Recovery of Soil Water,Groundwater, and Streamwater From Acidification at the Swedish Integrated Monitoring Catchments

Recovery from anthropogenic acidification in streams and lakes is well documented across the northern hemisphere. In this study, we use 1996–2009 data from the four Swedish Integrated Monitoring catchments to evaluate how the declining sulfur deposition has affected sulfate, pH, acid neutralizing capacity, ionic strength, aluminum, and dissolved organic carbon in soil water, groundwater and runoff. Differences in recovery rates between catchments, between recharge and discharge areas and between soil water and groundwater are assessed. At the IM sites, atmospheric deposition is the main human impact. The chemical trends were weakly correlated to the sulfur deposition decline. Other factors, such as marine influence and catchment features, seem to be as important. Except for pH and DOC, soil water and groundwater showed similar trends. Discharge areas acted as buffers, dampening the trends in streamwater. Further monitoring and modeling of these hydraulically active sites should be encouraged.     

Environmental Services Provided from Riparian Forests in the Nordic Countries

Riparian forests (RF) growing along streams, rivers and lakes comprise more than 2% of the forest area in the Nordic countries (considering a 10 m wide zone from the water body). They have special ecological functions in the landscape. They receive water and nutrients from the upslope areas, are important habitats for biodiversity, have large soil carbon stores, but may emit more greenhouse gases (GHG) than the uplands. In this article, we present a review of the environmental services related to water protection, terrestrial biodiversity, carbon storage and greenhouse gas dynamics provided by RF in the Nordic countries. We discuss the benefits and trade-offs when leaving the RF as a buffer against the impacts from upland forest management, in particular the impacts of clear cutting. Forest buffers are effective in protecting water quality and aquatic life, and have positive effects on terrestrial biodiversity, particularly when broader than 40 m, whereas the effect on the greenhouse gas exchange is unclear.     

Assessing the Impacts of Long-Range Sulfur and Nitrogen Deposition on Arctic and Sub-Arctic Ecosystems

For more than a decade, anthropogenic sulfur (S) and nitrogen (N) deposition has been identified as a key pollutant in the Arctic. In this study new critical loads of acidity (S and N) were estimated for terrestrial ecosystems north of 60° latitude by applying the Simple Mass Balance (SMB) model using two critical chemical criteria (Al/Bc = 1 and ANC_le = 0). Critical loads were exceeded in large areas of northern Europe and the Norilsk region in western Siberia during the 1990s, with the more stringent criterion (ANC_le = 0) showing the larger area of exceedance. However, modeled deposition estimates indicate that mean concentrations of sulfur oxides and total S deposition within the Arctic almost halved between 1990 and 2000. The modeled exceeded area is much reduced when currently agreed emission reductions are applied, and almost disappears under the implementation of maximum technically feasible reductions by 2020. In northern North America there was no exceedance under any of the deposition scenarios applied. Modeled N deposition was less than 5 kg ha⁻¹ y⁻¹ almost across the entire study area for all scenarios; and therefore empirical critical loads for the eutrophying impact of nitrogen are unlikely to be exceeded. The reduction in critical load exceedances is supported by observed improvements in surface water quality, whereas the observed extensive damage of terrestrial vegetation around the mining and smelter complexes in the area is mainly caused by direct impacts of air pollution and metals.     

The fate of sulfate in acidified pig slurry during storage and following application to cropped soil

Acidification of slurry with sulfuric acid is a recent agricultural practice that may serve a double purpose: reducing ammonia emission and ensuring crop sulfur sufficiency. We investigated S transformations in untreated and acidified pig slurry stored for up to 11 mo at 2, 10, or 20 degrees C. Furthermore, the fertilizer efficiency of sulfuric acid in acidified slurry was investigated in a pot experiment with spring barley. The sulfate content from acidification with sulfuric acid was relatively stable and even after 11 mo of storage the majority was in the plant-available sulfate form. Microbial sulfate reduction during storage of acidified pig slurry was limited, presumably due to initial pH effects and a limitation in the availability of easily degradable organic matter. Sulfide accumulation was observed during storage but the sulfide levels in acidified slurry did not exceed those of the untreated slurry for several months after addition. The S fertilizer value of the acidified slurry was considerable as a result of the stable sulfate pool during storage. The high content of inorganic S in the acidified slurry may potentially lead to development of odorous volatile sulfur-containing compounds and investigations are needed into the relationship between odor development and the C and S composition of the slurry.     

Rapid decline of persistent organochlorine pollutants in serum among young Swedish males

To investigate a possible time trend in serum concentrations of persistent organochlorine pollutants (POPs), representative samples of the young (median age 18 years) Swedish male population were investigated in the years 2000 and 2004. Due to their low age, these men were assumed not to have reached steady state of body burdens of POPs, why their serum concentrations were considered to represent ongoing dietary exposure. Serum concentrations of 2,2',4,4',5,5'-hexachlorobiphenyl (CB-153) and 1,1-dichloro-2,2-bis(4-chlorophenyl)-ethylene (p,p'-DDE), two biomarkers of exposure to POPs, were available for 274 and 223 men, respectively, in 2000 and for 200 men in 2004. The percentage of men with CB-153 or p,p'-DDE below the limit of detection (LOD) was significantly higher in 2004 than in 2000 (30% vs. none, p < 0.001 for CB-153 and 65% vs. 6%, p < 0.001 for p,p'-DDE). Moreover, the median serum concentration of CB-153 decreased from 66 ng g(-1) lipid to 19 ng g(-1), corresponding to a yearly decrease of about 26%. The analogous analysis was not done for p,p'-DDE since the median serum concentration in 2004 was below the LOD.     

Estimates of black carbon and size-resolved particle number emission factors from residential wood burning based on ambient monitoring and model simulations

In this paper we derive typical emission factors for coarse particulate matter (PM(10)), oxides of nitrogen (NO(x)), black carbon (BC), and number particle size distributions based on a combination of measurements and air quality dispersion modeling. The advantage of this approach is that the emission factors represent integrated emissions from several vehicle types and different types of wood stoves. Normally it is very difficult to estimate the total emissions in cities on the basis of laboratory measurements on single vehicles or stoves because of the large variability in conditions. The measurements were made in Temuco, Chile, between April 18 and June 15, 2005 at two sites. The first one was located in a residential area relatively far from major roads. The second site was located in a busy street in downtown Temuco where wood consumption is low. The measurements support the assumption that the monitoring sites represent the impact of different emission sources, namely traffic and residential wood combustion (RWC). Fitting model results to the available measurements, emission factors were obtained for PM(10) (RWC = 2160 +/- 100 mg/kg; traffic = 610 +/- 51 mg/veh-km), NO(x) (RWC = 800 +/- 100 mg/kg; traffic = 4400 +/- 100 mg/veh-km), BC (RWC = 74 +/- 6 mg/kg; traffic = 60 +/- 3 mg/veh-km) and particle number (N) with size distribution between 25 and 600 nm (N(25-600)) (RWC = 8.9 +/- 1 x 10(14) pt/kg; traffic = 6.7 +/- 0.5 x 10(14) pt/veh-km). The obtained emission factors are comparable to results reported in the literature. The size distribution of the N emission factors for traffic was shown to be different than for RWC. The main difference is that although traffic emissions show a bimodal size distribution with a main mode below 30 nm and a secondary one around 100 nm, RWC emissions show the main mode slightly below 100 nm and a smaller nucleation mode below 50 nm.     

Modeling riverine nutrient transport to the Baltic Sea: a large-scale approach

We developed for the first time a catchment model simulating simultaneously the nutrient land-sea fluxes from all 105 major watersheds within the Baltic Sea drainage area. A consistent modeling approach to all these major watersheds, i.e., a consistent handling of water fluxes (hydrological simulations) and loading functions (emission data), will facilitate a comparison of riverine nutrient transport between Baltic Sea subbasins that differ substantially. Hot spots of riverine emissions, such as from the rivers Vistula, Oder, and Daugava or from the Danish coast, can be easily demonstrated and the comparison between these hot spots, and the relatively unperturbed rivers in the northern catchments show decisionmakers where remedial actions are most effective to improve the environmental state of the Baltic Sea, and, secondly, what percentage reduction of riverine nutrient loads is possible. The relative difference between measured and simulated fluxes during the validation period was generally small. The cumulative deviation (i.e., relative bias) [Sigma(Simulated - Measured)/Sigma Measured x 100 (%)] from monitored water and nutrient fluxes amounted to +8.2% for runoff, to -2.4% for dissolved inorganic nitrogen, to +5.1% for total nitrogen, to +13% for dissolved inorganic phosphorus and to +19% for total phosphorus. Moreover, the model suggests that point sources for total phosphorus compiled by existing pollution load compilations are underestimated because of inconsistencies in calculating effluent loads from municipalities.     

Value of information analysis in remedial investigations

Site investigations of contaminated land are associated with high costs. From a societal perspective, just enough economic resources should be spent on investigations so that society's limited resources can be used optimally. The solution is to design investigation programs that are cost effective, which can be performed using value of information analysis (VOIA). The principle of VOIA is to compare the benefit at the present state of knowledge with the benefit that is expected after an investigation has been performed. A framework for VOIA of site investigations is presented based on Bayesian risk-cost-benefit decision analysis. The result is an estimate of the value of an investigation program and, for specific problems, the optimal number of samples. The main strength of the methodology is that it promotes clear thinking and compels the decision maker to reflect on issues that otherwise would be ignored. The main weakness is the complexity of VOIA models.     

Molecular orbital studies on brominated diphenyl ethers. Part I--conformational properties

Polybrominated diphenyl ethers (PBDEs) are widely used as additive flame retardants and quantities in the environment are on the rise. Because they are structurally related to polychlorinated biphenyls and also to thyroid hormones, there is serious concern that PBDEs may pose a danger to human health. Knowledge of their conformational properties is key to assessing their environmental fate and risk. The conformational properties of PBDEs were investigated by quantum chemical methods including semiempirical self-consistent field molecular orbital (SCF-MO), ab initio SCF-MO and density functional theory (DFT). Conformational analyses of model congeners 2,2',4,6'-tetrabromodiphenyl ether and 2,3,4,4',5,6-hexabromodiphenyl ether, based on energy maps calculated by semiempirical AM1 method, may indicate that all PBDE congeners except those with the tetra-ortho-bromination are conformationally flexible (or soft) due to low energy barriers for interconversion of stable conformers. The results of the conformational analyses are in conformity with recently published X-ray crystallographic data. For comparison with the results of the semiempirical method, higher level ab initio and DFT models were applied as well. The optimized geometries all lie well inside low energy regions on the maps and thus also ascertain the semiempirical calculations. According to computed geometric parameters and net atomic charges, the model B3LYP/3-21G* seemed to give better results than B3LYP/6-31G* and HF/6-31G*.     

Molecular orbital studies on brominated diphenyl ethers. Part II--reactivity and quantitative structure-activity (property) relationships

Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants and are increasingly turning up in the environment. Their structural similarities to polychlorinated biphenyls and thyroid hormones suggest they may be a risk to human health. The present study examines the reactivity of brominated diphenyl ethers (BDEs) on the basis of the electronic structures as calculated by semiempirical AM1 self-consistent field molecular orbital (SCF-MO) method. Frontier orbital energies were used to elucidate the reactivity of BDEs in electrophilic, nucleophilic and photolytic reactions. From an examination of the frontier electron densities, the regioselectivity, or orientation, of metabolic reactions of BDEs was predicted. Furthermore, satisfactory quantitative structure-activity (property) relationship (QSAR and QSPR) models were derived to calculate gas chromatographic and ultraviolet spectral properties and luciferase induction activities from the AM1-computed electronic parameters.