两次金汞齐—冷原子吸收光谱法测定大气中的痕量气态总汞

本文作者在已有仪器的基础上进行简单改装，建立了两次金汞齐—冷原子吸收光谱法测定大气中的微量气态总汞的方法。研究表明，这种方法最低检出限为０．０５ｎｇ；１００μｌ饱和汞蒸气连续测定结果表明其相对标准偏差＜１．４１％。在０～２．０ｎｇ汞量范围内标准工作曲线线性关系良好。运用该法，对贵州省万山汞矿、丹寨汞矿、清镇汞污染农田、省农科院和中国科学院地球化学研究所等地大气气态总汞进行了测定。这种分析方法还可以运用到其它环境样品微量汞的测定。     

燃煤电厂排放总气态汞连续自动监测技术的选择

介绍了汞连续排放监测系统和汞吸附管采样系统的主要特点,比较了不同仪器的测定原理、样品处理技术、检出限和测定汞的形态,报道了美国环境保护署认证中心关于两个系统的认证结果.建议将汞连续排放监测系统与汞吸附管监测系统两种技术联合用于我国燃煤电厂排放总气态汞的自动监测.     

固定污染源烟气中汞排放连续监测系统

介绍了中美两国法规对汞排放连续监测的要求，分析了烟气中汞排放连续监测的技术难点，指出现有的汞在线监测只能得到气态总汞的浓度。阐述了冷蒸气原子吸收光谱法、塞曼调制原子吸收光谱法、冷蒸气原子荧光法、原子发射光谱法、紫外差分吸收光谱法等气态元素汞的不同分析方法。通过对湿化学法与热转化单元的比较，得出热转化技术更加适合烟气汞的在线监测。分析了造成汞测量误差的相关因素，并提出了减少误差的措施。     

镀金石英砂吸附-AMA 254测汞仪测定大气中痕量汞的研究

采用镀金石英砂来富集大气中的气态总汞,AMA 254测汞仪测定。结果表明,不同采样时间下的单级吸附管的吸附效率均在90%以上,采样40min时的相对标准偏差为5%左右。与巯基棉吸附和吸收液吸收方法的对比显示,该方法具有吸收效果好、多次采样的精密度高、操作简便并且可以再生重复使用等优点。运用该法,对徐家汇等几个地点的大气总汞进行了测定。     

AMA254汞分析仪测定颗粒物中痕量总汞的研究

采用AMA254汞分析仪测定大气颗粒物和煤中的痕量总汞,建立了直接测定颗粒物中痕量总汞的分析方法.测定结果表明,在汞绝对含量为0～35ng范围内线性良好,测定大气颗粒物和煤中的痕量总汞的检出限分别为0.06ng/m3和0.02ng/g,标准样品测定的RSD≤0.78%,加标回收率为92%～108%.该方法具有无需消解直接进样测定、极其简便、省时等特点,适合多种固体样品中痕量汞的测定.     

便携式原子吸收测汞仪对气态汞的监测方法

研究和比较便携式原子吸收测汞仪测定气态汞的两种方法,即富集法和直读法。结果显示,富集法在一定范围内具有较好的线性相关性,R20.996,当采气体积为12 L时,检出限为5 ng/m~3,对于高浓度和低浓度气态汞的测定均有较好的稳定性,当气态汞浓度较低时可延长取样时间,增加采样体积,但测定时间较长,适合测定环境空气中的低浓度气态汞。直读法的检出限为0.89μg/m~3,且在测定高浓度含汞废气时,表现出较好的稳定性,同时可在持续排放气态汞条件下进行连续测定并读数,适合测定固定污染源排气中的气态汞。     

贵州东部某燃煤电厂汞排放对周边环境空气及土壤的影响

结合当地气象条件,测定贵州省东部某燃煤电厂下风向环境空气汞浓度分布情况,同时测定该燃煤电厂周边表层土壤中汞含量,并对其污染程度进行评价,探讨了土壤汞与理化性质间的相关性。结果表明,该燃煤电厂下风向环境空气汞浓度远高于北半球大气气态总汞背景值,空气汞浓度在2.7 km范围内随距离的增大而增大,在2.7~5.0 km范围内汞浓度随距离的增大而减小。电厂周边表层土壤汞含量是贵州省A层土壤Hg背景值的8.5倍,存在中度到重度程度的污染,土壤Hg与土壤pH呈正相关性,但与土壤有机质未表现出相关性。     

复合式吸收器采样还原一体化冷原子吸收法测定大气中的汞

目的研制一种高效率采集大气中汞的吸收器.方法利用一种集大泡式与玻砂板式吸收器为一体的复合式吸收器采样,并使采样还原一体化冷原子吸收法测定大气中汞.结果平均吸收率为96%,变异系数在4%～12%之间.结论复合式吸收器采样吸收效率高,适合于大气中微量汞的测定.     

北京市大气气态汞变化特征

采用Tekran 2537X大气汞分析仪在线测量北京市城区大气中气态元素汞(GEM,简称大气汞) 浓度,研究大气汞浓度随不同气象条件的变化特征。通过分析2016年10月—2017年9月大气汞监测数据发现,该监测点全年大气汞浓度为0.48～16.25 ng/m³,均值为(3.41±1.79)ng/m³。春季、夏季、秋季和冬季大气汞浓度均值依次为2.93 、2.95、4.27、3.37 ng/m³,其中,秋季大气汞浓度明显高于其他季节 。秋季大气汞浓度显著偏高可能由不利的大气扩散条件导致。大气汞夜间浓度显著高于白天浓度。同时,将大气汞与SO₂、CO及PM_2.5进行相关性分析,发现大气汞浓度变化趋势与SO₂、CO和PM_2.5呈显著正相关。结合风向和风速进行污染来源分析,得到该点位大气汞在西南和东北方向上受人为排放源影响较大。污染源类型分析表明,冬季大气汞与CO同源性强,主要来自本地供暖用煤。     

270年以来大气汞的沉降—自然释汞源与人为释汞源之冰芯记录

水生生态系统的汞污染及其引发的甲基汞在生物体内聚集是全球重要的环境问题。汞污染的主要机理是大气汞的迁移,研究冰川中总汞的质量浓度,能很好地揭示大气汞沉降的历史记录。对怀俄明州(Wyoming)弗里蒙特冰川上游(the UpperFremont Glacier,UFG)冰芯的研究,显示了近270年自然源与人为源的大气汞释放。     

Ambient elemental, reactive gaseous, and particle-bound mercury concentrations in New Jersey, U.S.: measurements and associations with wind direction

Two and a half years of data of ambient concentrations of elemental mercury (Hg(0)), reactive gaseous mercury (RGM), and particle-bound mercury (Hg(p)) were collected at measurement sites at Elizabeth, New Jersey and New Brunswick, New Jersey with Tekran sampling units. The data were processed, summarized, and analyzed from a variety of perspectives. Data quality control and quality assurance procedures are described. Wind direction and wind speed data for each of the sites were also collected. Significant temporal variations in concentrations of all three species were observed. Some significant directional variations were also seen. The sporadic nature of many of the temporal variations is consistent with and could reflect highly variable emissions patterns from anthropogenic mercury sources. Overall mean concentrations of all species were determined. These were, for Hg(0), Hg(p), and RGM respectively; 2.25 +/- 0.04 nanograms per cubic meter (ng/m(3)), 8.21 +/- 0.39 picograms per cubic meter (pg/m(3)), and 8.93 +/- 0.31 pg/m(3) (arithmetic means and 95% confidence intervals) at Elizabeth, and 2.15 +/- 0.02 ng/m(3), 10.73 +/- 0.45 pg/m(3), and 6.04 +/- 0.30 pg/m(3) at New Brunswick. Mean concentrations were determined for 16 different sectors representing wind directions. The impact of one known large source is suggested by these data. Reasons for some directional variations are not apparent and suggest a need for further investigation.     

Lichen biomonitoring of mercury emission and deposition in mining,geothermal and volcanic areas of Italy

Natural emissions of Hg are attracting increased interest both for their environmental implications and for possible applications in the exploration of mineral, petroleum and geothermal fields. However, daily and seasonal fluctuations in concentrations of Hg in the atmosphere, caused by meteorological and environmental variables, has made it very difficult to assess Hg anomalies by conventional analytical procedures. Some species of widespread foliose lichens from an abandoned cinnabar mining and smelting area (Mt. Amiata), geothermal fields (Larderello, Bagnore and Piancastagnaio, Central Italy), and active volcanic areas (Mt. Etna and Vulcano, Southern Italy) seem to be very suitable biomonitors of gaseous Hg; especially as lichen thalli have an Hg content which reflects average values measured in air samples. We discuss the advantages of quantitative biological monitoring by lichens with respect to conventional air sampling in large-scale monitoring.     

Application of cryofocusing hydride generation and atomic fluorescence detection for dissolved mercury species determination in natural water samples

The concentration levels of mercury (Hg) species in natural water samples are usually low. Consequently, accurate analysis with low detection limits is still a major problem. In this work, a method was applied for the simultaneous direct determination of dissolved mercury species in water samples by on-line hydride generation (HG), cryogenic trapping (CT), gas chromatography (GC) and detection by atomic fluorescence spectrometry (AFS). The suitability of the method for real samples with different organic matter and chloride contents was evaluated by recovery experiments in synthetic and natural spiked water samples. The HG method was compared with other current available methods for mercury analysis with respect to the different fraction of mercury analysed, i.e. 'reactive', 'reducible' or total. HG derivatization and SnCl2 reduction (with and without previous oxidation with BrCl) were applied to synthetic and natural (spiked and non-spiked) water samples. The influence of chloride and dissolved organic matter concentrations was studied. The results suggest that the HG procedure is suitable for the simultaneous determination of Hg2+ and MeHg+ in surface water samples. Inorganic mercury analysed by HG (i.e. reducible) is close to the total inorganic mercury.     

Speciation and mass-balance of mercury from pulverized coal fired power plants burning western Canadian subbituminous coals

This report summarizes the results of a study carried out on six pulverized coal-fired power plants in western Canada burning subbituminous coal for the mass-balance and speciation of mercury. The main objectives of this study were to: determine the total gaseous mercury (TGM) emitted from stacks of power plants using the Ontario Hydro method; identify the speciation of emitted mercury such as metallic (Hg(0)) and gaseous elemental (GEM) mercury; and perform mass-balance calculations of mercury for milled-coal, bottom ash, electrostatic precipitators (ESP) fly ash and stack-emitted mercury based on three tests. Sampling of mercury was carried out using the Ontario Hydro method and mercury was determined using the USEPA method 7473 by cold vapor atomic absorption (CVAAS). The sample collection efficiencies confirmed that both oxidized and the elemental mercury had been successfully sampled at all power plants. The total gaseous mercury emitted (TGM) is 6.95-15.66 g h(-1) and is mostly in gaseous elemental mercury (GEM, Hg(0)) form. The gaseous elemental mercury is emitted at a rate of 6.59-12.62 g h(-1). Reactive gaseous mercury (RGM, Hg(2+)) is emitted at a rate of 0.34-3.68 g h(-1). The rate of emission of particulate mercury (Hg(p)) is low and is in the range 0.005-0.076 g h(-1). The range of mass-balances for each power plant is more similar to the variability in measured mercury emissions, than to the coal and ash analyses or process data. The mass-balance calculations for the six power plants, performed on results of the three tests at each power plant, are between 86% and 123%, which is acceptable and within the range 70-130%. The variation in mass-balance of mercury for the six power plants is mostly related to the variability of coal feed rate.     

Biomonitoring with epiphytic lichens as a complementary method for the study of mercury contamination near a cement plant

The study was focused on understanding the mercury contamination caused by a cement plant. Active and passive biomonitoring with epiphytic lichens was combined with other instrumental measurements of mercury emissions, mercury concentrations in raw materials, elemental mercury concentrations in air, quantities of dust deposits, temperatures, precipitation and other measurements from the cement plant's regular monitoring programme. Active biomonitoring with transplanted lichens Pseudevernia furfuracea (L.) Zopf was performed at seven of the most representative sites around the cement plant and one distant reference site for periods of 3, 6 and 12 months. In situ lichens of different species were collected at the beginning of the monitoring period at the same sites. Mercury speciation of the plant exhaust gas showed that the main form of emitted mercury is reactive gaseous mercury Hg2?, which is specific for cement plants. Elemental mercury in air was measured in different meteorological conditions using a portable mercury detector. Concentrations in air were relatively low (on average below 10 ng m?3). In situ lichens showed Hg concentrations comparable to lichens taken from the background area for transplantation, indicating that the local pollution is not severe. Transplanted lichens showed an increase of mercury, especially at one site near the cement plant. A correlation between precipitation and Hg uptake was not found probably due to a rather uniform rainfall in individual periods. Dust deposits did not influence Hg uptake significantly. Lichens vitality was affected over longer biomonitoring periods, probably due to some elements in dust particles, their alkalinity and the influence of other emissions. Mercury uptake measured in vital transplanted lichens was in a good correlation with the working hours (i.e. emitted Hg quantity) of the kiln. The study showed that selected lichens could be used to detect low to moderate Hg emissions from a cement plant and that the biomonitoring procedure could be further standardized and used as part of an environmental monitoring programme.     

The impact of land use and season on the riverine transport of mercury into the marine coastal zone

In Mediterranean seas and coastal zones, rivers can be the main source of mercury (Hg). Catchment management therefore affects the load of Hg reaching the sea with surface runoff. The major freshwater inflows to the Baltic Sea consist of large rivers. However, their systems are complex and identification of factors affecting the outflow of Hg from its catchments is difficult. For this reason, a study into the impact of watershed land use and season on mercury biogeochemistry and transport in rivers was performed along two small rivers which may be considered typical of the southern Baltic region. Neither of these rivers are currently impacted by industrial effluents, thus allowing assessment of the influence of catchment terrain and season on Hg geochemistry. The study was performed between June 2008 and May 2009 at 13 sampling points situated at different terrain types within the catchments (forest, wetland, agriculture and urban). Hg analyses were conducted by CVAFS. Arable land erosion was found to be an important source of Hg to the aquatic system, similar to urban areas. Furthermore, inflows of untreated storm water discharge resulted in a fivefold increase of Hg concentration in the rivers. The highest Hg concentration in the urban runoff was observed with the greatest amount of precipitation during summer. Moderate rainfalls enhance the inflow of bioavailable dissolved mercury into water bodies. Despite the lack of industrial effluents entering the rivers directly, the sub-catchments with anthropogenic land use were important sources of Hg in the rivers. This was caused by elution of metal, deposited in soils over the past decades, into the rivers. The obtained results are especially important in the light of recent environmental conscience regulations, enforcing the decrease of pollution by Baltic countries.     

Mercury emission and dispersion models from soils contaminated by cinnabar mining and metallurgy

The laboratory flux measurement system (LFMS) and dispersion models were used to investigate the kinetics of mercury emission flux (MEF) from contaminated soils. Representative soil samples with respect to total Hg concentration (26-9770 μg g(-1)) surrounding a decommissioned mercury-mining area (Las Cuevas Mine), and a former mercury smelter (Cerco Metalúrgico de Almadenejos), in the Almadén mercury mining district (South Central Spain), were collected. Altogether, 14 samples were analyzed to determine the variation in mercury emission flux (MEF) versus distance from the sources, regulating two major environmental parameters comprising soil temperature and solar radiation. In addition, the fraction of the water-soluble mercury in these samples was determined in order to assess how MEF from soil is related to the mercury in the aqueous soil phase. Measured MEFs ranged from less than 140 to over 10,000 ng m(-2) h(-1), with the highest emissions from contaminated soils adjacent to point sources. A significant decrease of MEF was then observed with increasing distance from these sites. Strong positive effects of both temperature and solar radiation on MEF was observed. Moreover, MEF was found to occur more easily in soils with higher proportions of soluble mercury compared to soils where cinnabar prevails. Based on the calculated Hg emission rates and with the support of geographical information system (GIS) tools and ISC AERMOD software, dispersion models for atmospheric mercury were implemented. In this way, the gaseous mercury plume generated by the soil-originated emissions at different seasons was modeled. Modeling efforts revealed that much higher emissions and larger mercury plumes are generated in dry and warm periods (summer), while the plume is smaller and associated with lower concentrations of atmospheric mercury during colder periods with higher wind activity (fall). Based on the calculated emissions and the model implementation, yearly emissions from the "Cerco Metalúrgico de Almadenejos" decommissioned metallurgical precinct were estimated at 16.4 kg Hg y(-1), with significant differences between seasons.     

Measurements of fractionated gaseous mercury concentrations over northwestern and central Europe, 1995-99

Although it makes up only a few per cent. of total gaseous mercury (TGM) in the atmosphere, the fraction of oxidised (divalent) mercury plays a major role in the biogeochemical cycle of mercury due to its high affinity for water and surfaces. Quantitative knowledge of this fraction present in mixing ratios in the parts-per-10(15) (ppq) range is currently very scarce. This work is based on approximately 220 data for divalent gaseous mercury (DGM) collected during 1995-99 in ambient air. Over the course of the measurements, the sampling and analytical methods were modified and improved. This is described here in detail and includes transition from wet leaching and reduction procedures to thermo-reductive desorption, the use of annular as well as tubular denuders and adoption of an automated sampling system. The concentration of DGM exhibited a strong seasonal behaviour in contrast to atomic gaseous mercury, with low values in winter and maximum values in summer. The DGM/TGM ratios were frequently found to be below the detection limit (< or = 1%) and in the range 1-5%. A trend of diurnal DGM patterns was observed and implies photolytically induced sources. Scavenging of DGM during rain events was also noticed.     

Atmospheric-particulates-bound mercury Hg(p) study at five characteristic sampling sites in Taiwan

The main purpose for this study is to observe the seasonal and month variations for particulates-bound mercury Hg(p) in total suspended particulates (TSP) concentration, dry deposition at five characteristic sampling sites during years of 2009-2010 in central Taiwan. The results show that the highest and lowest monthly average particulates-bound mercury Hg(p) concentrations in TSP were occurred in Dec. and Oct. at Gao-mei (wetland), Chang-hua (downtown) and He-mei (residential) sampling site. In addition, the results show that the highest and lowest monthly average particulates-bound mercury Hg(p) dry deposition was occurred in Feb. and Oct. at Quan-xing (industrial) sampling site. This study reflected that the mean highest particulates-bound mercury Hg(p) concentrations in TSP and mean highest particulates-bound mercury Hg(p) dry deposition were occurred at Gao-mei (wetland) and Quan-xing (industrial). However, the mean lowest particulates-bound mercury Hg(p) concentrations in TSP and mean lowest particulates-bound mercury Hg(p) dry deposition were also occurred at Gao-mei (wetland). Regarding seasonal variation, the order of mean-particulates-bound mercury Hg(p) concentrations in TSP in winter and spring were Gao-mei (wetland) > Quan-xing (industrial) > Bei-shi (suburban/coastal) > Chang-hua (downtown) > He-mei (residential). Finally, the order of mean-particulates-bound mercury Hg(p) dry deposition in fall, spring and summer were Quan-xing (industrial) > Bei-shi (suburban/coastal) > Chang-hua (downtown) > He-mei (residential) > Gao-mei (wetland).