高效液相色谱-电感耦合等离子体质谱联用测定生物样品中的有机汞

建立了酸提取-高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICP-MS)测定生物样品中甲基汞、乙基汞、苯基汞等3种有机汞的分析方法。鱼肉和贝类样品经盐酸消解,苯萃取,硫代硫酸钠溶液反萃取后,采用醋酸铵/L-半胱氨酸缓冲盐及甲醇体系组成的流动相按一定比例进行梯度洗脱,经前处理的生物样品在液相色谱中经C18柱分离后,进入电感耦合等离子体质谱检测其甲基汞、乙基汞和苯基汞的浓度。3种有机汞化合物均在0.50~50.0μg/L范围内呈现良好的线性关系,线性相关系数(r)均大于0.9998。方法检出限为0.010~0.038mg/kg;3种有机汞样品加标的RSD均小于12.2%;两个水平的加标回收率在50.8~129%。     

基于两种样品前处理方法对比研究小冬克玛底冰川雪坑中痕量元素

通过对唐古拉山小冬克玛底冰川雪坑中非季风季节沉积的雪样分别进行酸化处理和消解处理后,利用高分辨扇形磁场等离子体质谱仪(ICP-SFMS)测试了样品中19种痕量元素(Ba、U、Sr、Rb、Tl、Mo、Cs、Pb、Sb、V、Cr、Mn、Fe、Co、Al、Cu、Ti、Li、As)的酸化浓度和总浓度.研究结果表明,痕量元素浓度的变化范围较大,元素Al的最大/最小浓度比为326(酸化浓度)和465(总浓度),元素Pb相应比值为27和48.雪冰中痕量元素的总浓度一般大于该元素的酸化浓度,其中,元素Pb、Fe、Sb、Ba、Al、Ti的酸化浓度占总浓度的平均比值分别为91%、76%、60%、52%、33%和21%.一般地,样品中不溶微粒含量越大,酸化浓度占总浓度的比值越小;不溶微粒含量越小,则相反.对痕量元素的富集系数(EF)分析表明,各元素总浓度EF均值小于酸化浓度EF均值,揭示了用酸化浓度计算EF存在对痕量元素人为来源影响的高估.人类排放是小冬克玛底冰川中痕量元素的来源之一,对于元素Mo和Sb,人类排放估计是主要来源.利用后向轨迹模型模拟出小冬克玛底冰川雪冰中痕量元素在非季风季节主要来源于青藏高原西部及中亚中东地区.     

Fenton法和类Fenton法降解土壤中的二苯砷酸

本文对Fenton法与类Fenton法降解土壤中的二苯砷酸(diphenylarsinic acid,DPAA)进行了研究.考察了H2O2投加量和催化剂种类(Fe2+/Fe3+)对红壤及黑土中DPAA降解效果的影响,并采用高效液相色谱-质谱联用法(HPLC-MS/MS)对降解中间产物进行了初步鉴定.结果显示,针对红壤与黑土分别采用类Fenton法与Fenton法,在H2O2投加浓度为1 mol·L-1,含铁催化剂浓度为0.25 mol·L-1,土水比为1∶3,反应时间为1h的条件下,红壤及黑土中DPAA的降解率均可达到65%以上.HPLC-MS/MS的分析结果表明,DPAA可脱苯环形成降解产物苯砷酸(phenylarsinic acid,PAA),而PAA进一步氧化生成无机砷,这可能是Fenton/类Fenton法降解DPAA的途径之一.     

Chemopreventive effects of ellagic acid against genotoxicity induced by benzo(a)pyrene

Benzo(a)pyrene (B(a)P) is a commonly used indicator for polycyclic aromatic hydrocarbons (PAHs) contamination. The use of certain phytochemicals and some polyphenolic compounds proved to be effective in blocking PAH-induced effects. The aim of the present study was to examine the possible inhibitory effects of ellagic acid (EA), present in berries and nuts, against B(a)P-mediated toxicity using in vitro and in vivo test systems. In vitro method included the Ames test, using Salmonella typhimurium tester strain TA100. In vivo experiments were based on mouse bone marrow micronucleus (MN) assay and immunoblotting. EA produced a decrease in the number of revertant colonies against B(a)P in the Ames assay. Further, there was a reduction in the mean number of micronucleated polychromatic erythrocytes in the presence of EA in the co-treatment protocol of the MN test. Western blotting results showed downregulation of CYP450 isoform CYP1A1 which prevented bioactivation of B(a)P. Thus, the present study demonstrates antimutagenic role played by EA against the mutagenic activity of B(a)P in both in vitro and in vivo systems.     

3种填料A.ferrooxidans挂膜效果及对模拟酸性矿山废水中Fe2+生物矿化能力比较

氧化亚铁硫杆菌（A.ferrooxidans）介导的生物矿化方法可促使酸性矿山废水（Acid Mine Drainage,AMD）中Fe离子向次生铁矿物转变. 采用固定化的方式来提高A.ferrooxidans密度有助于强化Fe²⁺的生物矿化能力.选取流化床19孔填料、弹性填料、悬浮球填料作为挂膜对象, 通过多批次的连续培养来考察3种填料的A.ferrooxidans挂膜能力及稳定挂膜所需周期,继而比较3种挂膜填料对模拟AMD中Fe²⁺的生物矿化能力,并估算A.ferrooxidans有效生物量.结果表明,3种填料（5.00 g）的A.ferrooxidans挂膜能力依次为弹性填料（1.76 g）＞流化床19孔填料（0.90 g）＞悬浮球填料（0.78 g）（干重）,且挂膜启动至稳定状态至少需要4批次.X射线衍射分析（X-ray diffraction,XRD）表明,3种填料表面 含矿生物膜均为施氏矿物和黄钾铁矾的混合物.以游离态A.ferrooxidans的Fe²⁺氧化速率作为参比,估算出流化床19孔填料、弹性填料、悬浮球填料生物膜中A.ferrooxidans有效生物量依次为1.67×10⁸、8.52×10⁸、1.92×10⁸ cells·g^-1 （干基）.研究还发现,等同Fe²⁺生物氧化速率下, A.ferrooxidans挂膜填料比游离态A.ferrooxidans具有更强的AMD矿化驱动能力.     

模拟黑麦草根系有机酸参与下炼锌废渣对斑马鱼抗氧化酶和神经毒性的影响

为评价多金属矿山废渣堆场生态修复过程中,废渣在先锋修复植物根系分泌的机酸参与下浸出液对周边环境生物的影响.以斑马鱼（Danio rerio）为受试生物,通过模拟添加典型先锋植物（黑麦草）根系分泌的有机酸（草酸和酒石酸）处理贵州威宁土法炼锌废渣,以废渣浸出液对受试生物抗氧化酶和乙酰胆碱酯酶（AchE）的不同响应为评价指标,研究各处理组对斑马鱼抗氧化系统、神经系统及组织学的影响.结果表明,两种有机酸的参与均会不同程度地降低炼锌废渣浸出液的pH,并导致废渣释放出更多重金属;暴露于有机酸参与的废渣浸出液14 d后,受试生物组织中的抗氧化酶受到显著影响,并因无法克服长时间的氧化应激最终引起丙二醇（MDA）在组织中累积;有机酸参与下废渣浸出液对斑马鱼具有明显的神经毒性,长时间暴露后受试生物出现游动迟缓、呼吸慢和鳃盖张合频率降低的现象;鳃组织存在上皮细胞水肿、增生或脱落、鳃丝充血和鳃小片扭曲或断裂的现象,而肌肉组织中出现更多肌纤维核增大、固缩和碎裂的现象.综上,选用适生性和耐受性较强、根系发达且有机酸分泌量较大的先锋植物来修复多金属废渣场地将可能促进废渣中重金属的释放并引起环境生物抗氧化系统和神经系...     

Estimation of Nonpoint Source Nitrate Concentrations in Indiana Rivers Based on Agricultural Drainage in the Watershed

Subsurface tile‐drained agricultural fields are known to be important contributors to nitrate in surface water in the Midwest, but the effect of these fields on nitrate at the watershed scale is difficult to quantify. Data for 25 watersheds monitored by the Indiana Department of Environmental Management and located near a U.S. Geological Survey stream gage were used to investigate the relationship between flow‐weighted mean concentration (FWMC) of nitrate‐N and the subsurface tile‐drained area (DA) of the watershed. The tile DA was estimated from soil drainage class, land use, and slope. Nitrate loads from point sources were estimated based on reported flows of major permitted facilities with mean nitrate‐N concentrations from published sources. Linear regression models exhibited a statistically significant relationship between annual/monthly nonpoint source (NPS) nitrate‐N and DA percentage. The annual model explained 71% of the variation in FWMC of nitrate‐N. The annual and monthly models were tested in 10 additional watersheds, most with absolute errors within 1 mg/l in the predicted FWMC. These models can be used to estimate NPS nitrate for unmonitored watersheds in similar areas, especially for drained agricultural areas where model performance was strongest, and to predict the nitrate reduction when various tile drainage management techniques are employed.     

Life cycle assessment analysis of active and passive acid mine drainage treatment technologies

Acid mine drainage (AMD), resulting from open-cast coal mining, is currently one of the largest environmental challenges facing the mining industry. In this study, a life cycle assessment (LCA) was conducted to evaluate the environmental impacts associated with the construction, operation and maintenance of different AMD treatment options typically employed. LCA is a well-reported tool but is not documented for AMD treatment systems despite their ubiquitous implementation worldwide. This study conducted detailed LCA analysis for various passive and active AMD treatment approaches implemented or considered at a major coal mine in New Zealand using a comparative functional unit of kg acidity removed per day for each treatment option. Eight treatment scenarios were assessed including active limestone and hydrated lime treatments, and compared to passive treatments using limestone and waste materials such as mussel shells. Both midpoint and endpoint LCA impact categories were assessed. Generally, the active treatment scenarios demonstrated greater LCA impacts compared to an equivalent level of treatment for the passive treatment approaches. Lime slaking had the greatest LCA impacts, while passive treatment approaches incurred consistently less impacts except for one passive treatment with a purchased energy scenario. A 50% reduction in transportation distances resulted in the lowest LCA impacts for all scenarios. This study highlights the importance of evaluating the environmental and social impacts of AMD treatment for the mining industry.     

植物细胞对环境胁迫的适应性应答Ⅰ:水杨酸对大蒜培养细胞中超氧化物歧化酶的增效诱导

大蒜培养细胞对水杨酸的应答比对温度和水分胁迫的应答更为强烈，其主要特征是抗氧化酶类超氧化物歧化酶的大量生成，同时还观察到水杨酸对冷胁迫或热休克介导的酶诱导作用的强化．上述结果暗示着自由基的生成是环境胁迫作用于植物细胞的机制之一，水杨酸诱导产生的抗氧化活性高于冷胁迫或热休克．这表明化学胁迫可能以一种与物理胁迫不同的方式诱导超氧化物歧化酶同工酶的生成     

A conceptual framework: Redefining forest soil's critical acid loads under a changing climate

Federal agencies of several nations have or are currently developing guidelines for critical forest soil acid loads. These guidelines are used to establish regulations designed to maintain atmospheric acid inputs below levels shown to damage forests and streams. Traditionally, when the critical soil acid load exceeds the amount of acid that the ecosystem can absorb, it is believed to potentially impair forest health. The excess over the critical soil acid load is termed the exceedance, and the larger the exceedance, the greater the risk of ecosystem damage. This definition of critical soil acid load applies to exposure of the soil to a single, long-term pollutant (i.e., acidic deposition). However, ecosystems can be simultaneously under multiple ecosystem stresses and a single critical soil acid load level may not accurately reflect ecosystem health risk when subjected to multiple, episodic environmental stress. For example, the Appalachian Mountains of western North Carolina receive some of the highest rates of acidic deposition in the eastern United States, but these levels are considered to be below the critical acid load (CAL) that would cause forest damage. However, the area experienced a moderate three-year drought from 1999 to 2002, and in 2001 red spruce (Picea rubens Sarg.) trees in the area began to die in large numbers. The initial survey indicated that the affected trees were killed by the southern pine beetle (Dendroctonus frontalis Zimm.). This insect is not normally successful at colonizing these tree species because the trees produce large amounts of oleoresin that exclude the boring beetles. Subsequent investigations revealed that long-term acid deposition may have altered red spruce forest structure and function. There is some evidence that elevated acid deposition (particularly nitrogen) reduced tree water uptake potential, oleoresin production, and caused the trees to become more susceptible to insect colonization during the drought period. While the ecosystem was not in exceedance of the CAL, long-term nitrogen deposition pre-disposed the forest to other ecological stress. In combination, insects, drought, and nitrogen ultimately combined to cause the observed forest mortality. If any one of these factors were not present, the trees would likely not have died. This paper presents a conceptual framework of the ecosystem consequences of these interactions as well as limited plot level data to support this concept. Future assessments of the use of CAL studies need to account for multiple stress impacts to better understand ecosystem response.