Atmospheric Impacts due to Anthropogenic Activities in Remote Areas: The Case Study of Admiralty Bay/King George Island/Antarctic Peninsula

The aim of the present work is to characterize the local atmospheric emissions levels and compare them to the component derived from global pollution in a remote site at South Hemisphere (Admiralty Bay located at King George Island in Antarctic Peninsula). Airborne particles, snow and soil/sediments samples were analyzed. Local-produced atmospheric aerosol dispersion was estimated for metals originated by fossil fuel burning from the permanent scientific stations using a simplified Gaussian model. Validation of atmospheric dispersion was established by in situ measurements. Soluble and insoluble particles deposited in freshly snow and airborne particles were analyzed by PIXE (Particle Induced X-Ray Emission) for the determination of the elemental mass concentration and to obtain the Mass Median Aerodynamic Diameter (MMAD). The results showed significant correlation between the concentration of atmospheric aerosol and the freshly deposited particles in the snow, and permitted an estimate of the atmospheric snow deposition factor for K, Cu, Zn, Fe, Pb, and Ti. Results of long-term aerosol data compilation suggest that besides the local aerosol sources, the continental atmospheric transport of airborne particles is not significantly affected by the airborne particles produced by local human impacts at King George Island.     

Elemental composition of aircraft-sampled aerosols above the southern bight of the North Sea

During the period from September 1988 to October 1989, 23 flights were carried out over the Dutch Continental Shelf of the North Sea and a total of 108 aerosol filter samples were collected. The samples were analyzed for Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br and Pb using both particle-induced X-ray emission (PIXE) and energy-dispersive X-ray fluorescence (EDXRF). The results from PIXE exhibited better precision and lower detection limits than those from EDXRF. Therefore the further discussion and interpretation was based on the PIXE data only. It was observed that Si, S, V, Mn, Ni, Cu and Pb were enriched with respect to the earth's crust. It was seen that winds from the sector Southeast-South contributed most significantly to the total aerosol concentration. The vertical profiles of several elements indicated that their concentration increases with proximity to the sea. Principal factor analysis on the data matrix containing elemental concentrations, height and wind direction parameters allowed us to identify 6 possible aerosol sources, namely, a composite of CaSO₄ and metallurgical activities, refuse incineration, residual oil combustion, quartz, soil dust and sea-salt aerosol.     

Size Distribution of Trace Elements and Major Ions in the Eastern Mediterranean Atmosphere

Size distribution of trace elements is measured at the Mediterranean coast of Turkey, by analyzing hi-vol impactor samples collected between August 1993 and May 1994. Mass median diameters of marine elements are between 4.6 and 5.3 μm, and those of crustal elements are between 3.0 and 3.5 μm. Mass median diameters of crustal elements are 30% smaller in samples impacted by Saharan Dust. Pollution derived elements, As, Cd, Mo, Pb, Se, and Zn have MMD's between 1.25 and 1.01 μm. Although 70–90% of the masses of these elements were associated with particles smaller than 2.1 μm, 10–30% of their mass was associated with coarse particles. Coarse component in concentrations of Cd, Pb, Sb and particulate Hg are due to adsorption of fine anthropogenic particles on coarse crustal aerosol, whereas coarse fraction Zn, As, Se, In, Mo and Au are crustal at Al concentrations > 100 ng m^?3. Bromine, Cr, Ni, and V have bimodal distributions. The fine component, which account for approximately 30–40% of their masses are due to anthropogenic sources, whereas the coarse component, which accounts for 30–50% of their masses are due to sea salt for Br, and crustal particles for Cr, Ni, and V.     

Vertical Distribution of Carbonyl Sulfide at Mt. Fuji, Japan

Atmospheric carbonyl sulfide (COS) mixing ratios measured over 24 h during five summer campaigns (2003–2007) in a forest at the foot of Mt. Fuji, Japan (35°21′ N, 138°43′ E; 1,300 m above sea level, a.s.l.) and at the summit (3,776 m a.s.l.) were compared. COS levels were lower at the foot than at the summit during four out of five summer campaigns. The ratios of COS mixing ratios at the foot of Mt. Fuji to those at the summit ranged from 0.7 to 0.9. These results provide evidence of biological consumption of COS in the East Asian atmospheric boundary layer. We also measured the vertical profile of ambient COS below the forest canopy. These data showed a clear gradient of COS mixing ratio: in the lowermost 1 m of the boundary layer, COS mixing ratios decreased markedly downward. Two of the different kinds of vertical distribution of COS presented here support the role of soil as a sink of atmospheric COS described by previous research using dynamic enclosure experiments.     

a new high-pressure squeezing technique for pore fluid extraction from terrestrial soils

A core consisting of minerogenic peat and organic-rich mineral sediments was collected at an altitude of 4275 m in the Ovejuyo valley, 100 km NE of La Paz in Bolivia. Age dating with 210Pb showed that the core represents approximately three centuries of sediment accumulation. None of the peats are ombrotrophic. Despite this, the Cd/Al, Cu/Al, Zn/Al, and Pb/Al ratios are all significantly higher in the surface layers, particularly in the top 6 cm: natural, abiological geochemical processes, therefore, cannot account for these elevated heavy metal/Al ratios. There are two possible explanations for the metal enrichments, relative to Al, in the surface layers: bioaccumulation by living plants, and anthropogenic atmospheric metal deposition. While the living plant layer may be responsible for the Cd, Cu, and Zn enrichments, this is an unlikely explanation for the Pb profile. In contrast to the other metals, the concentration of Pb in the first sample (dating from 1985-1994) is less than that of the second sample (dating from 1970-1985). The Pb/Al profile is consistent with the well documented, rapid increase in atmospheric Pb emissions during the present century (which accelerated following the introduction of leaded gasoline), and the decline in Pb pollution during the past 20 years (as a result of the introduction of unleaded gasoline). Thus, the Ovejuyo Valley mire has provided one of the first records of atmospheric Pb pollution in South America.     

Analysis of long-range transported acid aerosol in rime found at kyushu mountainous regions,Japan

Rime-ice and snow samples were collected at mountain sites in Kyushu, Japan during the winter of 1994, and both soluble and insoluble substances in the melted rime-ice were analyzed by ion chromatography, inductively coupled plasma-mass spectrometry (ICP/MS) and analytical electron microscopy, in order to find the evidences of long-range transport of air pollutants from the cities of the East Asian region. The relationships between Al, which is most often used as an index of soil components, and other elements were examined. The positive correlation was found between Al and three elements (Ti, Mn, Ba). Therefore, behaviors of these elements in rime-ice may be similar to that of soil particles. Furthermore, it was possible to classify the elements into three groups with the relation between a lead isotope ratio and concentration ratio of lead and zinc (Pb/Zn). In addition, numbers of particles were found in the rime-ice. The particles around 1 m in diameter were considered to be the combustion products of coal, whose Pb/Zn were similar to that of previous survey report in Korea. The existent forms of chemical species in rime-ice will become an important factor, when we consider the origin of air pollutants transported over long distances in the East Asian region.     

Aerosol and Precipitation Chemistry during the Summer at the Summit of Mt. Fuji, Japan (3776m a.s.l.)

Aerosol and precipitation samples were obtained at the summit of Mt. Fuji, the highest peak (3776m a.s.l.) in Japan, in the summers of 1997, 1998, and 1999. The mountaintop might be affected by valley wind during the afternoon, but is located in the free troposphere during the morning. The temporal variations of chemical species in the aerosol and precipitation samples correspond with meteorological conditions. The SO₄ ^2? in the aerosol and precipitation exhibits high concentration with low temperature air mass, indicating the influence of long range transport from the Asian Continent. The contribution of the free troposphere to the chemical species obtained at the summit is estimated to be at least 30% during the summer season.     

Factors influencing atmospheric deposition,stream export,and landscape accumulation of trace metals in forested watersheds

Wet and dry deposition inputs and streamflow output of Cd, Mn, Pb, Zn, and Al were measured intermittently at four deciduous forested watersheds in the southeastern United States between 1976 and 1982. Atmospheric inputs to each site were similar, varying by factors of 1.1 to 2.2 for the different metals. Metal levels in precipitation indicate that these sites are representative of rural, continental areas. Metals in rain exhibit significant temporal and spatial trends, with concentrations generally higher during summer than winter at all sites and generally lowest at the more remote site. The concentrations of Cd and Pb in both wet and dry deposition decreased between the period 1976 to 1977 and 1981 to 1982. Ion ratios and enrichment factors suggest that Mn is largely soil derived in atmospheric samples while Cd, Pb, and Zn are enriched over typical soil levels. Factor analysis indicates that soil components influence both Al and Mn while fine aerosol components influence Cd in wet and dry deposition. Both components influence the behavior of Pb. Dry deposition dominated the input of Mn and Al to each site, while wet deposition was the major input process for the other metals (54 to 85% of total). On an annual basis, deposited Cd, Pb, and Zn are strongly retained in each watershed: 2% of the Pb, 8 to 29% of the Cd, and 8 to 34% of the Zn inputs were transported in stream flow. Deposited Mn and Al are retained to a lesser degree and show a net loss from two sites. Metal export is controlled by stream pH, organic carbon, bedrock geology, and hydrologic characteristics of each site.     

Spatial distribution of soil heavy metal concentrations as indicator of pollution sources at Mount Križna (Great Fatra,central Slovakia)

The objective of this study was to test the suitability of a simple approach to identify the direction from where airborne heavy metals reach the study area as indication of their sources. We examined the distribution of heavy metals in soil profiles and along differently exposed transects. Samples were taken from 10 soils derived from the same parent material along N-, S-, and SE-exposed transects at 0—10, 10—20, and 20—40 cm depth and analyzed for total Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn concentrations. The heavy metal concentrations at 0—10 cm were larger than background concentrations in German arable soils except for Cr (Cd: 0.6—1.8 mg kg^—1; Cr: 39—67; Cu: 40—77; Ni: 87—156; Pb: 48—94; Zn: 71—129; Fe: 26—34 g kg^—1; Mn: 1.1—2.4). Decreasing Cd, Cu, Mn, and Pb concentrations with increasing soil depth pointed at atmospheric inputs. Aluminum and Ni concentrations increased with soil depth. Those of Fe, Cr, and Zn did not change with depth indicating that inputs at most equalled leaching losses. The Pb accumulation in the surface layer (i.e. the ratio between the Pb concentrations at 0—10 to those at 20—40 cm depth) was most pronounced at N-exposed sites; Pb obviously reached Mount Križna mainly by long-range transport from N where several industrial agglomerations are located. Substantial Cd, Cu, and Mn accumulations at the S- and SE-exposed sites indicated local sources such as mining near to the study area which probably are also the reason for slight Cr and Zn accumulations in the SE-exposed soils. Based on a principal component analysis of the total concentrations in the topsoils four metal groups may be distinguished: 1. Cr, Ni, Zn; 2. Mn, Cd; 3. Pb (positive loading), Cu (negative loading); 4. Al, Fe, indicating common sources and distribution patterns. The results demonstrate that the spatial distribution of soil heavy metal concentrations can be used as indication of the location of pollution sources.     

基于光谱分析的土壤重金属含量估算研究——以三江源区玉树县和玛多县为例

以三江源区玉树县和玛多县为研究区,利用实验室测定的As、Cu、Pb、Zn、Cr、Cd、Hg元素含量和室内采集的土壤原始光谱及其4种转换形式,建立了光谱指标与重金属含量的多元回归模型,利用决定系数(R2)、相对分析误差(RPD)及均方根误差(RMSE)评价模型的精度。研究结果表明,土壤As、Cu、Pb、Zn、Cr、Cd含量与SOM、Fe、Mn、Al、Mg等元素具有显著相关关系,Hg元素则未达到显著性水平。As、Cu、Pb、Zn、Cr和Cd元素估算模型回归方程R2达到了0.5以上,均通过了显著性检验,其中Pb、Zn和Cr元素验证样本RPD均达到了1.4以上,模型具备粗略估算能力;As、Cu和Cd元素验证样本RPD均低于1.4,模型不具备粗略估算能力。Hg元素估算模型回归方程的R2为0.28,未能通过显著性检验,无法用于对Hg含量的估算。     

Effects of cement production on the elemental composition of soils in the neighborhood of two cement factories

The effects of cement production on the elemental composition of soils in the neighborhood of two cement factories in Nigeria have been investigated using the XRF and PIXE/RBS techniques. The concentration of 21 elements viz:-Mg, Al, Si, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Sr, Pb, As, Zr, Rb and Br, were determined in about 30 samples. Calcium, P, S, Cr, Ni, Cu and Zn, were found to be relatively enriched in the soils of the cement factory premises. Calcium, a cement marker element, was found to be well correlated with Mg, S, Fe, Ni and Cu in the soils, and inversely proportional to the Si and Ti concentrations. From Ca/Si ratios and enrichment factors of the marker elements, it was found that soil contamination due to cement drops sharply with distance from the factories, and with increasing depth from the surface.     

Heavy Metals in the Aerosols Collected at Two Stations in Mallorca (Spain)

An extensive study of the different heavy metals (Fe, Mn Ni, Cr, Zn, Cd, Pb, Cu) present in the atmospheric aerosols collected at two stations in Mallorca located in the evirons of a new incinerator plant has been carried out. The aim of this study is to establish the quality of the air surrounding this new MSW (Municipal Solid Waste) incinerator on the island of Mallorca prior to its setting up. Besides, a study of the distribution of the analyzed metals in both the fine (diameter ≤1.5 μm) and coarse (diameter ≥1.5 μm) fractions of the aerosol has been performed. Concentrations of heavy metals in the atmospheric aerosols prior to the running of the new incinerator plant were found to be very low and similar to the values obtained at other Mediterranean stations.     

Changes of Al and Heavy Metal Concentrations in Slovak Soils During the Last 25 Years

The objective of this study was to investigate changes of total concentrations and various extract-defined Al and heavy metal fractions in Slovak agricultural soils during the last 25 years. We compared 7 stored soil samples collected between 1966 and 1970 with samples collected in 1994 at the same sites. Seven fractions of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn were determined with a sequential extraction procedure in all samples. Total concentrations of Cd, Zn, Mn, Ni, and Cu were lower in the 1994 samples; those of Al, Fe, Pb, and Cr were higher. Based on the initial concentrations, the average total concentration changes were: Cd(-10,3%)<Zn(-7,2%)<Mn(-4,8%)<Ni(-2,3%)<Cu(-1,4%)<Al(+2,1%)<Fe(+2,9%)<Cr(+7,4%)<Pb(+8,3%). This row is consistent with the decrease in metal mobility. The differences in salt-extractable metals showed the same pattern; however, changes were more pronounced than for total concentrations. The results suggest that decreases during the last 25 years are caused by higher leaching than deposition rates and increases vice versa. The highest increase in Cr and Pb concentrations is observed in the EDTA-extractable fraction, which mainly characterizes organically bound metals.     

Dominant Factors of Major and Minor Components and Formation of Hydroxyalkanesulfonate in Urban Dew-Water

Dew-water was collected from January 1999 to February 2000 in Yokohama, Japan and analyzed for not only soluble major components but also insoluble or trace components. The pH of dew-water ranged from 5.36 to 6.71 and volume-weighted average pH was 5.81. In dew-water, Si, Al, Fe, Cl, and Na were abundant and they were confirmed to be transported from natural sources, sea and soil dust. The concentrations of Si, Al, Fe, and Ti contained in coarse mode aerosol were several times higher in dew-water than those in rain-water, while the concentrations of V and Pb contained in fine mode aerosol were about the same level to each other. Besides these elements derived from aerosol, the elements derived from gaseous species are also major components in dew-water. The high concentration of weak acid is one of the significant characteristics of dew-water. Bisulfite ion in dew-water is the important species as the precursor of the sulfate ion but it is stable by forming hydroxyalkanesulfonate (HASA). The HASA concentrations were evaluated by using concentrations of total S(IV) and aldehydes and hydroxymethanesulfonate (HMSA) was shown to be the dominant species in S(IV).     

我国几种土壤中铁锰结核的元素组成和地球化学特点

The objective of this research was to isolate a dichlorvos （2,2-dichlorovinyl dimethyl phosphate）-degrading strain of Ochrobactrum sp., and determine its effectiveness in remediation of a dichlorvos-contaminated soil. A dichlorvos-degrading bacterium （strain DDV-1） was successfully isolated and identified as an Ochrobactrum sp. based on its 16S rDNA sequence analysis. Strain DDV-1 was able to utilize dichlorvos as a sole carbon source, and the optimal pH and temperature for its cell growth and degradation were 7.0 and 30 ℃, respectively. Also, the growth and degradation of strain DDV-1 showed the same response to dissolved oxygen. In addition, the soil degradation test indicated that in soil spiked with 100 mg L^-1 or 500 mg L^-1 dichlorvos and inoculated with 0.5% or 1.0% （v/v） strain DDV-1, complete degradation of dichlorvos could be achieved in 24 h. The present study showed that strain DDV-1 was a fast dichlorvos-degrading bacterium in soil. However, further research will be needed to clarify the degradation pathway and the properties of the key enzymes involved in its biodegradation.     

Inductively coupled plasma optical emission spectrometric determination of minerals in thyme honeys and their contribution to geographical discrimination

Twenty-four Spanish thyme honey samples were analyzed using inductively coupled plasma optical emission spectrometry (ICP-OES). Twenty-four minerals were quantified for each honey. The elements Al, As, Ba, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Na, P, Pb, S, Se, Si, Sr, and Zn were detected in all samples; seven elements are very abundant (Ca, K, Mg, Na, P, S, and Si), and six are not abundant (Al, Cu, Fe, Li, Mn, and Zn). Eleven of them are trace elements (As, Ba, Cd, Co, Cr, Ni, Mo, Pb, Se, Sr, and V) at <1 mg kg(-)(1). Classification of thyme honeys according to their origin (coast, mountains) was achieved by pattern recognition techniques on the mineral data. By means of principal component analysis, a good separation by geographical origin is obtained when scores for the two first principal components are plotted. Classification functions of 11 metals (Al, As, Cr, Cu, K, Li, Mg, Na, P, S, and V) were obtained using stepwise discriminant analysis and applied to classify correctly approximately 100% of the honey samples.     

Fluxes,residence times,and sources of some elements to Lake Michigan

Fluxes of 28 elements to Lake Michigan are calculated from literature data on sedimentation rates and concentrations in sediments and water. Lake Michigan residence times are roughly 10⁴ lower than oceanic residence times. A mass balance has been formulated for 24 elements, with soil and aerosol as the only sources. These sources provide fourfold excesses of Cu, Hg, Sb, Se, and V, and order of magnitude deficits for Ca, Mg, Na, and Cl, but account (to within 50%) for the observed inputs of Ag, Al, As, Br, Co, Cr, Fe, K, La, Mn, S, Si, Sc, Th, and Zn. Except for Al, Co, La, Si, and Th, deposition from aerosol accounts for at least one-fifth of the total input.     

Variation in the geochemistry of recent lake sediments along a west east pollution gradient in the Bergen area, Norway

Twenty nine lakes were sampled on a 62 km long west-east transect near Bergen, Norway from Sotra in the west to Norheimsund in the east. Top and bottom samples of 29 sediment cores, 20–40 cm long, were collected and 17 chemical elements were measured. Sphaeroidal carbonaceous particles from fossil fuel origin were counted in the surface sediments. The study was designed to answer two questions: (1) Does lake-sediment composition reflect variations in local atmospheric pollution? (2) What factors explain the observed variation in concentration of chemical elements along this transect? Ca, Cr, Mg, and Ni concentrations along the transect appear to result from differences in the content of these elements in bedrock. Hg, Pb, and Zn concentrations in the top sediments are dominated by input from anthropogenic sources. Variation of Cd, Fe, and Zn in the top sediments seems to be dependent on variation in lake-water pH. Hg and Zn from anthropogenic sources probably result from long-transported pollution. Pb and carbonaceous particles from anthropogenic sources possibly have a local origin.     

Evaluating the Contribution of Long-Range Transport of Heavy Metals from the Asian Continent to Their Concentrations in Sediment Cores from Lake Shinji,Western Japan

The historical trend of heavy metal pollution recorded in sediment cores from Lake Shinji, western Japan, was investigated to evaluate the contribution of increasing long-range transport of heavy metals from the Asian continent in recent years. The concentrations of Cd, Co, Cr, Cu, Ni, Pb, Sb, and Zn and lead isotope ratios were determined for sediment cores collected at two sites in the lake. Among the metals, Cd, Sb, and Zn showed markedly high concentrations since the 1970s. Moreover, a high Pb concentration and less radiogenic lead isotope ratios have been observed since the 1980s in the core from a site close to the mouth of a major river. Air masses from the Asian continent, including China, Russia, and South Korea, have less radiogenic lead isotope ratios than those from Japan. This suggests that the recent increase in Pb concentration in the sediment core is primarily due to the long-range transport of heavy metals from the Asian continent, followed by their deposition in the catchment area of the river. The concentration ratios of Pb/Cd, Pb/Sb, and Pb/Zn of the sediment around 2000 were calculated on the basis of the metal concentrations in excess of those before 1940. They were then compared with the volume-weighted annual average concentration ratios of Pb/Cd, Pb/Sb, and Pb/Zn of rain samples collected on the shore of the lake for 1999–2001. The result showed that the ratios of the former to the latter are 1.0 for Cd, 0.69 for Sb, and 0.31 for Zn. Thus, it is likely that the long-range transport of Cd and Sb from the Asian continent also contributes significantly to the recent increase in the concentrations of these metals in the sediment core from Lake Shinji. For Zn, however, the contribution from the Asian continent was evaluated to be small, suggesting the importance of local sources such as effluent discharges.     

Small Scale Heterogeneity of Soil Chemical Properties. II. Fractions of Aluminum and Heavy Metals

Soil aggregates from nine horizons of five forest sites in Bavaria were mechanically separated into an aggregate surface fraction and an aggregate core fraction. Seven operationally defined fractions of AI, Cd, Cu, Cr, Ni, Pb, and Zn were determined by a sequential extraction procedure within both aggregate fractions. The CEC, C_org, and oxides of Mn and Fe also were measured. The differences in metal concentrations between surface and core fractions were small but consistent: mainly lithogenic metals (Al, and, within a serpentine derived soil, Ni and Cr) showed lower total concentrations in the surface than in the core fraction. Metals originating primarily from atmospheric deposition form two groups. Cadmium, Pb, and Zn usually showed higher total concentrations in the surface fraction whereas Cu, Cr, and Ni showed no uniform trends. In general, lower proportions of the total metal concentration could be extracted by the residual extraction step (mainly bound within silicates) in the surface than in the core fraction. Accordingly, higher proportions could be extracted by the sum of all other steps (bound to cation exchangers, organic matter, and oxides) in the surface fraction, although in the aggregate surface fraction the concentrations of organic matter and oxides as well as the CEC were lower than in the core fraction. The fact that the sorption capacity of the surface is lower than of the core fraction has to be considered for the identification of external metal inputs. Based on these results, a new method to identify external inputs is proposed.