Photochemistry of halogenated benzene derivatives. part xii.∗ effects of sodium nitrite on the environmental phototransformation of bromoxynil (3,5‐dibromo‐4‐hydroxybenzonitrile) herbicide in water: The photoincorporation of nitrite ions into bromoxynil

Photoreactions of the herbicide bromoxynil (3,5‐dibromo‐4‐hydroxybenzonitrile) (1) were extensively studied in water containing various concentrations of sodium nitrite with radiation of wavelengths around 313 nm. In the absence of NaNO₂, the quantum yields for the photodecomposition of the herbicide I amounted to 0.054±0.005, while such data was in the range of 0.047 ±0.005 to 0.023 ±0.003 in the presence of 0.5 to 25.0 × 10^‐3 m of the inorganic salt. These quantum yield data for the phototransformation of 1 without and with the presence of sodium nitrite followed the Stern‐Volmer equation. The rates of the photolytic destruction of bromoxynil (1) in water were slower in the presence than in the absence of NaNO₂. For example, the irradiation of the 7.8 x 10^‐6M aqueous solution of 1 in the presence of 10 mM sodium nitrite gave rise to the production of three main photoproducts, viz., 3‐bromo‐4‐hydroxy‐5‐nitrobenzonitrile (2), 4‐hydroxy‐3‐nitrobenzonitrile (3), and an “unidentified photoproduct”; 4. In the case of this photoreaction of compound 1, the percentages of maximum concentration of the photoproducts 2, 3, and 4 were achieved after 14, 44.5, and 60‐min photolyses of 1, respectively; the starting material 1 completely disappeared after 60‐min photolysis. The photoproducts 2 and 3 were identified through the interpretation of the GC‐MS data. Both thhe mass and FT‐IR spectra of the product 4 indicated the possible presence of a COOH group in 4.     

Soil and plant biodegradation of chlorpyrifos in fields of cauliflower and brussels sprouts crops

For the protection of early and summer cauliflower and brussels sprouts crops against root fly, the insecticide chlorpyrifos was applied at planting onto soil around the stem of the plant, or in the planting line. In the soil, chlorpyrifos (1) was transformed into the insecticide metabolites oxon, 0,0‐diethyl‐0‐(3,5,6‐tri‐chloro‐2‐pyridinyl) phosphate (2), and 3,5,6‐trichloro‐2‐pyridinol (3). The soil half life time of chlorpyrifos could be 2.8 times greater (42 days relative to 15 days) when the field history as to cauliflower monoculture and insecticide treatments was short (1 year), than when it was long (8 years). Rains and season also had cumulative effects on the chlorpyrifos soil half life times. In the leaves of cabbage, chlorpyrifos and compound 3 were observed at concentrations which were higher, especially when their soil concentrations were high. Chlorpyrifos and compounds 2 and 3 however were not detected in the “flower” of cauliflower, nor in the brussels sprouts itself, the limit of sensitivity being 0.02 ppm of fresh weight.     

A new derivatization method for a determination of MX and related hydroxyfuranones in water

An extremely potent mutagen, 3‐chloro‐4(dichloromethyl)‐5‐hydroxy‐2(5/f)‐furanone (MX) is commonly present in chlorinated drinking water. Due to its high mutagenic activity and according to WHO guidelines its concentration should be controlled in drinking waters. Determination of MX is difficult due to ppt levels at which the compound usually exists in drinking waters. Derivatization with 2‐propanol is presented as a method which significantly lowers GC/MS detection level of MX. Suitability of 2‐propylation for derivatization of other hydroxyfuranones is also shown.     

同位素示踪法研究有机污染物在模拟水生生态系统中的行为

应用同位素示踪技术，研究了模拟水生生态系统中三氯苯、邻苯二甲酸正丁酯，２，４，６－三氯酚－＾１４Ｃ的分布、迁移、转化行为。实验周期后，水中污染物浓度分别降低了８９％，８０％，９５％以上，三氯苯在底泥和浮游生物中有积累。测定了标记物在水、悬浮物、＾１４ＣＯ２吸收溶液，ＸＡＤ－２树脂上的放射性强度。假设水中标记物的降解遵循一级速率过程，２４ｄ后，水中２，４，６－三氯酚－＾１４Ｃ浓度已降为原来浓度的５％     

Determination of chlorothalonil residues in coffee

Coffee beans were treated with the fungicide chlorothalonil (2,4,5,6‐tetrachloro‐1,3‐benzene‐dicarbonitrile) and the residues were determined by high‐performance liquid Chromatograph (HPLC). Several techniques including Soxhlet extraction (SE), microwave‐assisted extraction (MAE) and accelerated solvent extraction (ASE) were compared for the extraction of residues. A column clean‐up procedure was developed to remove the co‐extractives in the extract before HPLC analysis. The overall mean recoveries from extracts obtained by SE, MAE and ASE were 89.2 ±3.9, 88.4 ±1.9 and 82.8 ±0.3, respectively. The results show that MAE followed by HPLC is a viable alternative to the commonly used SE and gas Chromatographic analysis for the determination of chlorothalonil in coffee.     

6种蔬菜对施用含砷禽畜粪土壤中砷的吸收

由于现代集约化养殖业普遍使用有机胂制剂,禽畜粪中往往含有一定的砷(As).在水稻土中分别以2%和4%(w/w)比例施入含As鸡粪和猪粪及无机肥(N:0.2g·kg-1;P2O5;0.1g·kg-1;K2O:0.15g·kg-1(以干土计)),以不施肥为对照进行菜心、小白菜、油麦、茼蒿、苋菜和通菜6种蔬菜盆栽试验,研究比较含As禽畜粪施入土壤后蔬菜对土壤中As的吸收累积情况.结果表明,1)整体上施用鸡粪处理蔬菜生物量高于无机肥处理,而施用猪粪处理除通菜外5种蔬菜生物量均低于无机肥处理.2)施肥可降低除通菜外的5种蔬菜As含量,而施用鸡、猪粪可显著提高通菜As含量.3)菜心、小白菜、油麦和茼蒿地上部As含量与其生物量呈显著负相关(p<0.05,p<0.01);苋菜也表现为负相关,但未达到显著;通菜则表现为显著正相关(p<0.01).4)菜心、小白菜、油麦和茼蒿As吸收量整体表现为施用鸡粪>无机肥>猪粪≈不施肥;苋菜表现为无机肥>不施肥>鸡、猪粪;通菜则表现为鸡、猪粪>无机肥≈不施肥.整体上通菜As吸收量高于其他5种蔬菜.5)施肥可降低除通菜外5种蔬菜As吸收系数,而施用鸡、猪粪可显著提高通菜As吸收系数.建议含As禽畜粪在通菜上尽量少施.     

Release of Cd immobilized by soil constituents and its bioavailability

Release of Cd immobilized by soil constituents (clay, humic acids, bacterial cells) in vitro and under soil conditions and its bioavailability to lettuce were studied. The most resistant to extraction with 0.02 M EDTA in vitro as well as under soil conditions was cadmium immobilized by humic acids during decomposition of contaminated plant residues but Cd‐dead cells when 0.1 M NaNO₃ was the extractant.

Cadmium addition (3 mg kg^‐1) to soil and its form were without effect on plant growth and amount of metal accumulated in roots. Tops of plants grown in soil supplemented with Cd‐resting cells contained significantly less metal then other ones.     

Soil mycofloral responses following the exposure to 2, 4-D

2, 4-dichlorophenoxyacetic acid (2,4-D) is a post emergence herbicide. The tests were conducted to study the toxicity of 2,4-D using EC50 value in four dilutions. 2,4-D was applied at concentration of 25, 50, 75, 100, 200 and 300 mg l(-1) in the potato Dextrose agar medium. The effect of this herbicide was evaluated as the colony forming unit (CFU). EC50 value for 10(-3) dilution of soil was 138 +/- 5.944 mg l(-1). Soil physico-chemical parameters and mycofloral properties were also evaluated. Qualitatively 10 genera of fungi were observed in untreated soil, whereas 4 genera were found in 2,4-D administered dose.     

Endosulfan in the Chinese environment: monitoring and modeling

This paper reviews the usage and emissions of endosulfan, the newest member of the persistent organic pollutants (POPs), in China, and its fate and behavior in Chinese environment. Endosulfan usage in China has been estimated to be approximately 25700 t between 1994 and 2004. Concentrations of endosulfan in different environmental compartments in China, such as air, soil, water, and biota, but focusing at air and surface soil, have been summarized. Concentrations of total endosulfan in surface soil across China were ranged from below detection limit (BDL) to 19000 pg·g^?1 dry weight (dw), with geometric mean of 120 pg·g^?1dw. The results indicated that endosulfan sulfate had highest concentration in Chinese soil, followed by ??- and ??-endosulfan. Air concentrations of endosulfan in China were ranged 0?C340 pg·m^?3 for ??-endosulfan and 0?C121 pg·m^?3 for ??-endosulfan, with high concentrations occurred in the cotton production areas. Gridded usage inventories of endosulfan on a fine gridded system with a 1/4° longitude by 1/6° latitude resolution were compiled, from which, emission to air and residues in soil of endosulfan were calculated in each grid by using a modified simplified gridded pesticide emission and residue model (SGPERM), an integrated modeling system combining mathematical model, database management system, and geographic information system. Total emissions were around 10800 t from 1994 to 2004. Based on the emission and residue inventories, concentrations of ??- and ??-endosulfan in Chinese air and agricultural surface soil were also calculated for each grid cell, which are in general consistent with the published monitoring data.     

生物炭与炭基肥对大豆根际土壤细菌和真菌群落的影响

土壤微生物在农田土壤生态系统中发挥重要作用,然而秸秆生物炭与炭基肥处理对微生物群落的影响以及对农田生态环境的意义尚不清楚.以黄淮海平原豆-麦轮作为研究对象,采用荧光定量PCR和Illumina高通量测序技术比较不同施肥方式对土壤细菌和真菌群落的丰度、组成和多样性差异,探究秸秆还田、生物炭以及炭基肥添加对根际土壤微生物群...     

吉林西部不同土地利用方式下的生长季土壤CO2排放通量日变化及影响因素

利用GXH-3051A红外线分析仪,采用动态闭合气室法对吉林西部4种土地利用方式下土壤CO2排放通量日变化进行了定位测量,系统分析了环境因子及土壤理化性质等因素对土壤CO2排放通量日变化的影响。结果表明,水田、旱田、草地和盐碱地土壤CO2排放通量日变化均呈单峰曲线,但排放通量的日均值有较大差异,其中水田和草地排放量较高,分别为1.69μmol.m-2.s-1和1.24μmol.m-2.s-1;旱田和盐碱地较低,为0.50μmol.m-2.s-1和0.63μmol.m-2.s-1。各地类土壤CO2排放通量的日均值与其每天上午10:00土壤CO2排放通量值最为接近,即可用该时间测得的土壤CO2排放通量估测日平均值。土地利用方式和大气温度是造成土壤CO2日排放通量差异的主要因素,多年来该区土地利用方式的变化,改变了土壤表层10 cm内的土层温度、土壤含水率、有机碳含量、水解氮含量,进而影响土壤呼吸和CO2排放通量;区内水田土壤CO2排放通量与温度的相关性最高(R2=0.837 5),其次为旱田和草地。     

二苯甲酮类紫外防晒剂发光菌急性毒性及QSAR研究

二苯甲酮类化合物广泛用于防晒剂、塑料添加剂、香味剂等。随着紫外防晒产品的大量使用,其环境及健康风险越来越受到人们的关注。为揭示二苯甲酮类污染物的毒性特征,选择了14种二苯甲酮类化合物作为目标化合物,测试了它们对发光细菌的急性毒性效应。分别运用二维、三维定量构效相关技术和分子对接技术探讨了目标化合物的分子结构特征对毒性效应的影响。结果表明14种二苯甲酮类化合物对发光菌急性毒性的EC50值在17.67到243.82 mg·L-1范围内,其中2-羟基-4-甲氧基-5-磺酸基二苯甲酮的急性毒性最低,2,2',4,4'-四羟基二苯甲酮的毒性最高。羟基取代的二苯甲酮化合物的急性毒性随着分子中羟基数量的增加而升高;具有相同羟基数量的二苯甲酮类化合物,羟基位于苯环4-位时毒性最高,3-位时次之,2-位时毒性最低。QSAR结果表明,运用静电场、氢键受体场和氢键供体场能很好解释这类化合物的毒性特征,若在苯环4-位引入带正电荷的官能团、在苯环2-,4-位引入氢键受体,都将导致毒性升高。上述研究结果将为科学评价该类化合物的潜在生态风险提供基础数据。     

土壤酸化对油松生长的影响

褐色森林土酸化后,pH值下降,同时淋溶出大量Al离子和Mn离子。播种在酸化土壤中的油松种子萌发率稍有提高。生长在酸化土壤的油松苗的叶绿素含量,蒸腾强度,光合速率,相对生长率和干重均下降,原因是Al离子和Mn离子对油松的有毒害作用,并且阻止油松对钙离子和镁离子的吸收。表3参12     

利用根箱法解析水稻根际土壤中氮的行为

为研究水田土壤中氮的行为,施给15NH4 或15NO3-标记的硝胺(NH415NO3或15NH4NO3)的沙壤土(Shirasu soil)添充在根箱里,对Japonica水稻(品种Hinohikari)进行温室栽培6周.收割后,水稻植株分地上部和根部,对各自的全氮,15N atom％进行测定.根箱各区域的土壤按着鲜土形态进行采取后,对此全氮,NO3-N,水溶性NH4-N,KCl抽出NH4-N和其各自的15N atom％进行测定.研究结果表明,土壤全氮含量与栽培前相比,在非根际明显降低,但在根际比非根际要高,保持了与栽培前相同的水平.土壤NO3-N浓度从非根际到根际递增,但与其栽培前相比显著地降低,在整个根箱里,施给NO3-N的79％为因脱氮而损失.土壤中NO3-N的大部分来自于土壤氮化合物,来自施肥的比例却较低,尤其是在根际.反而,施给NO3-N的残存率约仅为16％左右,但其中有机态氮所占的比率在非根际里55％～86％,在根际却达到了93％.土壤水溶性NH4-N和KCl抽出NH4-N浓度靠近根际逐渐降低,而且在非根际两者匀由1∶10的比例存在,但在根际里水溶性NH4-N没被检索到.在非根际里,土壤KCl抽出NH4-N的35％～66％为来自施肥,但其比例在根际里却降到15％左右.在土壤中残存的来自施给NH4-N的氮化合物之中,有机态氮所占的比例在非根际里约为11％～65％,但在根际却达到了92％.以上结果表明,在水稻根际,氮的无机化和有机化的活性比非根际显著.     

In vitro mass multiplication of screw pines (<Emphasis Type="Italic">Pandanus</Emphasis> spp.) - an important costal bio- resource

An efficient in vitro mass multiplication protocol was developed for selected species of screw pine (Pandanus fascicularis Lam., P. furcatus Roxb.). The protocol could be successfully used for large scale production of planting materials leading to cultivation and making bio-fences or green belts in coastal areas, wetlands for protection and preventing soil erosion. This will facilitate the replenishment of the bio resource and also provide good breeding space for various fauna associated with it. For developing the tissue culture protocol, shoot tips and tillers from the mature plants were used as the explants. Surface sterilization with 0.1 % mercuric chloride for 1 min. Yielded good fraction (65 %) of contamination free explants. Explants inoculated in MS solid medium supplemented with 6-benzylaminopurine (BAP, 2.5 mg/l) and indole-3-acetic acid (IAA, 0.5 mg/l), induced 2–3 shoot buds in 5 weeks. These buds either individually or along with the explant portion, sub-cultured to fresh media containing the same hormonal combinations, resulted induction of 5–6 shoot buds in 4 weeks. Repeated subcultures of shoot buds in the same medium produced 8–10 shoot buds in every 4 weeks. Shoot elongation was achieved (~ 3 cm) by transferring the shoot clusters or individual shoots to basal medium, and the elongated shoots were rooted in vitro or ex vitro. Root induction in shoots (87.4 %) was achieved in MS medium supplemented with 0.1 mg/l indole-3-butyric acid (IBA). Rooted shoots were established in paper/polythene cups filled with fine sand, which subsequently recorded 85 % establishment under the shade-net house with proper irrigation. Plants grown in poly-bags were later successfully established in different field conditions and recorded 100 % survival.     

New O,O‐dimethyl (2,2,2‐trichloro‐1‐carbamoyloxy)‐ethyl phosphonates and their biological activity

A series of fifteen carbamoyl derivatives of O,O‐dimethyl (2,2,2‐trichloro‐l‐hydroxy) ethyl phosphonate (trichlorphon) was synthesized. A number of them showed higher insecticidal activity, having at the same time lower toxicity than the starting biologically active structure. A waste‐free technology for the production of the more promising representatives of this series could possibly be developed in the future.     

Metsulfuron‐methyl soil persistence and mobility in winter wheat and following green manure crops

A procedure has been developed for the analysis of metsulfuron‐methyl in the soil of field crops. The soil extracts are cleaned by repeated TLC, and metsulfuron‐methyl is simultaneously separated from its soil metabolites. Metsulfuron‐methyl is transformed by diazomethane into its N,N ‘‐dimethyl derivative which in the GC (electron capture detection) and GC‐MS apparatus is transformed into a benzisothiazole compound which is measured with great sensitivity. The sensitivity limit is 0.3 μg metsulfuron‐methyl kg^‐1 dry soil. The results of the chemical analyses are confirmed by bioassays using sugar beet as test plant. Metsulfuron‐methyl was measured in the soil of two winter wheat crops after post‐emergence application in the spring of 6 g metsulfuron‐methyl ha^‐1. In the 0–8 cm surface soil layer, the metsulfuron‐methyl soil half‐life was 78 days in 1997, and 67 days in 1998. During crop, metsulfuron‐methyl remained in the 0–8 cm surface soil layer. There, it was at a maximum concentration and herbicide efficiency in a 2 cm‐thick soil layer. This maximum concentration soil layer progressively moved down during crop, attaining the 4–6 cm surface soil layer at crop end. After the winter wheat harvest at the end of July, and the rotary‐tilling of the 0–10 cm surface soil layer before sowing of the green manures, 27% of the metsulfuron‐methyl initial dose still remained in the 0–10 cm surface soil layer. This residue progressively disappeared, and was no more detected at the middle of November. It had no, or only very low inhibiting effect on the growth of the green manures. Thus there is no concern about the possible phytotoxicity of persistent metsulfuron‐methyl soil residues towards the following crops, when metsulfuron‐methyl is applied at the rate of 6 g a.i.ha^‐1.     

Environmental risk assessment of metals contaminated soils at silvermines abandoned mine site,Co Tipperary,Ireland

A centuries long history of mining and mineral processing has resulted in elevated Cd, Pb and Zn soil concentrations in the vicinity of the Silvermines abandoned mine site (AMS), Co. Tipperary, Ireland. A process for preliminary evaluation of environmental risk was developed and implemented. Potential pathways of metal compound transport and deposition were mapped and used to optimise the subsequent site investigation. Elevated soil metals are shown to be predominantly in areas where metal deposition in soil is associated with water related pathways (surface runoff, seasonal groundwater seepage and floodplains). Extensive areas of soil in the surrounding district are classified as contaminated on the basis of Cd, Pb and Zn concentrations, both total and potential bioavailable (EDTA-extractable). The most affected areas, with metal concentrations in soil comparable with that within the AMS, were floodplains located 2–3 km downstream from the site. Assessment of the sequential effects on grass and grazing animals indicates that Pb poses the greatest risk due to its high toxicity and high concentrations in soil (more than 10 000 mg kg^–1). Within floodplain areas grazing cattle may intake a lethal dose of Pb. On the basis of the investigation an approach to risk assessment was developed which allowed quantified assessment of the risks related to individual metals, areas of contamination and contamination targets.     

Influences of suspended particles on the runoff of pesticides from an agricultural field at Askim, SE-Norway

Field and laboratory experiments were conducted to study the loss of particles from agricultural fields, and the role of suspended particles in carrying pesticides in surface runoff and drainage water. Propiconazole, a widely used fungicide was applied to experimental fields located at Askim, SE-Norway. Samples from surface runoff and drainage water were collected and analyzed for sediment mass, pesticides, particulate and dissolved organic carbon through a whole year. The surface soil and the runoff material were characterized by its particle size distribution, organic carbon content in size fractions and its ability to bind propiconazole. The results show that (1) particle runoff mostly occurred during the rainfall event shortly after harrowing in autumn. The highest particle concentration observed in the surface runoff water was 4600 mg l(-1), and in the drainage water 1130 mg l(-1); (2) the erosion of surface soil is size selective. The runoff sediment contained finer particle/aggregates rich in organic matter compared to its original surface soil; (3) the distribution coefficient (Kd) of propiconazole was significantly higher in the runoff sediment than in the parent soil. According to our calculation, particle-bound propiconazole can represent up to 23% of the total amount of propiconazole in a water sample with a sediment concentration of 7600 mg l(-1), which will significantly influence the transport behavior of the pesticide.     

Bewertung der potenziellen Grundwasserbelastung von deponierten Hochofengasschlämmen

Goal and Scope

Blast-furnace sludge is a waste originating from pig-iron production and contains contaminants such as lead, zinc, fluoride and cyanide assumably contaminating the groundwater by leaching.

Methods

We investigated the chemical composition of 27 samples of landfilled blast-furnace sludge in pore waters which were obtained by the centrifugation of fresh material and elution with water according to DIN 38414 part 4 (S 4).

Results

The pore waters as well as the eluates were neutral to alkaline (pH 7.3 to 10.7) and were dominated by alkali and alkaline-earth metals as well as sulphate and nitrate. The concentrations of all elements and compounds investigated were mostly clearly larger in the pore waters than in the eluates. The average concentrations of environmentally relevant constituents such as lead (0,18 mg?1), zinc (1,5 mg l?1), fluoride (10,6 mg l?1), and total cyanide (1.8 mg l?1) in the pore waters were distinctly larger than the inspection value of the German Federal soil Protection Ordinance for the pathway soil-groundwater. Lead, zinc, and total cyanide concentrations in the pore waters were largely underestimated by the eluates, as these concentrations were 70 to 90% lower in the eluates compared to the pore waters.

Conclusion

In the case of landfilled blast-furnace sludge, eluates according to DIN 38414 part 4 (S 4) provide low concentrations which are unrealistic to forecast concentrations in the seepage water.