Algal degradation of a known endocrine disrupting insecticide, alpha-endosulfan, and its metabolite, endosulfan sulfate, in liquid medium and soil

The role of algae in the persistence, transformation, and bioremediation of two endocrine disrupting chemicals, alpha-endosulfan (a cyclodiene insecticide) and its oxidation product endosulfan sulfate, in soil (incubated under light or in darkness) and a liquid medium was examined. Incubation of soil under light dramatically decreased the persistence of alpha-endosulfan and enhanced its transformation to endosulfan sulfate, over that of dark-incubated soil samples, under both nonflooded and flooded conditions. This enhanced degradation of soil-applied alpha-endosulfan was associated with profuse growth of indigenous phototrophic organisms such as algae in soil incubated under light. Inoculation of soil with green algae, Chlorococcum sp. or Scenedesmus sp., further enhanced the degradation of alpha-endosulfan. The role of algae in alpha-endosulfan degradation was convincingly demonstrated when these algae degraded alpha-endosulfan to endosulfan sulfate, the major metabolite, and endosulfan ether, a minor metabolite, in a defined liquid medium. When a high density of the algal inoculum was used, both metabolites appeared to undergo further degradation as evident from their accumulation only in small amounts and the appearance of an endosulfan-derived aldehyde. Interestingly, beta-endosulfan was detected during degradation of alpha-endosulfan by high density algal cultures. These algae were also capable of degrading endosulfan sulfate but to a lesser extent than alpha-endosulfan. Evidence suggested that both alpha-endosulfan and endosulfan sulfate were immediately sorbed by the algae from the medium, which then effected their degradation. Biosorption, coupled with their biotransformation ability, especially at a high inoculum density, makes algae effective candidates for remediation of alpha-endosulfan-polluted environments.     

短时间高温对蓝藻Anabaena 7120固氮酶活性的影响

蓝藻Anabaena 7120经短时间高温处理后,其固氮酶活性、吸氢和放氧活性均下降,固氮酶活性对氧和pH变化的敏感性增大,受分子氢支持和一氧化碳抑制的程度增高。光合抑制剂或弱光加剧短时间高温处理对蓝藻固氮酶活性的抑制程度。     

Isolation of a soil bacterium capable of biodegradation and detoxification of endosulfan and endosulfan sulfate

Endosulfan, an endocrine disrupting chemical, is a widely used cyclodiene organochlorine pesticide worldwide, and it blocks neuronal GABA(A)-gated chloride channels in mammals and aquatic organisms. Endosulfan and its metabolites, such as endosulfan sulfate, are persistent in environments and are considered as toxic chemicals. For bioremediation of endosulfan, in this study, an attempt was made to isolate an endosulfan and endosulfan sulfate degrading bacterium from endosulfan-polluted agricultural soil. Through repetitive enrichment and successive subculture using endosulfan or endosulfan sulfate as the sole carbon source, a bacterium KS-2P was isolated. The KS-2P was identified as Pseudomonas sp. on the basis of the results of a 16S rDNA sequencing analysis and MIDI test. The degradation ratios for endosulfan or endosulfan sulfate in minimal medium containing endosulfan (23.5 microg mL(-1)) or endosulfan sulfate (21 microg mL(-1)) were 52% and 71%, respectively. Our results suggest that Pseudomonas sp. KS-2P has potential as a biocatalyst for endosulfan bioremediation.     

Decomposition of algal cells and components and their stabilization through complexing with model humic acid-type phenolic polymers

Axenic cultures of Anacystis, Microcoleus, Plectonema and Synechococcus isolated from Greenfield sandy loam and of Anabaena flos-aquae, Nostoc muscorum and Chlorella pyrenoidosa from other sources were cultured under light and constant aeration and with [U-¹⁴C]-glucose in the nutrient medium. Whole cells, cell walls, cytoplasm and extracellular polysaccharides of selected species readily decomposed in the soil and after 22 weeks between 61 and 81% of the added C had evolved as CO₂. Complexing of cell wall and cytoplasmic preparations from A. flos-aquae and N. muscorum with model humic acid-type phenolic polymers reduced decomposition of the cell walls by 40% and of the cytoplasm by 70%. Over 50% of the residual 14C activity in the soil amended with whole algal cells remained in the 0.5% NaOH-extracted soil. With exception of Microcoleus sp. more of the residual ¹⁴C from cell walls, cytoplasm and polysaccharide fractions was present in the humic acid or fulvic acid fractions.     

渗透胁迫下的蓝藻固氮作用

渗透胁迫下,蓝菏的固氮活性下降,去铵阻抑速率减小,下降程度随渗透胁迫的增高而增大,光合使用受抑Ｏ２和Ｎ２分压增高均加剧渗透胁迫对固氮酶活性的抑制。添加外源蒸糖,供应ＣＯ２,同时供应ＣＯ２和Ｎ２或Ｈ２和Ｏ２时,渗透胁迫对固氮酶活性的抑制程度明显减弱。     

稀土铈对水华鱼腥藻生理特性及藻毒素释放的影响

随着稀土及其化合物的广泛应用,越来越多的稀土直接或间接进入水体,因而稀土对水生生态环境的影响备受关注。采用室内模拟试验,研究不同浓度（0~10.00mg·L-1）的稀土元素铈（Ce3＋）对水华鱼腥藻的影响,绘制了水华鱼腥藻的生长曲线,测定了藻蓝蛋白、类胡萝卜素、可溶性蛋白含量和过氧化物酶（POD）活性4项生理指标,以及培养基中总磷（TP）、微囊藻毒素-LR（MC-LR）的浓度。结果表明,和其他各组相比,在0.10mg·L-1Ce3＋处理下,水华鱼腥藻的生存量最为显著（P=0.008）,同时营养元素P被吸收后,培养基中残留的TP浓度达到最低值（1.52mg·L-1）。藻蓝蛋白、类胡萝卜素、可溶性蛋白含量和POD活性均随着Ce3＋浓度的升高呈现出先升高后降低的趋势。MC-LR在所有培养基中含量均较低,低于世界卫生组织（WHO）标准1.00μg·L-1。铈元素胁迫水华鱼腥藻产生的＂低促-高抑＂的Hormesis效应显著。     

氯化钠胁迫下蓝藻Anabaena 7120对氧的敏感性和氢的保护作用

正常培养液中NaCl浓度增高时,蓝藻固氮活性下降,对氧的敏感度增大,氧浓度愈高,敏感度愈大。分子氢可以削弱或消除氧对固氮酶活性的抑制,其良好效应主要表现在固氮反应初期。 添加光合抑制剂、CO_2、N_2,以及在厌氧条件下,氢对NaCl胁迫下受氧伤害蓝藻固氮酶活性的保护效应低于对正常生长蓝藻的保护效应。     

Dissipation of endosulfan in field-grown tomato (Lycopersicon esculentum) and cropped soil at Akumadan, Ghana

The dissipation and persistence of endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin 3-oxide) applied to field-grown tomato (Lycopersicon esculentum) were studied at a vegetable-growing location in Ghana. Plant tissue samples and cropped soil collected at 2 h-14 days and 8 h-112 days, respectively, after application, were analyzed by gas chromatography-electron capture detection (63Ni) to determine the content and dissipation rate of endosulfan isomers (alpha- and beta-endosulfan) and the major metabolite, endosulfan sulfate. After two foliar applications of commercial endosulfan at 500 g of active ingredient/hectare, the first-order reaction kinetic was confirmed to describe the dissipation of endosulfan residues in tomato foliage and cropped soil. However, functions that best fit the experimental data were the biphasic process for foliage and the monophasic process for cropped soil. Calculated DT 50 and DT 90 values for endosulfan residues in cropped soil were not significantly (p<0.05) different for each of the two isomers.     

纯培养条件下蓝细菌形成腐殖物质的可能性研究

采用红外光谱和元素分析,初步研究了纯培养条件下水华鱼腥藻(一种常见蓝细菌)不同生长期的菌体和胞外代谢物以及作为唯一基质形成的菌体混合物的结构特征。结果表明:蓝细菌样品的红外光谱图中均没有1 720 cm-1峰。2 926/1 650比值显示,水华鱼腥藻对数生长期与衰亡后期的菌体芳香物质含量高,复杂度与土壤富里酸接近,但低于土壤胡敏酸;微生物处理能使菌体混合物具有更多芳香族物质,但1 530 cm-1峰消失,表明部分C=C及氨基酸类物质被分解。相对于土壤腐殖物质,水华鱼腥藻菌体的H/C比值及(O+S)/C比值均较大,即缩合度较低而氧化度较高;经微生物处理后,其缩合度进一步降低,氧化度升高。总之,本实验条件下蓝细菌自发形成腐殖物质的可能性较低,且其作为唯一基质在其他微生物作用下形成的菌体混合物与土壤腐殖物质在结构上存在差距,但从蓝细菌的组成与结构上看,其可为腐殖物质的形成提供物质条件。该结果为土壤腐殖物质的形成研究与起源探索提供了一定的科学依据。     

Biodegradation kinetics of endosulfan by Fusarium ventricosum and a Pandoraea species

Endosulfan, classified as an organochlorine pesticide, is rated by the U.S. EPA as a Category 1 pesticide with extremely high acute toxicity. This study describes the biodegradation kinetics of endosulfan and the metabolic pathway utilized by Fusarium ventricosum and a Pandoraea sp. Complete disappearance of both alpha- and beta-endosulfan was observed during 12 days of incubation with F. ventricosum in flasks containing 100 mg L(-)(1) of endosulfan. The rate constants (k) for biodegradation of alpha- and beta-endosulfan by F. ventricosum using zero-order kinetics were 14.22 and 6.60 mg L(-)(1) day(-)(1), respectively. The Pandoraea sp. degraded about 95 and 100% of alpha- and beta-endosulfan, respectively, in 18 days of incubation in flasks spiked with 100 mg L(-)(1) of endosulfan. The rate constants (k) for biodegradation of alpha- and beta-endosulfan by the Pandoraea sp. were 8.19 and 3.78 mg L(-)(1) day(-)(1), respectively. Both fungal and bacterial strains formed less toxic endosulfan diol and endosulfan ether as metabolites during metabolism of endosulfan. The results of this study suggest that these novel strains may be used for the bioremediation of endosulfan-contaminated sites.     

蓝藻Anabaena 7120固氮酶活性表达和生理条件的关系

经暗处理24小时的蓝藻转到光下后,开始一段时间不表达固氮酶活性,嗣后出现活性,并随光照时间延长而增高;加蔗糖促进固氮酶活性的表达,但比预光下培养的蓝藻低.厌氧(氩和氮气中)、氧、光合抑制剂和MSX都延缓暗处理蓝藻固氮酶活性的表达,加蔗糖后固氮活性提前表达,并且活性有所提高。分子氢对暗处理蓝藻固氮酶活性及其表达有促进作用,而对光预处理蓝藻则未表现促进作用。氢和氧同时加入或加蔗糖,对光预处理蓝藻固氮酶活性的表达均有明显的促进作用。     

洞庭湖典型断面藻类组成及其与环境因子典范对应分析

2010年对洞庭湖6个典型断面进行了浮游藻类生物调查,共鉴定出7门72属（种）,浮游藻类的密度范围在67.2×104～161.9×104cell·L-1;各典型断面间浮游藻类组成以硅藻和隐藻占优势,藻类群落结构存在着明显的差异。藻类Margalef指数及Shannon-Wienner指数范围分别为3.64～4.03和3.03～3.24,水体水质状况良好。应用CANOCO4.5软件对获得的浮游植物数据和环境因子数据进行典范相关分析（CCA）,作出物种与环境因子关系的二维排序图。结果显示,典型断面藻类群落分布受水环境因子影响较为明显,整体上,DO和TN是影响洞庭湖典型断面藻类物种分布格局的主要因素。     

Determination of 2-methylisoborneol and geosmin produced by Streptomyces sp. and Anabaena PCC7120

A new sample preparation and enrichment technique, headspace liquid-phase microextraction (HS-LPME) linked to gas chromatography-mass spectrometry (GC-MS), was developed for the determination of the off-flavor odorants, 2-methylisoborneol and geosmin, produced by Streptomyces sp. and Anabaena PCC7120. Some of the factors that influence the extraction efficiency of HS-LPME, such as the type of extraction solvent, ionic strength of sample solution, and sample agitation rate, were studied and optimized by a single factor test. Other factors, including extraction temperature, extraction time, microdrop volume, and headspace volume were optimized by orthogonal array design. Extraction of 2-methylisoborneol and geosmin was conducted by exposing 2.5 microL of 1-hexanol for 9 min at 50 degrees C in the headspace of a 20 mL vial with a 10 mL of sample solution saturated by NaCl and stirred at 800 rpm. The developed protocol demonstrated good repeatability (relative standard deviations (RSDs) < 5%), wide linear ranges (10-5000 ng/L, r2 > 0.999), and low limits of detection (LODs) for 2-methylisoborneol and geosmin (0.05 ng/L for both analytes). Subsequently, the method was successfully applied to extract the analytes in bacterial cultures with high recoveries (from 94% to 98%). Compared with headspace solid-phase microextraction (HS-SPME), HS-LPME demonstrates better linearity, precision, and recovery. Importantly, the sensitivity is about 1 order of magnitude higher than that of most HS-SPME. The results showed that HS-LPME coupled with GC-MS is a simple, convenient, rapid, sensitive, and effective method for the qualitative and quantitative analysis of 2-methylisoborneol and geosmin.     

氯化钠影响下蓝藻Anabaena 7120的固氮活性和去铵阻抑

正常培养液中NaCl浓度增高时,蓝藻固氮活性明显下降,去铵阻抑速率也减慢。NaCl浓度越高,阻抑程度越大。如果NaCl浓度过高,固氮酶活性即完全丧失,铵阻抑效应也不能消除。低光照度、光合抑制剂、O_2、N_2以及N_2+CO_2都加剧高浓度NaCl对蓝藻固氮酶活性和去铵阻抑的阻抑,而外源蔗糖、H_2和H_2+O_2则有一定程度的促进。     

Fate of (14)C-labeled soybean and corn pesticides in tropical soils of Brazil under laboratory conditions

The dissipation rate of seven currently used soybean and corn pesticides in two tropical soils (Ustox and Psamments) of Brazil was studied in a laboratory incubation experiment. Dissipation half-lives of pesticides ranged between 2 (monocrotofos) and 90 days (endosulfan-beta). The contrasting clay contents of the studied tropical soils (130 versus 470 g of clay kg(-1) of soil) did not influence the dissipation dynamics of pesticides substantially. Mineralization to CO(2) was high [up to 78% of the applied radioactivity (AR)] for the studied organophosphorus compounds and deltamethrin, which also formed considerable amounts of bound residues (>20% of AR) during the 80 days of incubation. The highest portion of nonextractable residues was found for alachlor and simazine (55-60% of AR). In contrast, the nonpolar trifluralin and endosulfan formed only small amounts of bound residues (mostly <20% of AR) but showed the highest dissipation half-lives (>14 days) in the studied soils, also due to a low mineralization rate. When endosulfan-sulfate, as the main metabolite of endosulfan, was considered, the half-life time of endosulfan compounds (sum of -alpha, -beta, and -sulfate) was enhanced to >160 days in both soils. In comparison with the laboratory experiments, dissipation half-life times of chlorpyrifos, endosulfan-alpha, and trifluralin were shortened by a factor of 10-30 in field trials with the same soils, which was related to the volatilization potential of pesticides from soils.     

Functional complement of biogenic structures produced by earthworms, termites and ants in the neotropical savannas

Soil-engineering organisms (earthworms, termites and ants) affect the soil and litter environment indirectly by the accumulation of their biogenic structures (casts, pellets, galleries, crop sheetings nests…). An enzymatic typology was conducted on six types of biogenic structures: casts produced by two earthworms (Andiodrilus sp. and Martiodrilus sp.), a nest built by a soil-feeding termite (Spinitermes sp.), crop galleries built by another soil-feeding termite (Ruptitermes sp.) and soil pellets produced by two species of leaf-cutting ant (Acromyrmex landolti and Atta laevigata) and an control soil from a natural Colombian savanna. A total of 10 enzymes (xylanase, amylase, cellulase, α-glucosidase, β-glucosidase, β-xylosidase, N-acteyl-glucosaminidase, alkaline and acid phosphatases and laccase) were selected to characterize the functional diversity of the biogenic structures. Our results showed that (i) Martiodrilus casts were characterized by a broad enzymatic profile that was different from that of the soil. (ii) A. laevigata pellets and termite structures had a profile broadly similar to the soil only with some enzymes (iii) Andiodrilus casts had an enzyme profile very similar to that of the soil. These results suggest that the functional diversity of these structures is related to differences between species and not to differences between taxonomic groups. For the first time, we evaluated differences in enzyme typology between biogenic structures collected on the same site but produced by different organisms. These differences suggested species dependent pathways for the decomposition of organic matter.     

Collaborative study of the determination of endosulfan, endosulfan sulfate, tetrasul, and tetradifon residues in fresh fruits and vegetables.

A method for the determination of endosulfan I, endosulfan II, endosulfan sulfate, tetrasul, and tetradifon residues in fresh fruits and vegetables was studied collaboratively. The method consists of extraction of the product with acetonitrile, ether and elution from a Florisil column with mixtures of hexane, methylene chloride, and acetonitrile, and determination of the residues by electron capture gas-liquid chromatography. This method was studied by 8 collaborators, using apples and cucumbers as the samples. Each sample was spiked with 2 levels of each pesticide. The average per cent recoveries for apples and cucumbers, respectively were as follows: endosulfan I, 103.6 and 101.5; endosulfan II, 102.9 and 100.0; endosulfan sulfate, 100.9 and 92.9; tetrasul, 98.8 and 102.2; and tetradifon, 106.4 and 101.9. The method has been adopted as official first action.     

Der Einfluß variierter Düngergaben von Stickstoff,Kupfer und Magnesium auf den Ertrag von Hafer

The Influence of varying Amounts of Nitrogen, Copper and Magnesium on the Yield of Oat 1. In pot experiments with oat high amounts of copper (500 mg) copper sulfate/pot, comparable to 50 kg (Cu/ha) together with a high nitrogen supply as calcium nitrate led to a remarkable increase in yield of grain in comparison to a normal copper fertilization (50 mg copper sulfate/pot, comparable to 5 kg Cu/ha). When using high amounts of ammonium sulfate the observed effect of high amounts of copper was only small. 2. According to the results and to the copper content and copper uptake of the plant it was concluded, that nitrogen fertilization given as ammonium sulfate increased the availability of soil copper and/or fertilizer copper presumably by affecting the soil reaction. Nitrogen fertilization given as calcium nitrate therefore needs a higher copper level in the root medium either from soil or fertilizers in order to obtain the maximum yield. 3. It was assumed that the form of nitrogen fertilizers was responsible for the different availability of copper in these experiments, as the amount of available copper in the soil increased with the lowering of soil pH due to ammonium sulfate addition. 4. The high copper supply to the soil remarkably reduced the harmful effect of high amounts of nitrogen given as calcium nitrate but not as ammonium sulfate. 5. The nitrogen fertilization with calcium nitrate, especially in combination with a high copper supply, resulted in the reducing effect of a magnesium deficiency. 6. The harmful effect of high amounts of nitrogen, especially in the ammonium sulfate form, upon yield was reduced by an optimal magnesium supply. 7. The results presented suggest that for evaluating the copper status of the soil and for estimating the demands of copper fertilization, soil reaction and its change by the form of nitrogen fertilizers should more be taken in consideration.     

Interaction study of biochar with phosphate-solubilizing bacterium on phosphorus availability in calcareous soil

A large proportion of phosphate fertilizer applied to calcareous soils reacts with calcium. Changes in soil phosphorus (P) availability after single application of biochar and phosphate-solubilizing bacteria have been reported. However, interaction of biochar (increasing soil pH) and phosphate-solubilizing bacteria (decreasing soil pH) on P availability in calcareous soil is not well known. An incubation experiment was conducted to study how the interactive effects of biochars (produced from wheat straw and cow manure at 300°C and 500°C with residence time of 1, 3 and 6 h) at different rates (0, 5 and 10 t ha^?1) and phosphate-solubilizing Pseudomonas sp. IS8b2 affected on content of soil available P after 0, 60, 120 and 180 days of incubation (DOI) in a calcareous soil. After 60 DOI, the maximum value of available P (50.31 mg kg^?1) was observed in the compound treatment of Pseudomonas sp. IS8b2 and wheat straw biochar (10 t ha^?1) produced at 500°C with residence time of 3 h. We conclude that the combination use of wheat straw biochar and phosphate-solubilizing bacterium is promising to potentially improve soil P availability in calcareous soil, but further research at field scale is needed to confirm this.     

The short-term effects of endosulfan discharges on eucalypt floodplain soil microarthropods

The insecticide endosulfan is extensively used in the Australian cotton growing industry. Irrigation tailwater contaminated with endosulfan is released onto floodplains to avoid direct entry into river systems where endosulfan is highly toxic to fish. We examined the short-term effects of endosulfan, at levels likely to be present in tailwaters, on soil arthropods on such a floodplain near Moree, NSW. The study consisted of four treatments: a dry control (replicates untreated), wet control (replicates flooded with water only), 1 μg/l endosulfan and 10 μg/l endosulfan. Treatments were applied in the middle of summer and soil invertebrate samples were taken 1 week, 1 month and 2 months following treatment. Invertebrates were sorted to order level and oribatid mites to species. Endosulfan sulphate was detected in all treatments, including the two controls, most likely the result of spray drift. The focus of the experiment was therefore to explore the short-term impacts of endosulfan contaminated tailwater on communities that had been previously exposed to endosulfan. More than 7700 arthropods were collected from a total sample area of 0.336 m². The dominant groups were the prostigmatid and oribatid mites (35 species), collembolans and hemipterans. Our analyses did not detect any short-term effect of the endosulfan treatments on the number of individuals, spatial aggregations or community structure of the soil fauna. There were clear responses to changes in soil moisture related to treatment applications. The study, therefore, made two important findings: (1) a diverse and abundant soil fauna persists on floodplains exposed to endosulfan contaminated tailwater, and (2) this diverse and abundant soil fauna were unaffected by the addition of endosulfan at concentrations common to tailwater run-off from cotton fields. There is clearly a need to determine whether these findings can be extended to soil arthropod biodiversity in areas previously unexposed to endosulfan.