态浓度分别是露天栽培土壤的1.57、2.16、1.67、3.28、1.96、2.00倍.Pearson分析表明设施菜地土壤Cu、Zn、Cd均与土壤SOM呈极显著相关,说明其在来源上较强的相似性,进一步对设施栽培土壤主要投入品中Cu、Zn、Cd含量分析表明,猪粪、商品有机肥及土壤调理剂中Cu、Zn均超过了100mg/kg,Cd超过了1.0mg/kg,且投入量较大,是设施栽培土壤中Cu、Zn、Cd的主要贡献者,而秸秆和部分化肥(如尿素、硫酸钾)中的Cu、Zn、Cd含量均极低,对设施栽培土壤累积贡献微乎其微.pH值和CEC是影响Cu、Zn、Cd在土壤中累积活度的关键因素,其中随着pH值的升高土壤Cu活度表现了先升高后下降的趋势,而土壤Cd活度则表现了持续下降的趋势,仅在pH<6.26时达到了显著相关水平;土壤CEC的升高对土壤Cu活度表现了先下降后升高再下降的趋势,土壤Cd活度表现了先升高后缓慢下降再升高的趋势,而土壤Zn活度仅在CEC<5.83时随着CEC升高表现下降显著线性相关趋势.因此,防止设施栽培土壤Cu、Zn、Cd的累积与污染,选择重金属含量低的肥料和调控土壤理化特性(尤其是pH值、CEC)则是缓解设施栽培土壤重金属累积速率进而确保蔬菜质量安全的有效途径.     

Biofilm-overproducing Bacillus subtilis B12ΔYwcc decreases Cd uptake in Chinese cabbage through increasing Cd-immobilizing related gene abundance and root surface colonization

Biofilm-producing bacteria can decrease Cd uptake in vegetables, but mechanisms underlying this effect are poorly characterized. In this study, two mutant strains B12ΔYwcc and B12ΔSlrR were constructed from a biofilm-producing Bacillus subtilis strain B12. Then, the impacts of strain B12 and its high biofilm-producing mutant strain B12ΔYwcc and low biofilm-producing mutant strain B12ΔSlrR on Cd availability and uptake in Chinese cabbage and the related mechanisms were investigated in the Cd-polluted soil. Strain B12 and its mutants B12ΔYwcc and B12ΔSlrR increased the dry biomasses of edible tissues by 54%–130% compared with the controls. Strain B12 and its mutant B12ΔYwcc reduced the soil available Cd content by 36%–50% and root and edible tissue Cd contents by 23%–50% compared with the controls. Furthermore, the mutant strain B12ΔYwcc reduced the edible tissue Cd content by 40% and increased the polysaccharide content by 23%, invertase activity by 139%, and gene copies of the cumA by 4.5-fold, epsA by 7.1-fold, and cadA by 4.3-fold, which were involved in Cd adsorption in the rhizosphere soils, respectively, compared with strain B12. The polysaccharide content and cumA, epsA, and cadA gene copy numbers showed significantly reverse correlations with the available Cd content. Notably, the mutant strain B12ΔYwcc showed better ability to colonize the vegetable root surface than strain B12. These findings demonstrated that the biofilm-overproducing mutant strain B12ΔYwcc increased the polysaccharide production and Cd-immobilizing related cumA, epsA, and cadA gene copies, resulting in lower Cd availability and accumulation in Chinese cabbage in the Cd-polluted soil.