Intercomparison of methods for sampling and analysis of atmospheric mercury species

An intercomparison for sampling and analysis of atmospheric mercury species was held in Tuscany, June 1998. Methods for sampling and analysis of total gaseous mercury (TGM), reactive gaseous mercury (RGM) and total particulate mercury (TPM) were used in parallel sampling over a period of 4 days. The results show that the different methods employed for TGM compared well whereas RGM and TPM showed a somewhat higher variability. Measurement results of RGM and TPM improved over the time period indicating that activities at the sampling site during set-up and initial sampling affected the results. Especially the TPM measurement results were affected. Additional parallel sampling was performed for two of the TPM methods under more controlled conditions which yielded more comparable results.     

International field intercomparison measurements of atmospheric mercury species at Mace Head,Ireland

Eleven laboratories from North America and Europe met at Mace Head, Ireland for the period 11–15 September 1995 for the first international field intercomparison of measurement techniques for atmospheric mercury species in ambient air and precipitation at a marine background location. Different manual methods for the sampling and analysis of total gaseous mercury (TGM) on gold and silver traps were compared with each other and with new automated analyzers. Additionally, particulate-phase mercury (Hg_part) in ambient air, total mercury, reactive mercury and methylmercury in precipitation were analyzed by some of the participating laboratories. Whereas measured concentrations of TGM and of total mercury in precipitation show good agreement between the participating laboratories, results for airborne particulate-phase mercury show much higher differences. Two laboratories measured inorganic oxidized gaseous mercury species (IOGM), and obtained levels in the low picogram m^-3 range.     

Seasonal variation and spatial distribution of atmospheric mercury and its gas-particulate partition in the vicinity of a semiconductor manufacturing complex

This study investigated the tempospatial variation of atmospheric mercury and its gas-particulate partition in the vicinity of a semiconductor manufacturing complex, where a plenty of flat-monitor manufacturing plants using elemental mercury as a light-initiating medium to produce backlight fluorescence tubes and may fugitively emit mercury-containing air pollutants to the atmosphere. Atmospheric mercury speciation, concentration, and the partition of total gaseous mercury (TGM) and particulate mercury (Hg_p) were measured at four sites surrounding the semiconductor manufacturing intensive district/complex. One-year field measurement showed that the seasonal averaged concentrations of TGM and Hg_p were in the range of 3.30–6.89 and 0.06–0.14 ng/m³, respectively, whereas the highest 24-h TGM and Hg_p concentrations were 10.33 and 0.26 ng/m³, respectively. Atmospheric mercury apportioned as 92.59–99.01 % TGM and 0.99–7.41 % Hg_p. As a whole, the highest and lowest concentrations of TGM were observed in the winter and summer sampling periods, respectively, whereas the concentration of Hg_p did not vary much seasonally. The highest TGM concentrations were always observed at the downwind sites, indicating that the semiconductor manufacturing complex was a hot spot of mercury emission source, which caused severe atmospheric mercury contamination over the investigation region.     

Characteristic Study of Ambient Air Total Gaseous Mercury (TGM) Concentrations During Rainy and Non-Rainy Periods at a Traffic Site in Taiwan

This investigation studied the concentrations of ambient air total gaseous mercury (TGM) during the rainy periods at the Hung-Kuang traffic sampling site in central Taiwan from May 26 to June 16, 2014. The results were compared with those of a previous study for ambient air TGM during non-rainy daytime and nighttime periods at the Hung-Kuang traffic sampling site, which was conducted during March 21 to July 20, 2012. The observed mean concentration of ambient air TGM was 1.16 ng/m³ during the rainy periods at the Hung-Kuang traffic sampling site. The mean ambient air TGM concentrations were higher in the non-rainy sampling period in daytime than in the rainy sampling period from this study. The mean ratio of non-rainy sampling period in daytime to that of rainy sampling period for ambient air TGM were 3.15. Furthermore, the mean ambient air TGM concentrations were higher in the non-rainy sampling period in nighttime in than in the rainy sampling period for this study. The mean rations for non-rainy sampling period in nighttime to that of the rainy sampling period for ambient air TGM were 2.70. The results obtained in this study also revealed that the ambient air TGM concentrations during the rainy period had the lowest concentrations when compared with the other sampling sites in other world regions.     

Potential sources of atmospheric total gaseous mercury in the St. Lawrence River valley

The potential source contribution function (PSCF) has been used to study the source–receptor relationships for total gaseous mercury (TGM) found in air collected at two sites along the St. Lawrence River valley, namely at St. Anicet and Mingan. TGM concentrations have been measured with high time-resolution analysers (Tekran instrument). The source–receptor analyses have been applied with regards to the seasonality of TGM. Median TGM concentrations are significantly less (χ²: α=0.01) during the summertime than other periods at both sites. A total of 12 225 trajectory end-points for St. Anicet and 4480 trajectory end points for Mingan have been used to create potential source area maps. This study identifies preferred potential sources of TGM at St. Anicet during wintertime with strongest probability stretching from the Gulf of Mexico to the southern tip of Greenland. This pattern mimics, the North American anthropogenic Hg emission inventory. Furthermore, some Eurasian mercury air mass intrusions are suggested at Mingan during wintertime. The summertime period at Mingan points out some potential sources stretching from the american mid-west to the St. Lawrence River valley as well as areas around the southern tip of the Hudson Bay.     

Transport patterns and potential sources of total gaseous mercury measured in Canadian high Arctic in 1995

Trajectory cluster analysis and the potential source contribution function (PSCF) model have been used to investigate the source–receptor relationship for the total gaseous mercury (TGM) measured in the Canadian High Arctic (Alert, 82.5°N, 62.3°W) during 1995. Cluster analysis of 10-day back-trajectories in 1995 shows that the synoptic flows arriving at Alert are dominated by the air masses from the north. Long-range transport only occurs in the cold seasons while summertime flows tend to circulate in the Arctic Ocean. The potential source regions identified by the PSCF modeling include Eurasia and populated areas in the North America and Europe. Based on the modeling results, it is suggested that the elevated TGM concentrations found in the Arctic summer should be of geological origins, mainly from the evasion of volatile Hg⁰ from earth's surfaces. In the autumn and winter, mercury is transported to the receptor site from remote anthropogenic sources. The preferred sources of TGM in the spring cannot be clearly determined due to the Arctic springtime mercury depletion, which significantly reduces the number of trajectories contributing to PSCF values. Using TGM data of higher temporal resolution improves the sensitivity of the PSCF modeling results.     

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.     

Trend,seasonal and multivariate analysis study of total gaseous mercury data from the Canadian atmospheric mercury measurement network (CAMNet)

Long-term monitoring data of total gaseous mercury (TGM) concentrations from the Canadian Atmospheric Mercury Measurement Network (CAMNet) were analysed for temporal trends, seasonality and comparability within the network and compared to other network and model results. Data collected from 11 Canadian measurement sites between 1995 and 2005 were analysed. Sites within CAMNet were characterized by principle component analysis (PCA) into four main categories. For the first time since automated TGM measurements have been made within CAMNet, this paper reveals statistically significant decreasing TGM concentrations from rural locations in Canada during this time period. The largest declines were observed close to the urban areas of Toronto and Montreal, where levels fell by 17% at Point Petre, and 13% at St. Anicet, respectively. Many of the TGM changes are comparable with the overall trends observed in total mercury concentrations in precipitation, for similar time periods, at co-located or nearby National Atmospheric Deposition programme's Mercury Deposition Network (NADP-MDN) sites. The results show that these changes are mostly driven by local or regional changes in mercury emissions. Other sites within CAMNet reflect reported changes in hemispherical global background concentrations of airborne mercury, where slight decreases or no statistically significant trend in TGM concentrations exist over the same time period.     

Atmospheric mercury monitoring survey in Beijing,China

With the aid of one industrial, two urban, two suburban, and two rural sampling locations, diurnal patterns of total gaseous mercury (TGM) were monitored in January, February and September of 1998 in Beijing, China. Monitoring was conducted in six (two urban, two suburban, one rural and the industrial sites) of the seven sampling sites during January and February (winter) and in four (two urban, one rural, and the industrial sites) of the sampling locations during September (summer) of 1998. In the three suburban sampling stations, mean TGM concentrations during the winter sampling period were 8.6, 10.7, and 6.2 ng/m3, respectively. In the two urban sampling locations mean TGM concentrations during winter and summer sampling periods were 24.7, 8.3, 10, and 12.7 ng/m3, respectively. In the suburban-industrial and the two rural sampling locations, mean mercury concentrations ranged from 3.1-5.3 ng/m3 in winter to 4.1-7.7 ng/m3 in summer sampling periods. In the Tiananmen Square (urban), and Shijingshan (suburban) sampling locations the mean TGM concentrations during the summer sampling period were higher than winter concentrations, which may have been caused by evaporation of soil-bound mercury in warm periods. Continuous meteorological data were available at one of the suburban sites, which allowed the observation of mercury concentration variations associated with some weather parameters. It was found that there was a moderate negative correlation between the wind speed and the TGM concentration at this suburban sampling location. It was also found that during the sampling period at the same site, the quantity of TGM transported to or from the sampling site was mainly influenced by the duration and frequency of wind occurrence from certain directions.     

Estimates of air-sea exchange of mercury in the Baltic Sea

The concentrations of total gaseous mercury (TGM) in air over the southern Baltic Sea and dissolved gaseous mercury (DGM) in the surface seawater were measured during summer and winter. The summer expedition was performed on 02–15 July 1997, and the winter expedition on 02–15 March 1998. Average TGM and DGM values obtained were 1.70 and 17.6 ng m⁻³ in the summer and 1.39 and 17.4 ng m⁻³ in the winter, respectively. Based on the TGM and DGM data, surface water saturation and air-water fluxes were calculated. The results indicate that the seawater was supersaturated with gaseous mercury during both seasons, with the highest values occurring in the summer. Flux estimates were made using the thin film gas-exchange model. The average Hg fluxes obtained for the summer and winter measurements were 38 and 20 ng m⁻² d⁻¹, respectively. The annual mercury flux from this area was estimated by a combination of the TGM and DGM data with monthly average water temperatures and wind velocities, resulting in an annual flux of 9.5 μg m⁻² yr⁻¹. This flux is of the same order of magnitude as the average wet deposition input of mercury in this area. This indicates that reemissions from the water surface need to be considered when making mass-balance estimates of mercury in the Baltic Sea as well as modelling calculations of long-range transboundary transport of mercury in northern Europe.     

Dynamics of mercury fluxes and their controlling factors in large Hg-polluted floodplain areas

Environmental pollution by mercury (Hg) is a considerable environmental problem world-wide. Due to the occurrence of Hg volatilization from their soils, floodplains can function as an important source of volatile Hg. Soil temperature and soil water content related to flood dynamics are considered as important factors affecting seasonal dynamics of total gaseous mercury (TGM) fluxes. We quantified seasonal variations of TGM fluxes and conducted a laboratory microcosm experiment to assess the effect of temperature and moisture on TGM fluxes in heavily polluted floodplain soils. Observed TGM emissions ranged from 10 to 850 ng m⁻² h⁻¹ and extremely exceeded the emissions of non-polluted sites. TGM emissions increased exponentially with raised air and soil temperatures in both field (R²: 0.49-0.70) and laboratory (R²: 0.99) experiments. Wet soil material showed higher TGM fluxes, whereas the role of soil water content was affected by sampling time during the microcosm experiments.     

Atmospheric mercury in the marine boundary layer along a cruise path from Shanghai,China to Prydz Bay,Antarctica

The total gaseous mercury (TGM) measurements were performed using an automatic Mercury Vapor Analyze (model 2537B) aboard the Chinese research vessel (R/V) XueLong during the 24th China Antarctic Research Expedition from Shanghai, China to Prydz Bay, Antarctica in 2007. TGM ranged between 0.302 and 4.496 ng m^?3 with an average of 1.536 ± 0.785 ng m^?3 over the entire period. Geographically, TGM in the Northern Hemisphere and the Southern Hemisphere along the cruise path were 1.746 ± 0.513 and 1.471 ± 0.842 ng m^?3 in average, respectively. Higher TGM concentrations were observed in the coastal regions outside the polar region due primarily to air masses transported from the adjacent mainland reflecting the contribution from anthropogenic sources. The pronounced episode was recorded when ship passed through Sunda straits, which should be ascribed to the volcano plume and/or biomass burning contamination. In the maritime Antarctic TGM level was in agreement with the values by land-based observation, presenting a diurnal cycle with the maximum around midday and minimum at night. Atmospheric mercury destruction events dominated by the oxidation of atmospheric Hg⁰ were apparently observed in this region.     

Characteristics of mercury exchange flux between soil and air in the heavily air-polluted area,eastern Guizhou,China

To investigate the characteristics of mercury exchange between soil and air in the heavily air-polluted area, total gaseous mercury (TGM) concentration in air and Hg exchange flux were measured in Wanshan Hg mining area (WMMA) in November, 2002 and July–August, 2004. The results showed that the average TGM concentrations in the ambient air (17.8–1101.8 ng m⁻³), average Hg emission flux (162–27827 ng m⁻² h⁻¹) and average Hg dry deposition flux (0–9434 ng m⁻² h⁻¹) in WMMA were 1–4 orders of magnitude higher than those in the background area. It is said that mercury-enriched soil is a significant Hg source of the atmosphere in WMMA. It was also found that widely distributed roasted cinnabar banks are net Hg sources of the atmosphere in WMMA. Relationships between mercury exchange flux and environmental parameters were investigated. The results indicated that the rate of mercury emission from soil could be accelerated by high total soil mercury concentration and solar irradiation. Whereas, highly elevated TGM concentrations in the ambient air can restrain Hg emission from soil and even lead to strongly atmospheric Hg deposition to soil surface. A great amount of gaseous mercury in the heavily polluted atmosphere may cycle between soil and air quickly and locally. Vegetation can inhibit mercury emission from soil and are important sinks of atmospheric mercury in heavily air-polluted area.     

Seasonal and diel variation of atmospheric mercury concentrations in the Reno (Nevada,USA) airshed

This paper describes total gaseous mercury (TGM) concentrations measured in Reno, Nevada from 2002 to 2005. The 3-year mean and median air Hg concentrations were 2.3 and 2.1 ng m⁻³, respectively. Mercury concentrations exhibited seasonality, with the highest concentrations in winter, and the lowest in summer and fall. A well-defined diel pattern in TGM concentration was observed, with maximum daily concentrations observed in the morning and minimum in the afternoon. A gradual increase of TGM concentration was observed in the evening and over night. The early morning increase in TGM was likely due to activation of local surface emission sources by rising solar irradiance and air temperature. The subsequent decline and afternoon minimum in TGM were likely related to increased vertical mixing and the buildup of atmospheric oxidants during the day resulting in increased conversion to oxidized species that are quickly deposited, coupled with weakening of the surface emissions processes. The described diel pattern was seasonally modulated with the greatest amplitude in variation of TGM concentrations occurring in the summer. It is suggested based on the comparison of diel TGM pattern with other gaseous pollutants that natural source surface emissions are a dominant source of TGM in the study area.     

Aerosol trace metals,particle morphology and total gaseous mercury in the atmosphere of Oxford,UK

An investigation of atmospheric trace metals was conducted in Oxford, UK, a small city ～60 miles northwest of London, in 2007 and 2008. Concentrations of Sr, Mo, Cd, Pb, V, Cr, Mn, Fe, Co, Ni, Cu and Zn in aerosol were measured in bulk and size segregated samples. In addition, total gaseous mercury (TGM) concentrations were monitored semi-continuously by cold vapour-atomic fluorescence spectroscopy. Metal concentrations in Oxford were intermediate between previously reported levels of UK rural and urban areas for most metals studied and levels of Cd, Ni and Pb were within European guidelines. Metal concentrations appeared to be influenced by higher traffic volume on a timescale of hours. The influence of traffic on the aerosols was also suggested by the observation of carbonaceous particles via scanning electron microscopy (SEM). Air mass back trajectories suggest air masses arriving in Oxford from London and mainland Europe contained the highest metal concentrations. Aerosol samples collected over Bonfire Weekend, a period of intense firework use and lighting of bonfires in the UK, showed metal concentrations 6–46 times higher than at other times. Strontium, a tracer of firework release, was present at higher concentrations and showed a change in its size distribution from the coarse to fine mode over Bonfire Weekend. The presence of an abundance of spherical Sr particles was also confirmed in SEM images. The average TGM concentration in Oxford was 3.17 ng m^?3 (st. dev. 1.59) with values recorded between 1.32 and 23.2 ng m^?3. This is a higher average value than reported from nearby rural locations, although during periods when air was arriving from the west, similar concentrations to these rural areas were seen in Oxford. Comparison to meteorological data suggests that TGM in Oxford's air is highest when wind is arriving from the east/southeast. This may be due to emissions from London/mainland Europe with a possible contribution from emissions from a local crematorium situated 4 miles east of the sampling site. A diurnal pattern was also observed in the TGM data with a minimum concentration during the day when mercury may have been diluted by thermal mixing of the atmospheric boundary layer. Additionally, this diurnal pattern may reflect variations in a local source of TGM.     

Simultaneous measurements of total gaseous mercury at four sites on a 800 km transect: spatial distribution and short-time variability of total gaseous mercury over central Europe

Over a distance of approximately 800 km simultaneous measurements of total gaseous mercury (TGM) were performed at four sampling sites between Stockholm and Berlin. The time resolution of mercury concentration measurements was 5 min. During the sampling period from 26 June to 7 July 1995, event sampling for precipitation was carried out using bulk samplers. In addition to the mercury data, the most common meteorological and air-quality parameters were determined. Comparing the TGM background concentrations at the four sites, a weak but statistically significant south-to-north declining TGM gradient was found. From the most southern sampling site to the northern most site median values of 1.93, 1.78, 1.53 and 1.54 ng m^-3 TGM were detected. Compared with the median TGM concentration observed at the two Swedish sites, the regional background concentration near Berlin was elevated by about 25%. Whereas the 0.5 h average TGM concentration varies at the Swedish sampling sites in a very narrow range of only 0.69 ng m^-3, a much broader range of 3.28 ng m^-3 was observed at the southern sites. The increased TGM variability near Berlin was characterised by a diurnal cycle with a distinct maximum in the early morning hours (about 4:00 a.m.) before sun rise. The short time variability of the TGM concentration measured at the four sites on the south-to-north transect shows regional differences. A decreasing variability from the most southern to the most northern site became evident.     

Methylated mercury species in municipal waste landfill gas sampled in Florida,USA

Mercury-bearing material has been placed in municipal landfills from a wide array of sources including fluorescent lights, batteries, electrical switches, thermometers, and general waste. Despite its known volatility, persistence, and toxicity in the environment, the fate of mercury in landfills has not been widely studied. The nature of landfills designed to reduce waste through generation of methane by anaerobic bacteria suggests the possibility that these systems might also serve as bioreactors for the production of methylated mercury compounds. The toxicity of such species mandates the need to determine if they are emitted in municipal landfill gas (LFG). In a previous study, we had measured levels of total gaseous mercury (TGM) in LFG in the μg/m³ range in two Florida landfills, and elevated levels of monomethyl mercury (MMM) were identified in LFG condensate, suggesting the possible existence of gaseous organic Hg compounds in LFG. In the current study, we measured TGM, Hg⁰, and methylated mercury compounds directly in LFG from another Florida landfill. Again, TGM was in the μg/m³ range, MMM was found in condensate, and this time we positively identified dimethyl mercury (DMM) in the LGF in the ng/m³ range. These results identify landfills as a possible anthropogenic source of DMM emissions to air, and may help explain the reports of MMM in continental rainfall.     

Biomonitoring of airborne mercury with perennial ryegrass cultures

A biomonitoring network with grass cultures was established near a chlor-alkali plant and the mercury concentration in the cultures were compared with the average atmospheric total gaseous mercury (TGM). Biomonitoring techniques based on different exposure periods were carried out. When comparing the mercury concentration in the grass cultures, both the average atmospheric TGM concentration during exposure and the exposure time determined to a large extent the accumulation rate of TGM. The maximum tolerable level of mercury in grass (approximately equal to 110 microg kg(-1) DM) corresponds with an average TGM concentration of 11 ng m(-3) for 28 days exposure. The background concentrations in grass were on an average 15 microg kg(-1) DM and the effect detection limit (EDL) was 30 microg kg(-1) DM. This value corresponds with an average TGM concentration of 3.2 and 4.2 ng m(-3) for 28 and 14 days exposure, respectively, which is in turn the biological detection limit (BDL) of ambient TGM. Exposures for 7 days were less appropriate for biomonitoring.     

Trends in air concentration and deposition of mercury in the coastal environment of the North Sea Area

An evaluation of mercury observations from North Sea coastal stations during 1995–2002 has been performed. The mercury data originate from EMEP/OSPAR stations in Ireland, Netherlands, Germany, Norway and Sweden where mercury in precipitation and Total Gaseous Mercury (TGM) have been measured. A decreasing trend in mercury wet deposition is observed. The decrease is sufficiently large to be significant considering measurement precision and appears to occur at all the studied sites. The reduction in deposition is 10–30% when comparing the two periods 1995–1998 and 1999–2002. The trend is likely to be due to emission controls in Europe. In contrast, no decreasing trend in TGM could be observed during the same time periods. A plausible explanation is that the TGM concentration measured in the OSPAR area to a larger extent than before is dominated by the hemispherical background concentration of TGM.     

Characteristics of total gaseous mercury concentrations at a coastal area of the Yangtze Delta,China

In this study, we report on total gaseous mercury (TGM) field observations made in the rural area of Shanghai, Chongming Island, China, from September 2009 to April 2012. The average TGM was 2.65 ± 1.73 ng m^?3 in Chongming Island, which is higher than the TGM background value of the Northern Hemisphere (1.5–1.7 ng m^?3); this indicates that to some extent, the Chongming area has been affected by anthropogenic mercury emissions. The observed TGM follows a seasonal pattern; concentrations are highest in winter, followed by autumn, summer, and spring. There is also a clear diurnal variation in TGM. All peak values appear between 7:00 and 9:00 in all four seasons; this appears to be the result of the height change in the atmospheric boundary layer that occurs between day and night. TGM concentrations in Chongming remain high in the westerly wind direction, especially in the southwest direction because of its low frequency, so the greatest source contribution to TGM in Chongming lies to the northwest. Wind speed is also a significant factor affecting TGM, and was negatively correlated with TGM concentrations. TGM is also closely related to carbon monoxide (CO) concentrations, indicating that TGM is impacted by human activities. The slope of the linear fitting of TGM and CO demonstrates that the contribution of noncoal source emissions to TGM in summer is greater than in autumn, mainly because the high temperature and intensive sunlight in summer increase mercury emissions from natural sources.

Implications: Except for some studies in the coastal areas (e.g., Kang Hwa Island by Kim et al., 2006, An–Myun Island by Kim et al., 2002, and Okinawa by Chan et al., 2008), data specifically for coastal areas are lacking. Monitoring of total gaseous mercury (TGM) in the rural area of Shanghai, Chongming Island, can help us understand mercury distribution.