Increased nitrogen in runoff and soil following 13 years of experimentally increased nitrogen deposition to a coniferous-forested catchment at Gårdsjön, Sweden

Beginning in 1991, we have added nitrogen (N) to the 0.5-ha, N-poor, coniferous-forested catchment G2 NITREX at G?rdsj?n, Sweden, to investigate the consequences of chronic elevated N deposition. We have added 40 kg N ha-1 yr-1 in fortnightly doses of NH4NO3 to the ambient 15 kg N ha-1 yr-1 by means of a sprinkling system. NO3 concentrations in runoff increased during 13 years from<1 to 70 microeq L-1, and in 2004 comprised about 10% of N input. Inhibition of NO3 immobilisation due to increased availability of NH4 might explain the increased leaching of NO3. C and N pools in the forest floor increased but C/N ratio has not changed. The increase in NO3 leaching thus occurred independently of change in C/N ratio. The results from G?rdsj?n demonstrate that increased leaching of inorganic N and decrease in C/N ratio respond to increased N deposition at greatly different time scales.     

Nitrogen leaching and acidification during 19 years of NH₄NO₃ additions to a coniferous-forested catchment at Gårdsjön, Sweden (NITREX)

The role of nitrogen (N) in acidification of soil and water has become relatively more important as the deposition of sulphur has decreased. Starting in 1991, we have conducted a whole-catchment experiment with N addition at Gårdsjön, Sweden, to investigate the risk of N saturation. We have added 41 kg N ha⁻¹ yr⁻¹ as NH₄NO₃ to the ambient 9 kg N ha⁻¹ yr⁻¹ in fortnightly doses by means of sprinkling system. The fraction of input N lost to runoff has increased from 0% to 10%. Increased concentrations of NO₃ in runoff partially offset the decreasing concentrations of SO₄ and slowed ecosystem recovery from acid deposition. From 1990-2002, about 5% of the total N input went to runoff, 44% to biomass, and the remaining 51% to soil. The soil N pool increased by 5%. N deposition enhanced carbon (C) sequestration at a mean C/N ratio of 42-59 g g⁻¹.     

Parameter precision in the HBV-NP model and impacts on nitrogen scenario simulations in the Rönneå river, southern Sweden

The HBV-NP model is a newly developed water quality model that describes the turnover and fluxes of both nitrogen and phosphorous. It is based on the conceptual precipitation/runoff HBV model. The HBV-NP model was applied for simulation of nitrogen for the R?nne? catchment in southern Sweden. The catchment was divided into 64 subcatchments in the model. Discharge measurements from six stations and nitrogen measurements from 12 stations were used in the calibration of parameters in the model. Eight automatic calibrations were performed with different combinations of time periods, objective functions, and levels of the nitrogen load in the model. A regionally extended interpretation of the Nash-Sutcliffe R2 criterion was used in the calibration. In the evaluation of the criterion, the errors were summed over both time steps and sampling points. Scenario simulations of combined measures for reduction of nitrogen load into the sea by 30% were thereafter performed with the eight sets of parameters established by calibration. The model parameters were not uniquely defined by the calibration. However, the simulated relative reduction of nitrogen load into the sea was relatively insensitive to the choice of parameter set, given the available input sources, variables, and data.     

Identification and assessment of ship emissions and their effects in the harbour of Göteborg,Sweden

The effect of ship emissions in the urban environment of Göteborg has been studied by multivariate analysis. The simultaneous measurements of relevant gases and sub-micron particles make identification of ship plumes possible. Increased concentrations of these species due to ship emissions are quantified for ships entering the inner part of the harbour. Annual depositions of SO₂ and NO₂ are estimated to be 220 and 115 kg km⁻² yr⁻¹, respectively. Exposure of transient particles (less than 0.1 μm in diameter) to this part of the harbour increased by a factor of 3 in number concentration when a ship plume was recorded. Ni, Pb, V and Zn are shown to have positive correlation with NO emissions from ships.     

In situ tracer tests to determine retention properties of a block scale fracture network in granitic rock at the Aspö Hard Rock Laboratory, Sweden

Experiments were conducted at the Asp? Hard Rock Laboratory in order to improve the understanding of radionuclide retention properties of fractured crystalline bedrock in the 10-100 m scale (TRUE Block Scale Project, jointly funded by ANDRA, ENRESA, Nirex, JNC, Posiva and SKB). A series of tracer experiments were performed using sorbing tracers in three different flow paths. The different flow paths had Euclidian lengths of 14, 17 and 33 m, respectively, and one to three water conducting structures. Four tests were performed using different cocktails made up of radioactive sorbing tracers (22,24Na+, 42K+, 47Ca2+, 85Sr2+, 83,86Rb+, 131,133Ba2+ and 134,137Cs+). For each tracer injection, the breakthrough of sorbing tracers was compared to the breakthrough of a conservative tracer, 82Br-, 131I-, HTO and 186ReO4-, respectively. In the two longer flow paths, no breakthrough of 83Rb+ and 137Cs+ was observed after 8 months of pumping. Selected tracer tests were subject to basic modelling in which a one-dimensional (1D) advection-dispersion model, including surface sorption, and an unlimited matrix diffusion were used for the interpretation of the results. The results of the modelling indicated that there is a slightly higher mass transfer into a highly porous material in the block-scale experiment compared with in situ experiments performed over shorter distances and significantly higher than what would have been expected from laboratory data obtained from studies of the interactions in nonaltered intact rock.     

Bio- and toxic elements in mushrooms from the city of Umeå and outskirts,Sweden

Edible mushrooms (Albatrellus ovinus, Boletus edulis, Clitocybe odora, Gomphidius glutinosus, Leccinum scabrum, Leccinum versipelle, Lycoperdon perlatum, Suillus bovinus, Suillus luteus, and Xerocomus subtomentosus) collected from unpolluted areas of the city of Umeå and its outskirts in the northern part of Sweden were examined for contents of toxic metallic elements (Cd, Pb, and Ag) and essential macro- and microelements (K, Na, Ca, Mg, Cu, Fe, Mn, and Zn) using a validated method and a final measurement by flame atomic absorption spectroscopy (F-AAS). The median values of the toxic metallic element concentrations (in mg kg^?1 dry biomass, db) ranged from: 0.12–3.9, 0.46–5.1, and 0.91–6.2 for Ag, Cd and Pb, respectively. For the essential metallic elements, the median values of concentrations ranged from: 24000–58000, 15–2000, 59–610, 520–1900, 2.0–97, 16–150, 15–120, and 4.3–26 mg kg^?1 db for K, Na, Ca, Mg, Cu, Zn, Fe, and Mn, respectively. The baseline concentrations of the metallic elements determined in mushrooms were mainly affected by the fungal species. The assessed probable maximal dietary intake of Cd (0.002 mg kg^?1 body mass) solely from a mushroom meal was only slightly below a revised value of the tolerable weekly intake for this element, while for Pb (0.003 mg kg^?1 body mass) it was tenfold below the provisionally tolerable weekly intake.     

Use of benzo[a]pyrene relative abundance ratios to assess exposure to polycyclic aromatic hydrocarbons in the ambient atmosphere in the vicinity of a Söderberg aluminum smelter

The purpose of this study was to investigate the use of benzo[a]pyrene (B[a]P) relative abundance ratios (RARs) to assess exposure to polycyclic aromatic hydrocarbons (PAHs) in the urban atmospheric air in the vicinity of a horizontal stud S?derberg aluminum reduction facility. The B[a]P RARs refer to the concentration of individual PAHs measured in a given sample divided by the concentration of B[a]P found in the same sample. This study compared the B[a]P RARs calculated for the facility stack and three sites near the S?derberg aluminum smelter for three different sampling periods. Interperiod differences were significant for many of the PAHs, and the differences between the stations proved insignificant at p < 0.05. The differences between each individual station and the facility stack were significant for all PAHs. B[a]P RARs increased in value at the stations compared with the stack, indicating that B[a]P may be degraded or removed from the atmosphere at a rate greater than that of the majority of the measured PAHs. It is concluded that B[a]P and B[a]P RARs may be poor markers of exposure to PAHs in the vicinity of this S?derberg aluminum refinery for the entire mixture of PAHs present in the ambient atmosphere.     

Use of Benzo[a]pyrene Relative Abundance Ratios to Assess Exposure to Polycyclic Aromatic Hydrocarbons in the Ambient Atmosphere in the Vicinity of a Söderberg Aluminum Smelter

ABSTRACT

The purpose of this study was to investigate the use of benzo[a]pyrene (B[a]P) relative abundance ratios (RARs) to assess exposure to polycyclic aromatic hydrocarbons (PAHs) in the urban atmospheric air in the vicinity of a horizontal stud Söderberg aluminum reduction facility. The B[a]P RARs refer to the concentration of individual PAHs measured in a given sample divided by the concentration of B[a]P found in the same sample. This study compared the B[a]P RARs calculated for the facility stack and three sites near the Söderberg aluminum smelter for three different sampling periods. Interperiod differences were significant for many of the PAHs, and the differences between the stations proved insignificant at p < 0.05. The differences between each individual station and the facility stack were significant for all PAHs. B[a]P RARs increased in value at the stations compared with the stack, indicating that B[a]P may be degraded or removed from the atmosphere at a rate greater than that of the majority of the measured PAHs. It is concluded that B[a]P and B[a]P RARs may be poor markers of exposure to PAHs in the vicinity of this Söderberg aluminum refinery for the entire mixture of PAHs present in the ambient atmosphere.     

Scheelite weathering and tungsten (W) mobility in historical oxidic-sulfidic skarn tailings at Yxsjöberg,Sweden

Environmental Science and Pollution Research - More knowledge of the geochemical behavior of tungsten (W) and associated contamination risks is needed. Therefore, weathering of scheelite (CaWO4)...     

Spatial variations in the aeolian deposition of dust – the effect of a city: a case study in Be'er-Sheva,Israel

The effect of buildings on the dry deposition of dust particles was investigated in Be'er-Sheva, a desert city with about 140,000 inhabitants in southern Israel, and at two reference points in the surrounding rural area. The mineral and chemical composition of dust sampled at all sites was similar, reflecting the composition of the local loess soil, its likely origin. However, dust deposited in the traps set up in the vicinity of buildings in the city was significantly coarser than the dust which accumulated in similar traps at exposed sites in the countryside. The amount of dust (by weight) in the urban dust traps was on an average more than twice the amount deposited in the rural area. The differences in grain-size distribution and quantity of dust are attributed to the properties of the urban wind field and to various effects of human activity in the city.     

Wet deposition of mercury in the U.S. and Canada, 1996–2005: Results and analysis of the NADP mercury deposition network (MDN)

One of the most critical measurements needed to understand the biogeochemical cycle of mercury, and to verify atmospheric models, is the rate of mercury wet-deposition. The Mercury Deposition Network (MDN) operates sites across North America to monitor total mercury in wet-deposition. MDN's primary goal is to provide both spatial and temporal continental-scale observations of mercury wet-deposition fluxes to support researchers, modelers, policy-makers and the public interest. MDN represents the only continental-scale mercury deposition database with a >10-year record of continuous values. This study provides analysis and interpretation of MDN observations at 10 years (1996–2005) with an emphasis on investigating whether rigorous, statistically-significant temporal trends and spatial patterns were present and where they occurred. Wet deposition of mercury ranges from more than 25 μg m^?2 yr in south Florida to less than 3 μg m^?2 yr in northern California. Volume-weighted total mercury concentrations are statistically different between defined regions overall (Southeast ≈ Midwest > Ohio River > Northeast), with the highest in Florida, Minnesota, and several Southwest locations (10–16 ng L^?1). Total mercury wet-deposition is significantly different between defined regions (Southeast > Ohio River > Midwest > Northeast). Mercury deposition is strongly seasonal in eastern North America. The average mercury concentration is about two times higher in summer than in winter, and the average deposition is approximately more than three times greater in summer than in winter. Forty-eight sites with validated datasets of five years or more were tested for trends using the non-parametric seasonal Kendall trend test. Significant decreasing mercury wet-deposition concentration trends were found at about half of the sites, particularly across Pennsylvania and extending up through the Northeast.     

Hydrodynamic and geochemical constraints on pesticide concentrations in the groundwater of an agricultural catchment (Brévilles, France)

The monitoring of a spring and seven piezometers in the 3km(2) Brévilles agricultural catchment (France) over five and a half years revealed considerable spatial and temporal variability in the concentrations of atrazine and its metabolite deethylatrazine (both systematically quantified at the outlet spring): maximum 0.97 and 2.72microgL(-1), mean 0.19 and 0.59microgL(-1), respectively. Isoproturon, the pesticide applied in the greatest amount, was detected in only 10 of the 133 samples. These observations can only partly be explained by land use and intrinsic pesticide properties. Geochemical measurements and tritium dating showed the importance of the stratification of the sandy saturated zone and the buffer function of the unsaturated limestone. Principal component analysis on 39 monthly data series of atrazine, deethylatrazine, nitrate, chloride and piezometric levels revealed a temporal structuring of the data possibly reflecting the existence within the aquifer of two different reservoirs with time-variable contributions.     

Interaction of nitrogen dioxide (NO2) with a monolayer of oleic acid at the air–water interface – A simple proxy for atmospheric aerosol

The reactions between atmospheric oxidants and organic amphiphiles at the air–water interface of an aerosol droplet may affect the size and critical supersaturation required for cloud droplet formation. We demonstrate that no reaction occurs between gaseous nitrogen dioxide (1000 ppm in air) and a monolayer of an insoluble amphiphile, oleic acid (cis-9-octadecenoic acid), at the air–water interface which removes material from the air–water interface. We present evidence that the NO₂ isomerises the cis-9-octadecenoic (oleic) acid to trans-9-octadecenoic (elaidic) acid. The study presented here is important for future and previous studies of (1) the reaction between the nitrate radical, NO₃, and thin organic films as NO₂ is usually present in high concentrations in these experimental systems and (2) the effect of NO₂ air pollution on the unsaturated fatty acids and lipids found at the air–liquid surface of human lung lining fluid.     

Use of a food web model to evaluate the factors responsible for high PCB fish concentrations in Lake Ellasjøen, a high Arctic Lake

Background, aim, and scope

Lake Ellasjøen, located in the Norwegian high arctic, contains the highest concentrations of polychlorinated biphenyls (PCBs) ever recorded in fish and sediment from high arctic lakes, and concentrations are more than 10 times greater than in nearby Lake Øyangen. These elevated concentrations in Ellasjøen have been previously attributed, in part, to contaminant loadings from seabirds that use Ellasjøen, but not Øyangen, as a resting area. However, other factors, such as food web structure, organism growth rate, weight, lipid content, lake morphology, and nutrient inputs from the seabird guano, also differ between the two systems. The aim of this study is to evaluate the relative influence of these factors as explanatory variables for the higher PCB fish concentrations in Ellasjøen compared with Øyangen, using both a food web model and empirical data.

Methods

The model is based on previously developed models but parameterized for Lakes Ellasjøen and Øyangen using measured data wherever possible. The model was applied to five representative PCB congeners (PCB 105, 118, 138, 153, and 180) using measured sediment and water concentrations as input data and evaluated with previously collected food web data.

Results

Modeled concentrations are within a factor of two of measured concentrations in 60% and 40% of the cases in Lakes Ellasjøen and Øyangen, respectively, and within a factor of 10 in 100% of the cases in both lakes. In many cases, this is comparable to the variability associated with the data as well as the efficacy of the predictions of other food web model applications.

Discussion

We next used the model to quantify the relative importance of five major differences between Ellasjøen and Øyangen by replacing variables representing each of these factors in the Ellasjøen model with those from Øyangen, in separate simulations. The model predicts that the elevated PCB concentrations in Ellasjøen water and sediment account for 49%–58% of differences in modeled fish PCB concentrations between lakes. These elevated sediment and, to a lesser extent, water concentrations in Ellasjøen are due to PCB loadings from seabird guano. However, sediment–water fugacity ratios of PCBs are consistently greater in Ellasjøen compared with Øyangen, which suggests that internal lake processes also contribute to differences in sediment and water concentrations. We hypothesize that the nutrients associated with guano influence sediment–water fugacity ratios of PCBs by increasing the stock of pelagic algae. As both these algae and the guano settle, their organic carbon content is degraded faster than PCBs, which causes an extra magnification step in Ellasjøen before these detrital particles are consumed by benthic organisms, which are in turn consumed by fish. The model predicts that the remaining ～50% of the differences in PCB concentrations observed between the fish of these lakes are due to other subtle differences in their food web structures.

Conclusions

In conclusion, based on the results of a food web model, we found that the most dominant factors influencing the higher PCB fish concentrations in Lake Ellasjøen compared with Øyangen are the higher sediment and water concentrations in Ellasjøen, caused by seabird guano. Together, sediment and water are predicted to account for 49%–58% of differences in fish concentrations between lakes. Although seabird guano provides a source of nutrients to the lake, in addition to contaminants, empirical data and indirect model results suggest that nutrients are not leading to decreased bioaccumulation, in contrast to what has been observed in temperate, pelagic food webs.

Recommendations and perspectives

The results of this study emphasize the importance of considering even small differences in food web structure when comparing bioaccumulation in two lakes; although the food web structures of Ellasjøen and Øyangen differ only slightly, the model predicts that these differences account for most of the remaining ～50% of the differences in PCB fish concentrations between the two lakes. This study further demonstrates the utility of food web models as we were able to predict and tease apart the influence of various factors responsible for the elevated concentrations in the fish from Lake Ellasjøen, which would have been difficult using the field data alone.     

Benzo[b]fluoranthene, a potential alternative to benzo[a]pyrene as an indicator of exposure to airborne PAHs in the vicinity of Söderberg aluminum smelters

Benzo[b]fluoranthene (B[b]F) was used in relative abundance ratios (RARs), a parameter obtained by dividing the concentration of individual polycyclic aromatic hydrocarbons (PAHs) found in a given sample by the concentration of B[b]F in the same sample. The B[b]F RARs were derived for PAH concentrations measured at stacks and sampling stations in the vicinity of two S?derberg aluminum horizontal stud smelters (HSSs). The samples collected were analyzed by high-performance liquid chromatography using UV and fluorescence detection. A total of 15 PAHs were analyzed, but, due to the inefficiency of the sampling method used in collecting gaseous PAHs, only particulate PAHs were considered. Comparisons between the B[b]F RARs obtained simultaneously at the source (stack) and those obtained at sampling stations at the two smelters showed that B[b]F degrades more slowly than or at the same rate as most other particulate PAHs monitored. Twenty-three months of urban sampling in the vicinity of one of the aluminum HSSs are also presented, and the results indicate that B[b]F is more stable than all other particulate PAHs investigated. Sampling conducted during a smelter shutdown period confirmed that B[b]F was a much better marker of this source than was benzo[a]pyrene (B[a]P), the usual indicator. The remarkable stability of the benzo[k]fluoranthene (B[k]F)/B[b]F ratio is also discussed.     

Biodegradation of hydrocarbons vapors: Comparison of laboratory studies and field investigations in the vadose zone at the emplaced fuel source experiment, Airbase Vaerløse, Denmark

The natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone can only be predicted when information about microbial biodegradation rates and kinetics are known. This study aimed at determining first-order rate coefficients for the aerobic biodegradation of 13 volatile petroleum hydrocarbons which were artificially emplaced as a liquid mixture during a field experiment in an unsaturated sandy soil. Apparent first-order biodegradation rate coefficients were estimated by comparing the spatial evolution of the resulting vapor plumes to an analytical reactive transport model. Two independent reactive numerical model approaches have been used to simulate the diffusive migration of VOC vapors and to estimate degradation rate coefficients. Supplementary laboratory column and microcosm experiments were performed with the sandy soil at room temperature under aerobic conditions. First-order kinetics adequately matched the lab column profiles for most of the compounds. Consistent compound-specific apparent first-order rate coefficients were obtained by the three models and the lab column experiment, except for benzene. Laboratory microcosm experiments lacked of sensitivity for slowly degrading compounds and underestimated degradation rates by up to a factor of 5. Addition of NH3 vapor was shown to increase the degradation rates for some VOCs in the laboratory microcosms. All field models suggested a significantly higher degradation rate for benzene than the rates measured in the lab, suggesting that the field microbial community was superior in developing benzene degrading activity.     

Management implications of spatial–temporal variations of net anthropogenic nitrogen inputs (NANI) in the Yellow River Basin

Environmental Science and Pollution Research - It is an important content of environment management to accurately identify the time change and spatial distribution of net anthropogenic nitrogen...     

Benzo[b]fluoranthene,a Potential Alternative to Benzo[a]pyrene as an Indicator of Exposure to Airborne PAHs in the Vicinity of Söderberg Aluminum Smelters

ABSTRACT

Benzo[b]fluoranthene (B[b]F) was used in relative abundance ratios (RARs), a parameter obtained by dividing the concentration of individual polycyclic aromatic hydrocarbons (PAHs) found in a given sample by the concentration of B[b]F in the same sample. The B[b]F RARs were derived for PAH concentrations measured at stacks and sampling stations in the vicinity of two Söderberg aluminum horizontal stud smelters (HSSs). The samples collected were analyzed by high-performance liquid chromatography using UV and fluorescence detection. A total of 15 PAHs were analyzed, but, due to the inefficiency of the sampling method used in collecting gaseous PAHs, only particulate PAHs were considered. Comparisons between the B[b]F RARs obtained simultaneously at the source (stack) and those obtained at sampling stations at the two smelters showed that B[b]F degrades more slowly than or at the same rate as most other particulate PAHs monitored. Twenty-three months of urban sampling in the vicinity of one of the aluminum HSSs are also presented, and the results indicate that B[b]F is more stable than all other particulate PAHs investigated. Sampling conducted during a smelter shutdown period confirmed that B[b]F was a much better marker of this source than was benzo[a]pyrene (B[a]P), the usual indicator. The remarkable stability of the benzo[k]fluoranthene (B[k]F)/B[b]F ratio is also discussed.     

Oxygen,carbon, and nutrient exchanges at the sediment–water interface in the Mar Piccolo of Taranto (Ionian Sea,southern Italy)

In the shallow environment, the nutrient and carbon exchanges at the sediment–water interface contribute significantly to determine the trophic status of the whole water column. The intensity of the allochthonous input in a coastal environment subjected to strong anthropogenic pressures determines an increase in the benthic oxygen demand leading to depressed oxygen levels in the bottom waters. Anoxic conditions resulting from organic enrichment can enhance the exchange of nutrients between sediments and the overlying water. In the present study, carbon and nutrient fluxes at the sediment–water interface were measured at two experimental sites, one highly and one moderately contaminated, as reference point. In situ benthic flux measurements of dissolved species (O₂, DIC, DOC, N-NO₃ ^?, N-NO₂ ^?, N-NH₄ ⁺, P-PO₄ ^3?, Si-Si(OH)₄, H₂S) were conducted using benthic chambers. Furthermore, undisturbed sediment cores were collected for analyses of total and organic C, total N, and biopolymeric carbon (carbohydrates, proteins, and lipids) as well as of dissolved species in porewaters and supernatant in order to calculate the diffusive fluxes. The sediments were characterized by suboxic to anoxic conditions with redox values more negative in the highly contaminated site, which was also characterized by higher biopolymeric carbon content (most of all lipids), lower C/N ratios and generally higher diffusive fluxes, which could result in a higher release of contaminants. A great difference was observed between diffusive and in situ benthic fluxes suggesting the enhancing of fluxes by bioturbation and the occurrence of biogeochemically important processes at the sediment–water interface. The multi-contamination of both inorganic and organic pollutants, in the sediments of the Mar Piccolo of Taranto (declared SIN in 1998), potentially transferable to the water column and to the aquatic trophic chain, is of serious concern for its ecological relevance, also considering the widespread fishing and mussel farming activities in the area.