影响大气汞化学过程的敏感因子分析

为了分析汞在大气中的化学行为,在一个化学模式中加入汞的气相、气液平衡和液相反应,模拟大气汞及其化合物的演变规律,并分析了气象因子(云、光解率、温度)和化学因子(气态O3、H2O2、HO2、OH和气态零价汞Hg0(g))的初始体积分数对各形态汞及其化合物浓度和Hg0(g)转化率的影响.模拟结果表明,在中等大气污染条件下,Hg0(g)的每小时平均转化率为2.91%.敏感性试验结果表明,云量、光解率、温度、O3和Hg0(g)的初始体积分数对不同形态汞的影响较为显著.云量的增加、光解率的增加、臭氧初始体积分数的升高,各形态汞的平衡时间缩短,除气态氧化汞和一价汞离子外,其他形态汞的平衡浓度均会降低,Hg0(g)的转化率增加.温度增加将抑制Hg0(g)的转化.Hg0(g)的初始体积分数增加,各形态汞的浓度升高,但其平均转化率没有显著变化.不同因子对汞化学过程的相对作用对区域或全球大气汞的环境模拟具有指导意义.     

三峡水库消落带土壤与优势植物淹水后对土-水系统汞形态的影响

三峡库区消落带落干期植被生长茂盛,蓄水后消落带被淹没,土壤-植物系统在长时间淹水情况下,随着体系内物理化学性质的改变,汞形态也会发生变化,从而对库区水生生态系统中汞含量以及形态带来一定的影响.为此,本研究选取三峡库区4种优势植物室内栽培,再进行室内模拟淹水试验,研究淹水后土壤、水体中甲基汞(Me Hg)以及其他形态汞的变化.结果表明,淹水过程中植物的存在有利于土壤Me Hg的生成,同时对上覆水不同形态汞浓度影响显著.狗牙根作为消落带优势种,由于其体内总汞及甲基汞含量较高,淹水后对土壤以及上覆水系统中甲基汞以及其他汞形态的影响最为明显.淹水第90 d,狗牙根+土+江水(B1)处理土壤Me Hg的含量最高,为(1 135.86±113.84)ng·kg~(-1),是不加植物的对照处理土+江水(CK2)中土壤Me Hg含量的2倍左右;上覆水总甲基汞(TMe Hg)、溶解态甲基汞(DMe Hg)、总汞(THg)、溶解态汞(DHg)和活性汞(RHg)均呈峰值偏左的抛物线状变化,在第30 d时达到峰值,其中B1处理上覆水TMe Hg、THg和DHg最高,分别为(2.88±0.06)、(40.29±2.42)和(35.51±3.77)ng·L~(-1),三者中溶解态汞是其主要存在形式.因此可以推测三峡库区消落带植物淹水后将增加水库汞污染负荷.     

城市管道煤气生产中汞的分布特征

采用二次金汞齐 -冷原子吸收光谱法对贵阳市城市民用管道煤气中汞含量进行了测定。对煤气生产中使用的洗精煤及生产过程中产生的化学产品焦碳、煤焦油、焦炉煤气脱硫洗涤物硫浆中汞含量和分布进行了初步研究。管道煤气中汞的含量低于方法检测限 0 .0 5ng/m3,低于贵阳市大气中汞含量。在原煤转化为城市管道煤气过程中 ,原煤的洗选过程脱除了 70 %的汞 ;焦碳中汞含量占洗精煤汞含量的 1 1 .4 % ;焦油中汞含量占洗精煤中汞的 1 2 .6 % ;硫浆的生成过程脱除了煤气生产用洗精煤中 50 %的汞。     

北京城郊燃煤汞排放及其对当地空气环境的影响

为了解生活用煤汞含量水平,分析生活燃煤给当地环境空气中ρ(Hg)带来的影响,使用Lumex RA915+/M测汞仪,现场在线监测了北京市大兴区46户居民家庭燃煤炉口上方空气和村庄环境空气中的ρ(Hg),并对民用蜂窝煤及煤渣样品中的w(Hg)进行了实验室分析. 结果表明:燃煤炉口上方25 cm处空气中ρ(Hg)为20.4~4 583.5 ng/m3,平均值为823.9 ng/m3(n=46);村庄环境空气中ρ(Hg)为5~13 ng/m3,高于当地背景值(1~3 ng/m3);民用蜂窝煤样品中w(Hg)的平均值为326.6 ng/g(n=46),显著高于我国工业原煤中w(Hg)平均值(约150 ng/g);生活燃煤汞排放率达到99.76%,高于电厂等工业燃煤汞排放率. 鉴于生活用煤多为富汞的劣质煤,其w(Hg)及汞排放率远高于工业用煤,并且室内空气污染对人体健康的危害更为直接,因此,生活燃煤造成的汞污染问题应得到更大的重视.      

烟煤地下气化过程中硫的转化规律研究

在烟煤炭地下气化模型试验的基础上,研究了气化炉温度、气化工艺等对硫转化的影响;在纯氧气化工艺条件下,煤气中含硫气体的形态和含量主要受温度的影响,产生的H2S浓度在600～700℃达到最大值为7400mg·m-3,SO2在1000℃时达到最大值为270 mg·m-3.在纯氧-水蒸气工艺阶段,煤气中的含硫气体形态主要受煤气中氢气含量的影响,但在纯氧-水蒸气工艺后期,含硫气体量又转变为温度的函数.煤炭地下气化过程中,煤中的硫大部分以含硫气体的形式分布在煤气中;只有小部分硫分布在灰渣、焦油和冷凝水中.     

不同煤种对烟气中汞的形态和分布的影响

采用化学热平衡分析方法研究了不同煤种燃烧过程中汞元素的化学形态及其分布.选用的煤种为唐山烟煤、高平无烟煤、贵州六盘水贫煤、小龙潭褐煤、印尼褐煤及宜昌褐煤6个煤样,在50~700℃温度范围内,比较讨论了不同煤样在氧化性气氛中汞的化学形态和物理相.结果表明:烟气温度较低时,原煤中S元素含量对烟气中汞的形态和分布的影响占主导地位;而原煤中Cl-含量越多,低温时最容易实现从HgSO4到HgCl2的转化,高温时最难实现从HgCl2到单质Hg的转化;相对于其它煤种,S和Cl元素在褐煤燃烧过程中的这种影响相对弱些.     

农村分散式燃煤汞排放及周边环境汞污染研究——以贵州省厂头村为例

贵州省燃煤中汞含量较高,在贵州省农村分散式燃煤的使用是个普遍现象。为了解煤在分散式燃烧过程中造成的汞排放及其对周边环境的影响,本研究选取江南煤都贵州省具有代表性的高汞含量煤产区,黔西南州兴仁市厂头村为研究区,对农户所用煤和燃烧过程中的炉渣、烟气以及周边农用地表层土壤样品中的汞含量进行了分析,同时监测了当地农户室内和室外空气汞浓度变化。结果表明,研究区农户煤中汞含量为0. 34±0. 18 mg/kg,炉渣中汞含量为0. 13±0. 10 mg/kg,烟气中汞含量为23±16μg/m~3。研究区的土壤中总汞(THg)和甲基汞(MeHg)的含量分别为0. 37±0. 08 mg/kg和0. 64±0. 35μg/kg,THg与MeHg之间呈显著正相关(r=0. 375,P0. 05)。土壤总汞浓度低于土壤环境质量标准总汞风险筛选值。地累积指数法风险评价结果显示,研究区土壤总汞和甲基汞污染指数分别为0. 18±0. 33和0. 15±0. 79,存在一定的汞污染风险。     

贵阳市小型燃煤锅炉烟气中汞的形态及释放

选择贵阳市某厂的1台安装有湿法脱硫除尘的燃煤锅炉,研究湿法脱硫除尘前后燃煤烟气中颗粒态汞(Hgp)、氧化态汞(Hg2+)、原子态汞(Hg0)以及总汞(Hgt)的含量和形态分布。结果显示,湿法脱硫除尘后的颗粒态汞、氧化态汞、原子态汞分别约占总汞的10 4%,6 0%,83 6%。湿法脱硫除尘器对氧化态汞与颗粒态汞有很好的去除效率(分别为87 9%,76 1%),而对原子态汞的去除效率较差(为30 4%)。由于对该锅炉的年燃煤量统计有一定的误差以及烟气采样分析方法本身存在的误差,该锅炉输出的总汞略大于输入的总汞,质量平衡结果为:输出输入=103 6%～107 4%。煤经过燃烧后,总汞的释放因子为:41 7%残留在底灰中,65 7%进入烟气中,其中经过湿法脱硫除尘器的净化,26 7%的汞随除尘废水排放到水环境中,7 8%存在于经过除尘后的渣中,25 05%随清洁烟气释放到大气中。      

野鸭湖湿地土壤中砷汞分布特征及潜在风险评价

为了解野鸭湖湿地土壤砷汞元素分布规律、形态组成及元素累积影响因素,探讨土地利用对土壤砷汞时空变化的影响,在北京延庆县野鸭湖湿地公园及周围几个镇采集表层土壤,采用原子荧光光谱法对砷汞总量测定,并用五步连续萃取和原子荧光光谱法测定砷汞形态,同时利用相关分析研究As、Hg元素分布的影响因素。结果表明:As、Hg元素在野鸭湖湿地土壤中平均含量10.07、0.088 7mg/kg;均超出北京市土壤背景值,其中草地、耕地中少数采样点低于背景值。砷元素与钒、铁、锰显著正相关(r>0.4,p<0.01);汞与锰正相关,钒、铁、锰含量会在不同程度上影响As的分布;而锰是影响Hg分布的主要因素。As主要形态为残渣态,Hg主要形态为有机物结合态和残渣态。采用风险评价编码法对研究区域的砷汞元素进行潜在生态风险评价,2种元素生态风险均较低。     

脱硫废水添加对煤燃烧时汞析出特性的影响

为探究含氯脱硫废水溶液添加对煤燃烧时汞析出特性的影响,分别利用沉降炉和管式炉实验装置进行了3种煤在1200℃下的燃烧实验。实验时通过改变模拟脱硫废水溶液的添加量来控制燃煤中氯的质量分数分别为0.00%、0.02%、0.04%和0.06%。分析煤燃烧后烟气中汞浓度、吸收液、飞灰和煤灰中汞含量的变化情况发现:随着加氯量的增加,烟气中Hg0浓度逐渐降低,Hg2+浓度则逐渐升高,但对Hgt（气态总汞）浓度的提升效果相对较差。当加氯量为0.06%时,煤种B在沉降炉中燃烧后烟气中Hg0浓度下降约2.3 μg/m3,而Hg2+浓度提高约2.6 μg/m3,但Hgt浓度仅提高了0.3 μg/m3。氯的添加也会使飞灰中汞含量增加,煤灰中汞含量降低。通过综合对比分析沉降炉和管式炉实验结果发现:无论是否添加氯,煤在沉降炉中燃烧后烟气中Hg0比例均小于管式炉实验结果。当煤种B加氯量为0.06%时,在沉降炉和管式炉中燃烧后烟气中Hg0含量占比分别为50.6%和67.8%。此外,还发现3种煤粉在管式炉中加氯燃烧后汞的析出率提高趋势均较沉降炉明显。故含氯脱硫废水溶液的添加可以改变煤燃烧时汞的析出特性,且有利于促进烟气中Hg0的氧化,对燃煤烟气脱汞具有重要作用。     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.