Source characterization for atmospheric trace metals over Kiel Bight

Atmospheric concentrations of Na, Al, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Rb, Sr, Ba and Pb are reported for 59 weekly air filter samples collected over the Kiel Bight. The contributions of sea salt, mineral dust and anthropogenic emissions to each of these elements were assumed to be represented by the concentrations of indicator elements, which were Na, Al and Zn, respectively. Based on this assumption a multiple regression analysis was applied to the concentration data. The results showed that atmospheric sea salt contributed significantly only to Sr and, of course, Na. Considerable portions of Al, K, Ca, Ti, Cr, Mn, Fe, Rb, Sr and Ba were derived from mineral dust. Anthropogenic sources were responsible for total V, Ni, Cu, Zn, As and Pb, and there was an anthropogenic component for most of the other elements.Moreover, the anthropogenic contribution was characterized by a nearly constant composition with respect to Ca, Ti, Cr, Mn, Fe, Cu, Zn, As, Rb, Sr, Ba and Pb, indicating that trace metals over the Kiel Bight are mainly derived from one source area. This conclusion was confirmed by correlating anthropogenic trace metal concentrations with the wind direction. A 40° wind sector directed to the south of the sampling site was identified as the major pathway for the transport of anthropogenic trace metals to the Kiel Bight.     

Intermediate-range grid model for atmospheric sulfur dioxide and sulfate concentrations and depositions

A three-dimensional time-dependent grid type model for two chemically reacting species which undergo atmospheric transport, diffusion and wet and dry deposition over a region of several hundred km is presented. Accuracy and sensitivity of the model are discussed. The model is applied to the Rainy Lake Watershed using the available emissions and meteorological data. The model calculations are compared to National Atmospheric Deposition Program wet deposition data and snow core data.     

Levels and distribution of heavy metals in atmospheric particular matters over the northern South China Sea

Oceans play a significant role in the cycling of trace metals and persistent organic pollutants. In this study, aerosol samples covering the whole northern South China Sea (SCS) were collected in 2005 and 2007, respectively, for analysis of trace metals and major elements. The levels of trace metals detected ranged from 0.514 to 119 ng/m³ in 2005 and from 0.130 to 24.2 ng/m³ in 2007, respectively. Cu, Zn, and Pb were the three predominant metals with high enrichment factors (>10), indicating the strong anthropogenic inputs. The trace metals over SCS were comparable to the values in suburban and background sites of South China, but generally higher than those over other seas and oceans. Considering the fact that they were influenced by their proximity to source regions and air mass origins, the elevated metals in 2005 were probably attributed to the strong wind and long-range atmospheric transport driven by Asian monsoon.     

A new sampler for collecting separate dry and wet atmospheric depositions of trace organic chemicals

Studies conducted in Saskatchewan and elsewhere have demonstrated the atmospheric transport of agricultural pesticides and other organic contaminants and their deposition into aquatic ecosystems. To date these studies have focused on ambient concentrations in the atmosphere and in wet precipitation. To measure the dry deposition of organic chemicals, a new sampler was designed which uses a moving sheet of water to passively trap dry particles and gasses. The moving sheet of water drains into a reservoir and, during recirculation through the sampler, is passed through an XAD-2 resin column which adsorbs the trapped organic contaminants. All surfaces which contact the process water are stainless steel or Teflon. Chemicals collected can be related to airborne materials depositing into aquatic ecosystems. The sampler has received a United States patent (number 5,413,003 – 9 May 1996) with the Canadian patent pending.XAD-2 resin adsorption efficiencies for 10 or 50 μg fortifications of ten pesticides ranged from 76% for atrazine (2-chloro-4-ethylamino-6-isopropylamino-S-triazine) to 110% for triallate [S-(2,3,3-trichloro-2-phenyl)bis(1-methylethyl)carbamothioate], dicamba (2-methoxy-3,6-dichlorobenzoic acid) and toxaphene (chlorinated camphene mixture). Field testing using duplicate samplers showed good reproducibility and amounts trapped were consistent with those from high volume and bulk pan samplers located on the same site. Average atmospheric dry deposition rates of three chemicals, collected for 5 weeks in May and June, were: dicamba, 69 ng m^-2 da^-1; 2,4-D (2,4-dichlorophenoxyacetic acid), 276 ng m^-2 da^-1: and, γ-HCH (γ-1, 2, 3, 4, 5, 6-hexachlorocyclohexane), 327 ng m^-2 da^-1.     

A North Sea and Baltic Sea Model Ensemble Eutrophication Assessment

A method to combine observations and an ensemble of ecological models is suggested to produce a eutrophication assessment. Using threshold values and methodology from the Oslo and Paris Commissions (OSPAR) and the Helsinki Commission (HELCOM), four models are combined to assess eutrophication for the Baltic and North Seas for the year 2006. The assessment indicates that the entire southeastern part of the North Sea, the Kattegat, the Danish Straits, the Gulf of Finland, and the Gulf of Riga as well as parts of the Arkona Basin, the Bornholm Basin, and the Baltic proper may be classified as problem areas. The Bothnian Bay and parts of the Baltic proper, the Bornholm Basin, and the Arkona Basin are classified as potential problem areas. This method is a useful tool for the classification of eutrophication; however, the results depend on the threshold values, and further work is needed within both OSPAR and HELCOM to harmonize these values.     

Soluble and insoluble fractions of heavy metals in wet and dry atmospheric depositions in Bologna,Italy

Atmospheric depositions were collected monthly using a modified wet and dry sampler (dry deposition was collected on a water surface) located in Bologna, a northern Italian urban area, to evaluate the impact of airborne heavy metals on the local pollution load. Wet deposition samples were filtered and heavy metal contents in soluble and insoluble fractions were determined. The same procedure was applied to the water samples which collected dry deposition. The entire procedure was tested using a certified reference material (CRM), which provided satisfying recovery results. The percentage of heavy metal soluble fraction in dry deposition was generally lower than in wet one; Cd, V, Cu and Zn showed a higher average solubility than Cr, Ni and Pb both in wet and dry deposition. Factor analysis, after a varimax rotation of principal components, suggested possible anthropogenic sources which explain different metal deposition patterns. This data analysis also allowed to distinguish different clusters formed by monthly fluxes of heavy metals.     

Condensation nuclei concentrations over the Mediterranean Sea

Observations of condensation nuclei concentrations (Aitken nuclei) were made on board the Glomar Challenger during Mediterranean cruises in both 1970 and 1975. The data reveal number concentrations considerably greater than previously reported. The concentrations expected are about 1000–2000 cm⁻³ as opposed to open-ocean concentrations of about 400 cm⁻³ or less. The observed concentrations were significantly greater in 1975 than 1970 which may reflect increased industrial activity but other possible causes, such as different vegetative production of particles, cannot be ruled out.     

Size distributions of trace metals in atmospheric aerosols in the United Kingdom

The size distributions of Ba, Cd, Co, Cu, Hg, Mn, Ni, Pb, Sn, Se, Sr, Zn and Fe in atmospheric aerosols were measured using impactors at three background sites in central England and southern Scotland. Coarse aerosols (>10.0 μm) were found to be undercollected by a micro-orifice uniform deposit impactor (MOUDI) when compared to an isokinetic technique, to a degree dependent on the size distribution of individual metals. The size distributions obtained in Scotland, which were typically trimodal, differed from those in central England, where modes were more variable.Characteristic size distributions allowed identification of three main behavioural types: (i) metals whose mass resided mainly within the accumulation mode (Cd, Sn, Pb, Se), (ii) those which were distributed between fine, intermediate and coarse modes (Ni, Zn, Cu, Co, Mn, Hg), and (iii) those which were mainly found within coarse particles (Fe, Sr, Ba). The measured distributions are believed to result from a combination of processes including local anthropogenic and natural sources, long-range transport and resuspension.     

Size-dependent concentrations of trace metals in four Mediterranean gastropods.

In order to gain more information on the possible use of four gastropod species as metal biomonitors for the Mediterranean area, the influence of body weight upon Cd, Cr, Cu, Pb and Zn concentrations was studied in specimens collected at locations with different degrees of environmental pollution. The selected species were the marine snails Monodonta turbinata Born and Monodonta mutabilis Philippi, and the limpets Patella caerulea L. and Patella lusitanica Gmelin. Significant differences between metal concentrations in individuals from different stations were tested by ANCOVA on log-transformed data with log body weight as covariate. For all species a positive correlation between metal concentrations and body weight was observed, which means that the largest individuals contained the highest levels of metals. The inclusion of body weight as covariate in the statistical analysis explained from 81% to 99% of the metal variability within the organisms and enabled the achievement of improvements in the detection of differences among sites. The four selected species provided a rather univocal picture of bioavailable metal loads at the different stations of the experimental area. Except for Cd, the metal concentrations recorded at the clean stations were found to lie in the range of the lowest values reported in the literature and can be employed as useful background levels which can be referred to for intraspecific comparison within the Mediterranean area. It is concluded that in view of its distribution, unambiguous identification, resistance to pollution and accumulation patterns M. turbinata has considerable potential as a biomonitor of trace metals over the Mediterranean.     

Identifying source regions for the atmospheric input of PCDD/Fs to the Baltic Sea

PCDD/F contamination of the Baltic Sea has resulted in the European Union imposing restrictions on the marketing of several fish species. Atmospheric deposition is the major source of PCDD/Fs to the Baltic Sea, and hence there is a need to identify the source regions of the PCDD/Fs in ambient air over the Baltic Sea. A novel monitoring strategy was employed to address this question. During the winter of 2006–2007 air samples were collected in Aspvreten (southern Sweden) and Pallas (northern Finland). Short sampling times (24 h) were employed and only samples with stable air mass back trajectories were selected for analysis of the 2,3,7,8-substituted PCDD/F congeners. The range in the PCDD/F concentrations from 40 samples collected at Aspvreten was a factor of almost 50 (range 0.6–29 fg TEQ/m³). When the samples were grouped according to air mass origin into seven compass sectors, the variability was much lower (typically less than a factor of 3). This indicates that air mass origin was the primary source of the variability. The contribution of each sector to the PCDD/F contamination over the Baltic Sea during the winter half year of 2006/2007 was calculated from the average PCDD/F concentration for each sector and the frequency with which the air over the Baltic Sea came from that sector. Air masses originating from the south–southwest, south–southeast and east segments contributed 65% of the PCDDs and 75% of the PCDFs. Strong correlations were obtained between the concentrations of most of the PCDD/F congeners and the concentration of soot. These correlations can be used to predict the PCDD/F concentrations during the winter half year from inexpensive soot measurements.     

Model simulations of the Arctic atmospheric boundary-layer from the SHEBA year

We present Arctic atmospheric boundary-layer modeling with a regional model COAMPS, for the Surface Heat Budget of the Arctic Ocean (SHEBA) experiment. Model results are compared to soundings, near-surface measurements and forecasts from the ECMWF model. The near-surface temperature is often too high in winter, except in shorter periods when the boundary layer was cloud-capped and well-mixed due to cloud-top cooling. Temperatures are slightly too high also during the summer melt season. Effects are too high boundary-layer moisture and formation of too dense stratocumulus, generating a too deep well-mixed boundary layer with a cold bias at the simulated boundary-layer top. Errors in temperature and therefore moisture are responsible for large errors in heat flux, in particular in solar radiation, by forming these clouds. We conclude that the main problems lie in the surface energy balance and the treatment of the heat conduction through the ice and snow and in how low-level clouds are treated.     

Vertical distribution of atmospheric trace metals and their sources at Mumbai,India

In the modern times, due to high rise multistoried buildings, especially in metropolitan cities, the habitable heights have changed from the ground floor level to higher levels. Present study is focused at generating a vertical profile of aerosols and the elemental concentrations in an un-inhabited environment in the envelope of a high rise building in a relatively clean environment of Mumbai. This can serve as a base line information to study the vertical profile in polluted areas like city centres and street canyons. Suspended particulate matter (SPM) at different floors and particle size distribution of aerosols at 12th floor (top floor) have been estimated. Thirteen trace metals, namely Ca, Cd, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb and Zn were estimated in the SPM and in size separated aerosols, monitored over a period of 2 months. An attempt is also made to identify the sources of SPM at different heights using correlation matrix and factor analysis. The study indicates insignificant differences in the concentration levels of SPM and trace metals at different heights, when compared to the first floor level in the height range of 4.5–37.5 m. Of the 13 measured elements at the first floor level, Na (64.4%) and Ca (13.9%) constituted the dominant fractions followed by Fe (8.3%), Mg (5.7%), K (3.1%), Al (2.3%), Zn (1.3%) and Pb (0.5%). A similar distribution was also found for the 12th floor level (top floor). Factor analysis carried out using the measured elements, identified soil and sea salt spray as the main sources for the SPM at all the floors monitored.     

Temporal trends in the bioaccumulation of trace metals in herring, sprat, and cod from the southern Baltic Sea in the 1994–2003 period

This study is based on raw data obtained from 1 225 samples of herring (Clupea harengus), sprat (Sprattus sprattus), and cod (Gadus morhua) collected in the 1994–2003 period from the Polish coastal zone of the Baltic Sea. This paper presents the results of investigations of the contents of Cu, Zn, Cd, Pb, Hg, and As in fish. The aim was to identify temporal trends in trace metal contamination and variations in the concentrations of Hg in the flesh of herring, sprat, and cod of different lengths. A positive correlation between fish length and Hg concentration was noted for cod, sprat, and herring. The temporal trend analyses of heavy metal concentrations in the fish in the 1994–2003 period indicated ten significant downward trends out of eighteen tests; these referred to concentrations of Cd, Hg, and Pb in all the species studied, and to As in sprat. Concentrations of Cu and Zn remained stable in all the species studied, as did As in herring and cod. No upward trends were detected in the concentration of trace metals in the fish studied. Smaller scale temporal variations in concentrations of some elements were also observed and were associated with natural events, such as increased river discharge resulting from floods. The most likely factors which contributed to the observed downward trends in heavy metals concentrations in fish could possibly stem from lesser quantities of Cd, Pb, and Hg being introduced to the Baltic Sea with the waters of rivers from Baltic countries, including Poland, and atmospheric depositions in the 1994–2003 period. Diminishing trends of concentrations of these elements in Baltic Sea waters are also evidence of this. These facts might indicate that advantageous changes are occurring in the concentrations of heavy metals in the southern Baltic environment.     

Variability in climate change simulations affects needed long-term riverine nutrient reductions for the Baltic Sea

Changes to runoff due to climate change may influence management of nutrient loading to the sea. Assuming unchanged river nutrient concentrations, we evaluate the effects of changing runoff on commitments to nutrient reductions under the Baltic Sea Action Plan. For several countries, climate projections point to large variability in load changes in relation to reduction targets. These changes either increase loads, making the target more difficult to reach, or decrease them, leading instead to a full achievement of the target. The impact of variability in climate projections varies with the size of the reduction target and is larger for countries with more limited commitments. In the end, a number of focused actions are needed to manage the effects of climate change on nutrient loads: reducing uncertainty in climate projections, deciding on frameworks to identify best performing models with respect to land surface hydrology, and increasing efforts at sustained monitoring of water flow changes.     

Impact of mineral components and selected trace metals on ambient PM10 concentrations

PM10 levels of the mineral components Si, Al, Fe, Ca, Mg and some trace metals were measured at three different sites in the urban area of Vienna (Austria). Observed trace metal concentrations varied between less than 0.1 ng m^?3 (Cd) and approximately 200 ng m^?3 (Zn), mineral components showed enhanced concentrations ranging from 0.01 μg m^?3 (Ca) to 16.3 μg m^?3 (Si). The contribution of the respective mineral oxides to PM10 mass concentrations accounted on average for 26.4 ± 16% (n = 1090) of the PM10 mass, with enhanced rates in spring and autumn (monthly averages of up to 40%) and decreased contributions in the cold season (monthly averages below 10%). The atmospheric occurrence of Al, Ti and Sr could be assigned to crustal sources, whereas for the elements Ba, Ca, Fe, Mg, Mn and V an increased contribution of non-crustal origin was observed. PM10 levels of As, Cd, Co, Cr, Cu, Ni, Pb, Sb, Sn and Zn were predominantly derived from man-made emissions. Intersite comparison indicated that urban PM10 mass concentrations and PM10 levels of As, Pb and Zn were predominantly influenced from the transport of aerosols from outside into the city, whereas for the elements Ba, Mg, Ca, Cu and Fe a distinctly increased impact of local emissions was observed. The contribution of these urban emissions to total PM10 concentrations was estimated by calculating the so-called “urban impact”, which was found to be 32.7 ± 18% (n = 392) in the case of PM10 mass concentrations. The investigated elements accounted on average for 31.3 ± 19% (n = 392) of the observed PM10 mass increase. The mean values for the “urban impacts” of individual elements varied between 25.5% (As) and 77.0% (Ba).     

Reduction of Baltic Sea Nutrient Inputs and Allocation of Abatement Costs Within the Baltic Sea Catchment

The Baltic Sea Action Plan (BSAP) requires tools to simulate effects and costs of various nutrient abatement strategies. Hierarchically connected databases and models of the entire catchment have been created to allow decision makers to view scenarios via the decision support system NEST. Increased intensity in agriculture in transient countries would result in increased nutrient loads to the Baltic Sea, particularly from Poland, the Baltic States, and Russia. Nutrient retentions are high, which means that the nutrient reduction goals of 135 000 tons N and 15 000 tons P, as formulated in the BSAP from 2007, correspond to a reduction in nutrient loadings to watersheds by 675 000 tons N and 158 000 tons P. A cost-minimization model was used to allocate nutrient reductions to measures and countries where the costs for reducing loads are low. The minimum annual cost to meet BSAP basin targets is estimated to 4.7 billion €.     

Urine concentrations of selected trace metals in a cohort of Irish adults

Environmental Science and Pollution Research - Human biomonitoring studies are of increasing importance in regulatory toxicology; however, there is a paucity of human biomonitoring data for the...     

Estimates of ambient background concentrations of trace metals in soils for risk assessment

Site-specific or soil type-specific ambient background concentrations (ABCs) of trace metals in soils are needed for risk assessment. We investigated three different methods for estimating ABCs in soils using a dataset of 5691 soil samples from England and Wales. The concentrations of Co, Cr and Ni were strongly associated with Al and Fe, and multiple regressions explained 62-85% of their variation, and Al and Fe can therefore be used to predict ABCs for these metals. Soil texture had a major influence on the concentrations of Cd, Co, Cr, Cu, Ni and Zn, and the medians were 3-5 fold higher in clayey than in sandy soils. This was used to predict texture-specific ABCs. Lead concentration was higher in acidic peaty soils than in other soils. A probability graph method was used to estimate ABC for Pb in a population of relatively uncontaminated soils. Potential applications of ABCs are discussed.     

Organohalogen pollutants in herring from the northern Baltic Sea: concentrations, congener profiles and explanatory factors

Organohalogen contaminants were investigated in Baltic herring caught from three catchment areas in the Baltic Sea, off the coasts of Finland. Pools of both small and large herring were analysed for polychlorinated biphenyls (PCB), dibenzo-p-dioxins, dibenzofurans, naphthalenes, camphenes (toxaphene), polybrominated diphenyl ethers and the pesticide DDT and its metabolites. PCB concentrations per fresh weight in small herring were at the same level in all catchment areas, i.e. the Bothnian Bay, the Bothnian Sea and the Gulf of Finland, revealing no hot spots and reflecting most likely long term emissions and atmospheric deposition. Differences in the levels and/or congener profiles of other contaminants between catchment areas may be explained by point sources. Similar concentrations in small and large herring in the Gulf of Finland were possibly due to their common nutrition. In the other areas, differences between small and large herring most likely reflected their different food sources.