Visual MODFLOW在露天矿地下水模拟中的应用

用Visual MODFLOW建立了某露天矿地下水数值模型,运用其跟踪模拟(MODPATH)子模块及溶质运移模拟(MT3D)子模块对该露天矿地下水的水质点示踪和三维污染羽进行了模拟,模拟结果有助于识别该矿露天开采对地下水污染的污染源及污染途径,为预测露天矿开采期间地下水位及水质的变化,采用的监测与预保护措施提供了决策依据。     

Urea formation from carbon dioxide and ammonia at atmospheric pressure

Urea synthesis, currently the largest use of carbon dioxide in organic synthesis, is conventionally operated at high pressure and high temperature. Here, we report for the first time that urea forms at atmosphere and ambient temperatures by negative corona discharge in gas phase. The conversion of CO₂ and yields of a solid mixture of urea and ammonium carbamate, which was identified by the ¹³C NMR spectrum, rise with reducing temperatures and increasing molar ratios of NH₃/CO₂ and discharge frequencies. The conversion of carbon dioxide was found to be 82.16?% at 20?°C and 1?atm with a molar flow ratio of n(NH₃)/n(CO₂) of 2.5. High pressure and high temperature as energy inputs are not necessary.     

RBCA、CLEA及CalTOX模型在苯并[a]芘污染场地健康风险评估中的应用比较

为探讨不同模型对污染场地健康风险评估结果的影响,以苯并[a]芘为例,采用RBCA、CLEA和CalTOX模型对某工业污染场地表层土壤进行健康风险评估,分析了评估结果的差异和原因,同时对模型的主要暴露参数进行了敏感性分析,并推导出基于风险概率分布的土壤修复限值。结果表明,RBCA、CLEA和CalTOX模型计算的苯并[a]芘致癌总风险分别为2.40×10-4、6.32×10-4和7.04×10-6,且经口摄入和皮肤接触2个途径对人体健康造成的危害最大。降解作用是影响CalTOX模型风险评估结果不同于RBCA和CLEA模型的重要因素,3个模型间参数取值及方法学的差异也会导致风险评估结果不同。各模型暴露参数的敏感性排序也有差异。采用基于风险概率分布的方法推导土壤修复限值,RBCA、CLEA和CalTOX模型所得结果分别为0.18、0.08、0.13(不考虑降解作用CalTOX模型)和10.74(考虑降解作用CalTOX模型)mg·kg-1,为各模型直接推导值的1.5～2.6倍。基于风险概率分布的方法可有效降低风险评估过程中参数不确定性的影响,为工业污染场地土壤修复值的制定提供参考。     

Reduction of hexavalent chromium with scrap iron in a fixed bed reactor

The reduction of hexavalent chromium by scrap iron was investigated in continuous long-term fixed bed system. The effects of pH, empty bed contact time (EBCT), and initial Cr(VI) concentration on Cr(VI) reduction were studied. The results showed that the pH, EBCT, and initial Cr(VI) concentration significantly affected the reduction capacity of scrap iron. The reduction capacity of scrap iron were 4.56, 1.51, and 0.57 mg Cr(VI)·g^-1 Fe⁰ at pH 3, 5, and 7 (initial Cr(VI) concentration 4 mg·L^-1, EBCT 2 min, and temperature 25°C), 0.51, 1.51, and 2.85 mg Cr(VI)·g^-1 Fe⁰ at EBCTs of 0.5, 2.0, and 6.0 min (initial Cr(VI) concentration 4 mg·L^-1, pH 5, and temperature 25°C), and 2.99, 1.51, and 1.01 mg Cr(VI)·g^-1 Fe⁰ at influent concentrations of 1, 4, and 8 mg·L^-1 (EBCT 2 min, pH 5, and temperature 25°C), respectively. Fe(total) concentration in the column effluent continuously decreased in time, due to a decrease in time of the iron corrosion rate. The fixed bed reactor can be readily used for the treatment of drinking water containing low amounts of Cr(VI) ions, although the hardness and humic acid in water may shorten the lifetime of the reactor, the reduction capacity of scrap iron still achieved 1.98 mg Cr⁶⁺·g^-1 Fe. Scanning electron microscope equipped with energy dispersion spectrometer and X-ray diffraction were conducted to examine the surface species of the scrap iron before and after its use. In addition to iron oxides and hydroxide species, iron-chromium complex was also observed on the reacted scrap iron.     

桂林岩溶表层带土壤CO2体积分数时空变化规律及其意义

通过2010—2011年的监测建立了桂林盘龙洞坡地和洼地不同深度土壤CO2体积分数的季节性变化。监测土壤CO2体积分数空间上变化为:坡地80 cm>50 cm>30 cm;洼地80 cm>100 cm>50 cm>30 cm。监测土壤CO2体积分数时间上变化为2010年7月和2011年6月未CO2体积分数达到最高值,2010到2011年冬季为土壤CO2达到最低值。由于受到大气降水量急剧减少的影响2011年土壤CO2体积分数整体比2010年低。显示大气降水量也是影响土壤CO2体积分数的重要环境因素。为我国固碳减排科学的选择时间和空间提供有力的依据。     

低含量Pb对Cd处理下冬小麦根际土壤氧化还原酶活性、BIF及C/N的影响

为正确评价重金属污染下冬小麦根际土壤微生态系统的安全性和稳定性,采用盆栽试验法研究了铅(Pb)含量低于国家"土壤环境质量标准(GB 15618-1995)"规定的Ⅱ类土壤环境基准值(350.00 mg/kg,干土)时,与镉(Cd)复合处理对冬小麦幼苗根际土壤氧化还原酶活性、肥力指数(Biological index of fertility,BIF)及碳/氮(C/N)的影响.结果表明:(1)幼苗生长3周时,Cd处理下过氧化氢酶和多酚氧化酶活性显著(P<0.05)增加,脱氢酶活性显著(P<0.05)降低;7周时多酚氧化酶和过氧化氢酶活性显著(P<0.05)降低;12周时,多酚氧化酶和脱氢酶活性显著(P<0.05)降低.此外,根际土壤生物学肥力指标BIF值主要表现为降低,而根际土壤C/N值在幼苗生长3周和12周时显著(P<0.05)降低,7周时却极显著(P<0.01)升高.(2)低含量Pb与Cd对脱氢酶和过氧化氢酶活性、BIF值主要起协同抑制效应,对多酚氧化酶活性表现出拮抗效应.幼苗生长3周和12周时,低含量Pb可减轻Cd对C/N值的降低效应,7周时,低含量Pb和Cd协同促进C/N值升高.土壤Pb含量低于国家"土壤环境质量标准"规定的Ⅱ类土壤环境基准值时,仍会明显影响Cd污染下冬小麦幼苗根际土壤的生化功能特征.     

Characterization of soil low-molecular-weight organic acids in the Karst rocky desertification region of Guizhou Province, China

Soil low-molecular-weight (LMW) organic acids play important roles in the soil-forming process and the cycling of nutrients in Karst regions. In this study, we quantified the contents of LMW organic acids (including lactate, acetate, formate, malate, and oxalate) in soil solution over the Karst region of Guizhou Province, China using ion chromatography. The concentration of total LMW organic acids in topsoil solution ranged from 0.358 to 1.823 μmol·g^-1, with an average of 0.912 μmol·g^-1. The mean concentrations of lactate, acetate, formate, malate, and oxalate were 0.212±0.089, 0.302±0.228, 0.301±0.214, 0.014±0.018 and 0.086±0.118 μmol·g^-1, respectively. There were also significant difference in the contents of these acids among four phases of rocky desertification, and their concentrations decreased with the aggravation of rocky desertification. The concentrations of the LMW organic acids were significantly positive correlated each other. Significant positive correlations were also observed among individual LMW organic acids in soil solution, and between them and soil available P, available K, exchangeable Ca, respectively. Furthermore, the concentrations of LMW organic acids were significantly positively correlated with inorganic anions (chlorides, nitrates, and sulfates) in Karst topsoil solution. Therefore, the concentrations of soil LMW organic acids might be one of driving force in the Karst rock desertification process in Guizhou Province.     

石家庄地区雾霾天气下云滴和云凝结核的分布特征

2009年5~10月在石家庄地区对雾霾天气下的近地面到高空的云雾滴和云凝结核(CCN)进行了7架次飞机探测.利用PMS云粒子测量仪器、机载温湿仪和连续气流纵向热梯度云凝结核仪获得的云雾粒子和云凝结核(CCN)探测资料,分析了层积云(Sc)和高积云(Ac)中云粒子浓度、液态含水量、粒子算术平均直径和粒子有效平均直径的垂直分布特征;分析了CCN垂直和水平分布特征以及谱分布.结果表明雾霾天气状况下,云滴数浓度在102个/cm3量级上.高云粒子粒径总体大于低云粒子.云含水量平均值范围为0.03~0.14g/m3;地面到600 m高度内, CCN值的平均值为3034cm-3(过饱和度S=0.3%).对CCN的活化谱进行拟合表明石家庄属于典型大陆性核谱,云对CCN有消耗作用,逆温层的存在使得该区CCN浓度累积增加.     

Blood concentrations of lead,cadmium, mercury and their association with biomarkers of DNA oxidative damage in preschool children living in an e-waste recycling area

Reactive oxygen species (ROS)-induced DNA damage occurs in heavy metal exposure, but the simultaneous effect on DNA repair is unknown. We investigated the influence of co-exposure of lead (Pb), cadmium (Cd), and mercury (Hg) on 8-hydroxydeoxyguanosine (8-OHdG) and human repair enzyme 8-oxoguanine DNA glycosylase (hOGG1) mRNA levels in exposed children to evaluate the imbalance of DNA damage and repair. Children within the age range of 3–6 years from a primitive electronic waste (e-waste) recycling town were chosen as participants to represent a heavy metal-exposed population. 8-OHdG in the children’s urine was assessed for heavy metal-induced oxidative effects, and the hOGG1 mRNA level in their blood represented the DNA repair ability of the children. Among the children surveyed, 88.14% (104/118) had a blood Pb level >5 μg/dL, 22.03% (26/118) had a blood Cd level >1 μg/dL, and 62.11% (59/95) had a blood Hg level >10 μg/dL. Having an e-waste workshop near the house was a risk factor contributing to high blood Pb (r _s  = 0.273, p < 0.01), while Cd and Hg exposure could have come from other contaminant sources. Preschool children of fathers who had a college or university education had significantly lower 8-OHdG levels (median 242.76 ng/g creatinine, range 154.62–407.79 ng/g creatinine) than did children of fathers who had less education (p = 0.035). However, we did not observe a significant difference in the mRNA expression levels of hOGG1 between the different variables. Compared with children having low lead exposure (quartile 1), the children with high Pb exposure (quartiles 2, 3, and 4) had significantly higher 8-OHdG levels (β _Q2 = 0.362, 95% CI 0.111–0.542; β _Q3 = 0.347, 95% CI 0.103–0.531; β _Q4 = 0.314, 95% CI 0.087–0.557). Associations between blood Hg levels and 8-OHdG were less apparent. Compared with low levels of blood Hg (quartile 1), elevated blood Hg levels (quartile 2) were associated with higher 8-OHdG levels (β _Q2 = 0.236, 95% CI 0.039–0.406). Compared with children having low lead exposure (quartile 1), the children with high Pb exposure (quartiles 2, 3, and 4) had significantly higher 8-OHdG levels.     

Metals and metalloids in PM10 in Nandan County,Guangxi, China,and the health risks posed

Intense mining, smelting, and tailing activities of polymetallic ore deposits have affected the environment in Nandan County, Guangxi, China. Samples of particulates with aerodynamic diameters low or equal 10 μm (PM₁₀) were collected in Nandan County to investigate the concentrations of and health risks posed by 17 metals and metalloids in the PM₁₀. The metal and metalloid concentrations were lower than those found in other industrial cities. The mean Cr concentration was 7.48 ng/m³. Significant higher metal and metalloid concentrations were found in PM₁₀ from mining areas (Dachang and Chehe) than from the control area (Liuzhai) (p < 0.05). Principal component analysis indicated that the main sources of Ba, Co, Cr, Fe, K, Mg, Mo, Na, and Sr were resuspension of the soil produced through mineral erosion, the main sources of As, Cd, Cu, Pb, Sb, and Zn were smelting and mining activities, and the main source of Ni was fossil fuel combustion. Higher non-carcinogenic and carcinogenic risks were posed in Dachang and Chehe than in Liuzhai. The non-carcinogenic risks posed to adults and children by individual metals and metalloids in PM₁₀ at all the sites were low, but the non-carcinogenic risks posed to children by all the metals and metalloids together exceeded the safe level (i.e., risk value > 1). The carcinogenic risks posed by Cd, Ni, and Pb were negligible at all sites, while As, Co, and Cr posed potential carcinogenic risks to the residents.