中国地区大气汞的数值模拟研究

结合中国地区的汞排放,利用引入大气汞化学反应机制和干沉降模型的区域大气环境模式系统(Regional Atmospheric Environment Model System,Reg AEMS),对中国地区大气汞化物浓度和干沉降通量的时空分布特征进行模拟研究。研究结果表明,中国地区年均气态零价汞Hg0、氧化汞Hg O、氢氧化汞Hg(OH)2、氯化汞Hg Cl2和颗粒态汞HgP的沉降量分布类似。除西部、西北部地区Hg0的浓度较低外(0.5 ng·m-3),其他地区均高于全球背景浓度。各类汞化物浓度的季节变化明显,8月最低,2、3月最高。一次汞源区附近汞浓度随高度递减,在离源较远的地区,高层汞浓度较高。气态零价汞的干沉降速度的季节变化最明显,其干沉降通量在夏季最高。模拟区域中气态零价汞、氧化汞和颗粒态汞的年干沉降量分别为163.9、7.43和32.2 t。     

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.     

A compilation of field surveys on gaseous elemental mercury (GEM) from contrasting environmental settings in Europe,South America,South Africa and China: separating fads from facts

Mercury is transported globally in the atmosphere mostly in gaseous elemental form (GEM, \( {\text{Hg}}_{\text{gas}}^{0} \) ), but still few worldwide studies taking into account different and contrasted environmental settings are available in a single publication. This work presents and discusses data from Argentina, Bolivia, Bosnia and Herzegovina, Brazil, Chile, China, Croatia, Finland, Italy, Russia, South Africa, Spain, Slovenia and Venezuela. We classified the information in four groups: (1) mining districts where this contaminant poses or has posed a risk for human populations and/or ecosystems; (2) cities, where the concentration of atmospheric mercury could be higher than normal due to the burning of fossil fuels and industrial activities; (3) areas with natural emissions from volcanoes; and (4) pristine areas where no anthropogenic influence was apparent. All the surveys were performed using portable LUMEX RA-915 series atomic absorption spectrometers. The results for cities fall within a low GEM concentration range that rarely exceeds 30 ng m^?3, that is, 6.6 times lower than the restrictive ATSDR threshold (200 ng m^?3) for chronic exposure to this pollutant. We also observed this behavior in the former mercury mining districts, where few data were above 200 ng m^?3. We noted that high concentrations of GEM are localized phenomena that fade away in short distances. However, this does not imply that they do not pose a risk for those working in close proximity to the source. This is the case of the artisanal gold miners that heat the Au–Hg amalgam to vaporize mercury. In this respect, while GEM can be truly regarded as a hazard, because of possible physical–chemical transformations into other species, it is only under these localized conditions, implying exposure to high GEM concentrations, which it becomes a direct risk for humans.     

Distribution of mercury in the atmosphere over Idrija, Slovenia

Idrija mine, the second largest mercury mine in the world, was in use since 1490. More than 107 000 tons of Hg were produced in its five centuries of history until 1990 when production was reduced to a few hundred kilos per year. The average recovery rate of mercury has been estimated to 73%; much of the remaining 27% was dissipated into the environment. In spite of present minimal levels of production, and only a few days of smelter operation per year, a real time survey with a mercury Zeeman analyser in a car showed relatively high mercury concentrations in the air. Amounts of 300--4000 ng Hg ^m-3 have been found around both the major sources of mercury vapour, the smelter and mine ventilation shaft -- while the amounts at the Old Place, at the City Museum, and near the Nikova-Idrijca confluence are of the order of 50 ng m^-3. Polluted air will be transported from those sources to a degree which depends on the weather conditions, mainly the direction and intensity of the wind. The high mercury contents in the air are not only due to anthropogenic sources (smelter and the ventilation shaft, dumps and smelter slag used in construction), but may also partly be natural as in the Pront area, where the outcropping bedrock contains native mercury.     

Spatial and temporal distribution of atmospheric mercury species over the Adriatic Sea

Field measurements of atmospheric mercury and related species were carried out during an intensive cruise campaign performed over the Adriatic sea from October 26th to November 12th, 2004 on board the R/V Urania. Hg⁰ ranged between 0.8 and 3.3 ng/m³ with an average of 1.6 ± 0.4 ng/m³ over the entire period. Hg(II) concentrations ranged from 0.1 to 62.8 pg/m³ with an average of 6.7 ± 11.7 pg/m³ whereas Hg-p levels were in a range of 0.04 and 51 pg/m³ with an average of 4.5 ± 8 pg/m³. Higher Hg⁰ and Hg-p concentrations were observed in the Gulf of Venice and Gulf of Trieste due primarily to air masses transported from the mainland reflecting the contribution from anthropogenic sources. In contrast, higher Hg(II) concentrations observed during the first period of the cruise campaign were likely due to the occurrence of photo-oxidants production which are the main players of the gas phase oxidation of to Hg(II)_(g). These findings have been confirmed by the backward trajectories analysis of air masses crossing the studied area during selected days.     

Nitrogen excretion by some demersal macrozooplankton in Heron and One Tree Reefs,Great Barrier Reef,Australia

Nitrogen excretion rates of demersal macrozooplankton were measured together with nitrogen concentrations in the water column and sediments in lagoons of Heron Reef and One Tree Reef, Great Barrier Reef, Australia, during August and November 1991. Excretion rates increased with body weight, and weight-specific excretion rates of the demersal macrozooplankton were comparable to those of pelagic zooplankton and meiofauna in the Great Barrier Reef. Values of demersal macrozooplankton abundance from previous studies and excretion rates from this study were combined to estimate fluxes of ammonium from demersal macrozooplankton in coral reef lagoons. The estimated fluxes in the water column and sediments were 12 M NH₄ m^-2 d^-1 and 34 M NH₄ m^-2d^-1, respectively. These fluxes were compared with reported fluxes of ammonium in coral reef lagoons in the Great Barrier Reef, Australia. The estimated flux from the demersal macrozooplankton in the water column was 29 and 9% of those reported for microheterotroph regeneration and phytoplankton utilization, respectively. It was 10% of the reported advective flux during periods of low advection and 13% of the maximum efflux from sediments computed from diffusion models. The estimated flux from the demersal macrozooplankton in the sediments exceeded those reported for meiofauna, and was 5 to 32% and 2 to 13% of those reported for ammonification and utilization in sediments, respectively. The potential importance of demersal macrozooplankton in mediating sediment-water column exchanges in the absence of diffusive effluxes and when they swarm is discussed.     

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.     

High seasonal variation of atmospheric C and particle concentrations in Delhi,India

The highly populated Indian regions are currently in a phase of rapid economic growth resulting in high emissions of carbonaceous aerosols. This leads to poor air quality and impact on climate. The chemical composition of carbonaceous aerosols has rarely been studied in industrial areas of India. Here, we investigated carbonaceous aerosols in particulate matter (PM) monthly in the industrial area of Delhi in 2011. The concentrations of organic C and elemental C in PM₁₀ fraction were analyzed. Results show a clear seasonal variability of organic and elemental C. PM₁₀ ranged 95.9–453.5 μg m^?3, organic C ranged 28.8–159.4 μg m^?3, and elemental C ranged 7.5–44.0 μg m^?3; those values were higher than reported values. Organic and elemental C were correlated with each other in pre-monsoon and winter seasons, implying the existence of similar emission sources such as coal combustion, biomass burning and vehicular exhaust. The annual average contribution of total carbonaceous aerosols in PM₁₀ was estimated as 62 %.     

Mercury pollution in the Sonbhadra district of Uttar Pradesh,India, and its health impacts

The Sonbhadra district in the Singrauli area of Uttar Pradesh, India, has many coal mines and thermal power plants and is a critically polluted area. Many residents of this area reported adverse health conditions which may be linked to metal pollution, especially of mercury investigated here.

In May 2012, samples of water (23), soil (7), blood, hair, and nails from persons showing adverse health conditions selected at random were collected and analyzed for total mercury by atomic absorption spectrometry.

Twenty percent drinking water samples contained mercury from 3 to 26 μg L^?1 (3–26 times the permissible limit). Soil samples had 0.5–10.1 mg kg^?1 Hg.

The average concentrations of mercury in human blood, hair, and nails were found to be 34 μg L^?1, 7.4 mg kg^?1, and 0.8 mg kg^?1, respectively. Mercury concentrations in the blood of these persons were 45 and 28 μg L^?1 on average in the case of men and women. This is much higher than the safe level of 5.8 μg L^?1 set by the United States Environmental Protection Agency (USEPA).

It was concluded that all residents of Sonbhadra sampled could be suffering from mercury toxicity as the area is polluted by Hg released from the coal-fired thermal power plants.     

Endosulfan in the Chinese environment: monitoring and modeling

This paper reviews the usage and emissions of endosulfan, the newest member of the persistent organic pollutants (POPs), in China, and its fate and behavior in Chinese environment. Endosulfan usage in China has been estimated to be approximately 25700 t between 1994 and 2004. Concentrations of endosulfan in different environmental compartments in China, such as air, soil, water, and biota, but focusing at air and surface soil, have been summarized. Concentrations of total endosulfan in surface soil across China were ranged from below detection limit (BDL) to 19000 pg·g^?1 dry weight (dw), with geometric mean of 120 pg·g^?1dw. The results indicated that endosulfan sulfate had highest concentration in Chinese soil, followed by ??- and ??-endosulfan. Air concentrations of endosulfan in China were ranged 0?C340 pg·m^?3 for ??-endosulfan and 0?C121 pg·m^?3 for ??-endosulfan, with high concentrations occurred in the cotton production areas. Gridded usage inventories of endosulfan on a fine gridded system with a 1/4° longitude by 1/6° latitude resolution were compiled, from which, emission to air and residues in soil of endosulfan were calculated in each grid by using a modified simplified gridded pesticide emission and residue model (SGPERM), an integrated modeling system combining mathematical model, database management system, and geographic information system. Total emissions were around 10800 t from 1994 to 2004. Based on the emission and residue inventories, concentrations of ??- and ??-endosulfan in Chinese air and agricultural surface soil were also calculated for each grid cell, which are in general consistent with the published monitoring data.     

Seasonal distribution and speciation of mercury in a gold mining area,north-west province,South Africa

The seasonal speciation of mercury (Hg) was determined in water, soil, and sediments from watersheds located in the North-West province of South Africa. The study area is known to have a long history of mining activities which also include the recovery of gold from old tailings. Both inorganic (IHg) and methyl mercury (MHg) were detected at high concentrations (up to 8480 μg IHg kg^?1 and 13 μg MHg kg^?1) in surface sediments during dry season. A considerable remobilization of Hg from bottom sediments was observed in water from dry to wet season as well as the migration of Hg away from pollution sources due to seasonal influences. Hg in sediments mostly has been speciated as Hg⁰. Enhancement of Hg methylation occurred mainly in deeper sediments at regions corresponding to the lowest redox potential, higher pH, and enrichment of IHg. Hg values in borehole waters were very high (up to 3310 ng L^?1) suggesting a serious contamination of the site groundwater which needs to be addressed urgently in order to minimize further impact that affects the Vaal River and other water systems located nearby.     

封闭垃圾填埋场通过地表向大气释放汞的测定

利用动力学通量箱及自动测汞仪联用技术,于2004年3月中旬对贵阳市的一座封闭生活垃圾填埋场汞通过地表向大气释放的过程进行了研究。3个采样点的汞释放通量日均值分别为559.1、88.2、53.6ng·m-2·h-1,汞释放通量强度与表层基质中的汞含量密切相关,该测定值高于世界背景地区通量的1~2个数量级,说明封闭垃圾填埋场也是大气汞的潜在来源。汞释放通量呈现明显的昼夜变化规律,白天较高并在午间前后达到最大,而夜间降至最低。气相因子中光照强度与汞的释放过程相关性最高,其次分别是气温、相对湿度、地温和风速。氧化态汞的光致还原作用是可能垃圾填埋场Hg0生成的主要途径,降雨初期能促进地表汞的释放。     

Seasonal growth and productivity ofMacrocystis integrifolia in British Columbia,Canada

The seasonal growth rates and nitrogen and carbon fluxes were estimated for two subtidalMacrocystis integrifolia Bory kelp forests in British Columbia, Canada from changes in population structure through time. Mean relative growth rates of the forests varied from a high of 4.3% d^-1 to a low of-3.6% d^-1. Mean net assimilatioon rates of carbon (a photosynthesis analog) varied from a high of 0.66 g C m^-2 of foliage d^-1 to a low of-0.87 g C m^-2 d^-1. The leaf area index ranged from 0.3 to 11.9. Annual carbon input on a foliage area basis was calculated at 250 g C m^-2 yr^-1. Annual carbon input to the forest was estimated at 1 300 g C m^-2 of ocean bottom yr^-1. The yearly nitrate nitrogen input to the forest was estimated at 60 g N m^-2 of ocean bottom yr^-1. The net ecosystem production varied from-520 to +31 g C m^-2 of ocean bottom yr^-1. The intra-forest, inter-forest and seasonal variabilities of these productivity parameters are discussed.     

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 km² 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.

     

Mercury cycling in litter and soil in different forest types in the Adirondack region, New York, USA.

The fate of mercury in decomposing leaf litter and soil is key to understanding the biogeochemistry of mercury in forested ecosystems. We quantified mercury dynamics in decomposing leaf litter and measured fluxes and pools of mercury in litterfall, throughfall, and soil in two forest types of the Adirondack region, New York, USA. The mean content of total mercury in leaf litter increased to 134% of its original mass during two years of decomposition. The accumulation pattern was seasonal, with significant increases in mercury mass during the growing season (+4.9% per month). Litterfall dominated mercury fluxes into the soil in the deciduous forest, whereas throughfall dominated fluxes into the coniferous forest. The increase in mercury mass in decomposing deciduous litter during the growing season was greater than could be accounted for by throughfall inputs during the growing season (P < 0.05), suggesting translocation of mercury from the soil to the decomposing deciduous litter. This internal recycling mechanism concentrates mercury in the organic horizons and retards transport through the soil, thereby increasing the residence time of mercury in the forest floor. A mass balance assessment suggests that the ultimate fate of mercury in the landscape depends upon forest type and associated differences in the delivery and incorporation of mercury into the soil. Our results show that incorporation of mercury into decaying leaf litter increases its residence time in the landscape and may further delay the recovery of surface waters, fish, and associated biota following control of mercury emissions to the atmosphere.     

Carbonyl sulfide (COS) and carbon disulfide (CS2) exchange fluxes between cotton fields and the atmosphere in the arid area in Xinjiang,China

Due to the important roles of carbonyl sulfide (COS) and carbon disulfide (CS₂) in atmospheric chemistry, this study was designed to determine different proportions of COS and CS₂ fluxes contributed from different sources, i.e., vegetation, soil and roots, at monthly and hourly timescales in the arid area in Xinjiang, China. Results indicated that the seasonal net uptake of COS by vegetation was predominant in the growing season. The CS₂ fluxes from vegetation and soils had no significant seasonal variations compared with COS. The exchange rates of COS and CS₂ have been found to be stimulated by the addition of nutrients in the form of urea fertilizer. Compared with the results of plots that were treated only with nitrogen, the treatments with both nitrogen and sulfur displayed no significant difference in the exchange fluxes. The results of compartment experiments indicated that the aboveground plants had the highest uptake of COS and had a vital role in the uptake of COS during the main growth period. The shares of COS emissions from the soil and roots increased to 6–17% and 55–58%, respectively, in the total COS fluxes when conditions, such as drought and senescence, were unfavorable for the developmental of vegetation. Observations of the preliminary diurnal fluxes indicated that the fluxes that occurred at night, with contributions from soils and plants, accounted for 27% of the total daily uptake of COS uptake. These quantitative results may be reasonably accounted for the use of COS as a promising tracer to obtain independent constraints on terrestrial carbon exchange at regional to global scales for their response to special environmental conditions in semiarid area.

     

Stoffströme von Benzol unter besonderer Berücksichtung der Bundesrepublik Deutschland

In the Federal Republic of Germany, benzene is one of the most important basic materials for the chemical industry. Only a relatively small proportion of the pure benzene processed in the chemical industry is emitted into the environment (ca. 40t in 1991). But the substance is also a natural component of the crude oil in gasoline and is released during incomplete combustion or is formed out of other aromatic substances. The primary source of emissions, with more than 10,000 t/yr (approximately 85% of this from motor vehicles with Otto engines), is commercial motor vehicle transportation. Benzene concentrations in the environment are approximately <1 μg/m³ in rural areas, 20–30 μg/m³ near main roads (peak levels in highly urbanized regions with much traffic as high as approximately 100 μg/m³) and 7–15 μg/m³ in the vicinity of industrial polluters. It has not been possible to detect a specific trend over time during the last ten years. An increased exposure (approx. 350–27,000 μg/m³) is likely while filling the tank and within the motor vehicle (approx. 10–200 μg/m³) due to gasoline volatilization from pipes, etc. Compared to outdoor air, higher concentrations of benzene (approx, 2–11 μg/m³) are measured in the indoor air which contains additionally benzene from tobacco smoke, equipment, renovating work and heating. The primary exposure pathway of benzene in humans is inhalation. Apart from individuals with occupational exposure, smokers have the highest internal benzene burden. Measures undertaken during recent years to reduce the amount of emissions have been counteracted at least in part by the increase in motor vehicle traffic. Further measures to reduce the emissions or to change the transporttation policies must still be or have already been initiated.     

Concentrations of particulates in ambient air,gaseous elementary mercury (GEM), and particulate-bound mercury (Hg(p)) at a traffic sampling site: a study of dry deposition in daytime and nighttime

In this investigation, the concentrations of particles in ambient air, gaseous elemental mercury (GEM), and particulate-bound mercury (Hg(p)) in total suspended particulates (TSP) as well as dry deposition at a (Traffic) sampling site at Hung-kuang were studied during the day and night in 2012. The results reveal that the mean concentrations of TSP in ambient air, GEM, and Hg(p) were 69.72 μg/m³, 3.17, and 0.024 ng/m³, respectively, at the Hung-kuang (Traffic) sampling site during daytime sampling periods. The results also reveal that the mean rates of dry deposition of particles from ambient air and Hg(p) were 145.20 μg/m² min and 0.022 ng/m² min, respectively, at the Hung-kuang (Traffic) sampling site during the daytime sampling period. The mean concentrations of TSP in ambient air, GEM, and Hg(p) were 60.56 μg/m³, 2.74, and 0.018 ng/m³, respectively, at the Hung-kuang (Traffic) sampling site during the nighttime sampling period. The mean rates of dry deposition of particles and Hg(p) from ambient air were 132.58 μg/m² min and 0.016 ng/m² min, respectively, at the Hung-kuang (Traffic) sampling site during the nighttime sampling period.     

Mercury contamination and health risk to crops around the zinc smelting plant in Huludao City,northeastern China

The Huludao zinc plant in Liaoning province, northeast China was the largest in Asia, and its smelting activities had seriously contaminated soil, water and atmosphere in the surrounding area. For the first time, we investigated the total mercury (THg) content in maize, soybean, broomcorn, 22 vegetables, and the soil around their roots from eight sampling plots near the Huludao zinc plant. THg contents of the seeds of maize, soybean, and broomcorn are 0.008, 0.006, and 0.057 mg kg⁻¹, respectively, with the broomcorn being the highest, exceeding the maximum level of contaminant in food (GB2762-2005) by 4.7 times. The edible parts of vegetables are also contaminated with a range of mercury contents of 0.001–0.147 mg kg⁻¹ (dry weight). THg contents in plant tissue decrease in the order of leaves > root > stalk > grain. Using correlation analysis, we show that mercury in the roots of these plants is mainly derived from soil, and the uptake of gaseous mercury is the predominant path by which the mercury accumulated in the foliage. The average and maximum mercury daily intake (DI) of adult around the Huludao zinc plant via consuming vegetables are 0.015 and 0.051 μg/kg/d, respectively, and those of children are 0.02 and 0.07 μg/kg/d, respectively. The average and maximum weekly intakes of total mercury for adult are 2.1 and 7.1%, respectively, of the provisional tolerable weekly intake (PTWI), and 2.8 and 9.7%, respectively, of the PTWI for children.