Mercury in the Swedish environment — Recent research on causes,consequences and corrective methods

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 other European countries, while high level areas in the central parts are markedly affected by local historical emissions, mainly from the chlor-alkali industry. When comparing the input/output fluxes to watersheds it is evident that the present atmospheric deposition is much higher than the output via run-off waters, on average about 3 to 10 times higher, with the highest ration in the southern parts of Sweden. Obviously, Hg is accumulating in forest soils in Sweden at the present atmospheric deposition rate and, accordingly, the concentrations in forest soils are still increasing despite the fact that the emissions of Hg have drastically been reduced in Sweden during the last decades. The increased content of Hg in forest soils may have an effect on the organisms and the biological processes in the soils. Hg is by far the most toxic metal to microorganisms. In some regions in Sweden, the content of Hg in soils is already today at a level that has been proposed as a critical concentration. To obtain a general decrease in the Hg content in fish and in forest soils, the atmospheric deposition of Hg has to be reduced. The critical atmospheric load of Hg can be defined as the load where the input to the forest soils is less than the output and, consequently, where the Hg content in the top soil layers and the transport of Hg to the surface waters start to decrease. A reduction by about 80% of the present atmospheric wet deposition has to be obtained to reach the critical load for Scandinavia.     

Analysis on pedodiversity and spatial subset representativity—the German soil map 1:1,000,000

Knowledge about spatial soil variation in terms of measured pedodiversity, as well as the spatial distribution of soils in terms of spatial subset representativity, offers the possibility to estimate the quality and variance within a soil map. Additionally, it can help to identify representative sample locations. Demonstrated at the German soil map at a scale of 1:1,000,000, this study describes a methodology to analyze the distribution of taxonomical pedodiversity using the Simpson index and a new approach to derive representative spatial subsets based on a modified χ²‐test (χ_m²), which can be used as monitoring areas. To analyze the spatial composition of the soil map and to detect differences in the underlying mapping schemes of the German soil map 1:1,000,000, three different spatial data structures were studied: (1) the entire soil map, (2) the soil map segmented into geomorphological regions, and (3) the soil map segmented into the Federal States of Germany. Representative patches of varying sizes were statistically derived for all spatial subsets as well as the entire soil map ranging from 20 km × 20 km up to 70 km × 70 km. The results show that the measured pedodiversity is linked to both the geomorphology as well as the political borders of the Federal States. On the one hand, this reveals the uncertainty of measuring pedodiversity on the basis of soil‐class maps as the spatial representation of pedodiversity is influenced by the different mapping traditions and methods applied in the 16 Federal States of Germany. On the other hand, it allows the analysis of the aggregation schemes of different landscapes. The presented approach helps to understand large soilscapes and to compare different soil maps of different states and countries as well as to enhance the soil map with additional information. Furthermore, the representative patches can be used to select soil‐monitoring areas.     

Detection of potentially allergenic hazelnut (Corylus avellana) residues in food: a comparative study with DNA PCR-ELISA and protein sandwich-ELISA

Allergen detection is of increasing interest for food labeling purposes. A comparative study with a commercial hazelnut-specific PCR-ELISA and a sandwich-type ELISA detecting hazelnut protein was performed to investigate to what extent immunochemical and DNA-based techniques would correlate in the detection of trace amounts of potentially allergenic hazelnut residues. Both methods were highly sensitive and allowed the detection of even <10 ppm of hazelnut in complex food matrixes. The protein-ELISA was highly specific for hazelnut. However, some foods could lead to false-positive results at the 10 ppm level. The PCR-ELISA did not show any cross-reactions with non-hazelnut foods, thus reducing the probability of having false positives at the trace level. Forty-one commercial food products with and without hazelnut components on their labels were analyzed for the presence of hazelnut. Of the 27 products in which hazelnut components were detected, two samples were not identified by the protein-ELISA, and only one sample, namely one white chocolate having <1 ppm of hazelnut protein, was not detected by PCR-ELISA. The good correlation of the results of PCR-ELISA and protein-ELISA suggested that both PCR-based and immunochemical techniques are suitable for reliable detection of potentially allergenic hazelnut residues in foods at the trace level.     

Mechanical properties of metastable glacial till before and after water‐induced compaction

The mechanical properties of metastable soils have been approached from different backgrounds by civil engineers and soil scientists, with the main focus being on water‐induced self‐compaction rates. This study was conducted to determine the rebound‐recompression properties of metastable soil before and after wetting and to study the effect of water‐induced compaction on the mechanical stability depending on the overburden pressure. Rebound and recompression properties were measured with oedometer tests using sieved sandy loam, taken from a nonweathered Saalian glacial till layer, as the metastable test soil. The mechanical stability (preconsolidation load) of the dry and wetted soil was derived mathematically from recompression data after the test soil was unloaded. Void‐ratio changes during unloading and reloading were on a low level (Δe = 0.03). Rebound and recompression rates of the dry samples increased with load, whereas the void‐ratio change was twofold higher during recompression. Rebound rates of the wetted samples tended to decrease with load, while the recompression rates remained constant. Preconsolidation load calculated for the dry samples overestimated the simulated overburden pressure, whereas the wetted samples showed a high congruence. In both cases, the point of greatest curvature estimated in the earlier step of deviation gave values that were more realistic to the loads from which the unloading started. Our results indicate that both dry compaction and water‐induced compaction induce primarily plastic deformation. Furthermore, we found that in both the dry and wetted state the mechanical stability of the soil reflecting the overburden pressure remained constant.     

Intracellular and extracellular enzyme activity in soil with reference to elemental cycling

Enzyme activities play an important role for the transformation of elements and compounds in soil and, thus, were extensively analyzed for more than 4 decades. The activity of any enzyme in soil may not only be controlled by active organisms. Substantial parts of ‘extracellular’ enzymes may be stabilized by abiotic soil components maintaining their activity. Methods to discriminate the source of enzyme activity were summarized with emphasis on the approach plotting enzyme activity versus a feature integrating the microbial biomass after the addition of glucose and nitrate. Considering the quotient between enzyme activity and microbial biomass content, protease activity will be discussed with reference to nitrogen transformation in soils.     

Isoflucypram,the first representative of a new succinate dehydrogenase inhibitor fungicide subclass: Its chemical discovery and unusual binding mode

Succinate dehydrogenase inhibitors (SDHIs) have played a crucial role in disease control to protect cereals as well as fruit and vegetables for more than a decade. Isoflucypram, the first representative of a newly installed subclass of SDHIs inside the Fungicide Resistance Action Committee (FRAC) family of complex II inhibitors, offers unparalleled long‐lasting efficacy against major foliar diseases in cereals. Herein we report the chemical optimization from early discovery towards isoflucypram and the first hypothesis of its altered binding mode in the ubiquinone binding site of succinate dehydrogenase. © 2020 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.