中国城市汞污染及防治对策

简要综述了当前中国城市的汞污染状况。中国许多工业城市大气中的汞含量是纽约市大气中汞含量的数倍，甚至上百倍，在采暖期城市大气的汞污染更加严重；城市土壤中的汞含量是土壤环境背景值的数倍；河流的城市河段河水中汞质量浓度普遍很高，水质多在Ⅲ-V类；城市中的植物均有不同程度地受到汞污染，其汞含量高于国外城市的植物的汞含量；城市居民膳食中鱼的汞含量很高，对城市居民的健康产生了危害；城市居民头发中的汞质量分数大多低于1rng~kg。分析了我国城市中汞的来源并提出了防治城市汞污染的对策。     

煤改气后天津市采暖期大气污染特征的时空分布研究

燃煤供暖被认为是中国北方采暖期大气污染的主要来源之一,因此国家计划以天然气替代燃煤作为取暖燃料以减轻大气污染。基于2016-2017年天津采暖期前后的空气质量监测数据,探究"煤改气"后城市大气污染物的时空分布特征及影响因素,为大气污染治理提供依据。研究表明,煤改气后天津采暖期主要大气污染物有PM_(2.5)、PM10和NO_2 3种,CO日均质量浓度有超标现象发生,SO_2和O_3日均质量浓度均低于二级标准限值。与使用燃煤采暖时期相比,大气中SO_2、PM_(2.5)、PM_(10)和CO的日均质量浓度均有不同程度的降低,尤其是SO2浓度降幅高达70%,但NO_2质量浓度没有有效降低。从日变化特征来看,采暖期PM_(2.5)、PM10和CO的日变化规律受到了采暖活动影响,呈单峰单谷型的变化趋势。NO_2、SO_2和O_3的日变化规律与非采暖期相似,受采暖活动影响较小。由于受供暖和大气逆温层的影响,采暖期晚上至上午时段大气污染物(O3除外)的质量浓度远远高于非采暖期相同时段的质量浓度。天津大气污染物在非采暖期呈现出典型的"周末效应",但是在采暖期没有出现"周末效应"。冬季,周末白天人为活动较工作日更为活跃,与之相对应增加的城镇生活源可能是造成周末白天PM_(2.5)和PM_(10)质量浓度偏高及"周末效应"消失的主要原因。     

大气气溶胶中多环芳烃总量的测定

本文提供了一种测定大气气溶胶中多环芳烃(PAHs)总量的简易方法,包括样品采集、样品预处理、标样制备、真空升华提取和紫外光度法测定等步骤。在PAHs浓度为10μg/ml(n=24)时,方法的回收率为90—100％,变异系数为2.82％。采用本法对天津市采暖期(1984年12月)和非采暖期(1985年4月)大气气溶胶中PAHs的浓度及其相对含量进行了测定。     

北京市大气颗粒物PM2.5,PM10及降雪中的汞

研究了北京大气颗粒物PM25,PM10及降雪中的汞.结果表明,北京大气颗粒物PM25中汞的浓度为024—179ng·m-3,PM10中汞的浓度为038—302ng·m-3,冬季PM25和PM10中汞的浓度明显高于夏季;北京大气可吸入颗粒物中的汞均以细粒子(≤25μm)为主,冬季细粒子中汞的浓度高是细粒子多且其汞含量高共同作用的结果,而夏季则是细粒子中汞的含量高.降雪中汞的浓度在106—162ng·l-1之间,降雪中可溶性汞为总汞的一半左右.     

北京市典型地区大气可吸入颗粒物中汞的浓度水平和粒径分布

在北京市近郊和远郊区采集大气中可吸入颗粒物样品,分析其汞的浓度水平.结果表明,近郊大气可吸入颗粒物中汞的浓度高于远郊区,分别为1.28±1.30ng·m-3和0.79±0.68ng·m-3,而且冬、春两季的浓度明显高于夏、秋两季.可吸入颗粒物中的汞主要分布在细粒子中,且细粒子富集汞的能力较粗粒子强.     

大同市空气中多环芳烃与人尿中1—羟基芘的分析

用ＧＣ＾２／ＭＳ和ＨＰＬＣ鉴定出大同市空气中的多环芳烃化合物３５种，对大同市不同功能区空气中苯并（ａ）芘（ＢａＰ）和人尿中１－羟基芘同步采样分析。结果表明，不同功能区ＢａＰ浓度有显著差别：采暖期浓度急剧增加，城区浓度为对照点的１７倍，日均值达３３０ｎｇ／ｍ＾３。人尿中１－羟基芘的浓度与空气中ＢａＰ的浓度显著相关。采暖期城区尿中１－羟基芘的几何均值为１．８６μｍｏｌ／ｍｏｌ肌酐，非采暖期为１．１４μ     

单一汞同位素示踪大气与农田作物汞的交换过程

汞是引人注目的全球性污染物,植被叶片吸收是大气汞的主要去除途径之一.然而,当前对于大气-植被叶片汞通量交换过程及吸收后的汞在植被体内的归趋等认识尚有不明确之处.本文利用单一大气汞同位素标记技术,测定了大气汞浓度为0、2、5、10 ng·m~(-3)时,C3植物水稻与C4植物玉米叶片汞交换通量的变化特征,并分析了标记的汞同位素在植被体中根-茎-叶的分布比例.结果表明:(1)水稻和玉米叶片汞的沉降通量与大气汞浓度呈显著正相关关系;(2)植物叶片汞的沉降通量有明显的昼夜变化,水稻和玉米的吸收通量白天均高于晚上;(3)玉米对大气汞的补偿点白天为0.63 ng·m~(-3),夜间为2.85 ng·m~(-3);水稻白天为1.24 ng·m~(-3),夜间为1.32 ng·m~(-3),水稻对大气汞的富集能力强于玉米,但二者的补偿点均显著低于国内大气汞浓度;(4)植被从大气吸收的汞主要集中在植物地上部,水稻叶片分布88.92%,茎中分布11.08%,而玉米叶片分布90.95%,茎中分布7.09%,根中分布1.96%.这些结果表明,农田系统的植被能富集大气中的汞,并主要贮存在叶片内部,向茎、根迁移量较少,是大气汞的重要汇.上述结论为进一步估算中国农田系统的大气汞汇与认识汞在大气-叶片-茎-根-土壤中循环提供了科学依据.     

大同市空气中多环芳烃与人尿中1-羟基芘的分析

用GC~2/MS和HPLC鉴定出大同市空气中的多环芳烃化合物35种.对大同市不同功能区空气中苯并(a)芘(BaP)和人尿中1-羟基芘同步采样分析.结果表明,不同功能区BaP浓度有显著差别:采暖期浓度急剧增加,城区浓度为对照点的17倍,日均值达330ng/m~3.人尿中1-羟基芘的浓度与空气中BaP的浓度显著相关.采暖期城区尿中1-羟基芘的几何均值为1.86μmol/mol肌酐,非采暖期为1.14μmol/mol肌酐,均较北京市的均值高出五倍多.证明大同市由于直接燃煤,造成空气中多环芳烃的严重污染.     

冬季降雪过程对城市大气气态汞污染的影响

2009年降雪和非降雪期间对北京西北城区的气态总汞浓度进行了连续采样，比较了降雪期间、非降雪期间的气态总汞浓度日变化过程；降雪期间气态总汞浓度的降低和恢复过程。结果表明，降雪和非降雪期间大气气态总汞浓度的日均值有显著差异，降雪期间气态总汞的平均浓度为5．64ng·m^-3，非降雪期间的平均浓度为7．43ng·m^-3，前者约为后者的70％。降雪后约7h气态总汞浓度恢复到降雪前水平。研究中分析了气象因素（气压、风速、阵风速度、气温和相对湿度）对于气态总汞浓度的影响，结果表明：降雪期间主要受到风速（r=-0．527）和阵风速度（r=-0．574）的影响；非降雪期间主要受到风速（r=-0．691），阵风速度（r=-0．726）和相对湿度（r=0．692）的影响，并且相对湿度的影响与风速的影响相近。降雪和非降雪期间气态总汞的日变化有所差异：非降雪期间气态总汞浓度在午夜和清晨较高，日变化趋势与相对湿度一致；降雪期间气态总汞的日变化没有明显规律。     

天然石生苔藓汞含量及对大气汞污染的生物指示

采集贵州万山汞矿区6属7种优势种类苔藓84个样品,测定其汞含量,同时现场监测部分苔藓采样点近地表大气汞,定量分析苔藓汞和大气汞质量浓度之间的关系.结果显示,研究区苔藓汞质量浓度范围为0.96—126μg·g~(-1),平均值80±46μg·g~(-1),受触媒生产、废触媒回收等涉汞化工厂生产活动影响显著;苔藓汞与大气汞呈正相关关系,表现为线性拟合相关性系数r=0.93(n=12,P=0.01030),多项式拟合相关性系数r=0.96(n=12,P=0.01169),对数拟合相关性系数r=0.96(n=12,P=0.00469);选择对数拟合方程估算苔藓采样点大气汞浓度,发现拟合得到的大气汞空间分布特征和实测苔藓汞空间分布特征基本一致,从而通过定量/半定量方法证明了可以利用苔藓汞指示大气汞污染,为汞污染场地修复过程中的大气汞污染评价提供了新思路.     

Mercury pollution in a mining area of Guizhou,China: Fluxes over contaminated surfaces and concentrations in air,biological and geological samples

A dynamic flux chamber has been used to estimate fluxes of mercury over different types of surfaces in an abandoned open‐cut mine of Tongren prefecture, Guizhou province, China during spring and summer of 1996. The highest fluxes were obtained over cinnabar slag and contaminated soils, whereas the emissions above cinnabar ore were substantially lower. These fluxes was scaled up to estimate the contribution of mercury emissions to air from mercury wastes, compared to anthropogenic activities in the province of Guizhou, China. Atmospheric mercury concentrations measured were enhanced in the mining area (<1.3 μg m^‐3) compared to regional background sites (1.8–5.1 ng m^‐3). The spreading of mercury was estimated by using biological and geological samples. Moss bags have been employed to estimate long‐time dry‐ and wet‐deposition to this area.     

北京市场常见水产品中总汞、甲基汞分布特征及食用风险

以甲苯二次萃取-直接测汞的方法对北京市场常见水产品中的甲基汞进行分析测定,并评价了食用人群的暴露风险。分析样品包括大黄鱼（Pseudosciaena crocea）、虾（Penaeus chinensis）等9种常见海产品以及武昌鱼（Megalobrama amblycephala Yih）、鳙鱼（Aristichthys nobilis）2种淡水海产品。测定结果表明：海产品中总汞和甲基汞质量分数要远高于淡水鱼中的总汞和甲基汞质量分数,总汞绝大多数是以甲基汞的形式存在,所占比例从74.7%到96.0%不等;对其中3种鱼类的鱼体甲基汞分布研究表明：肌肉中的甲基汞质量分数最高,肝脏中次之,鱼鳃中质量分数最低。根据我国水产品甲基汞标准,本研究中水产品甲基汞质量分数均低于国家标准,但根据世界卫生组织（WHO）和美国环保署EPA颁布的甲基汞摄入量参考值,食用银鳕鱼等甲基汞质量分数相对较高的水产品仍然存在一定的风险,应注意限量。     

广东柘林湾养殖海域沉积物中汞的分布、累积及其生态风险

柘林湾是广东省养殖规模最大的海湾之一,为了解养殖海域沉积物中汞的分布、累积及其可能产生的生态风险,于2008年1月在柘林湾海域采集了5个站位的柱状沉积物和3个站位的表层沉积物,对其中的总汞含量进行了测定,并对其含量分布、累积特征进行了分析.结果表明,柘林湾海域表层沉积物中总汞平均含量为0.0645μg·g-1,径流输入是其空间分布特征的主要影响因素;柱状沉积物表层部分总汞含量相对较低,但不同采样区域柱样中总汞含量的垂直分布却有着显著的差异,网箱养殖区主要是由于汞近40年来来源变小导致沉积物表层部分中的总汞含量较底层低,而贝类养殖区则由于沉积后的再迁移作用使汞在氧化还原边界层富集累积;利用潜在生态危害指数法和沉积物质量基准法对此次调查的沉积物中汞的潜在生态风险进行的评价表明,汞虽对底栖生物基本无负面效应,但其潜在生态风险程度达到了中等水平,尤其是养殖区2号站位28～36cm、4号站位20～32cm和48～56cm以及6号站位36～56cm柱样中的汞甚至达到了高的潜在生态风险程度.因此,养殖区次表层沉积物中较高含量的汞应当引起足够重视.     

金矿区中国林蛙体内DNA甲基化水平

采集金矿附近山区河流水质、沉积物和当地两栖类动物中国林蛙样品,应用高效液相色谱仪测定污染区和对照区林蛙体内各组织器官的胞嘧啶(c)和5-甲基胞嘧啶(5-mc)含量,探讨因金矿开采引起的汞污染以及对林蛙体内组织器官DNA甲基化水平的变化,研究汞胁迫下,两栖类动物体内分子水平的影响。结果表明:金矿开采区河流水质和沉积物已受到甲基汞污染,污染区林蛙体内甲基汞含量远高于对照区;林蛙体内各组织器官中DNA甲基化水平发生不同的变化:污染区林蛙肝脏和皮肤中DNA甲基化水平高于对照区,肌肉和脑干DNA甲基化水平低于对照区;雄性林蛙肝脏和脑干DNA甲基化水平高于雌性,肌肉和皮肤DNA甲基化水平却低于雌性。以上结果说明汞胁迫下,中国林蛙体内组织器官DNA甲基化水平可以发生一定的变化,环境中重金属汞离子进入林蛙体内含量的不同,可以促进或抑制其体内甲基化水平的变化,引起基因毒性作用。     

北京市秋季大气颗粒物的污染特征研究

大气颗粒物是造成城市空气污染的重要原因之一,并已经成为我国北京等大中城市空气污染中的首要污染。为了分析北京市大气细颗粒物的污染水平及其影响因素,以大气中的PM10和PM2.5为研究对象,于2005年秋季在北京市设立了9个采样点进行采样监测,通过对所采集到的PM10和PM2.5质量浓度的对比来分析大气颗粒物的空间分布和时间变化特征,并建立起PM10和PM2.5质量浓度与风力、温度、湿度等气象条件的对应关系来分析各种气象因素对大气细颗粒物污染水平的影响。结果表明:北京市不同区域的PM10和PM2.5的质量浓度差异较大,同时,值得注意的是通过对同一地点同一采样时间大气颗粒物质量浓度的对比发现PM2.5质量浓度的空间分布并不完全同于PM10,这主要是与采样点所处的环境中不同污染源影响的强弱有关;气象条件稳定时,PM10和PM2.5质量浓度的日变化表现出一定的规律性,这种时间变化的特征主要取决于所在环境中排放的污染物变化情况;气象条件是影响PM10和PM2.5污染程度的重要因素,在一定的范围内,颗粒物质量浓度随着温度的上升而下降,随着相对湿度的升高而增大,随着风力的增强而减小。     

Atmospheric mercury at mediterranean coastal stations

Mercury in air has been measured at five coastal Mediterranean sites, involving measurements in Spain, France, Italy, Slovenia and Israel. Four two-weeks long measurements campaigns were performed at the five sites. The measurements were carried out during autumn 2003 and winter, spring and summer 2004. Total gaseous mercury/elemental gaseous mercury, particulate mercury and divalent gaseous mercury were measured in parallel at the five sites. The activities constituted a subtask of the EU funded MERCYMS research project, which also included Mediterranean Sea cruises where both mercury in air and water were measured. The result from an evaluation of all the coastal air data is presented. Mercury concentrations from the different sites are compared with similar data obtained in northern Europe and elsewhere. The result shows that the background concentration of mercury in Mediterranean coastal air is lower than earlier anticipated. Background concentrations of TGM, RGM and TPM corresponded to 1.75–1.80 ng m⁻³, 1–13 and 3–23 pg m⁻³, respectively. The measurements also showed that the mercury concentration occasionally can be very high in some areas due to local anthropogenic emissions. It is proposed that diurnal variation in RGM concentrations observed during situation with nocturnal inversion merely is an effect of meteorology rather than due to local photochemistry.     

Annual ambient atmospheric mercury speciation measurement from Longjing,a rural site in Taiwan

The main purpose of this study was to monitor ambient air particulates and mercury species [RGM, Hg(p), GEM and total mercury] concentrations and dry depositions over rural area at Longjing in central Taiwan during October 2014 to September 2015. In addition, passive air sampler and knife-edge surrogate surface samplers were used to collect the ambient air mercury species concentrations and dry depositions, respectively, in this study. Moreover, direct mercury analyzer was directly used to detect the mercury Hg(p) and RGM concentrations. The result indicated that: (1) The average highest RGM, Hg(p), GEM and total mercury concentrations, and dry depositions were observed in January, prevailing dust storm occurred in winter season was the possible major reason responsible for the above findings. (2) The highest average RGM, Hg(p), GEM and total mercury concentrations, dry depositions and velocities were occurred in winter. This is because that China is the largest atmospheric mercury (Hg) emitter in the world. Its Hg emissions and environmental impacts need to be evaluated. (3) The results indicated that the total mercury ratios of Kaohsiung to that of this study were 5.61. This is because that Kaohsiung has the largest industry density (~60 %) in Taiwan. (4) the USA showed average lower mercury species concentrations when compared to those of the other world countries. The average ratios of China/USA values were 89, 76 and 160 for total mercury, RGM and Hg(p), respectively, during the years of 2000–2012.     

Environmental geochemistry studies in the area of Idrija mercury mine, Slovenia

Five centuries of mining and processing of mercury ore in the Idrija area have resulted in widespread contamination of different environmental compartments. Environmental impacts on a regional and local scale, caused by atmospheric emissions from the Idrija ore roasting plant, were established in the investigations of mercury spatial distribution in soil and attic dust in 160 km(2) area. Very high values were determined in the Idrijca River valley, and they decrease exponentially with the distance from Idrija. Mercury concentrations in attic dust are higher than in surrounding soils and the attic dust/soil ratio changes with distance. Measurements of mercury in the air confirmed widespread dispersion of mercury and showed highly elevated mercury concentrations around roasting plant and mine ventilation shaft. Beside, systematic monitoring of mercury contents in the stream sediments has demonstrated that huge amounts of mercury are stored in areas where ancient overbank sediments were deposited, and there was no decrease in mercury concentration in active sediments during the last 15 years. Recently, interesting and extremely polluted locations of historical small-scale roasting sites in the Idrija surroundings were discovered. Ongoing geochemical study aims to determine the extreme pollution and significance of these sites for wider contamination of soils and aquatic systems. Presented studies have shown that Hg mining in Idrija caused intense pollution of local and regional environment including the aquatic systems in the Gulf of Trieste, which is seen as the final sink of a major part of the Hg stored in soils and river sediments in the Idrija area.     

灵芝中重金属的检测及其健康风险初步评价

为了研究灵芝中重金属的污染状况,对北京市一些药店及部分中医门诊部所售的不同产地灵芝中的As、Hg、Pb等重金属元素含量进行了测定.结果表明,灵芝中As含量范围为0.016￣0.239mg·kg-1,平均值0.117mg·kg-1,Hg含量范围从未检出到0.43mg·kg-1,平均值0.115mg·kg-1,Pb含量范围从未检出到0.256mg·kg-1,平均值0.047mg·kg-1,As、Pb含量均符合我国《药用植物及制剂进出口绿色行业标准》,Hg有5例超标,占样品总数的25%,主要是野生灵芝.健康风险初步评价结果表明,服用灵芝的人群,成人每人每日通过灵芝摄入As、Hg、Pb分别为0.18￣2.3μg、0.17￣2.3μg、0.07￣0.94μg,分别占每日允许摄入量(ADI)的0.14%￣1.9%、0.4%￣5.4%、0.03%￣0.4%,对人体健康风险不大.但是对于个别野生和人工种植灵芝而言,每日摄入总汞量可达0.47￣6.24μg,占ADI的1.1%￣15%,对人体健康存在一定的风险.