大连市居民头发典型重金属富集特征研究

测定了大连市居民102份头发样品中Pb、Cd、Hg、As等重金属含量,评估了其暴露风险,并对头发中重金属的含量与年龄、性别的关系进行了分析.结果表明,大连市居民头发中Pb、Cd、Hg、As含量均低于中国居民头发中重金属的建议正常值上限,4种重金属暴露风险较低.男性头发中Cd、Pb和As的平均含量明显高于女性(p0.05),其中As平均含量差异达到极显著水平(p0.01).PCA分析显示样本分布集中在第一排序轴和第二排序轴中间,表明性别并不是影响头发中重金属含量的主要因素.19～35岁年龄组居民头发中Cd和Pb含量最高,且均与56～75岁年龄组呈现显著差异(p0.05);As和Hg在56～75岁年龄组居民头发中含量最高,与其它组比较均达到了显著水平(p0.05).PCA和Pearson分析表明4种重金属间相关性较好,大连市居民对4种重金属暴露途径基本相同.     

铁碳促进O3/H2O2体系深度处理准好氧矿化垃圾床渗滤液尾水中难降解有机物

构建了铁碳-O_3/H_2O_2体系降解矿化垃圾床渗滤液尾水中有机物,并考察了体系O_3、铁碳及H_2O_2投加量、初始pH值和反应时间对铁碳-O_3/H_2O_2体系处理渗滤液尾水的影响.结果表明,在铁碳投加量为3 g·L~(-1),O_3投加量为9.798 mg·min~(-1),H_2O_2投加量为2 mL·L~(-1),初始pH值为3的条件下,反应10 min后,渗滤液尾水的COD和UV_(245)分别从711.96 mg·L~(-1)、0.19下降至295.04 mg·L~(-1)、0.10.类比实验结果表明,铁碳-O_3/H_2O_2体系对渗滤液尾水有机物具有较高的去除率,且可生化性得到提高(BOD/COD从0.04增加至0.40).紫外-可见和三维荧光光谱显示,废水中难降解有机物转化为小分子有机化合物且腐殖质的分子缩合度降低.最后,采用SEM-EDS、XRD和XPS技术对铁碳-O_3/H_2O_2体系的反应机理进行了解析,发现铁碳-O_3/H_2O_2反应的机理为铁碳微电解反应、铁氧化物-H_2O_2非均相芬顿反应、O_3/H_2O_2、铁碳-O_3非均相的高级氧化作用和铁基胶体对有机物的吸附沉淀作用.研究表明,铁碳-O_3/H_2O_2体系是一种能够有效去除矿化垃圾床渗滤液尾水中难降解有机物的方法.     

哈尔滨近地面O3浓度特征

伴随着经济发展和城镇化进程的加速,很多城市的臭氧浓度存在超标问题.本文选取2014—2017年哈尔滨城区污染数据及气象要素数据,对哈尔滨近地面层O_3时空分布特征及其与气象要素的关系进行了分析,结果表明:哈尔滨O_3日内单峰分布,最高值出现在下午14:00,最低值在清晨7:00.空间分布东南部最高,其次是南部,城中区较低.日间周末的近地面O_3浓度较高,而夜间工作日的O_3浓度较高.哈尔滨O_3浓度与平均气温正相关,与相对湿度负相关,与低于37 W·m~(-2)的紫外辐射正相关.     

亚慢性氟暴露致小鼠海马损伤的影响及分子机制研究

为探明亚慢性氟中毒致小鼠海马损伤及分子机制,选用ICR雄性小鼠140只,随机分为对照(C)、低氟(LF)、高氟(HF)、低氟(LF)+L钙离子通道激动剂(FPL)、低氟(LF)+L钙离子通道抑制剂(NIF)、高氟(HF)+激动剂(FPL)、高氟(HF)+抑制剂(NIF) 7组,分别饮用自来水、5、30 mg·L~(-1)氟化钠水溶液90 d,氟染毒第84 d分别腹腔注射生理盐水、FPL64176、Nifedipine7d.同时,采用开场行为及水迷宫检测学习记忆能力;通过HE切片染色观察海马形态结构;根据试剂盒说明检测脑组织谷胱甘肽过氧化物酶(GSH-PX)、总超氧化物歧化酶(SOD)酶活性及丙二醛(MDA)含量;利用RT-PCR和Western Blot法分别检测海马内凋亡相关分子CaMKⅡ和Bax、Bcl-2基因/蛋白表达.结果发现,HF组、LF+FPL组和HF+FPL组小鼠毛发粗糙,暴躁不安.LF、HF组小鼠自发活动、探究行为及空间学习记忆力显著下降(p0.05),海马细胞损伤,SOD、GSH-PX活性极显著下降(p0.01),CaMKⅡ基因/蛋白表达水平显著(p0.05)或极显著(p0.01)上调,Bax基因/蛋白表达水平显著(p0.05)或极显著(p0.01)上调,Bcl-2基因/蛋白表达水平显著(p0.05)或极显著(p0.01)下调,Bax与Bcl-2基因/蛋白表达水平比值显著(p0.05)或极显著(p0.01)上调;LF+FPL、HF+FPL处理加剧了上述基因/蛋白表达水平,LF+NIF、HF+NIF组可逆转上述基因/蛋白表达水平.结果提示,氟中毒致脑损伤与L型钙离子通道及下游相关分子表达异常密切相关,而L钙离子通道抑制剂(Nifedipine)能改善氟暴露造成的海马损伤.     

牛粪-化肥配施对水稻田氮磷迁移转化的影响

在控制外源N输入量相同的前提下,通过田间小区实验,探讨有机肥与化肥不同施用量（牛粪施用量：5,10,20t/hm²）对稻田田间土-水界面氮磷迁移转化特征的影响.结果表明：控制稻田水中NH₄⁺-N、NO₃^--N、TN和TP输出的最佳时期分别为施肥后的第5,30,7,20d,且TN和TP浓度随时间变化符合单指数衰减方程（0.7444≤R²≤0.9724;1.1×10^-6≤F≤0.0055）.采用牛粪部分代替化肥的施肥方式,在一定范围内能降低稻田退水中TN、TP输出负荷（41.8%、36.0%、64.3%;20.3%、39.1%、48.9%）,还可以降低稻田水中N/P,降低水体富营养化风险.同时,牛粪的施用可提高土壤中脲酶和磷酸酶的含量,促进氮磷向植物可吸收形态转化.综合经济成本和生态效益核算,采用10t有机肥代替无机肥的处理是相对经济环保的施肥方法,该施肥方式下,氮磷年输出负荷分别为17.70,1.26kg/hm².     

Potential of secondary aerosol formation from Chinese gasoline engine exhaust

Light-duty gasoline vehicles have drawn public attention in China due to their significant primary emissions of particulate matter and volatile organic compounds(VOCs). However,little information on secondary aerosol formation from exhaust for Chinese vehicles and fuel conditions is available. In this study, chamber experiments were conducted to quantify the potential of secondary aerosol formation from the exhaust of a port fuel injection gasoline engine. The engine and fuel used are common in the Chinese market, and the fuel satisfies the China V gasoline fuel standard. Substantial secondary aerosol formation was observed during a 4–5 hr simulation, which was estimated to represent more than 10 days of equivalent atmospheric photo-oxidation in Beijing. As a consequence, the extreme case secondary organic aerosol(SOA) production was 426 ± 85 mg/kg-fuel, with high levels of precursors and OH exposure. The low hygroscopicity of the aerosols formed inside the chamber suggests that SOA was the dominant chemical composition. Fourteen percent of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatile organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reductions of emissions of aerosol precursor gases from vehicles are essential to mediate pollution in China.     

Nanoencapsulation of hexavalent chromium with nanoscale zero-valent iron: High resolution chemical mapping of the passivation layer

Solid phase reactions of Cr(Ⅵ) with Fe(0) were investigated with spherical-aberration-corrected scanning transmission electron microscopy(Cs-STEM) integrated with X-ray energy-dispersive spectroscopy(XEDS). Near-atomic resolution elemental mappings of Cr(Ⅵ)–Fe(0) reactions were acquired. Experimental results show that rate and extent of Cr(Ⅵ) encapsulation are strongly dependent on the initial concentration of Cr(Ⅵ) in solution. Low Cr loading in nZⅥ(1.0 wt%) promotes the electrochemical oxidation and continuous corrosion of n ZⅥ while high Cr loading(1.0 wt%) can quickly shut down the Cr uptake. With the progress of iron oxidation and dissolution, elements of Cr and O counter-diffuse into the nanoparticles and accumulate in the core region at low levels of Cr(Ⅵ)(e.g., 10 mg/L). Whereas the reacted n ZⅥ is quickly coated with a newly-formed layer of 2–4 nm in the presence of concentrated Cr(Ⅵ)(e.g., 100 mg/L). The passivation structure is stable over a wide range of pH unless pH is low enough to dissolve the passivation layer. X-ray photoelectron spectroscopy(XPS) depth profiling reconfirms that the composition of the newly-formed surface layer consists of Fe(Ⅲ)–Cr(Ⅲ)(oxy)hydroxides with Cr(Ⅵ) adsorbed on the outside surface. The insoluble and insulating Fe(Ⅲ)–Cr(Ⅲ)(oxy)hydroxide layer can completely cover the n ZⅥ surface above the critical Cr loading and shield the electron transfer. Thus, the fast passivation of nZⅥ in high Cr(Ⅵ) solution is detrimental to the performance of nZⅥ for Cr(Ⅵ) treatment and remediation.     

Mercury flows in large-scale gold production and implications for Hg pollution control

Large-scale gold production(LSGP) is one of the five convention-related atmospheric mercury(Hg) emission sources in the Minamata Convention on Mercury. However, field experiments on Hg flows of the whole process of LSGP are limited. To identify the atmospheric Hg emission points and understand Hg emission characteristics of LSGP, Hg flows in two gold smelters were studied. Overall atmospheric Hg emissions accounted for 10%–17% of total Hg outputs and the Hg emission factors for all processes were 7.6–9.6 kg/ton. There were three dominant atmospheric Hg emission points in the studied gold smelters, including the exhaust gas of the roasting process, exhaust gas from the environmental fog collection stack and exhaust gas from the converter of the refining process. Atmospheric Hg emissions from the roasting process only accounted for 16%–29% of total emissions and the rest were emitted from the refining process. The overall Hg speciation profile(gaseous elemental Hg/gaseous oxidized Hg/particulate-bound Hg) for LSGP was 34.1/57.1/8.8. The dominant Hg output byproducts included waste acid, sulfuric acid and cyanide leaching residue. Total Hg outputs from these three byproducts were 80% in smelter A and 84% in smelter B. Our study indicated that previous atmospheric Hg emissions from large-scale gold production might have been overestimated.Hg emission control in LSGP is not especially urgent in China compared to other significant emission sources(e.g., cement plants). Instead, LSGP is a potential Hg release source due to the high Hg output proportions to acid and sludge.     

Long-term effects of sliver nanoparticles on the abundance and activity of soil microbiome

正Silver nanoparticles(Ag NPs)are among the most extensively used engineered nanomaterials because of their wellestablished antimicrobial and unique physicochemical properties(Yin et al.,2015).Applications of AgNPs have now been     

Relationship between physicochemical properties and dewaterability of hydrothermal sludge derived from different source

Sewage sludge (SS) and deinking sludge (DS) were used to comparatively study the hydrothermal dewatering of sludge with different components. For a better overview, an insight into the relationship between physicochemical properties and dewaterability of hydrothermal sludge was provided. Results found that not all kinds of sludge were suitably conditioned by hydrothermal treatment (HT) in term of the elevation of dewaterability. Higher hydrothermal temperature tended to enhance the dewaterability of SS rather than DS, which was supported by the variation of their physicochemical properties (including water distribution, bonding energy, extracellular polymeric substance (EPS), particles size, acid functional groups and zeta potential in this study). In addition, the changes in surface morphology suggested that the reverse effect of HT on sludge dewaterability was mainly due to their dewatering behavior. For SS, the destruction of EPS structure leaded to the release of bound water, thereby strengthening sludge dewatering. Conversely, “Bridging effect” generated by lignocellulose in DS was beneficial for sludge dewatering; however, the increasing hydrothermal temperature degraded part of lignocellulose and weakened “bridging effect”, finally resulting in worse dewaterability of DS.