Particulate-phase mercury emissions from biomass burning and impact on resulting deposition: a modelling assessment.

Mercury (Hg) emissions from biomass burning (BB) are an important source of atmospheric Hg and a major factor driving the interannual variation of Hg concentrations in the troposphere. The greatest fraction of Hg from BB is released in the form of elemental Hg(Hg(g)0) . However, little is known about the fraction of Hg bound to particulate matter (HgP) released from BB, and the factors controlling this fraction are also uncertain. In light of the aims of the Minamata Convention to reduce intentional Hg use and emissions from anthropogenic activities, the relative importance of Hg emissions from BB will have an increasing impact on Hg deposition fluxes. Hg speciation is one of the most important factors determining the redistribution of Hg in the atmosphere and the geographical distribution of Hg deposition. Using the latest version of the Global Fire Emissions Database (GFEDv4.1s) and the global Hg chemistry transport model, ECHMERIT, the impact of Hg speciation in BB emissions, and the factors which influence speciation, on Hg deposition have been investigated for the year 2013. The role of other uncertainties related to physical and chemical atmospheric processes involving Hg and the influence of model parametrisations were also investigated, since their interactions with Hg speciation are complex. The comparison with atmospheric HgP concentrations observed at two remote sites, Amsterdam Island (AMD) and Manaus (MAN), in the Amazon showed a significant improvement when considering a fraction of HgP from BB. The set of sensitivity runs also showed how the quantity and geographical distribution of HgP emitted from BB has a limited impact on a global scale, although the inclusion of increasing fractions HgP does limit Hg(g)0 availability to the global atmospheric pool. This reduces the fraction of Hg from BB which deposits to the world's oceans from 71 to 62 %. The impact locally is, however, significant on northern boreal and tropical forests, where fires are frequent, uncontrolled and lead to notable Hg inputs to local ecosystems. In the light of ongoing climatic changes this effect could be potentially be exacerbated in the future.

Atmospheric mercury concentrations observed at ground-based monitoring sites globally distributed in the framework of the GMOS network.

Long-term monitoring of data of ambient mercury (Hg) on a global scale to assess its emission, transport, atmospheric chemistry, and deposition processes is vital to understanding the impact of Hg pollution on the environment. The Global Mercury Observation System (GMOS) project was funded by the European Commission (http://www.gmos.eu) and started in November 2010 with the overall goal to develop a coordinated global observing system to monitor Hg on a global scale, including a large network of ground-based monitoring stations, ad hoc periodic oceanographic cruises and measurement flights in the lower and upper troposphere as well as in the lower stratosphere. To date, more than 40 ground-based monitoring sites constitute the global network covering many regions where little to no observational data were available before GMOS. This work presents atmospheric Hg concentrations recorded worldwide in the framework of the GMOS project (2010-2015), analyzing Hg measurement results in terms of temporal trends, seasonality and comparability within the network. Major findings highlighted in this paper include a clear gradient of Hg concentrations between the Northern and Southern hemispheres, confirming that the gradient observed is mostly driven by local and regional sources, which can be anthropogenic, natural or a combination of both.

Determination of Henry's law constant for elemental mercury.

The assessment of the global mercury cycle involves estimations of the evasion of mercury form oceanic waters. In such estimations Henry's law constant is often used. In this study the Henry's law constant for elemental mercury has been re-determined in MQ water and artificial sea water. Moreover, for the first time it has been determined for 1.5M sodium chloride (NaCl) solution which is of relevance for modeling of atmospheric waters at coastal locations. For all solutions, experiments has been conducted at five different temperatures between 278 and 308K, using a novel technique, for mercury, based on direct measurements of the portioning of mercury between the aqueous and gaseous phase. Elemental mercury was extracted from the water column and the logarithm of the mass of extracted mercury was plotted against time. A dimensionless Henry's law constant, defined as: [see text] was obtained from the slope of the curve. Almost no difference was observed in the values comparing the Milli-Q water and artificial sea water, however for the 1.5M NaCl solution a salting-out effect was seen, i.e. the solubility of mercury in the water phase decreased. The decreased solubility will generate an increase in the value of Henry's law constant.

A description of an automatic continuous equilibrium system for the measurement of dissolved gaseous mercury.

A novel continuous equilibrium system with high time resolution, i.e. every ten minutes, was developed to sample and determine dissolved gaseous mercury (DGM) in natural surface waters. The system is based on the opposite flow principle, can be connected to a ship's bow water system, and can be applied under most ambient conditions, such as high wind speeds and onboard a moving ship. For the DGM determination the system uses the measured equilibrium concentration of mercury established between the aqueous and gaseous phases, i.e. DGM = Hg(extr)/k(H'), where Hg(extr) is the measured mercury concentration in the outgoing gas phase and k(H') is the dimensionless Henry's Law constant at the desired temperature and salinity. The efficiency of the system was investigated via theoretical calculations and by comparing the continuous equilibrium system with discrete samples. The measurements obtained by the continuous equilibrium system agree within 13% at the 95% confidence level with the measurements of discrete samples obtained by the traditional technique. The theoretical calculations estimated that the continuous equilibrium system described here had an efficiency of 99% for determining the DGM concentration.

Urinary mercury in people living near point sources of mercury emissions.

As part of the European Mercury Emissions from Chlor Alkali Plants (EMECAP) project, we tested the hypothesis that contamination of ambient air with mercury around chlor alkali plants using mercury cells would increase the internal dose of mercury in people living close to the plants. Mercury in urine (U-Hg) was determined in 225 individuals living near a Swedish or an Italian chlor alkali plant, and in 256 age- and sex-matched individuals from two reference areas. Other factors possibly affecting mercury exposure were examined. Emissions and concentrations of total gaseous mercury (TGM) around the plants were measured and modeled. No increase in U-Hg could be demonstrated in the populations living close to the plants. This was the case also when the comparison was restricted to subjects with no dental amalgam and low fish consumption. The emissions of mercury to air doubled the background level, but contributed only about 2 ng/m(3) to long-term averages in the residential areas. The median U-Hg levels in subjects with dental amalgam were 1.2 microg/g creatinine (micro/gC) in Italy and 0.6 microg/gC in Sweden. In individuals without dental amalgam, the medians were 0.9 microg/gC and 0.2 microg/gC, respectively. The number of amalgam fillings, as well as chewing, fish consumption, and female sex were associated with higher U-Hg. The difference between the countries is probably due to higher fish consumption in Italy, demethylated methyl mercury (MeHg) being partly excreted in urine. Post hoc power calculations showed that if the background mercury exposure is low it may be possible to demonstrate an increase in U-Hg of as little as about 10 ng/m(3) as a contribution to ambient mercury from a point source.

Atmospheric mercury near a chlor-alkali plant in Sweden.

Atmospheric mercury species/fractions were measured near a chlor-alkali plant in Sweden during August 28 to September 4, 2001. The concentration of total gaseous mercury in the plume from the plant was measured using TEKRAN and GARDIS instruments. Gaseous elemental mercury was measured using a light detection and ranging (LIDAR) technique. From vertical LIDAR sweeps through the plume from the chlor-alkali plant mercury emission rates could be calculated. The concentrations of reactive gaseous mercury (RGM) in the plume and also inside the cell house were measured using annular KCl coated denuders. The RGM emission constitutes 0.5-1.0% of the total mercury emitted from the plant. The mercury concentration adsorbed on particles was measured as well as the mercury flux from soil. The data presented also include an intercomparison showing an excellent agreement between TEKRAN/GARDIS and LIDAR gaseous mercury measurements.

Distribution of TPM in Northern Europe.

Total particulate mercury (TPM) in air has been measured during five 2-week campaigns at five measurement sites in Northern Europe. The measurements covered four seasons and the result constitutes a unique TPM data set from this region. Evidence for transport of TPM on a regional scale is reported as well as the historical trend of TPM in south of Sweden. All TPM measurements were made using a new mini particulate sampler. The device consists of a quartz fibre filter contained in a quarts glass filter holder and is a modified version of the MiniSamplr. This approach proves to be reliable and more cost efficient in comparison to alternative methods. Tests made to evaluate the performance of the sampler in terms of precision and comparability with sampling on Teflon membrane filters are also reported.

Comparison of procedures for measurements of dissolved gaseous mercury in seawater performed on a Mediterranean cruise.

A comparison of manual procedures for measurements of dissolved gaseous mercury (DGM) in seawater was accomplished. The experiments were performed on board the Italian research vessel Urania during July 2000 as a subtask in the CNR "Med-Oceanor Project 2000". Water samples for DGM were collected by Go-Flo bottles and subsequently analysed for DGM on board the ship. Determinations of DGM were made in parallel by two groups using different analytical routines. The two sets of data obtained compare favourably. Based on the fieldwork and an additional laboratory study, analytical procedures are discussed and an optimised method to determine DGM is presented. In addition, a method for automated in situ measurements of DGM positioned in the water body was tested. This method has the potential to simplify studies of DGM dynamics, that is variation in concentration as a function of water temperature and solar radiation etc.