Seasonal and diurnal variations of atmospheric peroxyacetyl nitrate, peroxypropionyl nitrate, and carbon tetrachloride in Beijing

Atmospheric peroxyacetyl nitrate(PAN), peroxypropionyl nitrate(PPN), and carbon tetrachloride(CCl4) were measured from September 2010 to August 2011 in Beijing. PAN exhibited low values from mid-autumn to early spring(October to March) with monthly average concentrations ranging from 0.28 to 0.73 ppbV, and increased from early spring to summer(March to August), ranging from 1.37–3.79 ppbV. The monthly variation of PPN was similar to PAN, with low values(below detection limit to 0.18 ppbV) from mid-autumn to early spring, and a monthly maximum in September(1.14 ppbV). The monthly variation of CCl4was tightly related to the variation of temperature, exhibiting a minimum in winter(69.3 pptV) and a maximum of 180.6 pptV in summer. Due to weak solar intensity and short duration, PAN and O3showed no distinct diurnal patterns from morning to night during winter, whereas for other seasons, they both exhibited maximal values in the late afternoon(ca. 15:00 to 16:00 local time) and minimal values during early morning and midnight. Good linear correlations between PAN and PPN were found in autumn(R = 0.91), spring(R = 0.94), and summer(R = 0.81), with slopes of 0.130, 0.222, and 0.133, respectively, suggesting that anthropogenic hydrocarbons dominated the photochemical formation of PANs in Beijing. Positive correlation between PAN and O3 in summer with the low slopes( O3 / PAN) ranging from 9.92 to 18.0 indicated serious air pollution in Beijing, and strong negative correlation in winter reflected strong O3consumption by NO titration and less thermal decompositin of PAN.     

Efficient dechlorination of chlorinated solvent pollutants under UV irradiation by using the synthesized TiO2 nano-sheets in aqueous phase

Titanium dioxide(TiO2), which is the widely used photo-catalyst, has been synthesized by simple hydrothermal solution containing tetrabutyl titanate and hydrofluoric acid. The synthesized product has been applied to photo-degradation in aqueous phase of chlorinated solvents, namely tetrachloroethene(PCE), trichloroethene(TCE) and 1,1,1-trichloroethane(TCA). The photo-degradation results revealed that the degradation of these harmful chemicals was better in UV/synthesized TiO2 system compared to UV/commercial P25 system and UV only system. The photo-catalytic efficiency of the synthesized TiO2 was 1.4, 1.8 and 3.0 folds higher compared to the commercial P25 for TCA, TCE and PCE degradation, respectively. Moreover, using nitrobenzene(NB) as a probe of hydroxyl radical(.OH), the degradation rate was better over UV/synthesized TiO2, suggesting the high concentration of.OH generated in UV/synthesized TiO2system. In addition,.OH concentration was confirmed by the strong peak displayed in EPR analysis over UV/synthesized TiO2system. The characterization result using XRD and TEM showed that the synthesized TiO2 was in anatase form and consisted of well-defined sheet-shaped structures having a rectangular outline with a thickness of 4 nm, side length of 50 nm and width of 33 nm and a surface 90.3 m2/g. XPS analysis revealed that ≡Ti-F bond was formed on the surface of the synthesized TiO2. The above results on both photocatalytic activity and the surface analysis demonstrated the good applicability of the synthesized TiO2 nano-sheets for the remediation of chlorinated solvent contaminated groundwater.     

Arsenic removal from groundwater by acclimated sludge under autohydrogenotrophic conditions

Arsenic in the environment is attracting increasing attention due to its chronic health effects. Although arsenite(As(III)) is generally more mobile and more toxic than arsenate(As(V)), reducing As(V) to As(III) may still be a means for decontamination, because As(III) can be removed from solution by precipitation with sulfide or by adsorption or complexation with other metal sulfides. The performance of As(V) bio-reduction under autohydrogenotrophic conditions was investigated with batch experiments. The results showed that As(V) reduction was a biochemical process while both acclimated sludge and hydrogen were essential. Most of the reduced arsenic remained in a soluble form, although 20% was removed with no addition of sulfate, while 82% was removed when sulfate was reduced to sulfide. The results demonstrated that the reduced arsenic was re-sequestered in the precipitates, probably as arsenic sulfides. Kinetic analysis showed that pseudo first-order kinetics described the bio-reduction process better than pseudo second-order. In particular, the influences of pH and temperature on As(V) reduction by acclimated sludge under autohydrogenotrophic conditions and total soluble As removal were examined. The reduction process was highly sensitive to both pH and temperature, with the optimum ranges of pH 6.5–7.0 and 30–40°C respectively. Furthermore, Arrhenius modeling results for the temperature effect indicated that the As(V) reduction trend was systematic. Total soluble As removal was consistent with the trend of As(V) reduction.     

地下水中常见离子对纳米零价铁除Se（Ⅳ）动力学的影响

采用间歇实验对纳米零价铁(nZVI)除四价硒(Se(Ⅳ))进行实验性研究,考察了地下水中共存离子对nZVI除Se(Ⅳ)动力学的影响.结果表明,在厌氧条件下,当nZVI投加量为0.1 g·L-1,Se(Ⅳ)浓度为100μmol·L-1,NaCl浓度为0.01 mol·L-1,pH=7.0,T=25℃±1℃时,投加CO2-3或SO2-4浓度为1 mmol·L-1、腐殖酸(humic acid,HA)为5 mg·L-1时,明显抑制了Se(Ⅳ)的去除.投加0.5 mmol·L-1Ca2+或Mg2+时,对除Se(Ⅳ)影响不大;而Ca2+(3 mmol·L-1)、Mg2+(3 mmol·L-1)时,Se(Ⅳ)的去除效率明显下降.未加共存离子时,Se(Ⅳ)在20 min时基本去除完,共存离子存在的情况下,nZVI对Se(Ⅳ)的去除率在30 min时达到100%.反应过程中二价铁(Fe2+)随着Se(Ⅳ)的去除趋于平稳.ORP在反应过程中快速从正值下降至负值,由此说明nZVI除Se(Ⅳ)的过程发生了还原反应.     

1980~2010年浙江某典型河流硝态氮通量对净人类活动氮输入的动态响应

以浙江某典型流域为研究对象,基于1980～2010年的水质水量和氮源数据及LOADEST模型,估算了逐年河流NO-3-N通量和净人类活动氮输入(NANI),分析了河流NO-3-N通量和NANI的年际演化特征及其动态响应关系,探讨了每年NANI、滞留氮库、自然背景源对河流NO-3-N通量的贡献.结果表明,1980～2010年,河流NO-3-N通量和NANI总体上都呈现出先增后减的抛物线型变化趋势,均在1998年左右分别达到峰值5.74 kg·(hm2·a)-1和77.5 kg·(hm2·a)-1;过去31 a,河流NO-3-N通量和NANI分别净增加了～42%和～77%.化肥氮和大气氮沉降是NANI的主要来源,分别占了NANI的～48%和～40%.河流NO-3-N通量的年际变化不仅与NAIN(R2=0.27**)和化肥氮输入量(R2=0.32**)显著相关,而且与河流年均流量(R2=0.79**)或降雨量(R2=0.63**)具有更强的相关性,意味着河流NO-3-N的来源除了当年的NAIN,还受滞留氮库的影响.所建立的以NANI和流量为自变量的回归模型能很好地模拟河流NO-3-N通量变化(R2=0.94**).该模型预测结果显示,在NANI和流量分别降低30%的情况下,河流年均NO-3-N通量将分别减少～21%和～30%;每年的NANI、滞留氮库、自然背景源对河流当年NO-3-N通量的贡献率分别为～53%、～24%、～23%.河流NO-3-N通量长期的年际变化是NANI和水文要素共同作用的结果;但是,由于滞留氮库的影响,与源控制方式相比,增加"汇"景观应该能更加快速地削减河流NO-3-N通量.     

改性氢氧化镁制备及其去除地下水中Cr3+性能研究

氢氧化镁作为一种可缓慢释放OH-的碱,能使多数重金属离子转换为沉淀,而且不会引起太大的pH变化.但氢氧化镁难溶于水,在含水层中的迁移能力很差.若要用于地下水重金属污染修复,需要对氢氧化镁进行改性.因此,本文利用表面活性剂对氢氧化镁粉末进行改性,合成了氢氧化镁胶体,并对改性氢氧化镁的稳定性、粒度及其对Cr3+的稳定化效果进行了分析.结果表明,复配表面活性剂改性的氢氧化镁悬浮液稳定性好,粒径小,0.6~8.4μm的颗粒占82.41%.利用改性氢氧化镁对Cr3+污染地下水进行处理,其对Cr3+的去除机理主要为沉淀反应,氢氧化镁和Cr3+反应的质量比约为1.333∶1,氢氧化镁和初始Cr3+浓度对Cr3+的去除效果都有较大的影响.     

填埋场中铁的生物化学循环对反硝化的影响

在模拟填埋体系中,以填埋场稳定的垃圾为接种物,通过控制有机物和硝氮负荷,研究了铁的生物化学循环对反硝化的影响.结果表明,垃圾填埋场内蕴藏着能实现铁的厌氧氧化还原并同步还原硝氮的复合功能菌群.通过改变有机物和硝氮的负荷,可使得填埋场内持续进行着铁的氧化还原循环和同步氮素转化.从氮素转化产物来看,铁的循环体系中氨氮浓度比传统的反硝化体系低4 mmol·L-1.填埋场内铁的生物化学循环过程对于原位脱氮具有极大贡献.     

地下水中污染物的迁移传输及排泄通量研究

以辽宁某化工污染场地为研究对象,结合场地调查结果,应用地下水模型系统软件(GMS)中的MODFLOW和RT3D模型,建立了地下水中污染物的数值模型,探讨其迁移传输及排泄通量。根据模拟结果,地下水中苯、二氯苯和三氯苯的污染羽约在20年后达到动态平衡,污染羽不再随时间变化,污染物的自然衰减速率与污染源释放速率达到平衡。排泄通量估算表明:地下水向河流排泄的量在20年时达到稳定,地下水中苯、二氯苯和三氯苯向河流的排泄通量分别为每天180 g、6 100 g和5.5 g。由于污染物会导致污染生态环境和健康风险,建议从控制污染源、实施污染源区修复和切断迁移传输途径等多种措施控制风险。     

滹沱河冲洪积扇地下水中酞酸酯的污染现状与分布特征

2014年9月采集石家庄地区滹沱河冲洪积扇地下水水样,采用气相色谱-质谱法测定了US EPA优先控制的6种酞酸酯(PAEs),对PAEs分布特征与风险进行了分析.结果表明,研究区内51个点位仅1个点位未检出PAEs,检出的ΣPAEs范围为nd~28 873.1 ng·L~(-1),与国内其他研究区相比,研究区地下水中PAEs污染水平较重.PAEs及各组分的空间分布存在显著差异.3个地下水单元PAEs的平均污染水平总体表现为山间沟谷河谷裂隙孔隙水单元(G1)滹沱河冲洪积扇扇顶部孔隙水单元(G2)滹沱河冲洪积扇扇中部孔隙水单元(G3).在G2、G3单元共计39个点位中,有23个点位地下水中的PAEs以邻苯二甲酸甲酯(DMP)为主,而其余点位均因临近周边污染源,地下水中PAEs含量较高,且以邻苯二甲酸(2-乙基己基)酯(DEHP)、邻苯二甲酸丁酯(DBP)为主.研究区人群饮用受PAEs污染地下水的总非致癌风险指数和总致癌风险指数范围分别为7.6×10-9~1.1×10-2、nd~1.2×10-6,均小于US EPA推荐的可接受的水平,风险较小.     

新疆奎屯原生高砷地下水的分布、类型及成因分析

原生高砷地下水在全球分布广、危害大,严重威胁着全世界数亿人口的身体健康.为科学指导高砷地区地下水资源的合理开发利用,以中国大陆第一个砷中毒病区新疆奎屯为研究区域,分析了奎屯地区高砷地下水的分布规律、类型及成因.结果表明,奎屯地区有88.7%的地下水中砷浓度超出10μg·L~(-1),多为高砷地下水.高砷地下水多分布在深层承压含水层,砷浓度从南向北逐渐升高,与采样点海拔高度呈显著负相关.奎屯地区地下水整体呈弱碱性、碱性环境,氧化还原电位(Eh)均为负值,具有较强的还原性,属于还原性-弱碱性高砷地下水(I-2型).奎屯南面的天山与北面的河流沉积平原环境相结合,为该区地下水形成高砷提供了有利的地质环境.奎屯地区沉积层深厚,地下径流更替缓慢,相对封闭的水文地质条件使地下水中的砷富集而不易流失,强烈的蒸发可以使地下水中的砷进一步浓缩.同时,地下水的还原条件有利于含水层中砷的释放,砷浓度不仅受铁锰氧化物矿物还原的影响,而且受SO2-4还原和硫化物矿物沉淀的控制,吸附态砷的解吸附也是该地区地下水的富砷过程.