Long-term changes in concentration and deposition of atmospheric mercury over Scandinavia

Samples for measurements of total gaseous mercury (Hg) in air have been collected since 1980 in south-western part of Scandinavia. A collection program for precipitation samples used to determine changes in depositional fluxes of total Hg has been in operation since 1987. A comparison of today's total gaseous Hg levels in air and the total Hg concentrations in precipitation with the ones found earlier, shows a clear decrease with time. At the Swedish west-coast, yearly average air concentrations and median levels of 3.3 and 3.1 (1980–1984), 3.2 and 2.8 (1985–1989), and 2.7 and 2.6 ng Hg/m³ (1990–1992), respectively, were found. Increased average and median winter concentrations were always found, with levels at 3.7 and 3.4, 3.7 and 3.3, and 3.0 and 2.7 ng Hg/m³ for the respective time period. Higher winter values were expected due to increased anthropogenic emissions and changes in the mixing height of the atmosphere. The corresponding total wet deposition rates decreased from 27 (1987–1989) to 10 μg Hg/m² yr. (1990–1992). A finding of special interest was the decreased number of episodic events of high total gaseous Hg levels in air, from 1990 and further on. In addition, the frequency distribution of the concentrations of Hg in air seems to be different for these years compared to the other two time periods. A frequency distribution of air concentrations of Hg more resembling a normal distribution was found for the years 1990 to 1992. The decrease of the atmospheric burden of total gaseous Hg and deposition of total Hg are most probably connected to lower emissions in source areas on the European continent. It seems logical to state that the problem of high Hg depositional fluxes to Scandinavia, is best solved by abatement strategies on the regional scale.     

Lidar measurements of atmospheric mercury

Mercury is the only atmospheric pollutant that is present in the atmosphere in atomic form. The optical resonance line at 254 nm can be used for absorption measurements using different optical remote sensing techniques. Range-resolved Hg mapping can be performed using the differential absorption lidar (DIAL) technique. We have used the lidar technique both for mapping of industrial plumes and for background concentration measurements. Our studies also include Hg of geophysical origin.     

An update of the mercury inventory and atmospheric mercury fluxes to and from Finland

Finland, the northern-most agricultural/industrial country in the world, has been for some time steadily improving environmental mercury (Hg) research. This paper focuses upon Hg recovery during zinc production, uses of Hg, updating of information on Hg emissions and atmospheric transport of Hg to and from Finland. The recovery of Hg as a by-product of zinc production began in 1970. The highest amount of recovered Hg was noted to be 160 t in 1989. Total uses of Hg in different sectors were about 7.4 t in 1992, which had decreased by 50% since the year 1987. In 1992, the estimated Hg emission to air was 2 t yr^?1, whereas to water and land the emission was about 0.20 and 3.67 t yr^?1, respectively. Natural Hg emission in Finland was estimated to be about 0.4 t yr^?1 (range: 0.3 to 0.5 t yr^?1). In addition, an initial attempt was made to estimate the atmospheric Hg flux to and from Finland; these values were noted to be 2.7 and 2.1 t yr^?1, respectively.     

International field intercomparison of atmospheric mercury measurement methods

To determine the extent of comparability of sampling and analytical procedures for atmospheric mercury (Hg) being used by different scientific groups around the world and hence the compatibility of measurement results, the Atmospheric Environment Service (AES) co-ordinated a field intercomparison study in Windsor, Ontario, over a period of 5 days- during Sept./Oct.,1993. This study brought together 2 groups (University of Michigan Air Quality Laboratory; Chemistry Institute of GKSS) which performed conventional (manual) sample collection procedures for total gaseous mercury (TGM) and for particulate-phase mercury (PPM), followed by cold-vapor atomic fluorescence spectrophotometric (CVAFS) analysis in the respective laboratories. Two other groups (Ontario Hydro, and the Ontario Ministry of Environment & Energy) each operated a novel mercury vapor analyzer produced by Tekran Inc. of Toronto. As is the case for the manual methods, this analyzer also uses gold amalgamation and CVAFS. During the intercomparison, meteorological parameters (air temperature, barometric pressure, wind speed/direction and relative humidity) were obtained at the study site.     

Linkages between atmospheric mercury deposition and the methylmercury content of marine fish

Enhanced Hg deposition to productive marine systems may result in concurrent increases in monomethyl Hg (MMHg) concentrations of marine fish. Consequently, it is important to understand what effects an increasing Hg supply may have on the marine food chain. A simple ocean model is employed to estimate the fraction of total Hg inputs which is required to sustain “average” marine fish MMHg concentrations annually. Calculations show that upwelling zones require 20% of total annual Hg inputs, coastal zones 5%, and open-ocean regions only 0.02%. The value for coastal areas is similar to that calculated for the acidified basin of Little Rock Lake, Wisconsin, a small fresh water seepage lake. These calculations point to Hg source strength and rates of particle scavenging as being key factors in controlling the rate of transport to sites of methylation (and subsequent entry into the marine food chain). If biological variables (scavenging rates, primary productivity) remain constant while anthropogenically-derived Hg deposition increases, it is likely that concentrations in marine biota (including fish) will rise in accord.     

Biomonitoring of atmospheric mercury in the vicinity of Kilauea,Hawaii

The release of mercury from volcanic eruptions on the Island of Hawaii has been well documented, but the dispersion characteristics have not previously been studied in detail. Samples of lichens were collected from around the island, and subsequent analysis showed levels ranging from < 8 to 59 µg Hg g^-1. The distribution of the accumulation of mercury clearly shows that there is a major input from the active eruption sites, but that this is significantly modified by variations in wind patterns. Superimposed on this regional distribution are two localised sites where the mercury accumulation is exceptionally high; this is attributed to the release of steam from the circulation of shallow ground waters.     

Multielement analysis and mercury speciation in atmospheric samples from the Toronto area

Inductively coupled plasma atomic emission spectrometry. (ICP-AES), graphite furnace atomic absorption (GFAAS) and gas chromatography with an atomic absorption detector (GC-AAS) were used for the analysis of atmospheric samples collected in the Toronto area of Southern Ontario. Airborne particulate matter and particulate and soluble fractions of snow were analyzed for S, Al, Fe, Ca, Mg, P, Pb, Zn, Cu, Cr, Cd, Ni, As, and Hg. Also, determinations of organic Hg compounds in filtered snow were performed. The element concentrations in airborne particulate matter from Toronto were similar in amount to those found in other major cities and were the highest in winter. Regional differences in the chemical composition of snow were shown to be related to industrial density. The majority of elements existed in the highest concentrations in the soluble fraction of snow, except for Al, Fe, and Pb, which were largely present in particulate matter. Differences in the distribution of elements in particulate matter in fresh and old snow were observed and depended on particle size and element. The results demonstrated the usefulness of snow as an indicator of atmospheric pollution.     

Fluxes,pools, and turnover of mercury in Swedish forest lakes

In boreal forest lakes, high Hg concentrations in fish are common, even in remote areas. In this paper, the effects of atmospheric Hg pollution in Sweden are synthesized and related to a concept based on the strong interaction of Hg with biogenic matter (Hg/B). Based on this concept, a compartment model is developed to predict concentrations, pool sizes, flux rates and turnover times of Hg along the biogeochemical cycle, including atmosphere, forest soils, surface runoff, lake waters, and aquatic biota. The aim is to provide a conceptual framework, both for a comprehensive mechanistic model, and for predictions from readily available information, such as regional data on acid deposition, air temperature and surface runoff, and local data on the trophic status of lakes with respect to humus and nutrient concentrations. The model is in good agreement with observations from recent Swedish field studies in all compartments. It suggests a strong influence of climate on the susceptibility of soil and lake ecosystems in the boreal region to Hg contamination. The high Hg concentrations in fish from forest lakes can be largely attributed to the low productivity of both terrestrial and aquatic biota. The impact of historical point sources of Hg is considered, as well as the slow turnover of Hg in forest soils, both resulting in elevated fish Hg levels in humic lakes for centuries following atmospheric deposition.     

Cycling of methyl mercury and mercury — Responses in the forest roof catchment to three years of decreased atmospheric deposition

Studies of the biogeochemistry of total mercury (Hg) and methyl mercury (MeHg) in the Lake Gårdsjön watershed have shown that the atmosphere is the most important source of Hg and MeHg in the ecosystem. Soils are accumulating most of the deposited Hg and MeHg, but transport of Hg and MeHg from the forested catchments into the lake ecosystems is enough to explain elevated concentrations of MeHg in fish in more than 10 000 Swedish lakes. An experimental roof was constructed to study effects of decreased atmospheric input on an entire forested catchment. The experiment started in April 1991, and decreases in the output of both MeHg and Hg occurred during 1991, 1992 and 1993. Runoff fluxes from the control catchment during the pre-treatment period were related to the experimental catchment using regression analyses. Since April 1991, after three year experiment, predicted compared to measured fluxes showed that Hg output decreased by 32% and MeHg by 28%. The decrease in Hg was most obvious during high water flows in winter/spring while MeHg decreased during all seasons of the year. The decreased input of Hg and MeHg to the Forest Roof Catchment is the most probable explanation to the rapid decrease in output of Hg and MeHg by runoff from the catchment basin.     

Is mercury increasing in the atmosphere? The need for an atmospheric mercury network (AMNET)

Mercury uses in human endeavors will lead to a general, though variable, volatilization of Hg. Current estimates for anthropogenic interferences range from about 50 to 75% of the total annual Hg emissions to the atmosphere. Recent modeling suggests that the present atmospheric Hg burden has increased by a factor of 3 during the last 100 years with a current rate of increase of about 0.6% yr^?1 (ca. 0.01ng m^?3yr^?1). This impact, which is significant, can be examined and assessed empirically. To date, however, atmospheric Hg programs have not employed an experimental design sufficient to account for short time scale atmospheric Hg variations of natural and anthropogenic origin, and to resolve the long term temporal pattern. I am proposing an international research program, AMNET, or Atmospheric Hg Network, to address the important question, “Is Hg increasing in the atmosphere?” AMNET would examine temporal and spatial variations in atmospheric Hg and assess the influence of natural and anthropogenic sources on the global atmospheric Hg cycle. This program requires international support and cooperation. The experimental design of AMNET would follow the successful Atmospheric Lifetime Experiment Program (ALE), which examined the contemporary temporal changes in the atmospheric concentrations of the freons, methyl chloroform, carbon tetrachloride, and nitrous oxide. Following the ALE design, AMNET sampling stations would be maintained in both hemispheres and at sites free from strong local pollution sources of Hg (e.g., remote islands). Measurements would be made for a period of three to five years. The precision and accuracy of the Hg⁰ determinations must be ≥ 1%. The accurate resolution of the variability and secular trends in the atmospheric Hg burden can provide: (1) a direct quantitative assessment of the scale to which anthropogenic processes are affecting the natural biogeochemical cycling of Hg; (2) an essential refinement and constraint currently lacking in mass balance models; (3) an enhanced knowledge of the behavior of Hg in the atmosphere, and (4) an accurate data base required for global circulation atmospheric chemical Hg models.     

Elevated atmospheric CO2 affects the turnover of nitrogen in a European grassland

The availability of nutrients in the soil is key to the potential response of a plant to elevated CO₂ and is central to correctly predicting the response of terrestrial communities to climate change. In order for a plant to fully realise the potential of increased atmospheric CO₂, it must increase its nutrient uptake for the increased production of biomass as well as biochemical compounds. In this study the stable isotope ¹⁵N was used to follow the fate of nitrogen contained in litter in order to determine the effect elevated atmospheric CO₂ had on the loss of nitrogen from decomposing litter and the eventual re-use of this nitrogen. During the decomposition study, on a mass basis more ¹⁵N was transferred from the litter despite the litter grown in elevated CO₂ initially having a lower ¹⁵N signal. This was primarily related to a higher decomposition rate of the elevated CO₂ grown litter. Despite more nitrogen entering the below-ground community under elevated atmospheric CO₂, the additional N did not stay within the terrestrial community and was not exploited by the plants. The results confirm previous suggestions that Lolium perenne plants growing in elevated CO₂ have to derive at least a proportion of their nitrogen from a source external to either added fertiliser or decomposing litter     

Pre-industrial atmospheric deposition of mercury: Uncertain rates from lake sediment and peat cores

Lacustrine sediment cores from depositional areas have frequently been used to estimate pre-industrial rates of atmospheric Hg deposition. However, this approach tends to result in overestimates, partly because of Hg inputs from the catchment, partly because of a horizontal redistribution of sediments within lakes. Peat core studies may suffer from a vertical migration of Hg due to water table fluctuations. A natural Hg deposition rate around 2 μg m^?2 y^?1 is suggested to be more realistic than values of 3 to 12 μg m^?2 y^?1 reported from recent studies. The anthropogenic impact on the present Hg deposition may have been underestimated accordingly.     

Development and intercalibration of methods in nordic freshwater fish monitoring

The awareness of the effects of transboundary pollution has increased the necessity to use comparable methods and to initiate joint studies between countries in environmental monitoring. In freshwater fish monitoring a number of different methods have been used, strongly reducing the possibilities to comparative assessments between countries. In 1990, a workshop on freshwater fish sampling was initiated in order to develop and intercalibrate methods used in freshwater fish studies in the Nordic countries. During a three year period, a new type of multi-mesh gillnet to be used for fish monitoring in Norway, Finland and Sweden have been developed. Comparative studies and gillnet-selectivity assessments show that these new multi-mesh gillnets better describe the actual population structure of European perch (Perca fluviatilis), roach (Rutilus rutilus) and Arctic char (Salvelinus alpinus) than do the traditional gillnet series used in the Nordic countries. Ageing of fish is central in most environmental studies, however, the comparability of analyses performed at different laboratories may be low. Comparative age analyses between the three countries have been performed for a number of fish species. The results of ageing E. perch, whitefish (Coregonus sp.) and roach indicate that differences between laboratories can be reduced by intercalibration. In the future, the workgroup will be focused on a further development of joint methods within studies of freshwater fish and on joint intemordic assessments on species distribution, abundance and life history characteristics in relation to airborne pollutants and liming.     

西北各省季节降水变化及其贡献的差异分析

利用中国西北地区124个气象台站1951?2015年逐日降水资料,通过计算各季节降水量及降水日数贡献率,解析西北五省（区）不同季节各等级降水量及降水日数贡献率差异,明确不同季节降水量和降水日数变化对年降水量和降水日数变化,以及同季节内不同等级降水量和降水日数变化对当季降水量和降水日数变化的作用,以探究西北地区降水的时空变化特征。结果表明：（1）1951-2015年,西北地区年降水日数以0.1d·10a-1（P＜0.01）的速率极显著减少,各站点年平均降水日数及线性变化趋势差异较大;（2）1951-2015年,西北地区年平均降水量以3.9mm·10a-1（P＜0.01）的速率极显著增加,变化显著区域主要分布在新疆及青海地区;（3）研究区域降水季节分布不均,主要集中在夏季,其中各省（区）夏季降水量贡献率在50%～63%,降水日数贡献率在35%～48%,春秋两季降水接近,冬季降水最少;各季节降水均以小雨和中雨为主,各省（区）两者降水日数累计贡献率均在90%以上,暴雨仅发生在夏季且降水日数贡献率低于1%,秋季各等级降水分布与春季基本一致;（4）夏、秋季节降水量和降水日数变化是年降水和降水日数变化的主要原因,小雨至中雨降水量和日数变化是导致季节总降水量和降水日数变化的最主要原因,而春、冬季降水在年降水、大雨至暴雨在当季（年）降水中不占优势,故其作用不明显。     

Computing atmospheric transport and deposition of heavy metals over Europe: Country budgets for 1985

The Heavy Metal Eulerian Transport (HMET) model has been used to calculate the exchange of As, Cd, Pb and Zn between European countries in 1985. The model was run separately for each emitter country and the computed deposition field was used to calculate the contribution of the emitter to each receptor country. The results of these computations are presented in the form of a country budget matrix for each metal. Accuracy of such computations is dependant on the size and linearity of the numerical method applied to the transport equation. Exchange of heavy metals due to atmospheric transport over Europe is significant. Approximately 30% to 90% of the heavy metals emitted from each country is deposited in other countries. The remaining mass is deposited in European seas, Atlantic Ocean and transported outside the model domain. The largest part of the emission from each country is deposited in the same country. The next largest fraction is transported to the nearest neighbors. The results indicate also a significant long range ransport of heavy metals to the Soviet Union. This is partly justified by the size and location of this receptor country, as well as, the prevailing meteorological conditions in Europe. However, this large transport to USSR is slightly overestimated due to some artificial properties of the numerical method applied to basic model equations. In addition to the country budget, export versus import and emission versus deposition of metals were analyzed for each country. The largest positive difference between export and import was found for Poland, German Federal Republic and Yugoslavia (As, Cd and Zn), and United Kingdom, Italy and Belgium (Pb). The Soviet Union and Czechoslovakia are the countries where import of all metals is significantly larger than export. When emission versus deposition of heavy metals is analyzed, the Soviet Union has much higher emissions than deposition of all metals compared to other European countries.     

Design and initial tests of a dynamic enclosure chamber for measurements of vapor-phase mercury fluxes over soils

In an effort to establish reliable methodologies for measuring fluxes of mercury (Hg) across the soil-air interface, we have developed a field flux chamber built with FEP Teflon. To evaluate our field flux chamber system, a series of laboratory and field tests were performed. The observations of relatively low chamber blanks and low blank-to-sample ratios for the FEP Teflon chamber suggest its potential in Hg flux investigations. Despite its potential, Hg exchange rate measurements using the field flux chamber method must be made with great caution since it can be subject to contamination problems associated with the selection of chamber materials.     

An Eulerian model for atmospheric transport of heavy metals over Europe: Model description and preliminary results

This paper presents the Heavy Metals Eulerian Transport (HMET) model and simulation results for Europe for 1985. The HMET model takes into account emission, atmospheric transport and deposition of As, Cd, Pb and Zn computed on the EMEP grid system. Meteorological inputs consist of the velocity field at 925 hPa, precipitation and mixing height. Velocity field and precipitation are updated every 6 hr during the model run. New values of mixing height are available every 24 hr. The dry deposition velocities for each metal are variable in space and depend on the particle distribution function for each particular metal. Wet deposition is proportional to the precipitation intensity for the previous 6 hr and a constant scavenging ratio. Model equations are solved by means of the positive definite pseudospectral method which provides accurate numerical solutions for the advection problem. Comparison of the model results with available observations for 1985 indicate a good agreement for Cd and Pb, sufficient egreement for As and serious underestimation for Zn. Since the number of available observations for heavy metals in Europe in 1985 is relatively small, the model results presented in this paper should be considered as preliminary. However, the HMET model performance in computing these results shows that it can be easily and efficiently used as an operational tool and is especially useful for estimating transboundary transport of heavy metals in Europe.     

Relationships between the atmospheric deposition of trace elements,major ions,and mercury in florida: The FAMS project (1992–1993)

A multiple chemical tracer approach was used in an effort to account for the atmospheric Hg deposition measured throughout Florida as part of the Florida Atmospheric Mercury (FAMS) Study. Samples of bulk deposition and wet-only deposition were analyzed for a suite of major ions and trace elements in addition to Hg. Significant correlations were found between three groups of elements: Al, Mn, and Fe; Ni, Cu, Zn, and Cd; and As, V, and Pb. However, Hg did not correlate strongly with any of the other chemical tracers. Annual bulk deposition fluxes are attributed to sea-salt aerosols (Na, Cl), the delivery of Saharan dust (Al and Fe), the supply of anthropogenic pollutant aerosols (V, Ni, Cu, Zn, As, Cd, Pb), acidic aerosols (nitrate and nss-sulfate), and an unidentified source for Hg.     

Wet deposition of mercury and ambient mercury concentrations at a site in the Lake Champlain basin

The “Great Waters” program, established in the 1990 Clean Air Act Amendments, mandated that atmospheric deposition of hazardous air pollutants to Lake Champlain (including Hg) be assessed. An assessment of the magnitude and seasonal variation of atmospheric Hg deposition in the Lake Champlain basin was initiated in December 1992 with one year of event precipitation collection, as well as collection of vapor and particle phase Hg in ambient air. Samples were collected at the Vermont Monitoring Cooperative air monitoring site at the Proctor Maple Research Center in Underhill Center, VT. The average volume-weighted concentration for Hg in precipitation was 8.3 ng/L for the sampling year and the average amount of Hg deposited with each precipitation event was 0.069 μg/m². The total amount of Hg deposited through precipitation during 1993 was 9.26 μg/m²/yr. A seasonal pattern for Hg in precipitation was evident, with increased concentrations and deposition during spring and summer months. Meteorological analysis indicated the highest levels of Hg in precipitation were associated with regional transport from the south regardless of season, and with transport from the west, southwest and northwest during spring and summer months. Concentrations of ambient vapor phase Hg were typical of rural locations and consistent across seasons. Ambient particulate Hg concentrations averaged 11 pg/m³ with highest concentrations during the winter months.