桂林市表层土壤总汞分布特征研究

为了研究桂林市表层土壤汞污染情况,采集了不同功能区(包括校园区、风景旅游区、交通运输区、居民区、商业区、农业用地区和其他区域)的表层(0~10cm)土壤样品36个,采用硫酸-硝酸混合液浸提、原子荧光方法测定土壤中的总汞。结果表明,桂林市表层土壤的总汞质量浓度在0.136~1.873mg/kg,平均值为0.557mg/kg,中值为0.440mg/kg。各功能区土壤中汞的平均值均超过《土壤环境质量标准》(GB 15618—1995)的一级标准(0.15 mg/kg),以风景旅游区最高,为0.900 mg/kg,其次为商业区,为0.595 mg/kg。进一步对桂林市表层土壤总汞浓度与环境参数的关系进行了研究,结果表明,各采样点土壤的总汞浓度与有机质显著相关,与土壤pH无相关关系。     

汉沽附近大气中汞的污染状况调查

天津市汉沽区大气中汞的主要来源为天津化工厂氯碱电解车间汞盐泥堆,蓟运河排污口及沿岸土壤,河床底泥和河水等向大气释放与扩散的汞。现已查明,氯碱电解时管道逸出的氢气中夹带着大量的汞;以及疏通河道时挖出的含汞底泥搬运至东郊低洼地上所造成对大气的污染(类似污染源搬家)。从一系列监测数据证明,在特定的气象条件下,汉沽区中心地带自东至西大片区域受     

成都东郊稻田土中汞的分布特征研究

选取成都东郊唯一的火力发电厂周围的稻田土为研究对象,对稻田土中各种形态汞的分布特征进行了调查与研究,探讨稻田土中汞的分布规律,为分析和判断稻田土中汞的迁移和转化行为及该区汞污染土壤的修复提供重要依据。结果表明,处于火力发电厂烟尘排污口下风向的1#、2#、3#、4#采样点土样受到了严重的汞污染,呈现出高含汞特征,总汞平均质量浓度在9～41mg/kg,平均值为24.546mg/kg,远远超出《土壤环境质量标准》(GB 15618—1995)二级标准所规定的限值(0.5mg/kg),而处于排污口上风向的5#、6#、7#、8#土样没有受到明显的汞污染,大部分土样的总汞含量与成都市土壤汞平均含量接近;1#、2#、3#、4#土样中5种形态汞的垂直分布均呈现出随着土壤深度增加而减少的特征;1#、2#、3#、4#土样中的各形态汞平均百分比为有机结合态汞>硝酸溶汞>残渣态汞>铁锰氧化态汞>水溶和可交换态汞,土壤中含有的大部分汞化学性质比较稳定,难以被植物吸收利用,而易被植物吸收利用的水溶和可交换态汞虽然仅占极小一部分,但含量还是高于成都市土壤中水溶和可交换态汞的背景值。     

新型脱汞技术下粉煤灰中的含汞量及其堆存时汞的浸出特征研究

添加溴化钙、喷射活性炭或溴化活性炭等脱汞技术会将更多的汞转移到粉煤灰中,增加了粉煤灰在堆存过程中的环境风险。主要讨论了添加溴化钙、喷射活性炭或溴化活性炭等不同新型脱汞技术产生的粉煤灰(分别简称为BCFA、CFA、BFA)的理化特性,并模拟了极端酸性降雨条件下粉煤灰在堆存过程中汞的释放规律。结果表明,BCFA、CFA、BFA与常规协同控制脱汞下产生的粉煤灰(简称RFA,作为对照)的矿物组成与颗粒粒径无显著差异。添加不同量的溴化钙后BCFA中含汞量变化不明显,与RFA中含汞量差异也不明显;BFA和CFA中含汞量随喷射速率提高而逐渐增加,且明显高于RFA中含汞量。RFA、BCFA、CFA、BFA的浸出液含汞量在13.7~42.6ng/L,均低于《地表水环境质量标准》(GB 3838—2002)中Ⅰ类标准,因此不同新型脱汞技术产生的粉煤灰在堆存初期,即使在极端酸性降雨的条件下,也不会对周围水环境造成汞污染。     

六氯苯在中国典型持久性有机污染物污染场地中空间分布研究

在多年六氯苯生产车间及周围布设采样点,采取不同深度的土壤进行分析,研究持久性有机污染物(POPs)污染场地中六氯苯的空间分布规律.结果表明,生产车间附近污染严重,六氯苯的最高质量浓度为25 911.95 mg/kg,平均为4 944.07 mg/kg,在风力作用下六氯苯浓度向东南方向扩散;-3 m土层(以表土层为基准,表土层以下的土层深度为负值)中六氯苯最高质量浓度为369.63 mg/kg.平均为54.77 mg/kg,六氯苯浓度较表土层迅速下降,六氯苯污染中心位置与表土层对应;-5 m土层由于土壤类型为黏土或淤泥质黏土,六氯苯浓度相对于- m土层反而升高.平均质量浓度为92.13 mg/kg.纵观整个污染场地六氯苯的污染分布情况,污染中心位置向南移动,且六氯苯在垂直方向的迁移和浓度与土壤有机质含量相关.     

应用离子交换树脂法处理低浓度含汞废水

含汞废水是危害最大的工业废水之一。铜山制药厂采用硫化钠——明矾化学凝聚沉淀法处理红汞生产中产生的含汞废水。经过一年多运行,由于含汞废水中成分复杂,存在多种形态的汞化合物(有机汞、无机汞)、金属汞以及其他有机物和离子,对酸化pH值和硫化钠量不易控制,会使硫化汞形成螯合物溶解,处理后废水中汞浓度0.05～0.5mg/l,很难达到排放标准。为了探索技术上先进、经济上合理的治理途径,通过多次实验,选用了离子交换树脂法。     

氯盐对含汞土壤热脱附的影响

采用管式电阻炉对不同氯盐调理的含汞土壤进行热脱附实验,研究氯盐种类和炉温等对汞脱除效果的影响,分别从汞脱除率、热重测试和XRD汞形态分析3个方面进行评价.结果表明,不同温度下添加氯盐均对汞脱除率有明显提升.230℃时,添加氯化铁、氯化镁和氯化钙调理相比对照组(不添加氯盐),汞脱除率分别提升66.2％、49.3％和15.8％,即促进效果:FeCl3＞MgCl2＞CaCl2.在300℃下加热25 min时,添加氯化铁调理的汞脱除率为96.1～96.2％,与对照组相比,最高提升了68.3％.热重测试结果显示,载气对汞的挥发影响较小,湿法投加氯盐效果比干法投加更明显.炉尾晶体XRD分析结果表明,在低温条件下氯盐促进样品中汞向氯化汞转变从而提高了汞脱除率.添加氯盐调理提高了汞脱除率,同时缩短了汞热脱附达到稳定的时间.     

3种植物对Cd污染农田土壤的修复效果比较试验研究

通过盆栽试验研究了3种植物三叶鬼针草(Bidens pilosa L.)、紫茉莉(Mirabilis Jalapa)、中华景天(Sedum polytrich-oides)对上海地区2种质量浓度(1.2、12.0mg/kg)Cd污染农田土壤的修复效果,以探索其在上海地区Cd污染农田土壤修复中应用的可行性。结果表明:2种浓度下,三叶鬼针草对土壤Cd去除效果均最佳,1.2mg/kg处理下盆中土壤Cd质量浓度由原来的1.249 9mg/kg下降到0.861 7mg/kg,降低0.388 2mg/kg,Cd去除率为31.06%;12.0mg/kg处理下三叶鬼针草盆中土壤Cd质量浓度由原来的12.033 2mg/kg下降到10.020 6mg/kg,降低2.012 6mg/kg,Cd去除率为16.73%;紫茉莉和中华景天相比较而言,修复效果均较差。在2种浓度下,3种植物地上部分生物量排序均为三叶鬼针草>中华景天>紫茉莉。因此,建议将三叶鬼针草作为上海地区Cd污染农田土壤修复的优选植物。     

南京市紫金山土壤中6种重金属的污染特征和污染水平评价

为探究人类活动对南京市紫金山国家森林公园土壤重金属污染的影响,研究了紫金山土壤中6种重金属(Cu、Zn、Pb、Cr、Ni、Mn)的污染特征,并采用单因子指数法和内梅罗综合指数法进行了污染水平评价。结果表明:Cu的质量浓度范围为4.21~249.75mg/kg,平均值为64.08mg/kg;Zn的质量浓度范围为155.26~418.75mg/kg,平均值为212.34mg/kg;Pb的质量浓度范围为112.19~608.91mg/kg,平均值为319.57mg/kg;Cr的质量浓度范围为29.54~201.25mg/kg,平均值为127.36mg/kg;Ni的质量浓度范围为46.64~142.48mg/kg,平均值为76.16mg/kg;Mn的质量浓度范围为182.59~1 634.48mg/kg,平均值为1 008.93mg/kg。总体而言,上层样(0~20cm)的重金属浓度高于下层样(20~40cm),高海拔的重金属浓度低于低海拔的。内梅罗综合指数表明,所有采样点均处于重度污染状态。分析6种重金属的单因子指数发现,主要是因为Pb的单因子指数较大。     

几种硫化物对紫色土汞的稳定化效果及优化稳定条件

以西南地区广泛分布的紫色土-灰棕紫泥为对象,探讨了硫化物种类(S、Na_2S、FeS、Na_2S_2O_3和DTCR(二硫代氨基甲酸盐))、用量对不同水平汞污染土壤的稳定化效果。结果表明5种硫化物对土壤汞均具有显著的稳定化效果。固定S:Hg摩尔比为1:1条件下,在1.5～250 mg·kg~(-1)汞污染土壤中,几种硫化物稳定效率相对大小顺序:DTCRNa_2SNa_2S_2O_3SFeS。Na_2S和DTCR在高浓度汞污染土壤中均表现较高的稳定化效果,在不同汞污染浓度下均能在3d内使土壤浸出汞浓度满足美国固体废弃物毒性浸出程序(TCLP)浸出标准要求(0.2 mg·L~(-1)),Na_2S_2O_3稳定效果相对较差,对250 mg·kg~(-1)的汞污染土壤,稳定化处理时间需要15d才能达到浸出标准要求,当汞污染浓度≥150 mg·kg~(-1)时,S和FeS不能满足浸出标准要求。固定汞污染浓度为150 mg·kg~(-1)稳定化效果取决于硫化物的用量,其中,仍然以DTCR效果最好,S:Hg=1稳定化处理3 d时即可达汞浸出标准。Na_2S和Na_2S_2O_3则均需要在较高的浓度下才能实现汞的稳定化,但是过高的用量会导致土壤中HgS再次溶解,两者的最佳施用量为S:Hg=5。元素S和FeS则需要以S:Hg5稳定化处理7 d以上才能达到浸出标准要求。土壤中汞的浸出活性与其赋存形态有关,交换态(Exc-Hg)和碳酸盐结合态汞(Carb-Hg)与土壤浸出汞浓度呈显著正相关,高效稳定剂显著促进了汞向有机质结合态(OM-Hg)和残渣态(Res-Hg)转化。硫化物稳定化处理9个月内土壤中浸出汞浓度始终维持在极低水平,满足持续稳定化要求。     

Atmospheric mercury emission from artisanal mercury mining in Guizhou Province,Southwestern China

Mercury (Hg) mining is an important anthropogenic source of atmospheric Hg emissions. The Guizhou Province in Southwestern China is a region with extensive artisanal mercury mining (AMM), but little Hg emission data from this area is available. Using a mass balance method, we estimated emission factors from artisanal mercury mining in Wuchuan mercury mining area (WMMA) and Gouxi area (GX). Average emission factors were 18.2% in WMMA (ranging from 6.9% to 32.1%) and 9.8% in GX (ranging from 6.6% to 14.5%), respectively, which were 2.2–36.4 times higher than the literature values used to estimate Hg emission from Hg mining. Furthermore, the average Hg emission factor of AMM in WMMA was much higher than that in GX, indicating that double condensation processes practiced in GX resulted in higher recoveries and lower emission factors compared to single condensation process applied in WMMA. Atmospheric Hg emission was estimated to be 3.7–9.6 metric tons in 2004 for WMMA and 1.3–2.7 metric tons in 2006 for GX, indicating artisanal Hg mining was an important atmospheric Hg emission source in the study area.     

Comparison of mercury chemistry models

Five mercury (Hg) chemistry models are compared using the same data set for model initialisation. All five models include gas-phase oxidation of Hg(0) to Hg(II) (except for one model), fast reduction–oxidation aqueous reactions between Hg(0) and Hg(II), and adsorption of Hg(II) species to soot particles within droplets. However, the models differ in their detailed treatments of these processes. Consequently, the 48-h simulations reveal similarities but also significant discrepancies among the models. For the simulation that included all Hg species (i.e., Hg(0), Hg(II) and Hg(p)) as well as soot in the initial conditions, the maximum simulated Hg(II) aqueous concentrations ranged from 55 to 148 ng l⁻¹ whereas the minimum concentrations ranged from 20 to 110 ng l⁻¹. These results suggest that further experimental work is critically needed to reduce the current uncertainties in the formulation of Hg chemistry models.     

Anthropogenic mercury emissions in China

An inventory of mercury emissions from anthropogenic activities in China is compiled for the year 1999 from official statistical data. We estimate that China's emissions were 536 (±236) t of total mercury. This value includes open biomass burning, but does not include natural sources or re-emission of previously deposited mercury. Approximately 45% of the Hg comes from non-ferrous metals smelting, 38% from coal combustion, and 17% from miscellaneous activities, of which battery and fluorescent lamp production and cement production are the largest. Emissions are heaviest in Liaoning and Guangdong Provinces, where extensive smelting occurs, and in Guizhou Province, where there is much small-scale combustion of high-Hg coal without emission control devices. Emissions are gridded at 30×30 min spatial resolution. We estimate that 56% of the Hg in China is released as Hg⁰, 32% as Hg²⁺, and 12% as Hg^p. Particulate mercury emissions are high in China due to heavy burning of coal in residential and small industrial settings without PM controls. Emissions of Hg²⁺ from coal-fired power plants are high due to the absence of flue-gas desulfurization units, which tend to dissolve the soluble divalent mercury. Metals smelting operations favor the production of elemental mercury. Much of the Hg is released from small-scale activities in rather remote areas, and therefore the activity levels are quite uncertain. Also, emissions test data for Chinese sources are lacking, causing uncertainties in Hg emission factors and removal efficiencies. Overall, we calculate an uncertainty level of ±44% (95% confidence interval) in the estimate of total emissions. We recommend field testing of coal combustors and smelters in China to improve the accuracy of these estimates.     

Seasonal variation in dissolved gaseous mercury and total mercury concentrations in Juam Reservoir, Korea

Dissolved gaseous mercury (DGM) and total mercury (TM) concentrations were measured in Juam Reservoir, Korea. DGM concentrations were higher in spring (64+/-13pgL(-1)) and summer (109+/-15pgL(-1)), and lower in fall (20+/-2pgL(-1)) and winter (23+/-6pgL(-1)). In contrast, TM concentrations were higher in fall (3.2+/-0.1ngL(-1)) and winter (3.3+/-0.1ngL(-1)) than in spring (2.3+/-0.1ngL(-1)) and summer (2.2+/-0.4ngL(-1)). DGM concentrations were correlated with water temperature (p<0.0001), ORP (p<0.0001), UV intensity (UV-A: p=0.008; UV-B: p=0.003), and DOC concentration (p=0.0107). DGM concentrations varied diurnally with UV intensity. The average summer DGM (109+/-15pgL(-1)) and TM (2.2+/-0.4ngL(-1)) concentrations in Juam Reservoir were higher than the averages for North American lakes (DGM=38+/-16pgL(-1); TM=1.0+/-1.2ngL(-1)), but lower than levels reported for Baihua Reservoir in China.     

Gas-phase mercury reduction to measure total mercury in the flue gas of a coal-fired boiler

Gaseous elemental and total (elemental + oxidized) mercury (Hg) in the flue gas from a coal-fired boiler was measured by a modified ultraviolet (UV) spectrometer. Challenges to Hg measurement were the spectral interferences from other flue gas components and that UV measures only elemental Hg. To eliminate interference from flue gas components, a cartridge filled with gold-coated sand removed elemental Hg from a flue gas sample. The Hg-free flue gas was the reference gas, eliminating the spectral interferences. To measure total Hg by UV, oxidized Hg underwent a gas-phase, thermal-reduction in a quartz cell heated to 750 degrees C. Simultaneously, hydrogen was added to flash react with the oxygen present forming water vapor and preventing Hg re-oxidation as it exits the cell. Hg concentration results are in parts per billion by volume Hg at the flue gas oxygen concentration. The modified Hg analyzer and the Ontario Hydro method concurrently measured Hg at a field test site. Measurements were made at a 700-MW steam turbine plant with scrubber units and selective catalytic reduction. The flue gas sampled downstream of the selective catalytic reduction contained 2100 ppm SO2 and 75 ppm NOx. Total Hg measured by the Hg analyzer was within 20% of the Ontario Hydro results.     

Estimating contribution of precipitation scavenging of atmospheric particulate mercury to mercury wet deposition in Japan

Mercury wet deposition is dependent on both the scavenging of divalent reactive gaseous mercury (RGM) and atmospheric particulate mercury (Hg(p)) by precipitation. Estimating the contribution of precipitation scavenging of RGM and Hg(p) is important for better understanding the causes of the regional and seasonal variations in mercury wet deposition. In this study, the contribution of Hg(p) scavenging was estimated on the basis of the scavenging ratios of other trace elements (i.e., Cd, Cu, Mn, Ni, Pb and V) existing entirely in particulate form. Their wet deposition fluxes and concentrations in air, which were measured concurrently from April 2004 to March 2005 at 10 sites in Japan, were used in this estimation. The monthly wet deposition flux of mercury at each site correlated with the amount of monthly precipitation, whereas the Hg(p) concentrations in air tended to decrease during summer. There was a significant correlation (P<0.001) among the calculated monthly average scavenging ratios of trace elements, and the values in each month at each site were similar. Therefore, it is assumed the monthly scavenging ratio of Hg(p) is equivalent to the mean value of other trace elements. Using this scavenging ratio (W), the wet deposition flux (F) due to Hg(p) scavenging in each month was calculated by F=WKP, where K and P are the Hg(p) concentration and amount of precipitation, respectively. Relatively large fluxes due to Hg(p) scavenging were observed at a highly industrial site and at sites on the Japan Sea coast, which are strongly affected by the local sources and the long-range transport from the Asian continent, respectively. However, on average, at the 10 sites, the contribution of Hg(p) scavenging to the annual mercury deposition flux was 26%, suggesting that mercury wet deposition in Japan is dominated by RGM scavenging. This RGM should originate mainly from the in situ oxidation of Hg⁰ in the atmosphere.     

Atmospheric mercury cycles in northern Wisconsin

Total gaseous mercury (TGM) in the lower atmosphere of northern Wisconsin exhibits strong annual and diurnal cycles similar to those previously reported for other rural monitoring sites across mid-latitude North America. Annually, TGM was highest in late winter and then gradually declined until late summer. During 2002–04, the average TGM concentration was 1.4 ± 0.2 (SD) ng m^?3, and the amplitude of the annual cycle was 0.4 ng m^?3 (～30% of the long-term mean). The diurnal cycle was characterized by increasing TGM concentrations during the morning followed by decreases during the afternoon and night. The diurnal amplitude was variable but it was largest in spring and summer, when daily TGM oscillations of 20–40% were not uncommon. Notably, we also observed a diurnal cycle for TGM indoors in a room ventilated through an open window. Even though TGM concentrations were an order of magnitude higher indoors, (presumably due to historical practices within the building: e.g. latex paint, fluorescent lamps, thermometers), the diurnal cycle was remarkably similar to that observed outdoors. The indoor cycle was not directly attributable to human activity, the metabolic activity of vegetation or diurnal atmospheric dynamics; but it was related to changes in temperature and oxidants in outdoor air that infiltrated the room. Although there was an obvious difference in the proximal source of indoor and outdoor TGM, similarities in behavior suggest that common TGM cycles may be driven largely by adsorption/desorption reactions involving solid surfaces, such as leaves, snow, dust and walls. Such behavior would imply a short residence time for Hg in the lower atmosphere and intense recycling – consistent with the “ping-pong ball” or “multi-hop” conceptual models proposed by others.     

汞化合物的生物检测技术

为了对环境中的汞污染进行现场检测 ,需要开发简便、快速、灵敏的分析方法。生物检测技术是其中的一个重要研究方向。在分析中 ,对现有的汞化合物主要生物检测技术的原理、特点、研究现状及应用前景进行了评价