ALBERT

Notes: ABSTRACT During the last decade a new pattern of Hg pollution has been discerned, mostly in Scandinavia and North America. Fish from low productive lakes, even in remote areas, have been found to have a high Hg content. This pollution problem cannot be connected to single Hg discharges but is due to more widespread air pollution and long-range transport of pollutants. A large number of waters are affected and the problem is of a regional character. The national limits for Hg in fish are exceeded in a large number of lakes. In Sweden alone, it has been estimated that the total number of lakes exceeding the blacklisting limit of 1 mg Hg kg-1 in 1-kg pike is about 10 000. The content of Hg in fish has markedly increased in a large part of Sweden, exceeding the estimate background level by about a factor of 2 to 6. Only in the northernmost part of the country is the content in fish close to natural values. There is, however, a large variation of Hg content in fish within the same region, which is basically due to natural conditions such as the geological and hydrological properties of the drainage area. Higher concentrations in fish are mostly found in smaller lakes and in waters with a higher content of humic matter. Since only a small percentage of the total flow of Hg through a lake basin is transferred into the biological system, the bioavailability and the accumulation pattern of Hg in the food web is of importance for the Hg concentrations in top predators like pike. Especially, the transfer of Hg to low trophic levels seems to be a very important factor in determining the concentration in the food web. The fluxes of biomass through the fish community appear to be dominated by fluxes in the pelagic food web. The Hg in the lake water is therefore probably more important as a secondary source of Hg in pike than is the sediment via the benthic food chain. Different remedy actions to reduce Hg in fish have been tested. Improvements have been obtained by measures designed to reduce the transport of Hg to the lakes from the catchment area, eg. wetland liming and drainage area liming, to reduce the Hg flow via the pelagic nutrient chains, eg. intensive fishing, and to reduce the biologically available proportion of the total lake dose of Hg, eg. lake liming with different types of lime and additions of selenium. The length of time necessary before the remedy gives result is a central question, due to the long half-time of Hg in pike. In general it has been possible to reduce the Hg content in perch by 20 to 30% two years after treatments like lake liming, wetland liming, drainage area liming and intensive fishing. Selenium treatment is also effective, but before this method can be recommended, dosing problems and questions concerning the effects of selenium on other species must be evaluated. Regardless how essential these kind of remedial measures may be in a short-term perspective, the only satisfactory long-term alternative is to minimize the Hg contamination in air, soil and water. Internationally, the major sources of Hg emissions to the atmosphere are chlor-alkali factories, waste incineration plants, coal and peat combustion units and metal smelter industries. In the combustion processes without flue gas cleaning systems, probably about 20 to 60% of the Hg is emitted in divalent forms. In Sweden, large amounts of Hg were emitted to the atmosphere during the 50s and 60s, mainly from chlor-alkali plants and from metal production. In those years, the discharges from point sources were about 20 to 30 t yr 1. Since the end of the 60s, the emission of Hg has been reduced dramatically due to better emission control legislation, improved technology, and reduction of polluting industrial production. At present, the annual emissions of Hg to air are about 3.5 t from point sources in Sweden. In air, more than 95% of Hg is present as the elemental Hg form, HgO0. The remaining non-elemental (oxidized) form is partly associated to particles with a high wash-out ratio, and therefore more easily deposited to soils and surface waters by precipitation. The total Hg concentration in air is normally in the range 1 to 4 ng m-3. In oceanic regions in the southern hemisphere, the concentration is generally about 1 ng m−3, while the corresponding figure for the northern hemisphere is about 2 ng m-3. In remote continental regions, the concentrations are mainly about 2 to 4 ng m−3. In precipitation, Hg concentrations are generally found in the range 1 to 100 ng L−1. In the Nordic countries, yearly mean values in rural areas are about 20 to 40 ng L−1 in the southern and central parts, and about 10 ng L−1 in the northern part. Accordingly, wet deposition is about 20 (10 to 35) g km−2 yr−1 in southern Scandinavia and 5 (2 to 7) in the northern part. Calculations of Hg deposition based on forest moss mapping techniques give similar values. The general pattern of atmospheric deposition of Hg with decreasing values from the southwest part of the country towards the north, strongly suggests that the deposition over Sweden is dominated by sources in other European countries. This conclusion is supported by analyses of air parcel back trajectories and findings of significant covariations between Hg and other long range transported pollutants in the precipitation. Apart from the long range transport of anthropogenic Hg, the deposition over Sweden may also be affected by an oxidation of elemental Hg in the atmosphere. Atmospheric Hg deposited on podzolic soils, the most common type of forest soil in Sweden, is effectively bound in the humus-rich upper parts of the forest soil. In the Tiveden area in southern Sweden, about 75 to 80% of the yearly deposition is retained in the humus layer, chemically bound to S or Se atoms in the humic structure. The amount of Hg found in the B horizon of the soils is probably only slightly influenced by anthropogenic emissions. In the deeper layers of the soil, hardly any accumulation of Hg takes place. The dominating horizontal flow in the soils takes place in the uppermost soil layers (0 to 20 cm) during periods of high precipitation and high groun water level in the soils. The yearly transport of Hg within the soils has been calculated to be about 5 to 6 g km−2. The specific transport of total Hg from the soil system to running waters and lakes in Sweden is about 1 to 6 g km−2 yr1. The transport of Hg is closely related to the transport of humic matter in the water. The main factors influencing the Hg content and the transport of Hg in run-off waters from soils are therefore the Hg content in soils, the transport of humic matter from the soils and the humus content of the water. Other factors, for example acidification of soils and waters, are of secondary importance. Large peatlands and major lake basins in the catchment area reduce the out-transport of Hg from such areas. About 25 to 75% of the total load of Hg of lakes in southern and central Sweden originates from run-off from the catchment area. In lakes where the total load is high, the transport from run-off is the dominating pathway. The total Hg concentrations in soil solution are usually in the range 1 to 50, in ground water 0.5 to 15 and in run-off and lake water 2 to 12 ng L−1, respectively. The variation is largely due to differences in the humus content of the waters. In deep ground water with a low content of humic substances, the Hg concentration is usually below 1 ng L−1. The present amount and concentrations of Hg in the mor layer of forest soils are affected by the total anthropogenic emissions of Hg to the atmosphere, mainly during this century. Especially in the southern part of Sweden and in the central part along the Bothnian coast, the concentrations in the mor layer are markedly high. In southern areas the anthropogenic part of the total Hg content is about 70 to 90%. Here, the increased content in these soils is mainly caused by long-range transport and emissions from othe

Notes: Abstract Tropospheric mercury is dominated by gas phase species. In this paper, the gas phase reactions between the nitrate radical and volatile biogenic mercury species have been investigated. An upper limit for the gas phase rate coefficient for reaction between elemental mercury and NO3-radicals was determined to 4 × 10−15 cm3 molecule−1 s−1 by using the fast flow-discharge technique. The reaction between dimethyl mercury and NO3, previously shown to be rapid, has also been studied in the laboratory with respect to product distribution using FT-IR. The result from the product study is consistent with a transformation of dimethyl mercury into inorganic, divalent mercury. All carbon delivered as dimethyl mercury was transformed into formaldehyde, methanol and methyl peroxynitrate. Hg was observed as a minor (≈2%) product. By exclusion, HgO is proposed as the mercury-containing product. Thus, the reaction between dimethyl mercury and the nitrate radical is excluded as a source of monomethyl mercury species in the atmosphere.

Notes: The consecutive reactions of (CH3)2Si(OC2H5)2 and CH3Si(OC2H5)3 with methoxide ions were investigated in methanol solutions. The reverse transesterification reactions with ethoxide ions could be neglected in both cases since the concentration of ethoxide in methanol solution was assumed to be low due to the fast equilibrium reaction C2H5O- + CH3OH ⇌ C2H5OH + CH3O-. The progress of the reactions was followed by monitoring the formation of ethanol with a Fourier-transform infrared spectrometer. All rate constants were determined at 295 K. The reactions between the dialkoxydimethylsilanes and methoxide ions were assumed to consist of two consecutive steps that can be represented by the net reaction; (CH3)2Si(OC2H5)2 + 2CH3O- → (CH3)2Si(OCH3)2 + 2C2H5O-. The two consecutive rate constants were established as 1.93 ± 0.12M-1s-1 and 1.00 ± 0.12M-1s-1, respectively. The consecutive rate constants for the reactions between the trialkoxymethylsilanes and methoxide ions can be written according to the total reaction; CH3Si(OC2H5)3 + 3CH3O- → CH3Si(OCH3)3 + 3C2H5O-. The three rate constants corresponding to each consecutive step were established as 1.12 ± 0.09 M-1s-1, 0.82 ± 0.10 M-1s-1, and 0.51 ± 0.06 M-1s-1, respectively. © 1995 John Wiley & Sons, Inc.