基于光谱学和电化学方法的莠去津毒理作用评价

为探索莠去津对DNA的损伤及其毒性作用机制,采用紫外吸收光谱法、荧光光谱法以及电化学方法研究了莠去津与鲱鱼精DNA的相互作用,探讨了二者形成DNA加合物的作用方式.结果表明,莠去津与鲱鱼精DNA作用后,莠去津的紫外光谱呈现减色效应,并有轻微红移现象,而其荧光光谱强度明显增强;循环伏安法显示莠去津与DNA作用能引起莠去津还原电位正移,峰电流减小.以上实验结果表明,莠去津平面分子能够嵌插到DNA双螺旋链中,形成较稳定的加合物.采用电化学方法测得莠去津与鲱鱼精DNA的结合比为1:1,结合常数为1.2×105.该研究为莠去津毒理作用评价提供了一种简便的方法。     

Removal of atrazine from river waters by indigenous microorganisms

We report the first data for atrazine removal in low-turbidity freshwaters. Atrazine is a globally applied herbicide, contamination by which may lead to direct and indirect ecotoxicological impacts. Although a common contaminant of surface waters, microbial biodegradation of atrazine in this environment has been little studied, with most work focused on soils by means of selected, atrazine-degrading bacteria-enriched cultures. Here, we measured atrazine removal from river water using a batch incubation system designed to represent environmental conditions, with water from two contrasting UK rivers, the Tamar and Mersey. Atrazine and bacterial inocula prepared from the source water were added to cleaned river water for 21-day incubations that were analysed directly by electrospray ionisation-mass spectrometry. The experimental approach was validated using peptides of different molecular mass. Results show that atrazine concentrations decreased by 11% over 21 days in Tamar samples, a rural catchment with low population density, when atrazine was the only substrate added. In contrast no removal was evident in Mersey samples, an urban catchment with high population density. When a tripeptide was added as a co-substrate, atrazine removal in the Tamar water remained at 11% while that for the Mersey water increased from 0 to 37%. Although degradation of atrazine in aerobic freshwaters is predicted according to its chemical structure, our data suggest that the composition of the bacterial population determines whether removal occurs under these conditions and at these environmentally realistic concentrations.     

Alteration of photosystem II activity by atrazine on Chlamydomonas reinhardtii synchronized and asynchronized cell cycle cultures

Inhibition of photosystem II (PSII) activity by atrazine was investigated in the green alga Chlamydomonas reinhardtii during different states of the cell cycle. The algal cultures were maintained under continuous light or under light/dark cycle (16/8?h) to obtain homogenized cell cycle distribution. The cycle state of algal population was determined by the DNA content using flow cytometry and defined as newly divided cells before the initiation of DNA replication (G₀/G₁) and cells at the end of the replication cycle with fully duplicated DNA content (G₂/M). Under different synchronized states of the cell population, the photosynthetic activity was investigated after treatment at 10, 100, and 1000?µmol?L^?1 atrazine exposed for 24?h by using fluorescence parameters related to PSII activity measured with a plant efficiency analyzer and pulse-amplitude modulated methods. In this study, we found that the atrazine effect was different depending on cell cycle phases and the period of illumination. Algal cells under light–dark cycle showed inhibition of the PSII electron transport leading to an increase of heat energy dissipation by the PSII reaction center. Algal cells grown under continuous light was shown to be more resistant to atrazine than the cells grown under light–dark cycle.     

Residue dynamics of carbendazim and mancozeb in grape (Vitis Vinifera L.) berries

The residue dynamics of carbendazim and mancozeb in grape berries is reported. The fungicides were sprayed in accordance with the most critical use pattern i.e. 4 times at 15 days interval separately at recommended and double doses. The residues of each fungicide dissipated following 1st order rate kinetics. The half-lives of carbendazim and mancozeb were 7.3 and 8.1 days at recommended dose and 4.6 and 5.7 days at double dose. Ethylenethiourea (ETU), the toxic metabolite of mancozeb was detectable at harvest following four sprays of mancozeb at recommended dose. At double dose, however, the residues of ETU could be detected even after three sprays of mancozeb. The pre-harvest intervals for carbendazim and mancozeb were found to be 26 and 12 days at recommended dose and 33 and 17 days at double dose, respectively.     

Metabolic fate of mancozeb in tomato (Lycopersicon esculentum)

The metabolic fate of mancozeb in tomato (Lycopersicon esculentum Mill.) fruits was evaluated. Results indicate rapid dissipation of mancozeb and its metabolic conversion to ethylenethiourea (ETU), the carcinogenic metabolite. Treatment with mancozeb at flowering stage resulted translocation of ETU in newly emerged fruits indicating the systemic nature of ETU. ETU was detected within one hour of final spraying of mancozeb at the doses of 1.5 and 3?kg a.i./ha. The residue level of ETU increased up to 3-day for both the treatments, which then rapidly dissipated to safer metabolite ethyleneurea (EU) and reached the below detectable limit within 25 days. Cooking of fresh tomatoes caused decontamination of mancozeb residues, which was associated with simultaneous increase in ETU residues. The degradation pattern of ETU after application of mancozeb was slower as compared to the spraying of ETU as such on the crop. A pre-harvest interval of 25 days is recommended.     

水土环境介质中阿特拉津修复过程研究进展

除草剂阿特拉津农用后的残留物会随地表径流或地下渗漏作用进入江河湖泊等自然水体,由于阿特拉津的环境内分泌干扰作用,其会造成水资源污染和水生态失衡。根据阿特拉津的生产和使用状况,将阿特拉津的污染对象分为土壤、市政污水、河流湖泊等地表水和地下水系统模块,分别阐述了这几种环境介质中阿特拉津的物理、化学和生物修复技术以及阿特拉津在修复过程中的变化特点,介绍了土壤在淋溶过程中阿特拉津的固定手段和今后污染水体中阿特拉津修复的研究重点。     

Applications of natural polysaccharide-based beads for slow release herbicide formulation

This work deals with the use of polysaccharide-based beads for controlled release of the herbicide atrazine. This article discusses the release of the herbicide atrazine from neem-alginate-clay-based beads. Formulation characteristics such as entrapment efficiency, bead size, and diffusion mechanism for release of atrazine have been evaluated.     

Measurement of residues of benomyl and mancozeb pesticides in shrub and nonshrub cucumbers sampled from different regions of Mazandaran province (Iran)

Farmers use mancozeb against cucumber pests, such as Perono spoxa, in large amounts without consideration of potential chronic human health hazards resulting from pesticide accumulation in food and fruits. Considering the necessity of food for humans and importance of fruit in daily diet, as well as the determination of pesticide residues in food and fruits as mandated by WHO and FAO, the residues benomyl and mancozeb, the most prominently used pesticides in Iran, were measured. In this study cucumbers from 76 sample regions were used. Data showed that the amounts of benomyl was related to the type of cucumber in the regions, but there was no significant relationship between the amount of mancozeb and type of cucumber.     

Atrazin

Atmospheric occurrence and deposition of atrazine are measured. During the application of atrazine, highest concentrations reached 1.6 μg·1^?1 in liquid water of lowlying clouds touching mountain tops. Atmospheric deposition, however, hardly amounts to 0.4% of the flux on crop land by direct spraying. Airborne concentrations ranged from less than 0.005 ng·m^?3 to 0.32 ng·m^?3. Contrary to theoretical expectations, almost all atrazine was found in the particulate matter, indicating nonequilibrium with the gas phase. This may inhibit a rapid photochemical decomposition. Human health concerns and environmental risks due to the atmospheric occurrence and deposition of atrazine are judged as minor. This conclusion can be applied to many other, physicochemically related pesticides.     

Persistence of atrazine impact on aneuploidy in Pacific oysters,<Emphasis Type="Italic"> Crassostrea gigas</Emphasis>

Widespread use of the herbicide atrazine has incited much research on its toxicity in aquatic systems, where it is routinely detected due to runoff from cultivated fields. Moreover, the determination of the genotoxic effect of such pollutants in the marine environment has become a major requirement for ecosystem protection. In the Pacific oyster, Crassostrea gigas, hypodiploid aneuploid cells have regularly been reported. There is a negative correlation between this phenomenon and growth, as well as evidence for a genetic basis. A positive relationship between atrazine and aneuploidy has previously been demonstrated in C. gigas adults and juveniles. To evaluate the persistence of this impact, our study examined the offspring of the same adult population previously treated with different atrazine doses (10 µg l^–1, representing a peak value found in a polluted environment and 100 µg l^–1), and a seawater control. We observed that these offspring exhibited significantly higher aneuploidy levels when their parents had been exposed to atrazine (14.9–16.9% in comparison with the control where the levels ranged from 11.4% to 12.8%). In addition, the present study examined the aneuploidy level of a sample of juveniles, previously exposed for 3.5 months to the same doses of atrazine, then transferred to non-polluted conditions for an additional period of 2.5 months; this aneuploidy level remained significantly different between the treatments applied. These results demonstrate the persistence of an atrazine impact on Pacific oyster aneuploidy in time, within and between generations, indicating that this widely used compound may represent an important factor causing at least medium-term damage to genetic material.Communicated by S.A. Poulet, Roscoff     

乙草胺和莠去津对土壤微生物的影响及安全性评价

采用密闭法测定了乙草胺和莠去津对土壤微生物呼吸作用的影响，并对其使用的环境安全性进行了评价。结果表明，乙草胺和莠去津对土壤微生物基本无影响；它们对土壤微生物的安全性属于低毒级或无实际危害级农药。     

阿特拉津在天然水体沉积物中的吸附行为

本文研究了阿特拉津在几种水体沉积物中的吸附、解吸规律,并进一步探讨了沉积物浓度、pH值和离子强度对其吸附行为的影响．结果表明,不同沉积物对阿特拉津的吸附程度由沉积物本身的总有机碳、粘土矿物、阳离子交换容量、比表面积以及铁锰氧化物等理化特性综合作用的结果,有机碳不是影响阿特拉津吸附的唯一重要因素．连续吸附实验结果指出,化合物的起始浓度愈大,吸附时间愈长,阿特拉津的最大吸附容量也愈大,且在解吸过程中表现出一定的滞后性(即不可逆吸附)．沉积物浓度与其吸附量呈负相关;溶液的pH值增大,沉积物对阿特拉津吸附能力减弱;离子强度愈大,沉积物对阿特拉津吸附能力愈强．     

阿特拉津在土壤中的降解途径及其对持留性的影响

通过田间和实验室试验，研究了除草剂阿特拉津在土壤中的降解代谢规律及其与土壤特性的关系。试验表明，阿特拉津施用后、在作物生长期内可降解９０％以上，土壤酸碱度对阿特拉津在土壤中的代谢有显著影响。在碱性土壤中阿特拉津主要经过微生物代谢而被降解；在酸性土壤中化学水解占优势地位。阿特拉津在强酸性土壤中的持留性（半衰期为６３ｄ）低于弱酸性土壤中的持留性（半衰期为８４ｄ），而在碱性土壤中由于较强的微生物降解作用，其持留性（半衰期为５１ｄ）最低。     

Atrazine contamination in agricultural soils from the Yangtze River Delta of China and associated health risks

Atrazine is one of the most widely applied and persistent herbicides in the world. In view of limited information on the regional contamination of atrazine in soils in China, this study investigated the spatial distribution and environmental impacts of atrazine in agricultural soils collected from the Yangtze River Delta (YRD) as an illustrative analysis of rapidly developing regions in the country. The results showed that the concentrations of atrazine in the YRD agricultural soils ranged from <1.0 to 113 ng/g dry weight, with a mean of 5.7 ng/g, and a detection rate of 57.7 % in soils. Pesticide factory might be a major source for the elevated levels of atrazine in Zhejiang Province. The contamination of atrazine was closely associated with land use types. The concentrations and detection rates of atrazine were higher in corn fields and mulberry fields than in rice paddy fields. There was no significant difference in compositions of soil microbial phospholipids fatty acids among the areas with different atrazine levels. Positive relationship (R = 0.417, p < 0.05, n = 30) was observed between atrazine and total microbial biomass. However, other factors, such as soil type and land management practice, might have stronger influences on soil microbial communities. Human health risks via exposure to atrazine in soils were estimated according to the methods recommended by the US EPA. Atrazine by itself in all the soil samples imposed very low carcinogenic risks (<10^?6) and minimal non-cancer risks (hazard index <1) to adults and children.     

Unprecedented total mineralization of atrazine and cyanuric acid by anodic oxidation and electro-Fenton with a boron-doped diamond anode

This article reports the complete mineralization of atrazine. Atrazine has been the most widely used s-triazine herbicide. Atrazine occurs in natural waters and presents a potential danger for public health because atrazine is considered as an endocrine disruptor. The use of chemical, photochemical and photocatalytic advanced oxidation processes (AOPs) to decontaminate waters containing atrazine only allowed its conversion into the cyanuric acid as ultimate end products, since it cannot be completely degraded by hydroxyl radicals (^•OH) produced by these techniques. The same behavior was previously reported for anodic oxidation and electro-Fenton with Pt anode, although better performances were found using boron-doped diamond (BDD) anode but without explaining the role of generated ^•OH. Here, the oxidative action of these radicals in such electrochemical AOPs has been clarified by studying the mineralization process and decay kinetics of atrazine and cyanuric acid in separated solutions by anodic oxidation with BDD and electro-Fenton with Pt or BDD anode using an undivided cell with a carbon-felt cathode under galvanostatic conditions. Results showed that electro-Fenton with BDD anode was the more powerful treatment to degrade both compounds. Almost total mineralization, 97% total organic carbon (COT) removal, of atrazine was only feasible by this method with a faster removal of its oxidation intermediates by ^•OH formed at the BDD surface than that formed in the bulk from Fenton reaction, although the latter process caused a more rapid decay of the herbicide. Cyanuric acid was much slowly mineralized mainly with ^•OH produced at the BDD surface, and it was not degraded by electro-Fenton with Pt anode. These results highlight that electrochemical advanced oxidation processes (EAOPs) using a BDD anode are more powerful than the classical electro-Fenton process with Pt or PbO₂ anodes.     

微生物对地下水及土壤中阿特拉津降解的研究

从吉林市农药厂采集的污泥样品中筛选出降解阿特拉津（AT）能力较高的菌－JLNY01，JLNY02，通过条件实验表明，JLNY01在pH=6左右，此菌在10℃条件下，一定时间内驯化降解率可达83．6％，30℃时，6天内可达到对AT的完全降解，证明温度越高降解效果越好，JLNY02可直接在低温条件下进行降解，其降解率可达81．8％，而在高温条件下降解率仅达31．4％，证明此菌是一种嗜冷菌。     

吸附反应时间对除草剂阿特拉津吸附行为的影响

采用批量动态实验方法,对潮土中阿特拉津吸附特征随吸附反应时间变化进行了研究。结果表明,土壤吸附的阿特拉津量随反应时间的变化符合双曲线函数关系。在50μg·L-1～2000μg·L-1浓度系列下,在48h内,土壤颗粒对阿特拉津的吸附属于快反应,土壤吸附的阿特拉津量随吸附反应时间呈指数上升,为吸附实验结束(168h)时土壤吸附阿特拉津总量的58%到90%。当吸附反应时间超过48h后,随反应时间增加,土壤吸附阿特拉津量差异变化不显著。阿特拉津在潮土颗粒和土壤溶液中的相分配可用Freundlich方程描述。吸附容量因子Kf与吸附反应时间之间有极显著的线性正关系(r2=0.9063**,p<0.0001)。无量纲的非线性因子n与吸附反应时间之间也具有显著的线性负关系(r2=0.5666*,p=0.0192)。     

Extractable atrazine and its metabolites in agricultural soils from the temperate humid zone

Extractable atrazine and its metabolites (hydroxyatrazine, deethylatrazine and deisopropylatrazine) were evaluated in agricultural soils from the temperate humid zone (Galicia, NW Spain) under laboratory conditions. The experiment was performed with five soils with different properties (organic C, soil texture and atrazine application history), both unamended and treated with atrazine at field application rate. Measurements of the atrazine compounds were made at different time intervals (1, 3, 6, 9 and 12 weeks) during a 3-month incubation period. Results showed that only hydroxyatrazine was detected in the extractable fraction of the unamended soils, with values remaining relatively constant throughout the incubation period. Atrazine addition notably increased the concentration of the parent compound and its degradation products; deisopropylatrazine and hydroxyatrazine were the main metabolites detected in the extractable fraction of the treated soils, whereas deethylatrazine was not detected. After 7 days incubation, values of total extractable residues, expressed as percentage of initially added atrazine, ranged from 75 to 86% (25–68% of atrazine, 7–11% of hydroxyatrazine and 9–57% of deisopropylatrazine). The values decreased rapidly during the first 3 weeks of incubation, showing values of 2–8% in soils with higher atrazine application and from 28 to 30% in soils with lower application history. At the end of the incubation, 2–8% of total extractable residues were still detected (0–4% of atrazine, 2–3% of hydroxyatrazine and 0–2% of deisopropylatrazine), indicating a residual effect of atrazine addition. These variations in the extractable fraction indicated that most added atrazine was rapidly degraded, especially in soils with higher application history.     

皇竹草对土壤阿特拉津的修复作用

通过盆栽试验探讨了种植皇竹草（Pennisetum hydridum）对阿特拉津污染土壤的修复效果,阿特拉津对皇竹草生长的影响,以及皇竹草对土壤微生物数量的影响,以期为阿特拉津污染土壤的植物修复提供参考。结果表明：在≤200 mg.kg-1质量分数范围以内,种植皇竹草对土壤阿特拉津的初期降解效率比对照明显提高,最大提高了29.64%,达到显著或极显著差异;阿特拉津质量分数在≤200 mg.kg-1范围内对皇竹草株高没有影响,≤50 mg.kg-1质量分数范围内对生物量没有影响,根冠比变化不明显;随阿特拉津质量分数的增加皇竹草根际和非根际土壤中的细菌、真菌、放线菌数量均呈先增加后减少的趋势,在质量分数为100 mg.kg-1时达到最大,根际土壤中细菌和放线菌数量明显高于非根际土壤,真菌数量在根际与非根际土壤中变化不明显。说明种植皇竹草有助于阿特拉津降解效率的提高,且与种植皇竹草后改变了土壤微生物数量及皇竹草的生长状况有关。     

Study of atrazine degradation in soil from Kenyan sugarcane-cultivated fields in controlled laboratory conditions

A study to compare the extent of atrazine mineralization in soils from Kenyan sugarcane-cultivated fields with and without history of atrazine use was carried out in the laboratory under controlled conditions. The study was testing the hypothesis that repeated atrazine application to soil will not result in enhanced atrazine mineralization. The study was carried out with ¹⁴C-uniformly ring-labeled atrazine in a laboratory under controlled conditions. Atrazine mineralization to ¹⁴CO₂ in soil with no history of atrazine use was negligible (0.16%) after 163 days of soil incubation. The three metabolites hydroxyatrazine, desisopropylatrazine, and desethylatrazine in the proportion of 17.7%, 1.3%, and 2.6%, respectively, were in the soil after 75 days. In the soil from the sugarcane-cultivated field with history of atrazine use, atrazine mineralization was 89.9% after 98 days. The same soil, amended with mature compost, showed a lag phase of eight days before rapid atrazine mineralization was observed.