Endosulfan in China 1—gridded usage inventories

Background, aim, and scope  Endosulfan, an organochlorine pesticide (OCP), is genotoxic in mammalian cells and generally considered to be toxic and classified by the World Health Organization and the US Environmental Protection Agency as priority pollutants and a nominator for inclusion in a future iteration of the persistent organic pollutants treaty. Endosulfan is a currently used pesticide and still being used worldwide. The general trend of total global endosulfan use has increased continuously since the first year when this pesticide was applied. It is critical to create national endosulfan usage/emission inventories for China to carry out source–receptor relation analysis, risk assessment, and other research related to endosulfan in this country. Chinese inventories have been published for some OCPs, such as technical HCH and lindane, DDT, and chlordane; for endosulfan, however, there has not been any usage inventory available on any scales (national or provincial), although endosulfan has been widely used since 1994 in this country. This is the first part of the work. The goal of this paper is to quantify the historical production and usage of endosulfan in China and to compile gridded historical usage inventories of endosulfan for this country. Based on these usage inventories, emission and residue inventories will be created, which is the goal of the second part of the work. Materials and methods  Due to the lack of national production and usage information of endosulfan in China, a method to estimate the use of endosulfan was developed. First, information of crops on which endosulfan is applied and average endosulfan use and annual application frequencies of endosulfan on these crops were collected. Secondly, usage of endosulfan on each crop was estimated using the national cropland area for each province from Chinese government reports. Finally, with the help of GIS (geographic information system), the usage data of this insecticide was allocated to a grid system, with a 1/4° longitude by 1/6° latitude resolution, with a size for each grid cell of approximately 25 km by 25 km. Results and discussion  The use of endosulfan in agriculture in China started on cotton in 1994, and on wheat, tea, tobacco, apples, and other fruits in 1998. Endosulfan usage on cotton, wheat, tea, tobacco, and apples in China has been estimated to be approximately 25,700 t between 1994 and 2004. The province with the highest usage of endosulfan is Henan Province, with a total usage reaching 4,000 t, followed by the uses in Xinjiang Autonomous Region (3,200 t), Shandong Province (3,000 t), Hebei Province (2,100 t), and Anhui Province (1,900 t). Gridded usage inventories of endosulfan at a 1/4° longitude by 1/6° latitude resolution have been created, which indicate that the intensive endosulfan use was in the south of Hebei Province, west of Shandong Province, east of Henan Province, north of Anhui Province, east of Jiangsu Province, and some areas in Yunnan Province and Xinjiang Autonomous Region. General agreement has been found between the usage data from our estimation and the small amount of usage data published in China. Conclusions  This is the first national gridded endosulfan usage inventory produced for China. The annual applications of endosulfan from 1994 to 2004 in China were estimated based on the total areas of major crops, on which endosulfan was applied, and spatial distribution of the application was generated at provincial and prefecture levels. With the help of GIS, endosulfan usage based on prefecture was transferred to a 1/4° longitude by 1/6° latitude gridding system. The satisfaction of the inventories was supported by the consistence between the estimation of the annual usage and the reported annual production of endosulfan. Recommendations and perspectives  This gridded endosulfan usage inventory created in this study will be improved upon availability of new information of endosulfan. The usage inventories can be used to create gridded emission and residue inventories for this insecticide. It is believed that this work will pave the way for further endosulfan studies in China and beyond.     

强化土著微生物处理硝基苯和苯胺污染地下水

以硝基苯、苯胺为主要污染物的污染地下水为研究对象,加入激活剂(乳糖、Na2HPO4、乳糖+Na2HPO4、乙醇、牛肉膏、蛋白胨)激活土著微生物,并考察其对土著微生物生长及硝基苯、苯胺降解效果的影响。加入激活剂3d后测各个水样的脱氢酶活性,对培养9d后的水样进行气相色谱/质谱(GC/MS)分析。结果表明,加入乳糖的水样中,其微生物相对增长率达157.2%,硝基苯、苯胺的相对去除率分别为14.90%和0.79%;加入Na2HPO4和乙醇的水样中,其微生物增长和硝基苯、苯胺降解情况均没有明显变化;加入乳糖+Na2HPO4的水样中,微生物相对增长率达180.3%,硝基苯、苯胺的相对去除率分别为24.20%和1.21%;加入牛肉膏的水样中,微生物的相对增长率为830.7%,硝基苯、苯胺的相对去除率分别为99.99%和99.67%;加入蛋白胨的水样中,其微生物相对增长率为686.0%,硝基苯、苯胺的相对去除率分别为99.33%和58.94%。GC/MS分析结果表明,加入激活剂后对氯苯胺、1-甲基-4-硝基苯等其他有机物的降解率均有提高。由此可见,通过激活土著微生物修复有机物污染地下水是可行的。     

基于PROMETHEEⅡ法的污染场地土壤修复技术筛选及应用

依据当前污染场地土壤修复技术特点以及场地特征,构建4层12指标21方案的污染土壤修复技术决策分析结构,运用多属性决策分析方法——PROMETHEEⅡ偏好排序法,对当前场地修复技术以及典型场地条件进行了客观分析和综合评价,实现基于具体修复目标的污染场地土壤修复技术择优筛选,并采用该方法对虚拟特定污染场地的土壤修复技术筛选进行了实例应用。这为污染场地的治理和修复提供了方法依据和理论参考。     

The adaptive response of lichens to mercury exposure involves changes in the photosynthetic machinery

Lichens are an excellent model to study the bioaccumulation of heavy metals but limited information is available on the molecular mechanisms occurring during bioaccumulation. We investigated the changes of the lichen proteome during exposure to constant concentrations of mercury. We found that most of changes involves proteins of the photosynthetic pathway, such as the chloroplastic photosystem I reaction center subunit II, the oxygen-evolving protein and the chloroplastic ATP synthase β-subunit. This suggests that photosynthesis is a target of the toxic effects of mercury. These findings are also supported by changes in the content of photosynthetic pigments (chlorophyll a and b, and β-carotene). Alterations to the photosynthetic machinery also reflect on the structure of thylakoid membranes of algal cells. Response of lichens to mercury also involves stress-related proteins (such as Hsp70) but not cytoskeletal proteins. Results suggest that lichens adapt to mercury exposure by changing the metabolic production of energy.     

Effect of humic acids on physicochemical property and Cd(II) sorption of multiwalled carbon nanotubes

Zinc pyrithione is used as an antifouling agent. However, the environmental impacts of zinc pyrithione have recently been of concern. Zinc induces diverse actions during oxidative stress; therefore, we examined the effect of zinc pyrithione on rat thymocytes suffering from oxidative stress using appropriate fluorescent probes. The cytotoxicity of zinc pyrithione was not observed when the cells were incubated with 3 μM zinc pyrithione for 3 h. However, zinc pyrithione at nanomolar concentrations (10 nM or more) significantly increased the lethality of cells suffering from oxidative stress induced by 3 mM H₂O₂. The application of zinc pyrithione alone at nanomolar concentrations increased intracellular Zn²⁺ level and the cellular content of superoxide anions, and decreased the cellular content of nonprotein thiols. The simultaneous application of nanomolar zinc pyrithione and micromolar H₂O₂ synergistically increased the intracellular Zn²⁺ level. Therefore, zinc pyrithione at nanomolar concentrations may exert severe cytotoxic action on cells simultaneously exposed to chemicals that induce oxidative stress. If so, zinc pyrithione leaked from antifouling materials into surrounding environments would be a risk factor for aquatic ecosystems. Alternatively, zinc pyrithione under conditions of oxidative stress may become more potent antifouling ingredient.     

Electrogeneration of H(2) for Pd-catalytic hydrodechlorination of 2,4-dichlorophenol in groundwater

A novel electrolytic groundwater remediation process, which used the H₂ continuously generated at cathode to achieve in situ catalytic hydrodechlorination, was developed for the treatment of 2,4-dichlorophenol (2,4-DCP) in groundwater. Catalytic hydrodechlorination using Pd supported on bamboo charcoal and external H₂ showed that 2,4-DCP was completely dechlorinated to phenol within 30 min at pH ? 5.5. In a divided electrolytic system, the catalytic hydrodechlorination of 2,4-DCP in cathodic compartment by H₂ generated at the cathode under 20 and 50 mA reached 100% at 120 and 60 min, respectively. Two column experiments with influent pHs of 5.5 (unconditioned) and 2 were conducted to evaluate the feasibility of this process. The 2,4-DCP removal efficiencies were about 63% and nearly 100% at influent pHs of 5.5 and 2, respectively. Phenol was solely produced by 2,4-DCP hydrodechlorination, and was subsequently degraded at the anode. A low pH could enhance the hydrodechlorination, but was not necessarily required. This study provides the preliminary results of a novel effective electrolytic process for the remediation of groundwater contaminated by chlorinated aromatics.     

Subcellular distribution and toxicity of cadmium in Potamogeton crispus L

The submerged macrophyte Potamogeton crispus L. was subjected to varying doses of cadmium (0, 20, 40, 60 and 80 μM) for 7 d, and the plants were analyzed for subcellular distribution of Cd, accumulation of mineral nutrients, photosynthesis, oxidative stress, protein content, and ultrastructural distribution of calcium (Ca). Leaf fractionation by differential centrifugation indicated that 48-69% of Cd was accumulated in the cell wall. At all doses of Cd, the levels of Ca and B rose and the level of Mn fell; the levels of Fe, Mg, Zn, Cu, Mo, and P rose initially only to decline later. Exposure to Cd caused oxidative stress as evident by increased content of malondialdehyde and decreased contents of chlorophyll and protein. Photosynthetic efficiency, as indicated by the quenching of chlorophyll a fluorescence (Fv/Fm, Fo and Fm), decreased significantly, the extent of decrease being directly proportional to the concentration of Cd. Increased amounts of precipitates of calcium were noticed in the treated plants, located either outside the cell membrane or in chloroplasts, mitochondria, the nucleus, and the cytoplasm whereas control plants showed small deposits of the precipitates around surface of the vacuole membrane and in the intercellular space but rarely in the cytoplasm. Photosynthetic efficiency and oxidative stress could be used as indicators of physiological end-points in determining the extent of Cd phytotoxicity.     

Photodegradation of quinestrol in waters and the transformation products by UV irradiation

Quinestrol is synthetic estrogen used in contraceptive and hormone replacement therapy and occasionally for treating breast cancer and prostate cancer. It can make its way into the environment through sewage discharge and waste disposal produced by human excretions. In this study, the photodegradation kinetics of quinestrol in various conditions was investigated by UV and solar irradiation. The affecting factors were studied including concentration of hydrogen peroxide, different water types, and the initial concentrations of quinestrol. Concurrently, the transformation products and presumed pathways of quinestrol in distilled water by UV irradiation were identified and proposed. The results showed that the degradation of quinestrol in both irradiation conditions followed the pseudo-first-order kinetics. More rapid degradation was observed by UV irradiation (k = 0.018 min⁻¹) than solar irradiation (k = 0.004 h⁻¹), and the photodegradation rate of quinestrol depended on the concentration of hydrogen peroxide, the initial concentration of quinestrol and water types. The transformation products of quinestrol in distilled water were identified by gas chromatography/mass spectrometry. When exposed to UV irradiation, quinestrol in aqueous solution was rapidly degraded, giving at least ten photodegradation products. The chemical structures of ten degradation products were identified on the basis of mass spectrum interpretation and literature data.     

SO2-4/TiO2光催化降解苯酚

以工业硫酸氧钛为原料水解制得SO42-/TiO2光催化剂,并以苯酚为目标降解物,考察了SO24-/TiO2的光催化性能。结果表明:随着SO42-/TiO2制备过程中焙烧温度的升高,其光催化活性逐渐增加,650℃焙烧获得的SO24-/TiO2的光催化活性最好,此后再升高温度会因催化剂中硫的挥发而下降;在确定苯酚原液初始浓度为50 mg/L条件下,SO42-/TiO2的光催化降解苯酚的最佳工艺条件为反应时间2 h、苯酚pH为7、催化剂用量1 g/L。XRD、SEM和FTIR的分析结果显示实验温度下制得的SO42-/TiO2均为锐钛型TiO2;其间掺杂的SO24-在TiO2表面分散性较好,没有聚集成大的颗粒;红外分析的结果初步判定低温(<550℃)焙烧制得的催化剂SO42-在TiO2表面是螯合双配位吸附,高温焙烧时(>550℃)SO42-在TiO2表面是桥式配位吸附。     

外源Cd对不同利用方式红壤脲酶活性的影响

采用室内培养实验,通过将外源Cd添加到同一母质、全镉含量相近的不同利用方式的红壤中(林地、水稻土和菜园土),研究了外源Cd污染对不同利用方式红壤脲酶活性的影响。结果表明:整个培养过程中,Cd污染对3种红壤脲酶活性都有抑制作用,且随重金属浓度的增强而增强。同剂量Cd污染对3种红壤脲酶活性的抑制效应不同,大小为林地>水稻土>菜园土。实验设定的Cd处理水平下,对林地、水稻土和菜园土脲酶活性产生显著抑制作用(p<0.05)的Cd浓度分别为5、30和50 mg/kg土。