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.     

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.     

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.     

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.     

Leaching of mercury from peat soil

The factors influencing the sorption and leaching of mercury in peat soil were studied using small additions of labelled mercury in peat lysimeters. Additions of chloride, fertilizer or sterilant did not affect the leaching of mercury. Complete drying of the peat improved the leaching of mercury probably because of changes in the physical properties of the peat soil.     

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     

Factors influencing the total mercury and methyl mercury in the hair of the fishermen of Kuwait

Total and methyl mercury (MeHg) levels in the hair of fishermen are described anticipating that they represent the critical group for dietary exposure. One-hundred human hair samples were collected from fishermen (Egyptians: age range 25-60), living in Doha Fishing Village, Kuwait. Thirty-five additional samples were taken from a control group working in a local construction company (age range 26-35). Overall mean concentrations in the hair of the population of fishermen are 4.181+/-3.220 and 4.025+/-3.130 microg g(-1) for total and MeHg, respectively. The equivalent values for the control are 2.617+/-1.404 and 2.556+/-1.391 microg g(-1) for total and MeHg, respectively. MeHg concentrations are strongly correlated to those of total Hg ( [Formula: see text], [Formula: see text] ) and MeHg concentrations in human hair are unrelated to age and duration of residence in Kuwait but show a positive correlation with the quantity of fish consumed. Levels of Hg in hair also show a tendency to increase in those who prefer to eat the entire fish, including the heads. In general, the concentrations of total and MeHg in fishermens' hair are twice the WHO 'normal' level (2.0 microg g(-1)) but are still less than the WHO threshold level (10.0 microg g(-1)). The results also show that grey hair contains undetectable amounts of Hg and therefore does not reflect individual exposure to this contaminant.     

Estimating mercury emissions from a zinc smelter in relation to China’s mercury control policies

Mercury concentrations of flue gas at inlet/outlet of the flue gas cleaning, electrostatic demister, reclaiming tower, acid plant, and mercury contents in zinc concentrate and by-products were measured in a hydrometallurgical zinc smelter. The removal efficiency of flue gas cleaning, electrostatic demister, mercury reclaiming and acid plant was about 17.4%, 30.3%, 87.9% and 97.4% respectively. Flue gas cleaning and electrostatic demister captured 11.7% and 25.3% of the mercury in the zinc concentrate, respectively. The mercury reclaiming tower captured 58.3% of the mercury in the zinc concentrate. About 4.2% of the mercury in the zinc concentrate was captured by the acid plant. Consequently, only 0.8% of the mercury in the zinc concentrate was emitted to the atmosphere. The atmospheric mercury emission factor was 0.5 g t⁻¹ of zinc produced for the tested smelter, indicating that this process offers the potential to effectively reduce mercury emissions from zinc smelting.     

Transformations of elemental mercury to inorganic and organic forms in mercury and hydrocarbon co-contaminated soils.

There are many industrial sites, such as gas processing plants, that are contaminated with both mercury and hydrocarbons. These sites tend to be localized but can have very high concentrations of mercury in the soil and heterogeneous distribution of hydrocarbons. The original form of mercury in many cases was elemental mercury from broken manometers. Over time the mercury has become redistributed within soil and has undergone chemical transformations into new forms. The forms of mercury will govern the chemical behavior and the availability of the mercury to biological receptors. The availability of the mercury is important as it will govern the risk associated with the contaminated soil and will also determine the effectiveness of any attempts at remediation. In the present study a chemical extraction protocol was used to determine the forms of mercury in soil originally contaminated by spillage of elemental mercury and petroleum hydrocarbons. Chemical extractions have been used in the past to determine the forms of mercury in uncontaminated soils and several researchers have used them to study contaminated soils. However, to date, no researchers have studied the forms of mercury in soils following years of weathering of elemental mercury after a spill. This study shows that decades after the original spill the elemental mercury has transformed and is dominantly (up to 85%) associated with soil organic matter, and to a lesser extent the mineral fraction of soil.     

Evaluation of an offline method for the analysis of atmospheric reactive gaseous mercury and particulate mercury

Reactive gaseous mercury (RGM) and particulate mercury (PHg) were collected in Milwaukee, WI, between April 2004 and May 2005, and in Riverside, CA, between July 25 and August 7, 2005 using sorbent and filter substrates. The substrates were analyzed for mercury by thermal desorption analysis (TDA) using a purpose-built instrument. Results from this offline-TDA method were compared with measurements using a real-time atmospheric mercury analyzer. RGM measurements made with the offline-TDA agreed well with a commercial real-time method. However, the offline TDA reported PHg concentrations 2.7 times higher than the real-time method, indicating evaporative losses might be occurring from the real-time instrument during sample collection. TDA combined with reactive mercury collection on filter and absorbent substrates was cheap, relatively easy to use, did not introduce biases due to a semicontinuous sample collection strategy, and had a dynamic range appropriate for use in rural and urban locations. The results of this study demonstrate that offline-TDA is a feasible method for collecting reactive mercury concentrations in a large network of filter-based samplers.     

Long-term mercury dynamics in UK soils

A model assuming first-order losses by evasion and leaching was used to evaluate Hg dynamics in UK soils since 1850. Temporal deposition patterns of Hg were constructed from literature information. Inverse modelling indicated that 30% of 898 rural sites receive Hg only from the global circulation, while in 51% of cases local deposition exceeds global. Average estimated deposition is 16 μg Hg m⁻² a⁻¹ to rural soils, 19 μg Hg m⁻² a⁻¹ to rural and non-rural soils combined. UK soils currently hold 2490 tonnes of reactive Hg, of which 2140 tonnes are due to anthropogenic deposition, mostly local in origin. Topsoil currently releases 5.1 tonnes of Hg⁰ per annum to the atmosphere, about 50% more than the anthropogenic flux. Sorptive retention of Hg in the lower soil exerts a strong control on surface water Hg concentrations. Following decreases in inputs, soil Hg concentrations are predicted to decline over hundreds of years.     

The influence of ozone on atmospheric emissions of gaseous elemental mercury and reactive gaseous mercury from substrates

Experiments were performed to investigate the effect of ozone (O₃) on mercury (Hg) emission from a variety of Hg-bearing substrates. Substrates with Hg(II) as the dominant Hg phase exhibited a 1.7 to 51-fold increase in elemental Hg (Hg^o) flux and a 1.3 to 8.6-fold increase in reactive gaseous mercury (RGM) flux in the presence of O₃-enriched clean (50 ppb O₃; 8 substrates) and ambient air (up to ∼70 ppb O₃; 6 substrates), relative to clean air (oxidant and Hg free air). In contrast, Hg^o fluxes from two artificially Hg^o-amended substrates decreased by more than 75% during exposure to O₃-enriched clean air relative to clean air. Reactive gaseous mercury emissions from Hg^o-amended substrates increased immediately after exposure to O₃ but then decreased rapidly. These experimental results demonstrate that O₃ is very important in controlling Hg emissions from substrates. The chemical mechanisms that produced these trends are not known but potentially involve heterogenous reactions between O₃, the substrate, and Hg. Our experiments suggest they are not homogenous gas-phase reactions. Comparison of the influence of O₃ versus light on increasing Hg^o emissions from dry Hg(II)-bearing substrates demonstrated that they have a similar amount of influence although O₃ appeared to be slightly more dominant. Experiments using water-saturated substrates showed that the presence of high-substrate moisture content minimizes reactions between atmospheric O₃ and substrate-bound Hg. Using conservative calculations developed in this paper, we conclude that because O₃ concentrations have roughly doubled in the last 100 years, this could have increased Hg^o emissions from terrestrial substrates by 65–72%.     

Atmospheric mercury pollution at an urban site in central Taiwan: mercury emission sources at ground level

Total gaseous mercury (Hg) (TGM), gaseous oxidized Hg (GOM), and particulate-bound Hg (PBM) concentrations and dry depositions were measured at an urban site in central Taiwan. The concentrations were 6.14 ± 3.91 ng m⁻³, 332 ± 153, and 71.1 ± 46.1 pg m⁻³, respectively. These results demonstrate high Hg pollution at the ground level in Taiwan. A back trajectory plot shows the sources of the high TGM concentration were in the low atmosphere (<500 m) and approximately 50% of the air masses coming from upper troposphere (>500 m) were associated with low TGM concentrations. This finding implies that Hg is trapped in the low atmosphere and comes from local Hg emission sources. The conditional probability function (CPF) reveals that the plumes of high TGM concentrations come from the south and northwest of the site. The plume from the south comes from two municipal solid waste incinerators (MSWIs). However, no significant Hg point source is located to the northwest of the site; therefore, the plumes from the northwest are hypothesized to be related to the combustion of agricultural waste. Dry deposition fluxes of Hg measured at this site considerably exceeded those measured in North America. Overall, this area is regarded as a highly Hg contaminated area because of local Hg emission sources.