Reactive Gaseous Mercury Concentrations Research Articles

Gas-particle partitioning of atmospheric reactive mercury and its contribution to particle bound mercury in a coastal city of the Yangtze River Delta, China

Abstract Speciated atmospheric mercury including reactive gaseous mercury (RGM), particle bound mercury (PBM), and gaseous elemental mercury (GEM) were measured for a two-year period in Ningbo city, the Yangtze River Delta, China. Averaged concentrations of PBM and RGM were 316 ± 377 pg m−3 and 100 ± 123 pg m−3, respectively, with the highest RGM/PBM ratio in summer (0.73 ± 1.31) and the lowest in winter (0.35 ± 0.56). The relationship between RGM/PBM ratio and PM2.5 was nonlinear. When PM2.5 fell in the range of 15–100 μg m−3, the PBM increased, the RGM decreased, and the RGM/PBM ratio showed an obvious decreasing trend as PM2.5 increased. An empirical linear relationship between log(1/Kp) and 1/T was obtained for different seasons. The correlation coefficient and slope of the equation were highest in winter, suggesting that T explained more for Kp variation and RM transferred quickly to the particle phase in the cold season. The relationships between Kp and aerosol compositions show that Kp increased with increasing fractions of Organics (Org), nitrate (NO3), and chloride (Chl) and decreasing fractions of sulfate (SO4) and ammonium (NH4) in aerosols. Principle component analysis - multiple linear regression (PCA-MLR) was used to evaluate the relative contributions of gas-particle partitioning of RM and sectional primary emissions to PBM in different seasons. The results show that the contributions of RM partitioning to PBM were 28.0% in spring, 28.3% in summer, 31.2% in autumn, and 39.2% in winter, which was well explained by the seasonal variations of temperature and aerosol compositions.

Speciated atmospheric mercury and sea–air exchange of gaseous mercury in the South China Sea

Abstract. The characteristics of the reactive gaseous mercury (RGM) and particulate mercury (HgP) in the marine boundary layer (MBL) are poorly understood, due in part to sparse data from the sea and ocean. Gaseous elemental Hg (GEM), RGM, and size-fractionated HgP in the marine atmosphere, and dissolved gaseous Hg (DGM) in surface seawater, were determined in the South China Sea (SCS) during an oceanographic expedition (3–28 September 2015). The mean concentrations of GEM, RGM, and Hg2.5P were 1.52±0.32 ng m−3, 6.1±5.8 pg m−3, and 3.2±1.8 pg m−3, respectively. A low GEM level indicated that the SCS suffered less influence from fresh emissions, which could be due to the majority of air masses coming from the open oceans, as modeled by back trajectories. Atmospheric reactive Hg (RGM + Hg2.5P) represented less than 1 % of total atmospheric Hg, indicating that atmospheric Hg existed mainly as GEM in the MBL. The GEM and RGM concentrations in the northern SCS (1.73±0.40 ng m−3 and 7.1±1.4 pg m−3, respectively) were significantly higher than those in the western SCS (1.41±0.26 ng m−3 and 3.8±0.7 pg m−3), and the Hg2.5P and Hg10P levels (8.3 and 24.4 pg m−3) in the Pearl River estuary (PRE) were 0.5–6.0 times higher than those in the open waters of the SCS, suggesting that the PRE was polluted to some extent. The size distribution of HgP in PM10 was observed to be three-modal, with peaks around < 0.4, 0.7–1.1, and 5.8–9.0 µm, respectively, but the coarse modal was the dominant size, especially in the open SCS. There was no significant diurnal pattern of GEM and Hg2.5P, but we found that the mean RGM concentration was significantly higher in daytime (8.0±5.5 pg m−3) than in nighttime (2.2±2.7 pg m−3), mainly due to the influence of solar radiation. In the northern SCS, the DGM concentrations in the nearshore area (40–55 pg L−1) were about twice as high as those in the open sea, but this pattern was not significant in the western SCS. The sea–air exchange fluxes of Hg0 in the SCS varied from 0.40 to 12.71 ng m−2 h−1 with a mean value of 4.99±3.32 ng m−2 h−1. The annual emission flux of Hg0 from the SCS to the atmosphere was estimated to be 159.6 t yr−1, accounting for about 5.54 % of the global Hg0 oceanic evasion, although the SCS only represents 1.0 % of the global ocean area. Additionally, the annual dry deposition flux of atmospheric reactive Hg represented more than 18 % of the annual evasion flux of Hg0, and therefore the dry deposition of atmospheric reactive Hg was an important pathway for the input of atmospheric Hg to the SCS.

Concentrations and gas-particle partitioning of atmospheric reactive mercury at an urban site in Beijing, China

Measurements of speciated atmospheric mercury play a key role in identifying mercury behavior in the atmosphere. In this study, we measured speciated atmospheric mercury, including gaseous elemental mercury (GEM), reactive gaseous mercury (RGM), and particulate bound mercury (PBM) (<2.5 μm), in 2015 and 2016 at an urban site in Beijing, China. The mean concentrations of GEM, RGM, and PBM were 4.70 ± 3.53 ng m−3, 18.47 ± 22.27 pg m−3, and 85.18 ± 95.34 pg m−3, respectively. The concentration of PM2.5 significantly affected the distribution of reactive mercury between the gaseous and particulate phases. With the raising of PM2.5 levels, PBM concentrations increased, on the contrary, the concentrations of RGM decreased gradually. The mean concentration of PBM during air-pollution events was more than three times that during clear days. During days with air pollution, the relative humidity significantly affected the gas-particle partitioning of reactive mercury. The linear relationships between gas-particle partitioning coefficient and meteorological factors (air temperature and relative humidity) were obtained over the four seasons. The data also showed that the gas-particle partitioning coefficient of reactive mercury was related to particle composition (e.g., Cl−, BC). The data present in this paper suggested the influence of anthropogenic emissions on reactive mercury in Beijing urban. And the findings will contribute to understand the gas-particle partitioning of reactive mercury and its influencing factors with complex urban pollution.

Seasonal variations of ambient air mercury species nearby an airport

This study focuses on the collection of ambient air mercury species (total gaseous mercury (TGM), reactive gaseous mercury (RGM), gaseous element mercury (GEM) and particulate bound mercury (PBM) pollutants at airport nearby sampling site during the year of Apr. 2016 to Mar. 2017 by using Four-stage gold amalgamation and denuder. The results indicated that the average TGM, RGM and GEM concentrations were 5.04±2.43ng/m3, 29.58±80.54pg/m3, 4.70±2.63ng/m3, respectively during the year of Apr. 2016 to Mar. 2017 (n=49) period at this airport sampling site nearby. In addition, the results also indicated that the average PBM concentrations in TSP and PM2.5 were 0.35±0.08ng/m3 and 0.09±0.03ng/m3, respectively. And the average PBM in TSP concentrations order follows as summer>autumn>spring>winter, while the average PBM in PM2.5 concentrations order follows as spring>summer>winter>autumn. Moreover, the average TGM, RGM and GEM concentrations order follow as spring>summer>autumn>winter. Finally, the Asian continent has the highest average mercury species concentrations (TGM, RGM, GEM and PBM) when compared with the American and European continents, and the average mercury species concentrations (TGM, RGM, GEM and PBM) displayed declined trends for North America (United States and Canada) and Europe (Spain, Sweden and Southern Baltic) during the years of 2004–2014. Also noteworthy is that the average mercury species concentrations (TGM, RGM, GEM) displayed increasing trends in China and Taiwan during the years of 2008–2016. Japan and Korea are the only two exceptions. Those above two countries mercury species concentrations displayed decreasing trends during years of 2008–2015.

Characteristics and Sources of Speciated Atmospheric Mercury at a Coastal Site in the East China Sea Region

ABSTRACTAtmospheric mercury is a global concern due to its ability of long-range transport. In order to understand the characteristics and sources of speciated mercury in the East China Sea region, a coastal monitoring site was established on Chongming Island in Shanghai, China. Total gaseous mercury (TGM), reactive gaseous mercury (RGM) and particulate-bound mercury (PHg) were monitored during 2009–2012. The overall average TGM, RGM and PHg concentrations were 2.65 ± 1.73 ng m–3, 8.0 ± 8.8 pg m–3 and 21.5 ± 25.4 pg m–3, respectively. TGM has a sharp increase at 5:00 in the morning and reaches peak at about 8:00, which is probably caused by the downward mixing of enhanced TGM aloft originated from regional sources. Wind roses suggest that urban Shanghai area has a considerable contribution to TGM in Chongming. Repartitioning of reactive mercury from particles to the air under the influence of air temperature could be one major source of RGM. Four heavy mercury pollution episodes were selected for source analysis. Mercury pollution in the summer event is mainly from the southwest direction with high ∆TGM/∆CO ratio and has the most influence on the North China Plain (NCP) region. The winter event is mainly under the influence of industrial pollution from the NCP region. The autumn event is contributed by both industrial pollution and biomass burning in North and Northeast China exhibiting a lower slope of ∆PHg/∆TGM. Springtime Asian long-range transport (ALRT) is crucial to the mercury background of North America. However, in the spring event identified in this study the mercury outflow from low altitude through East China mostly ascended to high altitude during the transpacific airmass transport. This provides an important incentive for future studies to focus on the way of mercury outflow from East Asia.

Characteristics of Speciated Atmospheric Mercury in Chongming Island, Shanghai

Continuous monitoring of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate mercury (PBM) was conducted in the Dongtan wetland park in Chongming Island, Shanghai from March 2014 to February 2015. The average concentrations of GEM, RGM, and PBM were (2.75±1.13) ng·m-3, (13.39±15.95) pg·m-3, and (21.89±40.42) pg·m-3, respectively, higher than the background concentrations of Northern Hemisphere. The atmospheric mercury showed obvious seasonal variations, with the highest seasonal average GEM concentration in summer (3.65 ng·m-3), which was mainly influenced by natural sources, while lower GEM concentrations appeared in autumn and winter influenced mainly by anthropogenic sources. The concentration of RGM was highest in spring and lowest in winter, mainly influenced by the wind direction, while PBM showed higher concentrations in autumn and winter, when heavy fine particulate pollution episodes occurred frequently. The concentrations of GEM and PBM were generally elevated in nighttime and lower in daytime caused by the mixing condition of the air masses. Most of the high RGM concentration values occurred in the afternoon of all seasons due to the higher atmospheric oxidation. The concentrations of GEM and PBM were higher in the west wind due to the emission from anthropogenic sources in Shanghai, Jiangsu, etc. The RGM concentration in southeast wind was obviously higher than those in other wind directions. The RGM was mainly from the anthropogenic sources, and the smaller wind in the southeast direction was against the dispersion of RGM.

Speciated atmospheric mercury in the marine boundary layer of the Bohai Sea and Yellow Sea

The objectives of this study are to identify the spatial and temporal distributions of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM), and fine particulate mercury (HgP2.5) in the marine boundary layer (MBL) of the Bohai Sea (BS) and Yellow Sea (YS), and to investigate the relationships between mercury species and meteorological parameters. The mean concentrations of GEM, RGM, and HgP2.5 were 2.03 ng m−3, 2.5 pg m−3, and 8.2 pg m−3 in spring, and 2.09 ng m−3, 4.3 pg m−3, and 8.3 pg m−3 in fall. Reactive mercury (RGM + HgP2.5) represented < 1% of total atmospheric mercury (GEM + RGM + HgP2.5), which indicated that most mercury export in the MBL was GEM and the direct outflow of reactive mercury was very small. Moreover, GEM concentrations over the BS were generally higher than those over the YS both in spring and fall. Although RGM showed a homogeneous distribution over the BS and YS both in spring and fall, the mean RGM concentration in fall was significantly higher than that in spring. In contrast, the spatial distribution of HgP2.5 generally reflected a gradient with high levels near the coast of China and low levels in the open sea, suggesting the significant atmospheric mercury outflow from China. Interestingly, the mean RGM concentrations during daytime were significantly higher than those during nighttime both in spring and fall, while the opposite results were observed for HgP2.5. Additionally, RGM positively correlates with air temperature while negatively correlates with relative humidity. In conclusion, the elevated atmospheric mercury levels in the BS and YS compared to other open seas suggested that the human activities had a significant influence on the oceanic mercury cycle downwind of China.

Observational Evidence for Involvement of Nitrate Radicals in Nighttime Oxidation of Mercury.

In the atmosphere, reactive forms of mercury species can be produced by oxidation of the dominant gaseous elemental mercury (GEM). The oxidation of GEM is an important driver for deposition, but oxidation pathways currently are poorly constrained and likely differ among regions. In this study, continuous measurements of atmospheric nitrate radical (NO3) concentrations and mercury speciation (i.e., elemental and reactive, oxidized forms) were performed during a six week period in the urban air shed of Jerusalem, Israel during summer 2012, to investigate the potential nighttime contribution of nitrate radicals to oxidized mercury formation. Average nighttime concentrations of reactive gaseous mercury (RGM) were almost equivalent to daytime levels (25 pg m(-3) and 27 pg m(-3) respectively), in contrast to early morning and evening RGM levels which dropped to low levels (9 and 13 pg m(-3)). During daytime, the presence of RGM was increased when solar radiation exceeded 200 W m(-2), suggesting a photochemical process for daytime RGM formation. Ozone concentrations were largely unrelated to daytime RGM. Nighttime RGM concentrations were relatively high (with a maximum of 97 pg m(-3)) compared to nighttime levels in other urban regions. A strong correlation was observed between nighttime RGM concentrations and nitrate radical concentration (R(2) averaging 0.47), while correlations to other variables were weak (e.g., RH; R(2) = 0.35) or absent (e.g., ozone, wind speed and direction, pollution tracers such as CO or SO2). Detailed analyses suggest that advection processes or tropospheric influences were unlikely to explain the strong nighttime correlations between NO3 and RGM, although these processes may contribute to these relationships. Our observations suggest that NO3 radicals may play a role in RGM formation, possibly due to a direct chemical involvement in GEM oxidation. Since physical data, however, suggest that NO3 unlikely initiates GEM oxidation, NO3 may play a secondary role in GEM oxidation through the addition to an unstable Hg(I) radical species.

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.

A 2-year record of atmospheric mercury species at a background Southern Hemisphere station on Amsterdam Island

Abstract. Although essential to fully understand the cycling of mercury at the global scale, mercury species records in the Southern Hemisphere are scarce. Under the framework of the Global Mercury Observation System (GMOS) project, a monitoring station has been set up on Amsterdam Island (37°48´ S, 77°34´ E) in the remote southern Indian Ocean. For the first time in the Southern Hemisphere, a 2-year record of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particle-bound mercury (PBM) is presented. GEM concentrations were remarkably steady (1.03 ± 0.08 ng m−3) while RGM and PBM concentrations were very low and exhibited a strong variability (mean: 0.34 pg m−3, range: &lt; detection limit–4.07 pg m−3; and mean: 0.67 pg m−3, range: &lt; detection limit–12.67 pg m−3, respectively). Despite the remoteness of the island, wind sector analysis, air mass back trajectories and the observation of radonic storms highlighted a long-range contribution from the southern African continent to the GEM and PBM budgets from July to September during the biomass burning season. Low concentrations of GEM were associated with southerly polar and marine air masses from the remote southern Indian Ocean. This unique data set provides new baseline GEM concentrations in the Southern Hemisphere midlatitudes while mercury speciation along with upcoming wet deposition data will help to improve our understanding of the mercury cycle in the marine boundary layer.

Atmospheric mercury speciation and mercury in snow over time at Alert, Canada

Abstract. Ten years of atmospheric mercury speciation data and 14 years of mercury in snow data from Alert, Nunavut, Canada, are examined. The speciation data, collected from 2002 to 2011, includes gaseous elemental mercury (GEM), particulate mercury (PHg) and reactive gaseous mercury (RGM). During the winter-spring period of atmospheric mercury depletion events (AMDEs), when GEM is close to being completely depleted from the air, the concentration of both PHg and RGM rise significantly. During this period, the median concentrations for PHg is 28.2 pgm−3 and RGM is 23.9 pgm−3, from March to June, in comparison to the annual median concentrations of 11.3 and 3.2 pgm−3 for PHg and RGM, respectively. In each of the ten years of sampling, the concentration of PHg increases steadily from January through March and is higher than the concentration of RGM. This pattern begins to change in April when the levels of PHg peak and RGM begin to increase. In May, the high PHg and low RGM concentration regime observed in the early spring undergoes a transition to a regime with higher RGM and much lower PHg concentrations. The higher RGM concentration continues into June. The transition is driven by the atmospheric conditions of air temperature and particle availability. Firstly, a high ratio of the concentrations of PHg to RGM is reported at low temperatures which suggests that oxidized gaseous mercury partitions to available particles to form PHg. Prior to the transition, the median air temperature is −24.8 °C and after the transition the median air temperature is −5.8 °C. Secondly, the high PHg concentrations occur in the spring when high particle concentrations are present. The high particle concentrations are principally due to Arctic haze and sea salts. In the snow, the concentrations of mercury peak in May for all years. Springtime deposition of total mercury to the snow at Alert peaks in May when atmospheric conditions favour higher levels of RGM. Therefore, the conditions in the atmosphere directly impact when the highest amount of mercury will be deposited to the snow during the Arctic spring.

Atmospheric mercury concentration and chemical speciation at a rural site in Beijing, China: implications of mercury emission sources

Abstract. Continuous measurements of atmospheric mercury concentration and speciation play a key role in identifying mercury sources and its behavior in the atmosphere. In this study, speciated atmospheric mercury including gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particle-bound mercury (PBM) were continuously measured at Miyun, a rural site in Beijing, China, from December 2008 to November 2009. The average GEM, RGM and PBM concentrations were found to be 3.22 ± 1.74, 10.1 ± 18.8 and 98.2 ± 112.7 pg m−3, respectively, about 2–20 times higher than the background concentration of the Northern Hemisphere. The results indicated that atmospheric mercury concentrations in northern China were highly affected by anthropogenic emissions. The atmospheric mercury showed obvious seasonal variations, with the highest seasonal average GEM concentration in summer (3.48 ng m−3) and the lowest value in winter (2.66 ng m−3). In autumn and winter a diurnal variation of GEM was observed, with peak levels in the late afternoon till midnight. Most of the high RGM concentration values occurred in the afternoon of all seasons due to the higher oxidation. The PBM concentration was higher in early morning of all seasons because of the the temperature inversion that increases in depth as the night proceeds. The ratio of GEM to CO indicates that residential boilers play an important role in the elevation of GEM in winter. The ratio of RGM to O3 could be an indicator of the contribution of local primary sources. The ratio of PBM to PM2.5 reveals that the air mass from the east and southwest of the site in spring and summer carries more atmospheric mercury. The HYSPLIT back-trajectory analysis indicated that the monitoring site is affected by local, regional and interregional sources simultaneously during heavy pollution episodes. The results from the potential source contribution function (PSCF) model indicate that the atmospheric transport predominantly from the northwest contributes to the elevated atmospheric mercury in winter and autumn, while the North China Plain (NCP) region and the northern part of the Yangtze River Delta (YRD) region are the major source areas for mercury pollution in spring and summer.

Atmospheric mercury over sea ice during the OASIS-2009 campaign

Abstract. Measurements of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate mercury (PHg) were collected on the Beaufort Sea ice near Barrow, Alaska, in March 2009 as part of the Ocean-Atmosphere-Sea Ice-Snowpack (OASIS) and OASIS-Canada International Polar Year programmes. These results represent the first atmospheric mercury speciation measurements collected on the sea ice. Concentrations of PHg averaged 393.5 pg m−3 (range 47.1–900.1 pg m−3) and RGM concentrations averaged 30.1 pg m−3 (range 3.5–105.4 pg m−3) during the two-week-long study. The mean concentration of GEM during the study was 0.59 ng m−3 (range 0.01–1.51 ng m−3) and was depleted compared to annual Arctic ambient boundary layer concentrations. It is shown that when ozone (O3) and bromine oxide (BrO) chemistry were active there is a positive linear relationship between GEM and O3, a negative one between PHg and O3, a positive correlation between RGM and BrO, and none between RGM and O3. For the first time, GEM was measured simultaneously over the tundra and the sea ice. The results show a significant difference in the magnitude of the emission of GEM from the two locations, with significantly higher emission over the tundra. Elevated chloride levels in snow over sea ice are proposed to be the cause of lower GEM emissions over the sea ice because chloride has been shown to suppress photoreduction processes of RGM to GEM in snow. Since the snowpack on sea ice retains more mercury than inland snow, current models of the Arctic mercury cycle may greatly underestimate atmospheric deposition fluxes because they are based predominantly on land-based measurements. Land-based measurements of atmospheric mercury deposition may also underestimate the impacts of sea ice changes on the mercury cycle in the Arctic. The predicted changes in sea ice conditions and a more saline future snowpack in the Arctic could enhance retention of atmospherically deposited mercury and increase the amount of mercury entering the Arctic Ocean and coastal ecosystems.

Oxidation of elemental Hg in anthropogenic and marine airmasses

Abstract. Mercury (Hg) is a neurotoxin that bioaccumulates in the food chain. Mercury is emitted to the atmosphere primarily in its elemental form, which has a long lifetime allowing global transport. It is known that atmospheric oxidation of gaseous elemental mercury (GEM) generates reactive gaseous mercury (RGM) which plays an important role in the atmospheric mercury cycle by enhancing the rate of mercury deposition to ecosystems. However, the primary GEM oxidants, and the chemical composition of RGM are poorly known. Using speciated mercury measurements conducted at the Mt. Bachelor Observatory since 2005 we present two previously unidentified sources of RGM to the free troposphere (FT). Firstly, we observed elevated RGM concentrations, large RGM/GEM-ratios, and anti-correlation between RGM and GEM during Asian long-rang transport events, demonstrating that RGM is formed from GEM by in-situ oxidation in some anthropogenic pollution plumes in the FT. During the Asian pollution events the measured RGM/GEM-enhancement ratios reached peak values, up to ~0.20, which are significantly larger than ratios typically measured (RGM/GEM &lt; 0.03) in the Asian source region. Secondly, we observed very high RGM levels – the highest reported in the FT – in clean air masses that were processed upwind of Mt. Bachelor Observatory over the Pacific Ocean. The high RGM concentrations (up to 700 pg m−3), high RGM/GEM-ratios (up to 1), and very low ozone levels during these events provide observational evidence indicating significant GEM oxidation in the lower FT in some conditions.

Mercury Studies around the Mediterranean Sea Basin: Ten years of Measurements and Modeling results

Only a few years ago the presence of Reactive Gaseous Mercury (RGM) was believed to be almost exclusively the result of anthropogenic emissions and that sustained high RGM concentrations in the MBL were not considered likely. During the past ten years, an in-depth investigation was carried out in the Marine Boundary Layer (MBL) of the Mediterranean Sea to quantify and possibly explain spatial and temporal patterns of Hg-species concentrations. This paper provides an overview of modeling results and atmospheric measurements performed during several cruise campaigns performed aboard the Research Vessel (RV) URANIA of the CNR over the Mediterranean sea basin. RGM concentrations have been modelled using a photochemical box model of the MBL and compared to measured data obtained during the research cruises. The comparison results supports the hypothesis that there are daytime mercury oxidation reactions occurring which have not yet been identified. Major findings of key studies carried out during ten years of ship-borne activities have been highlighted.

A comparison of data quality control protocols for atmospheric mercury speciation measurements

Significant advances in the measurement of atmospheric mercury species have been made in the past 10 years yet limited protocols on quality control (QC) and assurance on this data have been published in the literature. Recently, considerable work has been done to develop quality control and assurance programs within North America. Environment Canada and the National Atmospheric Deposition Network (NADP) independently developed programs, RDMQ™ and AMQC, respectively, to QC atmospheric mercury speciation data (including gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and mercury associated to particles (PHg)). These 2 programs were assessed by the criteria on which the data is QCed and comparability of the final data products. Results show that the criteria used to flag data compare well within the 4 tested sites and that the number of flags for each criterion is generally comparable. The QC programs were applied to 2 distinct data sets and the final QCed data was compared. From a mid-latitude site, the final data sets compare very well and showed there to be a 0.3, 8.6 and 15% difference in the mean GEM, RGM and PHg concentrations post QC of each program. It is recommended that either the RDMQ or the AMQC programs be employed for a typical mid-latitude site. When the QC programs were applied to highly variable data, the data do not compare as well for RGM and PHg. Results showed a 2.7, 27 and 33% difference in the mean GEM, RGM and PHg concentrations, respectively, post QC of each program. It is recommended that RDMQ be used for data that is highly variable with high RGM/PHg concentrations as it allows for more manual correction over the QCed data. This investigation of 2 QC programs produced comparable data and that either of these programs can be used as standard methods for the quality control of atmospheric mercury speciation data.

Natural and anthropogenic atmospheric mercury in the European Arctic: a fractionation study

Abstract. Gaseous elemental mercury (GEM) is converted to reactive gaseous mercury (RGM) during springtime Atmospheric Mercury Depletion Events (AMDE). This study reports the longest time series of GEM, RGM and particle-bound mercury (PHg) concentrations from a European Arctic site. From 27 April 2007 until 31 December 2008 composite GEM, RGM and PHg measurements were conducted in Ny-Ålesund (78° 54′ N, 11° 53′ E). The average concentrations of the complete dataset were 1.6 ± 0.3 ng m−3, 8 ± 13 pg m−3 and 8 ± 25 pg m−3 for GEM, RGM and PHg, respectively. For the complete dataset the atmospheric mercury distribution was 99 % GEM, whereas RGM and PHg constituted &lt;1 %. The study revealed a seasonal distribution of GEM, RGM and PHg previously undiscovered in the Arctic. Increased concentrations of RGM were observed during the insolation period from March through August, while increased PHg concentrations occurred almost exclusively during the spring AMDE period in March and April. The elevated RGM concentrations suggest that atmospheric RGM deposition also occurs during the polar summer. RGM was suggested as the precursor for the PHg existence, but long range transportation of PHg has to be taken into consideration. Still there remain gaps in the knowledge of how RGM and PHg are related in the environment. RGM and PHg accounted for on average about 10 % of the depleted GEM during AMDEs. Although speculative, the fairly low RGM and PHg concentrations supported by the predominance of PHg with respect to RGM and no clear meteorological regime associated with these AMDEs would all suggest the events to be of non-local origin. With some exceptions, no clear meteorological regime was associated with the GEM, RGM and PHg concentrations throughout the year.

Mercury wet deposition in rural Korea: concentrations and fluxes

The characteristics of Hg wet deposition were investigated in a rural area of Korea from August 2006 to July 2008. The volume weighted mean (VWM) Hg(T) concentration and cumulative Hg(T) flux were 8.8 ng L(-1) and 9.4 μg m(-2) per year, respectively. The VWM Hg(T) concentration varied seasonally, similar to the seasonal pattern in atmospheric Hg(p) concentration. The enhancement of both VWM Hg(T) and atmospheric Hg(p) concentrations in spring and winter was likely caused by the long-range transport of Hg from China. Monthly VWM Hg(T) and atmospheric Hg(p) concentrations were well correlated (R(2) = 0.36); however, there was no correlation between VWM Hg(T) and RGM (reactive gaseous mercury) concentrations, suggesting that Hg(p) was responsible for the majority of the Hg in wet deposition at this site. The VWM Hg(T) concentration in snow was statistically higher than in rain. In addition, the atmospheric Hg(p) concentration appeared to be elevated for snow events as well. This suggests that both elevated Hg(p) concentrations and the enhanced scavenging efficiency of snow for Hg(p) were responsible for the elevated VWM Hg(T) concentrations measured during snow events.

Ambient Mercury Sources in Rochester, NY: Results from Principle Components Analysis (PCA) of Mercury Monitoring Network Data

Continuous atmospheric measurements of speciated mercury (Hg) (elemental mercury (Hg⁰), reactive gaseous mercury (RGM), and particulate mercury (Hgp)) were made in Rochester, NY from Dec 2007 to May 2009. Continuous measurements of ozone (O₃), sulfur dioxide (SO₂), carbonmonoxide (CO), particulate matter (PM₂.₅), and meteorological data were also available. A principle components analysis (PCA) of 3886 observations of 13 variables for the period identified six major factors. Melting snow was observed to be a source of Hg⁰in winters. Positive correlations between RGM and O₃ in the spring and summer may be indicative of Hg⁰ oxidation. RGM concentrations increased simultaneously with SO₂ suggesting the influence of coal fired power plants (CFPP). The fifth factor (F5) containing O₃ (high negative loading), CO (positive loading), Hg⁰ and Hg(p) (positive), and/or RGM (negative) was identified as a mobile source which was usually observed during morning rush hours (6:00-9:00 a.m.). The concentrations of the three mercury species from the direction of the CFPP were significantly reduced following the shutdown of this source.

Global Concentrations of Gaseous Elemental Mercury and Reactive Gaseous Mercury in the Marine Boundary Layer

Gaseous elemental mercury (GEM) and reactive gaseous mercury (RGM) were measured during an eight month circumnavigation to obtain knowledge of their worldwide distributions in the marine boundary layer (MBL). Background GEM concentrations were found to be 1.32 ± 0.2 ng/m(3) (summer) and 2.62 ± 0.4 ng/m(3) (spring) in the northern hemisphere and 1.27 ± 0.2 ng/m(3) (spring and summer) in the southern hemisphere. Radiation and relative humidity are shown to control diurnal cycles of RGM. During the cruise the ship passed areas of clean MBL air, air influenced by biomass burning (South Atlantic) and air with high concentrations of GEM and RGM of unknown origin (Antarctic). High GEM concentrations above the Atlantic indicate that emission from the ocean can be an important GEM source. Our data combined with data from earlier cruises provides adequate information to establish a seasonal cycle for the Atlantic. Results show a cycle similar to that found at Mace Head, Ireland but with larger amplitude. We have improved the basic knowledge of mean GEM and RGM concentrations in the MBL worldwide and shown how natural sources and reemissions can affect GEM concentrations in the MBL.