贵阳市阿哈湖水体和沉积物间隙水中汞的含量和形态分布初步研究

为了弄清楚酸性矿井废水的排放是否对阿哈湖造成了汞污染,我们研究了阿哈湖中汞的各种赋存形态(包括溶解气态汞、活性汞、颗粒态汞、溶解态汞、溶解态甲基汞、颗粒态甲基汞,以及沉积物间隙水体的溶解态汞和溶解态甲基汞)及其在水体和沉积物间隙水中的剖面分布.实验数据表明,溶解态甲基汞浓度在沉积物下2～5 cm处最高,随深度增加而逐渐降低,与硫酸盐还原菌(SRB)的分布相吻合,说明水体-沉积物界面是甲基汞的产生地点;并且在沉积物中高浓度硫酸根浓度高达1100mg/L时,硫酸根浓度与甲基汞浓度依然一致.     

乌江流域东风水库水体中不同形态汞的时空分布特征

为弄清东风水库水体中不同形态汞的时空分布特征,在春季和夏季对东风水库进行采样,分别利用两次金汞齐-冷原子荧光法(CVAFS)和蒸馏-乙基化结合气相色谱冷原子荧光法(GC-CVAFS)测定总汞(THg)和甲基汞(MeHg)浓度。结果表明,东风水库THg(0.63~3.06 ng/L)和MeHg浓度(0.023~0.081 ng/L)与未受污染的天然湖泊水平相当,水库未受到明显的汞污染。夏季总汞(THg)、颗粒态汞(PHg)以及颗粒态甲基汞(PMeHg)浓度均值分别是春季的1.8、2.9和1.7倍,但春季总甲基汞(TMeHg)和溶解态甲基汞(DMeHg)高于夏季。季节性降雨强度的差异可能是导致东风水库水体不同形态汞浓度季节性变化的主要原因。此外,东风水库上游水体THg和PHg显著高于中下游水体,表明东风水库的修建对THg具有一定的拦截作用。     

河流对阿哈水库汞迁移转化过程的影响

阿哈水库是贵阳市饮用水源,二十世纪九十年代之前阿哈水库流域的煤窑废水污染是其主要污染源;之后,矿山煤窑废水经集中治理,状况得到很大改善,生活水排放成为主要污染源。阿哈水库入库河流总汞浓度为7.1~47.9 ng/L;甲基汞浓度为0.16~2.50 ng/L;活性汞浓度为0.25~2.43 ng/L,且随季节变化明显,枯水期<丰水期。阿哈水库入库河流汞的主要存在形态为颗粒态汞,总汞与颗粒态汞呈显著正相关。阿哈水库唯一的出湖河流小车河中,各种形态的汞均较入湖河流中的汞含量大大减少,这表明水库的沉淀和拦截净化作用相当显著。     

龙滩水库枯水期N、P元素空间分布特征

为研究龙滩水库枯水期溶解态氮、磷营养元素的空间分布特征,在龙滩水库枯水期(2017年1月份)进行分层采样,现场测定水体理化性质及实验室分析水中营养盐浓度。结果表明:龙滩水库水温出现明显垂直分层:0~10m为温跃层;10~60m为混合层;60m以下为底温层;pH值为7.63~7.92,水体呈弱碱性。溶解无机氮(DIN)平均浓度为4.75mg/L。水体溶解性氨氮、硝态氮、亚硝态氮平均值为0.07mg/L、2.62mg/L、2.05mg/L,分别占DIN的1.6%、55.2%、43.2%,硝态氮、亚硝态氮是组成龙滩水库溶解无机氮的主要成分。磷酸盐平均浓度为0.04mg/L。参照潜在性富营养化评价标准,N/P(质量比)比值为73.84,说明龙滩水库枯水期属于磷限制潜在性富营养状态,营养状态空间分布特征:坝前水体双江口红水河镇小马场。     

原子荧光光谱法用于水系沉积物中迁移毒性态汞的形态分析

水系沉积物中汞可分为三种形态，即迁移毒性态、亚迁移态和惰性态。建立了用原子荧光光谱法测定迁移态毒性汞中无机汞和有机汞的分析方法，并将该方法应用于武汉市涨渡湖沉积物中汞形态分析。方法检出限为0．004μg/L，精密度（RSD，n=11）为4．2％，回收率为92．2％～105．4％。     

广西百朗地下河水和沉积物中有机氯农药的分布特征

为了解典型岩溶地区广西乐业百朗地下河表层水和沉积物中有机氯农药的分布特征,采集地下河不同断面的水和沉积物样品,利用气相色谱仪测定了19种有机氯农药。结果表明:(1)百朗地下河表层水中19种有机氯农药总量(∑OCPs)浓度为1.95～71.45ng/L,HCHs和DDTs浓度分别为未检出至58.40ng/L和未检出至0.44ng/L;(2)沉积物中∑OCPs浓度为0.75～14.85ng/g,HCHs和DDTs浓度分别为0.11～3.52ng/g和0.03～2.90ng/g;(3)地下河表层水和沉积物中有机氯农药的分布与吸附作用、环境温度以及和地下河连通的天坑的底部的土壤侵蚀有关,即因温差作用,大气沉降的有机氯农药易富集在天坑底部(“冷陷阱效应”),并在土壤侵蚀作用下向水体移动,使地下河沉积物中有机氯农药浓度升高;(4)百朗地下河出口沉积物吸附系数最低,但水中有机氯农药浓度较高且种类最多,推测可能是地下河沉积物中因有机氯农药被释放而引起二次污染;(5)表层沉积物中大多数断面的异狄氏剂浓度及乐业县城附近断面的DDTs和DDD浓度在风险评估低值与风险评估中值之间,表明百朗地下河处于较低的生态风险水平;(6)目前,流域部分断面尚有新的γ-HCH(林丹)和DDTs农药输入。由于有机氯农药长期累积,可能对地下河生态系统造成危害,应采取防治措施。      

乌江流域新建水库水体汞的分布特征

20世纪80年代以来在北美和北欧,许多新修建的水库鱼体中甲基汞浓度较建库以前有了很大提高[1,2].研究表明,筑坝形成的水体环境有利于汞的活化、甲基化和生物累积[3],使流域内的水库成为高风险的甲基汞污染"敏感生态系统"4.     

水体溶解态黑碳的分子标志物苯多羧酸的气相色谱-质谱分析

苯多羧酸分子标志物法是定量水体中溶解态黑碳的常用方法,然而由于部分苯多羧酸,尤其是硝基苯多羧酸商业化标准品的缺失,采用该方法定量溶解态黑碳仍需进一步完善和优化。本文通过已有的苯多羧酸商业化标准品,建立了气相色谱-质谱联用仪(GC-MS)分离和定量 9 种缺少商业化标准品苯多羧酸的分析方法。并首次将菲-D10 作为溶解态黑碳的替代物,指示苯多羧酸法定量溶解态黑碳过程中的损失率。结果表明,该方法具有良好的重现性(RSD=10.34%),方法检出限为 0.67~5.38 ng/L。本文采用该方法分析了大亚湾表层水体溶解态黑碳的分布特征,其浓度范围为 30.38~46.19 μg/L,平均值为(38.93±6.17)μg/L,空间分布表现为从湾内到外海递减的趋势。     

汞矿区稻田土壤汞形态分布特征及对甲基化的影响

汞污染区稻米甲基汞超标现象普遍存在,汞在土壤中的形态分布被认为是影响甲基化过程的重要因素之一.本研究选取贵州省万山废弃汞矿区和土法炼汞区为研究区域,在水稻生长期间对稻田土壤剖面中总汞、甲基汞及形态汞进行测定,结合土壤环境因子指标,讨论土壤汞形态分布特征对甲基化的影响.研究表明,汞矿区稻田土壤中总汞和甲基汞均表现出随土壤深度加深而逐渐降低的趋势,且主要以有机结合态和残渣态形式存在,占总汞的98％以上.在废弃汞矿区,不同形态汞可能会转化为生物难以利用的形态:溶解态与可交换态、特殊吸附态与氧化态汞可能先转变为有机结合态,再转变为残渣态汞.在土法炼汞区表现为硫酸盐还原与铁还原过程驱动的汞甲基化过程,并且有机结合态汞可能也参与了甲基化过程.     

重庆典型岩溶区地下河水体有机氯农药污染初步研究

利用GC-ECD对重庆典型岩溶区地下河水体中有机氯农药(OCPs)进行检测,结果表明,地下河水中OCPs浓度为3.41～51.34ng/L,均值为13.23ng/L;滴滴涕(DDTs)浓度为0.07～2.37ng/L,均值为0.72ng/L;六六六(HCHs)浓度为1.16～39.82ng/L,均值为7.89ng/L。南川湾滩地下河水体有机氯农药污染最为严重,其上游纸厂排放废水是影响该地下河有机氯农药污染的主要原因。与国内外其它河流相比较,研究区地下河水体有机氯农药含量处于中低水平。由于岩溶区特殊的二元结构,地表水体一旦受到污染,将直接影响到地下水体。因此,对岩溶地下河进行有机污染物的调查研究具有重要的现实意义      

Distribution and speciation of mercury in the Hongfeng Reservoir,Guizhou Province,China

The water, pore water, sediment, and fish samples were collected from the Hongfeng Reservoir in November 2003 and February 2004 in accordance with trace metal protocols. The average concentrations of total mercury （THg）, dissolved mercury （DHg）, reactive mercury, dissolved gaseous mercury, total methylmercury, and dissolved methylmercury in the water columns were 8.00, 5.70, 0.63, 0.05, 0.16, and 0.07 ng/L, respectively. THg and DHg in the water columns, THg in pore water and THg in lake sediments of the Hongfeng Reservoir showed the level of mercury in the Hongfeng Reservoir was higher than in other natural waters in the world due to the loading of a lot of waste water with relatively high concentrations of mercury, whereas methylmercury concentrations in fish （wet weight） varied from 1.73-51.00 ng/g, much lower than in most remote lakes and reservoirs reported in northern Europe and North America. Methylmercury distributions in pore water and sediments showed methylation occurred mainly in the upper several centimeters of sediment cores in the Hongfeng Reservoir. The concentrations of dissolved organic carbon, total suspended particles, total Hg, and methylmercury were higher at Houwu than those at Daba in November 2003. It is suggested that other pollutants such as N and P from fishing farm and other waste water at Houwu, which resulted in deterioration of water quality, affected the concentrations and distributions of mercury species in the reservoir.     

The concentration and distribution of different mercury species in the water columns and sediment of Aha Lake

In order to find out whether Aha Lake was polluted by the acid mining waste water or not, the concentration and distribution of different mercuryspecies in the water columns and sediment profile collected from Aha Lake were investigated. It was found that discernible seasonal variation of different mercury species in water body were obtained in the Aha Reservoir. With regards to the whole sampling periods, the concentrations of HgP in the Aha Reservoir water body were evidently correlated to the concentrations of total mercury, showing that total mercury was mostly associated with particle mercury. The concentrations of methylmercury in water body were also evidently correlated to the concentrations of dissolved mercury. The dissolved mercury evidently affects the distribution and transportation of methylmercury. However, there is no correlation between methylmercury and total mercury. The dissolved mercury, reactive mercury, dissolved methylmercury levels in the water body of high flow period were much higher than those in low flow period. The distribution, speciation and levels of mercury within the Aha Reservoir water body were governed by several factors, such as the output of river, the release of sediment . Discernible seasonal variation of total mercury and methylmercury in porewater was described during the sampling periods, with the concentrations in high flow period generally higher than those in low flow period. The methylmercury in pore water column was evidently correlated to that of the sediment. The results indicated that highly elevated MeHgD concentrations in the porewater were produced at the depths from 2 to 5 cm in the sediment profile, and decreased sharply with depth. A positive correlation has been found between MeHgD formation and sulfate reducing bacterial activity. These highly elevated concentrations of MeHgD at the intersurface between waters and sediments suggest a favorable methylation condition. Moreover,     

Mercury speciation and distribution in Aha Reservoir which was contaminated by coal mining activities in Guiyang, Guizhou, China

Two sampling campaigns were carried out in March and August 2005 representing dry and wet seasons, respectively, to investigate the distribution patterns of Hg species in the water column and sediment profiles at two sampling stations in Aha Reservoir located in Guiyang, Southwestern China. Aha Reservoir has been contaminated by Hg due to small scale coal mining activities. Mercury concentrations in both water and sediment were elevated. A clearly seasonal variation of dissolved Hg (DHg), particulate Hg (PHg) and total Hg (THg) concentrations in the water column was observed. The concentrations of these Hg species in the wet season were significantly higher than in the dry season. Runoff input and diffusion of Hg from sediments could be the reasons for elevated concentrations of these Hg species in the wet season. The contaminated sediment is acting as a secondary contamination source for both inorganic Hg (IHg) and methylmercury (MeHg) to the overlying water. The cycling of Mn in the sediment governs the diffusion process of IHg to the water column. In the dry season (winter and spring), Mn occurs as MnO₂ because the uppermost part of sediment is in an oxic condition and Hg ions are absorbed by MnO₂. In the wet season (summer and fall), the uppermost part of the sediment profile is in a reduced condition because of stratification of the water column and MnO₂ is reduced to Mn²⁺, which results in transformation of Hg²⁺ into porewater as Mn²⁺ became soluble. This causes a higher diffusive flux of IHg from sediment to overlying water in the wet season. Both sampling stations showed a consistent trend that THg concentrations decreased in the uppermost part of sediment cores. This demonstrated that the measures taken to reduce ADM contamination to Aha Reservoir also reduced Hg input to the reservoir. Methyl Hg diffusive fluxes from sediment to overlying water were higher in the wet season than the dry season demonstrating that high temperatures favor Hg methylation processes in sediment.     

Benthic fluxes of mercury species in a lagoon environment (Grado Lagoon,Northern Adriatic Sea,Italy)

The role of the major biogeochemical processes in Hg cycling at the sediment–water interface was investigated in the Grado Lagoon (Northern Adriatic Sea). This wetland system has been extensively contaminated from the Idrija Hg Mine (Slovenia) through the Isonzo River suspended load carried by tidal fluxes. Three approaches were used to study the sediment–water exchange of total Hg (THg), methylmercury (MeHg), reactive Hg (RHg) and dissolved gaseous Hg (DGHg): (1) estimation of diffusive fluxes from porewater and overlying water concentrations, (2) measurements of benthic fluxes using a deployed light benthic chamber in situ and (3) measurements of benthic fluxes during oxic–anoxic transition with a laboratory incubation experiment. The THg solid phase, ranging between 9.5 and 14.4 μg g⁻¹, showed slight variability with depth and time. Conversely, MeHg contents were highest (up to 21.9 ng g⁻¹) at the surface; they tended to decrease to nearly zero concentration with depth, thus suggesting that MeHg production and accumulation occur predominantly just below the sediment–water interface. Porewater MeHg concentrations (0.9–7.9 ng L⁻¹, 0.15–15% of THg) varied seasonally; higher contents were observed in the warmer period. The MeHg diffusive fluxes (up to 17 ng m⁻² day⁻¹) were similar to those in the nearby Gulf of Trieste [Covelli, S., Horvat, M., Faganeli, J., Brambati, A., 1999. Porewater distribution and benthic flux of mercury and methylmercury in the Gulf of Trieste (Northern Adriatic Sea). Estuar. Coast. Shelf Sci. 48, 415–428], although the lagoon sediments contained four-fold higher THg concentrations. Conversely, the THg diffusive fluxes in the lagoon (up to 110 ng m⁻² day⁻¹) were one- to two-fold higher than those previously estimated for the Gulf of Trieste. The diurnal MeHg benthic fluxes were highest in summer at both sites (41,000 and 33,000 ng m⁻² day⁻¹ at the fishfarm and in the open lagoon, respectively), thus indicating the influence of temperature on microbial processes. The diurnal variations of dissolved THg and especially MeHg were positively correlated with O₂ and inversely with DIC, suggesting an important influence of benthic photosynthetic activities on lagoon benthic Hg cycling, possibly through the production of organic matter promptly available for methylation. The results from the dark chamber incubated in the laboratory showed that the regeneration of dissolved THg was slightly affected by the oxic–anoxic transition. Conversely, the benthic flux of MeHg was up to 15-fold higher in sediments overlain by O₂ depleted waters. In the anoxic phase, the MeHg fluxes proceeded in parallel with Fe fluxes and the methylated form reached approximately 100% of dissolved THg. The MeHg is mostly released into overlying water (mean recycling efficiency of 89%) until the occurrence of sulphide inhibition, due to scavenging of the available Hg substrate for methylation. The results suggest that sediments in the Grado Lagoon, especially during anoxic events, should be considered as a primary source of MeHg for the water column.     

The concentrations and distribution of mercury in aquatic ecosystem of Baihua Reservoir

1Introduction Thebiogeochemicalcycleofmercuryinaqueous systemisthekeyfactorleadingtotheexpansionof mercurypollutiononaglobalscaleandthesafetyof fishconsumers.Dissolvedgaseousmercury(DGM)e vasionisconsideredasoneofthemostimportantmer curysourcesforatmosphere.Atthesametime,this procedurewillreducetheHgburdeninthewatercol umnandmaythusdecreasemethylmercuryproduction andaccumulationinfish(Nriagu,1994).TheBaihua ReservoirissituatedinGuizhouProvince,andithas sufferedseriousmercurycontaminationfr…     

Source Identification of Florida Bay's Methylmercury Problem: Mainland Runoff Versus Atmospheric Deposition and <Emphasis Type="Italic">In situ</Emphasis> Production

The first advisory to limit consumption of Florida Bay fish due to mercury was issued in 1995. Studies done by others in the late 1990s found elevated water column concentrations of both total Hg (THg) and methylmercury (MeHg) in creeks discharging from the Everglades, which had its own recognized mercury problem. To investigate the significance of allochthonous MeHg discharging from the upstream freshwater Everglades, we collected surface water and sediment along two transects from 2000 to 2002. Concentrations of THg and MeHg, ranging from 0.36 ng THg/L to 5.98 ng THg/L and from <0.02 ng MeHg/L to 1.79 ng MeHg/L, were elevated in the mangrove transition zone when compared both to upstream canals and the open waters of Florida Bay. Sediment concentrations ranged from 5.8 ng THg/g to 145.6 ng THg/g and from 0.05 ng MeHg/g to 5.4 ng MeHg/g, with MeHg as a percentage of THg occasionally elevated in the open bay. Methylation assays indicated that sediments from Florida Bay have the potential to methylate Hg. Assessment of mass loading suggests that canals delivering stormwater from the northern Everglades are not as large a source as direct atmospheric deposition and in situ methylation, especially within the mangrove transition zone.     

Behavior of mercury in an urban river and its accumulation in aquatic plants

The characteristics of mercury in the aquatic environment have been intensively studied in mining areas with heavy mercury pollution but little work has been conducted in urban areas, with no significant Hg source. This paper presents a study of the Haihe River, which flows through an urban area in North China. The concentrations of total mercury (THg) and methylmercury (MeHg) in the river water were 3.6–31.2 and 0.12–3.21 ng/l, and the corresponding values in river sediment were 22.9–374.8 and 0.03–0.46 μg/kg. These values are lower than the reported values from mining areas. The THg concentration in sediment samples collected from the urban areas was higher than that from the rural areas and the global background levels, indicating the influence of urbanization on mercury contamination. Samples of typical riparian and floating plants, reed and hornwort, were collected. Correlation analysis showed that sediment is the major source of THg and MeHg in reed and water is the major source of MeHg in hornwort. The higher bioaccumulation factor of reed indicates its higher potential to accumulate MeHg from the environment.     

Distribution and speciation of mercury in surface water in Wanshan Hg-mined areas, Guizhou Province, China

Mercury as a toxic element poses environmental concerns, especially in historically Hg-mined districts. The Wanshan Hg mine located in the eastern part of Guizhou Province, southwestern China, ranks the largest Hg-producing district in China. Mining at Wanshan was initiated in 221 B.C., but ceased in 2001. Approximately 22000 tons of Hg, 6000 tons of cinnabar and large quantities of mine-wastes had been produced at Wanshan. Significant quantities of calcines, which were piled irregularly near the old mine processing sites and retorts, continue to impact the local environments in the Wanshan area. In this study, a regional contamination of mercury in surface waters collected from the Meizixi, Dashuixi, Huandao and Gaolouping rivers, whose upstreams or branches originate from the hilly karstic area and receive drainage arising from the calcines, was investigated by determining all Hg species in a base-flow and a flood-flow season. Reactive, dissolved, particulate, and total Hg concentrations in surface water varied from 0.60 to 400 ng/L, 11 to 430 ng/L, 1.4 to 9210 ng/L, and 15 to 9260 ng/L, respectively. Total methylmercury in water samples ranges from 0.31 to 25 ng/L. The concentrations of total Hg and particulate Hg in water samples collected during the flood season are higher than those in the base-flow season, whereas, the concentrations of dissolved and reactive Hg are lower with the peak values observed in water samples collected in the base-flow season. A strong positive correlation between total Hg and particulate Hg is noticed in the water samples collected from Hg-mined areas with the proportion higher than 80%.     

Mercury distribution, partitioning and speciation in coastal vs. inland High Arctic snow

Atmospheric mercury deposition on snow at springtime has been reported in polar regions, potentially posing a threat to coastal and inland ecosystems receiving meltwaters. However, the post-depositional fate of Hg in snow is not well known, and no data are available on Hg partitioning in polar snow. During snowmelt, we conducted a survey of Hg concentrations, partitioning and speciation in surface snow and at depth, over sea ice and over land along a 100 km transect across Cornwallis Island, NU, Canada. Total Hg concentrations [THg] in surface snow were low (less than 20 pmol L⁻¹) and were significantly higher in marine vs. inland environments. Particulate Hg in surface snow represented up to 90% of total Hg over sea ice and up to 59% over land. At depth, [THg] at the snow/sea ice interface (up to 300 pmol L⁻¹) were two orders of magnitude higher than at the snow/lake ice interface (ca. 2.5 pmol L⁻¹). Integrated snow columns, sampled over sea-ice and over land, showed that particulate Hg was mostly bound to particles ranging from 0.45 to 2.7 μm. Moreover, melting snowpacks over sea ice and over lake ice contribute to increase [THg] at the water/ice interfaces. This study indicates that, at the onset of snowmelt, most of the Hg in snow is in particulate form, particularly over sea ice. Low Hg levels in surface snow suggest that Hg deposited through early spring deposition events is partly lost to the atmosphere from the snowpack before snowmelt. The sea ice/snow interface may constitute a site for Hg accumulation, however. Further understanding of the cycling of mercury at the sea ice/snow and sea ice/seawater interfaces is thus warranted to fully understand how mercury enters the arctic food webs.     

Fractionation,distribution and transport of mercury in rivers and tributaries around Wanshan Hg mining district,Guizhou province,southwestern China: Part 1 – Total mercury

The Wanshan Hg mining area in Guizhou, China, was one of the world’s largest Hg producing regions. Numerous mine-waste and calcines still remain, leaching Hg to local rivers and streams and potentially impacting the local population. Several studies have been published on local environmental impacts of these mining and retorting residues, but a comprehensive, regional survey on the distribution of Hg in the rivers in the region, as presented in this paper, has not previously been conducted. This study focuses on the regional distribution and temporal variation of aqueous Hg fractions in the five main watercourses draining the Wanshan Hg mining and retorting area, covering more than 700 km². Three sampling campaigns were carried out in 2007 and 2008, covering high flow, normal flow and low flow periods. Total (THg), particulate (PHg), dissolved (DHg) and reactive (RHg) Hg fractions were determined. All rivers had the highest Hg concentrations at sample sites about 100–500 m downstream of the mine wastes. Total Hg concentrations ranged from extremely high (up to 12,000 ng L⁻¹) at the sample site just 100 m below mine wastes, to quite low in tributary streams (1.9 ng L⁻¹, about 14 km downstream of the mine wastes). Total Hg and PHg concentrations were usually highest during high flow periods in the Hg-contaminated areas (i.e. THg ? 50 ng L⁻¹), while in the less-impacted downstream areas (with THg < 50 ng L⁻¹) the Hg concentrations were usually lowest during high flow periods. Although highly elevated concentrations of Hg in water samples were found just downstream of the mine wastes, the concentrations decreased sharply to well below 50 ng L⁻¹ (US EPA Hg concentration standard for protection of fresh water), within only 6–8 km downstream. Concentrations of THg were highly dominated by and correlated with PHg (R² = 0.996–0.999, P < 0.001); PHg constituted more than 80% of THg in Hg-contaminated areas, and could account for 99.6% of the THg close to the mine wastes.