NaCl-丙醇双水相体系分离富集草甘膦生产废水中草甘膦铵盐

利用草甘膦生产废水中接近饱和的NaC1与丙醇形成的双水相体系分离富集废水中部分残留的草甘膦铵盐,达到了资源循环利用和资源的高效回收.通过分析表面活性剂种类及用量,pH,丙醇质量分数和NaC1质量分数4个因素确定了最佳萃取条件.最后对该方案进行仿真验证,表明利用该方案对实际废水的处理比较理想,实现了90.7％的高回收率,完全符合工业化要求.     

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. DT(50) 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, (14)C-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.     

Interactions between plant and rhizosphere microbial communities in a metalliferous soil

In the present work, the relationships between plant consortia, consisting of 1-4 metallicolous pseudometallophytes with different metal-tolerance strategies (Thlaspi caerulescens: hyperaccumulator; Jasione montana: accumulator; Rumex acetosa: indicator; Festuca rubra: excluder), and their rhizosphere microbial communities were studied in a mine soil polluted with high levels of Cd, Pb and Zn. Physiological response and phytoremediation potential of the studied pseudometallophytes were also investigated. The studied metallicolous populations are tolerant to metal pollution and offer potential for the development of phytoextraction and phytostabilization technologies. T. caerulescens appears very tolerant to metal stress and most suitable for metal phytoextraction; the other three species enhance soil functionality. Soil microbial properties had a stronger effect on plant biomass rather than the other way around (35.2% versus 14.9%). An ecological understanding of how contaminants, ecosystem functions and biological communities interact in the long-term is needed for proper management of these fragile metalliferous ecosystems.     

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.     

Use of selected autochthonous soil bacteria to enhanced degradation of hydrocarbons in soil

A mixed population of soil hydrocarbon degrading bacteria was used to accelerate the biodegradation of a petrochemical waste. An aromatic hydrocarbon storage tank bottom was mixed with soil (10% w/w). After a month 43% of the hydrocarbons were degraded in uninoculated and in fertilized soil, while 65% were degraded in inoculated soil. Nutrient supplemented vermiculite seems to be a good possibility to produce effective hydrocarbon degrading inoculants.     

Effect of manure on glyphosate and trifluralin mineralization in soil

Manure additions to soil may alter soil chemical, physical, and biological characteristics, and thereby change pesticide fate processes in soil. This is the first study to examine the impact of liquid hog manure amendments on glyphosate and trifluralin mineralization in soil. Experiments were conducted in soil microcosms in the laboratory for a total of 332 (glyphosate) and 430 (trifluralin) days. The rate and amount of mineralization of both glyphosate and trifluralin were significantly influenced by the additions of fresh manure to soil in the laboratory and by the history of manure applications in the field. However, the maximum difference in herbicide mineralization between soils that were free of manure application and those amended with manure in the field or in the laboratory was only 6.1% and 7.3% of that initially applied, for trifluralin and glyphosate, respectively. Therefore, we conclude that liquid hog manure application to soil will have no significant effect on the mineralization of glyphosate and trifluralin under field conditions.     

Interactions between earthworms and arsenic in the soil environment: a review

Chemical pollution of the environment has become a major source of concern. In particular, many studies have investigated the impact of pollution on biota in the environment. Studies on metalliferous contaminated mine spoil wastes have shown that some soil organisms have the capability to become resistant to metal/metalloid toxicity. Earthworms are known to inhabit arsenic-rich metalliferous soils and, due to their intimate contact with the soil, in both the solid and aqueous phases, are likely to accumulate contaminants present in mine spoil. Earthworms that inhabit metalliferous contaminated soils must have developed mechanisms of resistance to the toxins found in these soils. The mechanisms of resistance are not fully understood; they may involve physiological adaptation (acclimation) or be genetic. This review discusses the relationships between earthworms and arsenic-rich mine spoil wastes, looking critically at resistance and possible mechanisms of resistance, in relation to soil edaphic factors and possible trophic transfer routes.     

水溶液中典型混凝剂与分散染料的直接反应机理

为了深入揭示分散染料的混凝去除机理,选择AlCl₃、FeCl₃、CaCl₂作为混凝剂,分散红玉S-2GFL、分散黄棕S-2RFL、分散蓝BBLS作为去除对象,在不投加其他任何颗粒物的条件下,通过测定染料粒径、Zeta电位和改变混凝剂投加顺序等方式,探究了分散染料与混凝剂的直接反应机理。结果表明：3种混凝剂均可使染料颗粒表面电位接近0 mV,此时AlCl₃和FeCl₃对染料的去除率超过60%,但 CaCl₂对染料去除率仅为15%左右,说明此体系下电中和不是染料被直接混凝沉淀去除的单一主导内因;投加3种混凝剂后染料粒径均明显增大,说明混凝剂水解产物与分散染料结合是导致染料被去除的重要前提之一;通过改变混凝剂投加顺序发现,对于同种染料,先投加混凝剂的去除率远低于后投加混凝剂的去除率,说明混凝剂水解终产物的物理吸附不应是染料与混凝剂结合的主因;沉淀物的傅里叶红外图谱显示,在580 cm⁻¹和475 cm⁻¹处分别检测到Al—O和Fe—O的特征峰,且XRD结果进一步显示AlCl₃、FeCl₃与染料结合形成了新的共聚物,这表明选用的无机混凝剂去除这3种分散染料的主导机理应是特定的化学结合作用。以上研究结果对丰富混凝去除相关染料的作用机理和开发相关复合药剂具有一定的理论指导意义。     

Biodegradation of the herbicide glyphosate by filamentous fungi in platform shaker and batch bioreactor

The biodegradation conducted by microorganisms on herbicide glyphosate (N-phosphonomethylglycine) was investigated. Five strains of filamentous fungi belonging to the Fusarium genre were grown on Czapeck medium without phosphorous and supplemented with the addition of glyphosate. The assays were conducted to determine the ability of use as a phosphorous source, the inhibition caused by presence of herbicide, and the biodegradation in shaker and bioreactor by Fusarium strains. It was observed that the herbicide did not show any negative effect on microrganisms by quantity of the biomass. Among the strains tested, no inhibition was noted by the addition of glyphosate even at a high concentration. All strains studied were able to biodegrade it and use the herbicide as a phosphorous source. The formation of consortium was not better than the strains tested in pure culture. The biodegradation in the bioreactor was better than in the shaker. However, there wasn't any influence on biodegradation rate by changing the amount of oxygen in the system.     

Biodegradation of the herbicide glyphosate by filamentous fungi in platform shaker and batch bioreactor

The biodegradation conducted by microorganisms on herbicide glyphosate (N-phosphonomethylglycine) was investigated. Five strains of filamentous fungi belonging to the Fusarium genre were grown on Czapeck medium without phosphorous and supplemented with the addition of glyphosate. The assays were conducted to determine the ability of use as a phosphorous source, the inhibition caused by presence of herbicide, and the biodegradation in shaker and bioreactor by Fusarium strains. It was observed that the herbicide did not show any negative effect on microrganisms by quantity of the biomass. Among the strains tested, no inhibition was noted by the addition of glyphosate even at a high concentration. All strains studied were able to biodegrade it and use the herbicide as a phosphorous source. The formation of consortium was not better than the strains tested in pure culture. The biodegradation in the bioreactor was better than in the shaker. However, there wasn't any influence on biodegradation rate by changing the amount of oxygen in the system.     

Isomerization of beta-HCH in aqueous solution

beta-HCH was shaken with distilled water at 25 +/- 1 degree C for different time intervals and filtered. The ether extract of the filtrate on analysis by gas liquid chromatography showed the presence of four isomers, alpha, beta, gamma and delta, besides other compounds, thereby indicating isomerization of the beta-isomer in aqueous solution. Further, the ether extract, when dried and dissolved in acetone, showed high toxicity to mosquito larvae, flour beetle larvae and house-flies thereby indicating conversion of the inert beta-isomer to more toxic forms corroborating GLC analysis. Acetone solution of pure beta-HCH was found nontoxic against the insects tested.     

Chemistry of methylmercurials in aqueous solution

The kinetics of acid cleavage of dimethylmercury (DMM) was studied in aqueous solution. At 25°C and pH 5, DMM has an acidolysis half-life of about 33 years. Cleavage of dimethylmercury by mercuric species is pH-dependent and is slow at the concentrations of mercuric species in solution in the aquatic environment. Dimethylmercury and methylmercuric ion do not undergo sunlight photodegradation. The evaporative loss of dimethylmercury from water can be compared with oxygen diffusion based on the ratio of transfer constants.     

Hydrolysis and photolysis of oxytetracycline in aqueous solution

Oxytetracycline ((2Z,4S,4aR,5S,5aR,6S,12aS)-2-(amino-hydroxy-methylidene)-4-dimethylamino-5,6,10,11,12a-pentahydroxy-6-methyl-4,4a,5,5a-tetrahydrotetracene-1,3,12-trione) is a member of tetracycline antibiotics family and is widely administered to farm animals for the purpose of therapeutical treatment and health protection. Increasing attention has been paid to the environmental fate of oxytetracycline and other veterinary antibiotics with the occurrence of these antibiotics in the environment. The hydrolysis and photolysis degradation of oxytetracycline was investigated in this study. Oxytetracycline hydrolysis was found to obey the first-order model and similar rate constant values ranging from 0.094 ± 0.001 to 0.106 ± 0.003 day^{? 1} were obtained at different initial concentration ranging from 10 to 230 μ M. Solution pH and temperature were shown to have remarked effects on oxytetracycline hydrolysis. The hydrolysis in pH neutral solution appeared to be much faster than in both acidic and alkaline solutions. Oxytetracycline half-life decreased from 1.2 × 10² to 0.15 day with the increasing temperature from 4 ± 0.8 to 60 ± 1°C. The presence of Ca^{2 +} made oxytetracycline hydrolytic degradation kinetics deviate from the simple first-order model to the availability-adjusted first-order model and greatly slowed down the hydrolysis. Oxytetracycline photolysis was found to be very fast with a degradation rate constant at 3.61 ± 0.06 day^{? 1}, which is comparable to that of hydrolysis at 60°C. The presence of Ca^{2 +} accelerated oxytetracycline photolysis, implying that oxytetracycline become more vulnerable to sunlight irradiation after chelating with Ca^{2 +}. The photolysis may be the dominant degradation pathway of oxytetracycline in shallow transparent water environment.     

UV及UV/US降解对二氯苯水溶液的研究

使用紫外光（UV）和超声波（US）降解水溶液中的对二氯苯（p-DCB）。考察了p-DCB初始浓度,初始pH、腐殖酸和H2O2的存在对p-DCB光解的影响。结果表明,较低的初始浓度或弱酸性pH有利于p-DCB降解。溶液中存在20 mg/L的腐殖酸可使p-DCB的反应速率常数提高32.6%。加入氧化剂H2O20=0.1 mmol/L,［H2O20=0.1 mmol/L,pH0=5.8,反应180 min条件下,p-DCB的降解率为95.5%。超声波对p-DCB的降解速率（14.6×10-3/min）大约是紫外光（4.3×10-3/min）的3.4倍,紫外光 超声波耦合时的降解速率（20.6×10-3/min）大于两者单独降解速率的加合。在各种实验条件下,p-DCB的降解均遵循表观一级动力学。     

超声波降解四环素类抗生素废水

采用超声波降解模拟废水中四环素类抗生素(TCs):土霉素(OTC)、四环素(TC)和金霉素(CTC),考查废水初始浓度、初始pH、超声波输入功率密度、曝气量和自由基清除剂(正丁醇)对降解效率的影响。结果表明,超声波可以快速高效地降解废水中的TCs,CTC最易被降解,TC和OTC次之;在OTC、TC和CTC初始浓度0.25 mg/L,初始pH=8.2,声功率密度1.2 W/mL,气水体积比30∶1的条件下,超声波辐照20 min后去除率分别达到76.8%、84.0%和94.4%。在实验研究条件下,TCs去除率均随初始浓度(0.25~2.00 mg/L)的增大而降低,但总去除浓度升高;碱性条件有利于TCs降解,去除率随初始pH(6~11)升高而升高;功率密度(0.24~1.96 W/mL)越高,TCs去除率也越高;曝气后TCs的去除率明显升高,随着气水比(10∶1~60∶1)的增大,去除率逐渐上升;正丁醇有效抑制TCs超声波降解,可推断TCs主要降解途径为自由基氧化。TCs超声波降解过程符合伪一级动力学反应特征。     

Biodegradation of fluoranthene by soil fungi

A selection of 39 strains of micromycetes known as good degraders of polychlorinated aromatic compounds, mostly isolated from soil and belonging to various taxonomic groups, have been investigated for fluoranthene degradation. Toxicity assays, first evaluated on solid medium MEA, have not shown any toxicity of fluoranthene (1-100 mg.L-1) towards fungi. Whereas, consumption assays on a solid synthetic medium showed a toxicity at 100 mg.L-1. The degradation of fluoranthene (10 mg.L-1) was then investigated in a liquid synthetic medium for 4 days and evaluated by HPLC. Among the 39 strains tested, 18 degraded fluoranthene at 60% or more. Zygomycetes appeared to be the most efficient group (mean degradation: 90%). Among 18 performant strains, 10 had not yet been reported in the literature: Sporormiella australis, Cryptococcus albidus, Cicinobolus cesatii, Pestalotia palmarum, beauveria alba, Aspergillus terreus. Cunninghamella blakesleeana, C. echinulata, Mortierella ramanniana and Rhizopus arrhizus. Fluoranthene adsorption on fungi was very low for the strains which degraded well fluoranthene (mean adsorption: 4%). Whereas, some strains adsorbed it much more such as Colletotrichum dematium (47%) and Penicillium italicum (43%).     

Photochemical behaviour of carbendazim in aqueous solution

To elucidate the photochemical behaviour of carbendazim (or MBC) in superficial waters, photolysis studies have been carried out in aqueous solutions at several pH using a UV light source (high pressure mercury arc lamp) or a solar light simulator (xenon arc lamp). The kinetics of photodecomposition of carbendazim was determined using HPLC-DAD and the identification of photoproducts was carried out with HPLC-MS (ESI negative and positive mode). According to the experimental results carbendazim is a rather stable molecule in the dark or in environmental conditions. The pH influence of the environmental medium on the photodegradation rate has been confirmed. The photochemical process can be considerably accelerated in alkaline solutions using HPK-quartz irradiation (quantum efficiency at pH 9 phi = 3.1 x 10(-3) degraded molecule per absorbed photon) while the photodegradation is not as efficient under a simulated sun irradiation (quantum efficiency in the suntest phi = 10(-4) at pH 7). Three photoproducts have been tentatively identified in pure water: 2-aminobenzimidazole, benzimidazole isocyanate and monocarbomethoxy-guanidine (issued from the cleavage of the benzimidazole ring). The last one seems very stable and could be accumulated in the environment.     

磺胺二甲嘧啶在水溶液中的光化学降解

研究了4种光源(高压汞灯、氙灯、紫外灯和太阳光)下磺胺二甲嘧啶(SM2)的光化学降解(简写为光解)动力学.结果表明:(1)4种光源下,SM2的光解符合一级动力学方程,光解速率常数依次为紫外灯＞高压汞灯＞氙灯＞太阳光.(2)在相同条件下,SM2的光解速率常数随着初始浓度的增加而减小.(3)SM2在不同pH的缓冲溶液下的光...     

Abiotic degradation of imazethapyr in aqueous solution

The photodegradation of imazethapyr [2-(4,5-dihydro-4-méthyl-4-(1-méthylethyl)-5-oxo-1H-imidazol-2-yl)-5-ethyl-3-pyridinecarboxylic acid] in aqueous solution in the presence of titranium dioxide (TiO2) and humic acids (HA) at different ratios of herbicide/TiO2 and herbicide/humic acids was studied at pH 7.0. Irradiation was carried out with polychromatic light using Heraeus apparatus equipped with xenon lamp to simulate sunlight having a spectral energy distribution similar to solar irradiation (>290 nm). The concentration of remaining herbicide was followed using a High Pressure Liquid Chromatograph (HPLC) equipped with UV detector at 230 nm. In pure aqueous solution imazethapyr degrades slowly and the photodegradation leads to the formation of two metabolites labelled A and B. The presence of TiO2 caused enhancement of the degradation rate. The presence of HA induced an increase of the photodegradation of the pesticide with respect to pure aqueous solution.     

Environmental fate of glyphosate and aminomethylphosphonic acid in surface waters and soil of agricultural basins

Argentinian agricultural production is fundamentally based on a technological package that combines no-till and glyphosate in the cultivation of transgenic crops. Transgenic crops (soybean, maize and cotton) occupy 23 million hectares. This means that glyphosate is the most employed herbicide in the country, where 180–200 million liters are applied every year.