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.     

Development and application of a regional-scale atmospheric mercury model based on WRF/Chem: a Mediterranean area investigation

The emission, transport, deposition and eventual fate of mercury (Hg) in the Mediterranean area has been studied using a modified version of the Weather Research and Forecasting model coupled with Chemistry (WRF/Chem). This model version has been developed specifically with the aim to simulate the atmospheric processes determining atmospheric Hg emissions, concentrations and deposition online at high spatial resolution. For this purpose, the gas phase chemistry of Hg and a parametrised representation of atmospheric Hg aqueous chemistry have been added to the regional acid deposition model version 2 chemical mechanism in WRF/Chem. Anthropogenic mercury emissions from the Arctic Monitoring and Assessment Programme included in the emissions preprocessor, mercury evasion from the sea surface and Hg released from biomass burning have also been included. Dry and wet deposition processes for Hg have been implemented. The model has been tested for the whole of 2009 using measurements of total gaseous mercury from the European Monitoring and Evaluation Programme monitoring network. Speciated measurement data of atmospheric elemental Hg, gaseous oxidised Hg and Hg associated with particulate matter, from a Mediterranean oceanographic campaign (June 2009), has permitted the model’s ability to simulate the atmospheric redox chemistry of Hg to be assessed. The model results highlight the importance of both the boundary conditions employed and the accuracy of the mercury speciation in the emission database. The model has permitted the reevaluation of the deposition to, and the emission from, the Mediterranean Sea. In light of the well-known high concentrations of methylmercury in a number of Mediterranean fish species, this information is important in establishing the mass balance of Hg for the Mediterranean Sea. The model results support the idea that the Mediterranean Sea is a net source of Hg to the atmosphere and suggest that the net flux is ≈30 Mg year^?1 of elemental Hg.     

Sources and deposition of reactive gaseous mercury in the marine atmosphere

Observations of reactive gaseous mercury (RGM) in marine air show a consistent diurnal cycle with minimum at night, rapid increase at sunrise, maximum at midday, and rapid decline in afternoon. We use a box model for the marine boundary layer (MBL) to interpret these observations in terms of RGM sources and sinks. The morning rise and midday maximum are consistent with oxidation of elemental mercury (Hg⁰) by Br atoms, requiring <2 ppt BrO in most conditions. Oxidation of Hg⁰ by Br accounts for 35–60% of the RGM source in our model MBL, with most of the remainder contributed by oxidation of Hg⁰ by ozone (5–20%) and entrainment of RGM-rich air from the free troposphere (25–40%). Oxidation of Hg⁰ by Cl is minor (3–7%), and oxidation by OH cannot reproduce the observed RGM diurnal cycle, suggesting that it is unimportant. Fitting the RGM observations could be achieved in the model without oxidation of Hg⁰ by ozone (leaving Br as the only significant oxidant) by increasing the entrainment flux from the free troposphere. The large relative diurnal amplitude of RGM concentrations implies rapid loss with a lifetime of only a few hours. We show that this can be quantitatively explained by rapid, mass-transfer-limited uptake of RGM into sea-salt aerosols as HgCl₃^? and HgCl₄^2?. Our results suggest that 80–95% of Hg^II in the MBL should be present in sea-salt aerosol rather than gas-phase, and that deposition of sea-salt aerosols is the major pathway delivering Hg^II to the ocean.     

Measurement of Particulate Bound Mercury,Gaseous Elemental Mercury,and Reactive Gaseous Mercury Concentrations by Using an Ambient Air Mercury Collection System

In this investigation, the concentrations of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate bound mercury (PBM) in ambient air were measured at the Hung Kuang (traffic) sampling site during September 27 to October 6, 2014. An ambient air mercury collection system (AAMCS) was utilized to measure simultaneously PBM, GEM, and RGM concentrations in ambient air. The results thus obtained demonstrate that the mean concentrations of PBM, GEM, and RGM were 38.57 ± 11.4 (pg/m³), 17.67 ± 5.56 (ng/m³) and 10.78 ± 2.8 (pg/m³), respectively, at this traffic-sampling site. The mean GEM/PBM and GEM/RGM concentration ratios were 458 and 1639, respectively. The results obtained herein demonstrate that AAMCS can be utilized to collect three phases of mercury simultaneously. The mean PBM, GEM, and RGM concentrations herein were compared with others found in Asia, America, Europe and Antarctica. The mean PBM, GEM, and RGM concentrations were found to be lowest in Asia and Antarctica. The mean PBM concentration in Europe was approximately eight times that in this investigation. The mean GEM and RGM concentrations in this study were 1.21 and 170 times those found in the United States.     

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%.     

Studies of potential sources that contributed to atmospheric mercury in Toronto,Canada

This study identified sources of mercury (Hg) in downtown Toronto, Canada by analyzing gaseous elemental mercury (GEM), mercury associated with particles with sizes less than 2.5 microns (PHg < 2.5), and gaseous oxidized inorganic mercury (GOIM), commonly referred to as reactive gaseous mercury (RGM), and air pollutants (CO, NO_x, O₃, PM_2.5, SO₂) concentrations between Dec 2003 and Nov 2004. The data were analyzed using Positive Matrix Factorization (PMF) model, Principal Components Analysis (PCA), ratio analysis, back trajectories, and correlation analyses. The analyses suggest industrial sources (chemical production, metal production, sewage treatment), rather than coal combustion, were the major contributors to measured Hg levels. Overlap in source profiles for the Hg sources listed in the Canadian National Pollutant Release Inventory (NPRI) and lack of source profiles for urban sources were the major limitations to positively identifying sources from the PMF and PCA factors. Correlation analyses revealed direct emissions were the sources of GOIM in spring, summer, and fall, and the occurrence of GEM oxidation by ozone in the summer. Elevated Hg events are attributed to emissions from urban sources near the sampling site, regional point sources, and photochemical processes involving ozone.     

Evidence for short-range transport of atmospheric mercury to a rural,inland site

Atmospheric mercury (Hg) species, including gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate-bound mercury (Hg_p), were monitored near three sites, including a cement plant (monitored in 2007 and 2008), an urban site and a rural site (both monitored in 2005 and 2008). Although the cement plant was a significant source of Hg emissions (for 2008, GEM: 2.20 ± 1.39 ng m^?3, RGM: 25.2 ± 52.8 pg m^?3, Hg_p 80.8 ± 283 pg m^?3), average GEM levels and daytime average dry depositional RGM flux were highest at the rural site, when all three sites were monitored sequentially in 2008 (rural site, GEM: 2.37 ± 1.26 ng m^?3, daytime RGM flux: 29 ± 40 ng m^?2 day^?1). Photochemical conversion of GEM was not the primary RGM source, as highest net RGM gains (75.9 pg m^?3, 99.0 pg m^?3, 149 m^?3) occurred within 3.0–5.3 h, while the theoretical time required was 14–23 h. Instead, simultaneous peaks in RGM, Hg_p, ozone (O₃), nitrogen oxides, and sulfur dioxide in the late afternoon suggested short-range transport of RGM from the urban center to the rural site. The rural site was located more inland, where the average water vapor mixing ratio was lower compared to the other two sites (in 2008, rural: 5.6 ± 1.4 g kg^?1, urban: 9.0 ± 1.1 g kg^?1, cement plant: 8.3 ± 2.2 g kg^?1). Together, these findings suggested short-range transport of O₃ from an urban area contributed to higher RGM deposition at the rural site, while drier conditions helped sustain elevated RGM levels. Results suggested less urbanized environments may be equally or perhaps more impacted by industrial atmospheric Hg emissions, compared to the urban areas from where Hg emissions originated.     

Air-Surface Exchange of Mercury with Soils Amended with Ash Materials

Abstract

Air-surface exchange of mercury (Hg) was measured from soil low in Hg (0.013 mg/kg) amended with four different ash materials: a wood ash containing ～10% coal ash (0.070 mg/kg Hg), a mixture of two subbituminous coal fly ashes (0.075 mg/kg Hg), a subbituminous coal ash containing ～10% petroleum coke ash (1.2 mg/kg Hg), and an ash from incinerated municipal sewage sludge (4.3 mg/kg Hg) using a dynamic flux chamber. Ash was added to soil to simulate agricultural supplements, soil stabilization, and pad layers used in livestock areas. For the agricultural amendment, ～0.4% ash was well mixed into the soil. To make the stabilized soil that could be used for construction purposes, ～20% ash was mixed into soil with water. The pad layer consisted of a wetted 1-cm layer of ash material on the soil surface. Diel trends of Hg flux were observed for all of the substrates with significantly higher Hg emissions during the day and negligible flux or deposition of Hg during the night. Hg fluxes, which were measured in the summer months, were best correlated with solar radiation, temperature, and air O₃ concentrations. Mean Hg fluxes measured outdoors for unamended soils ranged from 19 to 140 ng/m² day, whereas those for soil amended with ash to simulate an agricultural application ranged from 7.2 to 230 ng/m² day. Fluxes for soil stabilized with ash ranged from 77 to 530 ng/m² day and for soil with pads constructed of ash ranged from ?50 to 90 ng/m² day. Simple analytical tests (i.e., total Hg content, synthetic precipitation leaching procedure, heating, and indoor gas-exchange experiments) were performed to assess whether algorithms based on these tests could be used to predict Hg fluxes observed outdoors using the flux chamber. Based on this study, no consistent relationships could be developed. More work is needed to assess long-term and seasonal variations in Hg flux from (intact and disturbed) substrates before annual estimates of emissions can be developed.     

Temporal distribution and potential sources of atmospheric mercury measured at a high-elevation background station in Taiwan

Measurements of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM), and particulate mercury (PHg) have been conducted at Lulin Atmospheric Background Station (LABS) in Taiwan since April 2006. This was the first long-term free tropospheric atmospheric Hg monitoring program in the downwind region of East Asia, which is a major Hg emission source region. Between April 13, 2006 and December 31, 2007, the mean concentrations of GEM, RGM, and PHg were 1.73 ng m^?3, 12.1 pg m^?3, and 2.3 pg m^?3, respectively. A diurnal pattern was observed for GEM with afternoon peaks and nighttime lows, whereas the diurnal pattern of RGM was opposite to that of GEM. Spikes of RGM were frequently observed between midnight and early morning with concurrent decreases in GEM and relative humidity and increases in O₃, suggesting the oxidation of GEM and formation of RGM in free troposphere (FT). Upslope movement of boundary layer (BL) air in daytime and subsidence of FT air at night resulted in these diurnal patterns. Considering only the nighttime data, which were more representative of FT air, the composite monthly mean GEM concentrations ranged between 1.06 and 2.06 ng m^?3. Seasonal variation in nighttime GEM was evident, with lower concentrations usually occurring in summer when clean marine air masses prevailed. Between fall and spring, air masses passed the East Asian continent prior to reaching LABS, contributing to the elevated GEM concentrations. Analysis of GEM/CO correlation tends to support the argument. Good GEM/CO correlations were observed in fall, winter, and spring, suggesting influence of anthropogenic emission sources. Our results demonstrate the significance of East Asian Hg emissions, including both anthropogenic and biomass burning emissions, and their long-range transport in the FT. Because of the pronounced seasonal monsoon activity and the seasonal variation in regional wind field, export of the Asian Hg emissions to Taiwan occurs mainly during fall, winter, and spring.     

Scientific uncertainties in atmospheric mercury models II: Sensitivity analysis in the CONUS domain

In this study, we present the response of model results to different scientific treatments in an effort to quantify the uncertainties caused by the incomplete understanding of mercury science and by model assumptions in atmospheric mercury models. Two sets of sensitivity simulations were performed to assess the uncertainties using modified versions of CMAQ-Hg in a 36-km Continental United States domain. From Set 1 Experiments, it is found that the simulated mercury dry deposition is most sensitive to the gaseous elemental mercury (GEM) oxidation product assignment, and to the implemented dry deposition scheme for GEM and reactive gaseous mercury (RGM). The simulated wet deposition is sensitive to the aqueous Hg(II) sorption scheme, and to the GEM oxidation product assignment. The inclusion of natural mercury emission causes a small increase in GEM concentration but has little impact on deposition. From Set 2 Experiments, it is found that both dry and wet depositions are sensitive to mercury chemistry. Change in model mercury chemistry has a greater impact on simulated wet deposition than on dry deposition. The kinetic uncertainty of GEM oxidation by O₃ and mechanistic uncertainty of Hg(II) reduction by aqueous HO₂ pose the greatest impact. Using the upper-limit kinetics of GEM–O₃ reaction or eliminating aqueous Hg(II)–HO₂ reaction results in unreasonably high deposition and depletion of gaseous mercury in the domain. Removing GEM–OH reaction is not sufficient to balance the excessive mercury removal caused by eliminating the HO₂ mechanism. Field measurements of mercury dry deposition, better quantification of mercury air-surface exchange and further investigation of mercury redox chemistry are needed for reducing model uncertainties and for improving the performance of atmospheric mercury models.     

Evaluation of an Offline Method for the Analysis of Atmospheric Reactive Gaseous Mercury and Particulate Mercury

Abstract

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.     

Temporal variability of mercury speciation in urban air

Semi-continuous measurements of ambient mercury (Hg) species were performed in Detroit, MI, USA for the calendar year 2003. The mean (±standard deviation) concentrations for gaseous elemental mercury (GEM), particulate mercury (HgP), and reactive gaseous mercury (RGM) were 2.2±1.3 ng m⁻³, 20.8±30.0, and 17.7±28.9 pg m⁻³, respectively. A clear seasonality in Hg speciation was observed with GEM and RGM concentrations significantly (p<0.001) greater in warm seasons, while HgP concentrations were greater in cold seasons. The three measured Hg species also exhibited clear diurnal trends which were particularly evident during the summer months. Higher RGM concentrations were observed during the day than at night. Hourly HgP and GEM concentrations exhibited a similar diurnal pattern with both being inversely correlated with RGM. Multivariate analysis coupled with conditional probability function analysis revealed the conditions associated with high Hg concentration episodes, and identified the inter-correlations between speciated Hg concentrations, three common urban air pollutants (sulfur dioxide, ozone, and nitric oxides), and meteorological parameters. This analysis suggests that both local and regional sources were major factors contributing to the observed temporal variations in Hg speciation. Boundary layer dynamics and the seasonal meteorological conditions, including temperature and moisture content, were also important factors affecting Hg variability.     

Mercury in the Mediterranean. Part 2: processes and mass balance

Mass balance of contaminants can provide useful information on the processes that influence their concentrations in various environmental compartments. The most important sources, sinks and the equilibrium or non-equilibrium state of the contaminant in individual environmental compartments can also be identified. Using the latest mercury speciation data, the results of numerical models and the results of recent studies on mercury transport and transformation processes in the marine environment, we have re-evaluated the total mercury (HgT) mass balance in the Mediterranean Sea. New calculations have been performed employing three distinct marine layers: the surface layer, the thermocline and the deep sea. New transport mechanisms, deep water formation and density-driven sinking and upwelling, were included in the mass balance calculations. The most recent data have even enabled the calculation of an approximate methylmercury (MeHg) mass balance. HgT is well balanced in the entire Mediterranean, and the discrepancies between inputs and outputs in individual layers do not exceed 20 %. The MeHg balance shows larger discrepancies between gains and losses due to measurement uncertainties and gaps in our knowledge of Hg species transformation processes. Nonetheless, the main sources and sinks of HgT (deposition and evasion) and MeHg (fluxes from sediment, outflow through the Gibraltar Strait) are in accordance with previous studies on mercury in the Mediterranean Basin. Mercury in the Mediterranean fish harvest is the second largest MeHg sink; about 300 kg of this toxic substance is consumed annually with sea food.     

Mercury in the Mediterranean,part I: spatial and temporal trends

The present paper provides an overview of mercury studies performed in the Mediterranean Sea region in the framework of several research projects funded by the European Commission and on-going national programmes carried out during the last 15 years. These studies investigated the temporal and spatial distribution of mercury species in air, in the water column and sediments, and the transport mechanisms connecting them. It was found that atmospheric concentrations of Hg compounds, particularly oxidised Hg species observed at five coastal sites in the Mediterranean Sea Basin, are significantly higher compared with those recorded at five coastal sites distributed across N Europe, most probably due to natural emissions. Hg levels in water are comparable to other oceans. Anthropogenic and natural point sources show locally limited enrichments, while natural diffusive sources influence Hg speciation over larger areas. Results and statistic comparison of mercury species concentrations within Mediterranean compartments will be presented and discussed.     

Mercury in Precipitation at an Urbanized Coastal Zone of the Baltic Sea (Poland)

Wet deposition is an important source of metals to the sea. The temporal variability of Hg concentrations in precipitation, and the impact of air masses of different origins over the Polish coastal zone were assessed. Samples of precipitation were collected (August 2008–May 2009) at an urbanized coastal station in Poland. Hg analyses were conducted using CVAFS. These were the first measurements of Hg concentration in precipitation obtained in the Polish coastal zone. Since Poland was identified as the biggest emitter of Hg to the Baltic, these data are very important. In the heating and non-heating season, Hg concentrations in precipitation were similar. Hg wet deposition flux dominated in summer, when the production of biomass in the aquatic system was able to actively adsorb Hg. Input of metal to the sea was attributed to regional and distant sources. Maritime air masses, through transformation of Hg(0), were an essential vector of mercury in precipitation.     

An Assessment of the Significance of Mercury Release from Coal Fly Ash

Abstract

Some mercury (Hg) naturally present in coal is retained in the fly ash remaining after combustion. Concern has been raised regarding the potential for release of this Hg to the environment. The exchange of Hg between fly ash and the atmosphere was measured in the laboratory and in situ at a fly ash landfill. All samples of fly ash used in the laboratory study, with the exception of that derived from lignite-type coal, acted as a sink for atmospheric Hg. Deposition rates were found to increase as air Hg concentrations increased and to decrease with incident light and increased temperature. Addition of water to fly ash samples resulted in re-emission of deposited atmospheric Hg. Deposition was the dominant flux measured in situ at a fly ash landfill. Atmospheric Hg was deposited to all samples collected as part of two demonstration projects using carbon injection for enhanced Hg capture. Hg concentrations of extracts derived using U.S. Environmental Protection Agency Method 1312 (Synthetic Precipitation Leaching Procedure) were ≤14.4 ng/L. Data developed demonstrate that fly ash, including that collected from Hg removal projects, will release little Hg to the air or water, and under certain conditions, absorbs Hg from the air.     

Atmospheric mercury concentrations and speciation measured from 2004 to 2007 in Reno, Nevada, USA

Atmospheric elemental, reactive and particulate mercury (Hg) concentrations were measured north of downtown Reno, Nevada, USA from November 2004 to November 2007. Three-year mean and median concentrations for gaseous elemental Hg (Hg⁰) were 1.6 and 1.5 ng m⁻³ (respectively), similar to global mean Hg⁰ concentrations. The three-year mean reactive gaseous Hg (RGM) concentration (26 pg m⁻³) was higher than values reported for rural sites across the western United States. Well defined seasonal and daily patterns in Hg⁰ and RGM concentrations were observed, with the highest Hg⁰ concentrations measured in winter and early morning, and RGM concentrations being greatest in the summer and mid-afternoon. Elevated Hg⁰ concentrations in winter were associated with periods of cold, stagnant air; while a regularly observed early morning increase in concentration was due to local source and surface emissions. The observed afternoon increase and high summer values of RGM can be explained by in situ oxidation of gaseous Hg⁰ or mixing of RGM derived from the free troposphere to the surface. Because both of these processes are correlated with the same environmental conditions it is difficult to assess their overall contribution to the observed trends.     

Atmospheric mercury distribution in Northern Europe and in the Mediterranean region

Mercury species in air have been measured at five sites in Northwest Europe and at five coastal sites in the Mediterranean region during measurements at four seasons. Observed concentrations of total gaseous mercury (TGM), total particulate mercury (TPM) and reactive gaseous mercury (RGM) were generally slightly higher in the Mediterranean region than in Northwest Europe. Incoming clean Atlantic air seems to be enriched in TGM in comparison to air in Scandinavia. Trajectory analysis of events where high concentrations of TPM simultaneously were observed at sites in North Europe indicate source areas in Central Europe and provide evidence of transport of mercury on particles on a regional scale.     

Urban–rural differences in atmospheric mercury speciation

Measurements of gaseous elemental mercury (GEM), particulate mercury (Hg_p), and reactive gaseous mercury (RGM) were concurrently recorded at an urban site in Detroit and a rural site in Dexter, both in Michigan for the calendar year 2004. Their average concentrations (±standard deviation) for the urban area were 2.5 ± 1.4 ng m^?3, 18.1 ± 61.0 pg m^?3, and 15.5 ± 54.9 pg m^?3, respectively, while their rural counterparts were 1.6 ± 0.6 ng m^?3, 6.1 ± 5.5 pg m^?3, and 3.8 ± 6.6 pg m^?3, respectively. The medians of urban-to-rural ratios of Hg concentrations indicate approximately 1-fold, 2-fold, and 3-fold gradients between Detroit and Dexter for GEM, Hg_p, and RGM, respectively. The urban–rural differences in Hg also varied considerably on different temporal scales and with wind flow patterns, which was most evident in RGM. Our results show that while Hg at both sites was impacted by regional sources, meteorological conditions, and photochemical transformations, the extent of variations in the observed urban-to-rural gradients, particularly in RGM, cannot be fully accounted for by these processes. Both analyses of the annual data and case studies indicate that the more variable and episodic nature of Hg, particularly RGM, seen in Detroit compared with Dexter, was the result of direct impact from local anthropogenic sources.     

Mercury (Hg) emissions from domestic biomass combustion for space heating

Three mercury (Hg) species (gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and fine particulate-bound mercury (PBM_2.5)) were measured in the stack of a small scale wood combustion chamber at 400 °C, in the stack of an advanced wood boiler, and in two areas influenced by wood combustion. The low temperature process (lab-scale) emitted mostly GEM (∼99% when burning wood pellets and ∼95% when burning unprocessed wood). The high temperature wood boiler emitted a greater proportion of oxidized Hg (approximately 65%) than the low temperature system. In field measurements, mean PBM_2.5 concentrations at the rural and urban sites in winter were statistically significantly higher than in warmer seasons and were well correlated with Delta-C concentrations, a wood combustion indictor measured by an aethalometer (UV-absorbable carbon minus black carbon). Overall the results suggest that wood combustion may be an important source of oxidized mercury (mostly in the particulate phase) in northern climates in winter.