Bottom-up approach for the reaction of xenobiotics and their metabolites with model substances for natural organic matter by electrochemistry-mass spectrometry (EC-MS)

Risk assessment of xenobiotics requires a comprehensive understanding of their transformation in the environment. As most of the transformation processes usually involve a redox reaction or a hydrolysis as the first steps of the transformation, we applied an approach that uses an electrochemical cell to investigate model “redox” reactions in aqueous solutions for environmental processes. We investigated the degradation of a variety of xenobiotics from polar to nonpolar and analyzed their degradation products by on-line coupling of electrochemistry with mass spectrometry (EC-MS). Furthermore, we evaluated possible binding reactions with regard to the generation of non-extractable residues with some model substances (catechol, phthalic acid, γ-l-Glutamyl-l-cysteinyl-glycine (GSH) and l-histidine) deduced from a natural organic matter (NOM) structure model and identified possible binding-sites.Whereas typically investigations in soil/water-systems have been applied, we used to our knowledge for the first time a bottom-up approach, starting from the chemicals of interest and different model substances for natural organic matter to evaluate chemical binding mechanisms (or processes) in the EC-MS under redox conditions. Under oxidative conditions, bindings of the xenobiotics with catechol, GSH and histidine were found, but no reactions with the model compound phthalic acid were observed. In general, no chemical binding has yet been found under reductive conditions. In some cases (i.e. benzo[a]anthracene) the oxidation product only underwent a binding reaction, whereas the xenobiotic itself did not undergo any reactions.EC-MS is a promising fast and simple screening method to investigate the environmental behavior of xenobiotics and to evaluate the potential risks of newly synthesized substances.     

Release of pentachlorophenol from black carbon-inclusive sediments under different environmental conditions

To investigate the feasibility of using black carbon (BC) in the control of hydrophobic organic contaminants (HOCs) in sediment, we added BCs from various sources (rice straw charcoal (RC), fly ash (FC) and soot (SC)) to sediment to create different BC-inclusive sediments and studied the release of pentachlorophenol (PCP) in the sediments under different condition. Different pH values had no obvious effect on the release of PCP in BC-inclusive sediment, but solid/liquid ratio, temperature, salinity and dissolved organic matter (DOM) content had significant influences on the release of PCP in all sediments except the RC-inclusive sediment. Adding 2% RC to sediment resulted in a 90% decrease in PCP release, which was a greater decrease than observed with FC- and SC-inclusive sediments. Therefore, from the standpoint of HOC release, the application of RC is feasible for organic pollution control in the water environment.     

红壤模拟铜污染下紫云英根表形态及其组织和细胞结构变化

采用根形态研究、显微镜观察和透射电子显微镜观察,研究了红壤模拟铜污染下紫云英根表形态及其组织、细胞结构变化.结果表明:当污染铜为0～40mg·kg^-1时,紫云英生长发育正常,根形态完好,功能正常.当污染铜水平在50 mg·kg^-1以上时,紫云英根开始出现受害症状:表现在根粗短呈淡褐色,根毛少且短,主根弯曲,并分出较短的叉根;表皮层出现皱缩;细胞壁略呈波浪形,厚薄不均,质膜界线不明显.紫云英地上部分生长发育受影响,产量开始下降.铜污染水平达到200mg·kg^-1时,根腐烂、组织黑色化、细胞壁断裂,胞质严重收缩解离,紫云英死亡,表明供试红壤临界铜污染浓度为50mg·kg^-1,并且紫云英根对土壤铜污染的耐性随生育期延长而增强,根细胞壁是根耐毒的主要部位.     

土壤中铬的形态及其转化

通过土壤中不同结合态铬的逐级提取方法的研究,提出了以１ｍｏｌ／Ｌ ＮＨ４Ａｃ,２ｍｏｌ／Ｌ ＨＣｌ和５％Ｈ２Ｏ２－２ｍｏｌ／Ｌ ＨＣｌ提取的铬分别为交换态铬,沉淀态铬和有机结合态铬。自然土壤中铬主要以沉淀态铬和残渣态铬形式存在,还原条件下,土壤中铬有向有机结合态铬转化的趋势,降低土壤ｐＨ,水溶态和代换态铬含量增加,沉淀态和残渣态铬含量降低,添加Ｃｒ（Ⅲ）能使土壤本身ｐＨ值下降,添加Ｃｒ（Ⅵ）使土壤     

Removal of nitrogen from wastewater with perennial ryegrass/artificial aquatic mats biofilm combined system

To develop a cost-effective combined phytoremediation and biological process,a combined perennial ryegrass/artificial aquatic mat biofilm reactor was used to treat synthetic wastewater.Influent ammonium loading,reflux ratio,hydraulic retention time(HRT) and temperature all had significant effects on the treatment efficiency.The results indicated that the effluent concentration of ammonium increased with increasing influent ammonium loading.The reactor temperature played an important role in the nitrification process.The ammonium removal efficiency significantly decreased from 80% to 30%-50% when the reactor temperature dropped to below 10°C.In addition,the optimal nitrogen removal condition was a reflux ratio of 2.The nitrate and ammonium concentration of the effluent were consistent with the HRT of the combined system.The chemical oxygen demand(COD) removal efficiency was at a high level during the whole experiment,being almost 80% after the start-up,and then mostly above 90%.The direct uptake of N by the perennial ryegrass accounted for 18.17% of the total N removal by the whole system.The perennial ryegrass absorption was a significant contributor to nitrogen removal in the combined system.The result illustrated that the combined perennial ryegrass/artificial aquatic mat biofilm reactor demonstrated good performance in ammonium,total N and COD removal.     

微囊藻毒素导致鲫鱼淋巴细胞凋亡的研究

采用离体细胞培养诱导方法,以鲫鱼(Garassiusauratus)为实验材料,研究了两种微囊藻毒素microcystinLR(MCLR)和microcystinRR(MCRR)在低浓度下(1nmol·L-1,5nmol·L-1和10nmol·L-1)对鲫鱼淋巴细胞的毒性效应.结果表明,鲫鱼淋巴细胞分别经两种微囊藻毒素体外诱导2h后,出现细胞核固缩的典型细胞凋亡形态学特征;琼脂糖凝胶电泳检测到明显的细胞凋亡的生物化学特征梯状DNA(DNAladder);并且两种藻毒素诱导的细胞凋亡呈时间和剂量效应关系.该研究表明微囊藻毒素可导致鱼类淋巴细胞产生凋亡,因而可能影响鱼类免疫功能.     

Assessment of phenanthrene bioavailability in aged and unaged soils by mild extraction

It has become apparent that the threat of an organic pollutant in soil is directly related to its bioavailable fraction and that the use of total contaminant concentrations as a measure of potential contaminant exposure to plants or soil organisms is inappropriate. In light of this, non-exhaustive extraction techniques are being investigated to assess their appropriateness in determining bioavailability. To find a suitable and rapid extraction method to predict phenanthrene bioavailability, multiple extraction techniques (i.e., mild hydroxypropyl-β-cyclodextrin (HPCD) and organic solvents extraction) were investigated in soil spiked to a range of phenanthrene levels (i.e., 1.12, 8.52, 73, 136, and 335 μg g^− 1 dry soil). The bioaccumulation of phenanthrene in earthworm (Eisenia fetida) was used as the reference system for bioavailability. Correlation results for phenanthrene suggested that mild HPCD extraction was a better method to predict bioavailability of phenanthrene in soil compared with organic solvents extraction. Aged (i.e., 150 days) and fresh (i.e., 0 day) soil samples were used to evaluate the extraction efficiency and the effect of soil contact time on the availability of phenanthrene. The percentage of phenanthrene accumulated by earthworms and percent recoveries by mild extractants changed significantly with aging time. Thus, aging significantly reduced the earthworm uptake and chemical extractability of phenanthrene. In general, among organic extractants, methanol showed recoveries comparable to those of mild HPCD for both aged and unaged soil matrices. Hence, this extractant can be suitable after HPCD to evaluate risk of contaminated soils.     

Development of a novel solid-phase extraction element for the detection of nonylphenol in the surface water of Hangzhou

Nonylphenol (NP) is a representative environmental endocrine-disrupting chemical and persistent toxic pollutant. Previous studies have shown that the average concentration of NP in environmental waters was approximately tens to hundreds of ng L(-1) and it could even reach up to tens of μg L(-1). A simple, fast and accurate method employing a novel solid-phase extraction element named "Magic Chemisorber" (MC) followed by high-performance liquid chromatography (HPLC) using a fluorescence detector (FLD) was used for detecting NP. The most important parameters that affect the extraction process, including extraction time, desorption time, desorption solvent and repeatability, were optimized. The MC-HPLC method showed good linearity with concentrations of NP from 10 to 200 μg L(-1), a correlation coefficient of 0.9995 and the limit of detection (LOD) and limit of quantification (LOQ) of this method was 0.44 and 1.47 μg L(-1), respectively. Compared to commercial polydimethylsiloxane (PDMS) glass fiber, MC had both higher capacity and recovery and it could be used repeatedly. Using the MC-HPLC method we found that the concentration of NP in river water from Hangzhou city ranged from 8.54 ± 1.23 μg L(-1) (Qiantang River) to 65.77 ± 3.69 μg L(-1) (Tiesha River), which was similar to that of international regions heavily polluted with NP and higher than that of Bohai Bay, the Yellow River and the Pearl River Delta in China. This level of NP pollution is possibly related to the rapid development of the textile, printing and paper industries of Zhejiang province.     

CuO负载在TiO2和CeO2-TiO2上对NO+CO反应的催化作用

用N0＋C0微反流动法、TPR、XRD、BET和NO-TPD等技术研究了CuO在Ti02和Ce02-Ti02上对N0＋CO的催化还原作用。实验表明，不同负载量的Cu0在Ti02上，其N0＋CO的反应活性以Cul2-Ti为最佳，在反应温度为400℃时，NO的转化率达到100%；且CuO负载在CeO2-TiO2上其活性随CeO2含量的增加而提高，Cul2-CelO-Ti在300℃时就能使NO达到100℃转化。XRD和TPR结果显示，该体系催化活性的高低，与CuO在TiO和CeO2/TiO2上高度分散的Cu物种及形成细颗粒的晶相CuO物种有非常密切的关系；NO-TPD结果显示，催化剂还原活性的高低和NO在催化剂表面的脱出与分解难易程度有关。     

阜新地区土地荒漠化演变与生态建设

以RS和GIS作为信息获取与分析工具，通过对1978年、1989年研究区土地荒漠化遥感影像解译分析，对阜新地区21年来土地荒漠化的演变规律进行了系统的研究。结果表明，荒漠化的空间演变经历了“强化－逆转－强化”的过程，荒漠化则表现为“重度荒漠化逆转，轻度荒漠化扩展”的演为格局，不同类型的荒漠化（风蚀荒漠化、水蚀荒漠化、盐渍荒漠化）分别有不同的演变规律。在此基础上，对土地荒漠化进行了区位划分，提出了土地荒漠化区分区治理的模式，并从恢复生态学角度提出了区域生态恢复的政策和法律对策。