铜和镍对大麦根伸长的联合毒性研究

重金属的复合污染在环境污染中普遍存在,所以复合污染的联合毒性研究对于准确评价重金属污染有着重要的意义.本论文以大麦根伸长为研究对象,探索了铜(Cu)和镍(Ni)对大麦根伸长的联合毒性.基于Cu-Ni混合物的剂量-效应曲线,运用扩展的浓度加和(CA)与独立作用(RA)两个模型对不同浓度组合的Cu-Ni混合物的交互作用及联合毒性进行预测.结果表明,扩展的CA和RA模型均能较好地预测Cu-Ni混合物对大麦根伸长的联合毒性,低剂量的Ni能缓解Cu对大麦根伸长的毒性作用,但是低剂量的Cu对Ni的生物毒性没有显著影响.研究阐明了Cu、Ni复合作用对大麦根伸长联合毒性的效应机理.     

我国四个大气背景点颗粒物浓度及其元素分布特征

选择全国由南至北的4个大气背景站(广东南岭、湖北神农架、山西庞泉沟和吉林长白山),于2013年分4个季度同步采集环境空气颗粒物PM10和PM2.5样品,采用微波消解电感耦合等离子体质谱法测定滤膜样品中60余种元素.结果表明,4个背景点PM2.5日均质量浓度平均值为17μg·m-3,PM10为29μg·m-3,低于《环境空气质量标准》(GB 3095—2012)规定的一级浓度限值.第一季度的PM10和PM2.5最高,除长白山第三季度高于第四季度之外,其他3个点位均呈现第二季度第四季度第三季度的趋势.PM2.5和PM10二者呈线性正相关,4个季度的PM2.5/PM10比值均小于0.5,第二、第三季度较高,而第一、第四季度较低.PM10和PM2.5中元素随季节变化不大,PM2.5含量在同一水平上低于PM10.Na、Mg、Al、S、K、Ca、Fe、Zn质量浓度在0.1—10μg·m-3之间,P、Ti、Mn、Ni、Cu、Ba、Pb质量浓度在10—100 ng·m-3之间,Cd、Co、Ge、Ga、Zr、Sr、V等质量浓度在0.01—10 ng·m-3之间.K、Al、Ca含量大于10%,S、Mg、Na、Fe、Zn、Pb、Mn含量大于1%,Cu、P、Ba、Ti量介于0.5%—1%,其他痕量元素含量所占比例小于0.5%.     

京津冀冬季与夏季PM_(2.5)/PM_(10)及其水溶性离子组分区域性污染特征分析

为研究京津冀地区冬、夏两季大气颗粒物质量浓度与水溶性离子组成特征,于2013年2月、7月对北京、天津、石家庄及4个国家大气背景点进行了PM2.5及PM10的采样,分析了质量浓度及9种水溶性离子,结果表明:(1)京津冀地区颗粒物污染冬季重于夏季,冬季污染水平石家庄天津北京,夏季污染天津、北京石家庄,区域内PM2.5与PM10之间有很好的相关性,相关系数r冬季为0.8796,夏季为0.8424,说明整个区域颗粒物污染有较为相近的来源,大气颗粒物污染表现出区域性特征;(2)京津冀地区PM2.5及PM10中的9种水溶性离子浓度规律为NO-3、SO2-4、NH+4Cl-、Ca2+K+、Na+F-、Mg2+.该地区水溶性离子污染冬季最重为石家庄,夏季则为北京;(3)在京津冀地区二次离子NO-3、SO2-4、NH+4是主要的污染离子,3种离子质量浓度总和在PM2.5、PM10中冬季分别占48.9%、27.8%,夏季分别占58.7%、48.5%.二次离子主要集中在PM2.5中,其对细离子浓度的升高起到直接作用,且二次离子的构成关系也在发生变化.整个区域向硝酸型污染转变,二次离子的季节分布也呈现区域特征,冬季NO-3离子质量浓度比重最大.夏季则为SO2-4;(4)粒径越小富集水溶性离子的能力越强,在PM1中分布了50%以上的水溶性离子,73.9%—94.8%的水溶性离子分布在PM2.5中.     

流域水文干旱等级预测问题的研究

采用滦河潘家口水库控制流域9个水文站1958-2009年的逐月流量数据,通过计算各站12个月时间尺度的标准化径流指数(SRI),得到了实测水文干旱等级序列。根据干旱等级转换的观测频数,提出了基于三维列联表的对数线性干旱预测模型,并计算了干旱等级转换间的优势及其置信区间,以估算干旱等级转换的概率,实现了滦河潘家口水库控制流域预见期为1个月和2个月的水文干旱等级预测。选取2000-2009年的水文干旱演变过程对预测模型进行了验证。结果表明:干旱等级转换的三维列联表呈现一种强对角线趋势,各站三维对数线性模型的检验显著性水平p均大于检验水准α(0.05),观测频数与期望频数吻合程度高,且预见期为1个月的水文干旱等级预测精度较高,可用于滦河潘家口水库控制流域短期水文干旱预警。但预见期为2个月的水文干旱等级的预测误差较大,需根据流域的气候特征及下垫面的物理状态对模型进行进一步的改进。因此,如何综合应用气象和水文干旱监测信息,并采用对数线性预测法建立新的模型对水文干旱进行提前预警是需要解决的重要问题。     

三维Pd/OMC粒子电极体系电催化泛影酸盐还原脱碘研究

以泛影酸盐(DTZ)的高效还原脱碘为目标,通过硼氢化钠还原法制备钯负载有序介孔碳(Pd/OMC)作为粒子电极,以碳纤维(CFP)电极作为主阴极,建立了三维电极电催化还原体系.该体系在低阴极电位下(-0.6～-0.8 V)可实现电化学/感应电化学的耦合还原,其脱碘速率是单独阴极体系的2.38～3.65倍;在阴极电位高于析氢电位(-1.5 V)时,可实现电化学/感应电化学/化学催化加氢多还原过程协同去除碘代有机物,其反应速率为单独阴极体系的1.27～4.69倍.进一步研究了DTZ初始浓度、Pd/OMC投加量及Pd的负载量对DTZ还原去除的影响.电化学测试结果表明三维电化学体系具有良好的电子传递能力与电还原性能.利用自由基淬灭实验与ESR自由基捕获对活性还原物种分析,表明原子H~*在三维电化学还原脱碘过程中起重要作用.     

我国涉汞危废处置企业中汞分布特征及风险评价

为了解涉汞危废企业对周边环境的影响及其潜在风险,加强涉汞危险废物的监督管理,通过2007年至2013年对13个持环保部发证的涉汞危废处置企业每年一次的监督性监测,分析了我国涉汞危废处置企业不同环境介质中汞分布特征及其风险。研究结果显示,2007年至2013年我国涉汞危废处置企业土壤、地下水、无组织排放气体中汞的浓度范围分别为0.75~28.4 mg·kg-1、1.0×10-5~1.3×10-4mg·L-1、3.9×10-4~4.0×10-3mg·m-3。利用风险商的方法对不同介质中汞进行初步的生态风险评价,结果显示土壤中汞存在较高的风险(RQ≥1),除2009年和2012年,其他所有年份高风险的企业超过50%,风险商的范围为0.44~56.8,呈逐渐上升趋势。地下水中汞存在潜在的风险(0.1RQ1)。无组织排放气体中汞的风险较低(RQ≤0.1),可以忽略。     

Effects of rape straw and red mud on extractability and bioavailability of cadmium in a calcareous soil

Screening of cost-effective soil amendments is important to develop “in situ” remediation techniques for cadmium (Cd) contaminated soils. In this study, different soil amendments, including red mud, a by-product of the alumina industry, and acid-treated, nano-treated by nano-particle milling, nano and acid-treated red muds, zeolite, corn straw, and rape straw, were evaluated to immobilize Cd in two added levels (2 and 5 mg Cd·kg^-1 soil) in a calcareous soil by single and sequential extractions and by cucumber (Cucumis sativus L.) pot experiments. Results indicated that cruciferous rape straw significantly decreased the concentrations of water soluble, extractable Cd in soils, and Cd in cucumber plants, and it was more effective than gramineous corn straw. Also, red mud generally decreased the extractability and bioavailability of Cd added to calcareous soils more effectively than zeolite. Furthermore, the efficiency of red mud could be increased by the treatment of nano-particle milling due to the increase in specific surface area of red mud. It is potential to use rape straw and red mud as soil amendments to develop a cost-effective and efficient “in situ” remediation technology for Cd mildly contaminated calcareous soils.     

Field evidence of decreased extractability of copper and nickel added to soils in 6-year field experiments

The phytotoxicity of added copper (Cu) and nickel (Ni) is influenced by soil properties and field aging. However, the differences in the chemical behavior between Cu and Ni are still unclear. Therefore, this study was conducted to investigate the extractability of added Cu and Ni in 6-year field experiments, as well as the link with their phytotoxicity. The results showed that the extractability of added Cu decreased by 6.63% (5.10%–7.90%), 22.5% (20.6%–23.9%), and 6.87% (0%–17.9%) on average for acidic, neutral, and alkaline soil from 1 to 6 years, although the phytotoxicity of added Cu and Ni did not change significantly from 1 to 6 years in the long term field experiment. Because of dissolution of Cu, when the pH decreased below 7.0, the extractability of Cu in alkaline soil by EDTA at pH 4.0 could not reflect the effects of aging. For Ni, the extractability decreased by 18.1% (10.1%–33.0%), 63.0% (59.2%–68.8%), and 22.0% (12.4%–31.8%) from 1 to 6 years in acidic, neutral, and alkaline soils, respectively, indicating the effects of aging on Ni were greater than on Cu. The sum of ten sequential extractions of Cu and Ni showed that added Cu was more extractable than Ni in neutral and alkaline soil, but similar in acidic soil.

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土壤理化性质对外源六价铬植物毒性的影响

以我国11种具有代表性的土壤为研究对象,通过外源添加Cr(Ⅵ)进行大麦根伸长毒性测试,以了解土壤理化性质对Cr(Ⅵ)的大麦毒性阈值包括半数效应抑制浓度(EC50)和10％效应抑制浓度(EC10)的影响.结果表明,土壤理化性质对Cr(Ⅵ)的植物毒性有显著影响,通过对数-对数剂量效应模型和刺激效应模型预测EC50值和EC10值,其变化范围分别为8.27～241.34 mg·kg-1和2.87～124.65 mg·kg-1,其最大值和最小值相差分别达到了29.2倍和43.4倍.相关分析结果表明,铁、铝氧化物含量、pH值和有机碳含量与Cr(Ⅵ)对大麦根伸长的毒性阈值相关关系显著(P<0.05),其中,铝氧化物含量和铁氧化物含量分别为控制EC50和EC10最重要的单一因子(R2=0.448、R2=0.429),其次为pH值和有机碳含量.基于相关性因子和Cr(Ⅵ)对大麦的毒性阈值建立了一元和多元线性回归方程,最优方程可以分别解释70.1％的EC50和60.4％的EC10变异,表明利用土壤理化性质建立的模型可以较好地预测土壤外源Cr(Ⅵ)对大麦的毒性阈值.     

Genotypic variations in the accumulation of Cd exhibited by di erent vegetables

It is an important approach to use the Cd-contaminated soils properly by growing low accumulator or excluder plants for Cd to produce safe foods. To find the suitable vegetable species for growing in Cd-contaminated soils, in the present study the variations in the Cd accumulation for twenty eight vegetable species and several cultivars of five common vegetables (cowpea, kidney pea, bitter gourd, cucumber and squash) were investigated in two soil Cd levels (1 and 2 mg/kg Cd). Experimental results showed that highly significant di erences in Cd concentration were evident among 28 vegetables. For example, spinach Cd concentrations were 110-fold and 175-fold higher than that of sweet pea under the 1 and 2 mg/kg Cd exposures, respectively. For Cd accumulation, the order of vegetable species was: leafy vegetables > solanaceous vegetables > kale vegetables > root vegetables > allimus > melon vegetables > legumes. Distinctive di erences were also identified when comparing di erent cultivars of the five common vegetables with an average range of 0.003–0.094 mg/kg Cd. Our results indicated that a large genotypic variation existed among vegetable species or cultivars when subjected to Cd exposure. Therefore, it is important and feasible to elect/breed vegetable species/cultivars with low accumulation of Cd, especially in mildly Cd-contaminated soils.