Origin and distribution of trace elements in high-elevation precipitation in southern China

Introduction

During a 2009 investigation of the transport and deposition of trace elements in southern China, 37 event-based precipitation samples were collected at an observatory on Mount Heng, China (1,269?m asl).

Methods

Concentrations of trace elements were analyzed using inductively coupled plasma?Cmass spectrometry and the wet deposition fluxes were established. A combination of techniques including enrichment factor analysis, principal component analysis, and back trajectory models were used to identify pollutant sources.

Results

Trace element concentrations at Mount Heng were among the highest with respect to measured values reported elsewhere. All elements were of non-marine origin. The elements Pb, As, Cu, Se, and Cd were anthropogenic, while Fe, Cr, V, Ba, Mn, and Ni were of mixed crustal/anthropogenic origin. The crustal and anthropogenic contributions of trace elements were 12.8 % (0.9?~?17.4 %) and 87.2 % (82.6?~?99.1 %), with the maximum crustal fraction being 17.4 % for Fe. Coal combustion, soil and road dust, metallurgical processes, and industrial activities contributed to the element composition.

Conclusions

Summit precipitation events were primarily distant in origin. Medium- to long-range transport of trace elements from the Yangtze River Delta and northern China played an important role in wet deposition at Mount Heng, while air masses from south or southeast of the station were generally low in trace element concentrations.     

Overall dry deposition velocities of trace elements measured at harbor and traffic site in central Taiwan

For reasonable and convenient assessments of the characteristics of the dry deposition velocities between Taichung harbor site and Wuchi town site in central Taiwan, the overall dry deposition velocities of several metallic elements were calculated as the particulate diameter (D(p)) distributions of large particles (D(p) > 10 microm), coarse particles (10 microm < D(p) < 2.5 microm), and fine particles (D(p) < 2.5 microm) based on the ambient measurements during March-December of 2004. In this work, the dry deposition fluxes showed the higher correlation with coarse particle concentrations than large particle concentrations; however, the least well correlation was observed between the dry deposition fluxes and the fine particle concentrations. The calculated best-fit overall dry deposition velocities obtained using coarse particle concentrations varied from approximately 0.2 cm s(-1) for Cr to 1.5 cm s(-1) for Pb and 0.2 cm s(-1) for Fe to 2.6 cm s(-1) for Pb at Taichung harbor and Wuchi town site, respectively. In general, the crustal elements had higher deposition velocities than anthropogenic elements. In addition, overall dry deposition velocities for crustal elements were higher in Wuchi town site than in Taichung harbor site. The results identified the dry deposition flux was mainly contributed from large and coarse particles due to their high deposition velocities. The results also indicated that the best approach to estimate overall dry deposition was by depending on the characteristics of particles with diameters larger than 2.5 microm.     

Biomonitoring trace element atmospheric deposition using lichens in China

Concentrations of 32 elements, Ag, As, Au, Ba, Ca, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Mo, Na, Nd, Ni, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, U, W, Yb, and Zn were determined by instrumental neutron activation analysis (INAA) in the early preserved epiphytic lichens (Parmotrema recticulatum) from the remote southwestern China area in the 1960s, 1980s and 1990s. The concentrations of Ag, As, Ce, Cr, Cs, Eu, Fe, Hf, La, Nd, Ni, Sc, Se, Sm, Tb, U, Yb and Zn were dropped down by the temporal prolongation. The elemental concentration levels obtained from the organisms indicate that the extent of heavy metal atmospheric deposition among the sampling sites has been declining during the past decades.     

Recent atmospheric Pb deposition at a rural site in southern Germany assessed using a peat core and snowpack,and comparison with other archives

In a peat bog from Black Forest, Southern Germany, the rate of atmospheric Pb accumulation was quantified using a peat core dated by ²¹⁰Pb and ¹⁴C. The most recent Pb accumulation rate (2.5 mg m⁻² y⁻¹) is similar to that obtained from a snowpack on the bog surface, which was sampled during the winter 2002 (1 to 4 mg m⁻² y⁻¹). The Pb accumulation rates recorded by the peat during the last 25 yr are also in agreement with published values of direct atmospheric fluxes in Black Forest. These values are 50 to 200 times greater than the “natural” average background rate of atmospheric Pb accumulation (20 μg m⁻² y⁻¹) obtained using peat samples from the same bog dating from 3300 to 1300 cal. yr B.C. The isotopic composition of Pb was measured in both the modern and ancient peat samples as well as in the snow samples, and clearly shows that recent inputs are dominated by anthropogenic Pb. The chronology and isotopic composition of atmospheric Pb accumulation recorded by the peat from the Black Forest is similar to the chronologies reported earlier using peat cores from various peat bogs as well as herbarium samples of Sphagnum and point to a common Pb source to the region for the past 150 years. In contrast, Pb contamination occurring before 1850 in southwestern Germany, differs from the record published for Switzerland mainly due to the mining activity in Black Forest. Taken together, the results show that peat cores from ombrotrophic bogs can yield accurate records of atmospheric Pb deposition, provided that the cores are carefully collected, handled, prepared, and analysed using appropriate methods.     

Spatial patterns in wet and dry deposition of atmospheric mercury and trace elements in central Illinois,USA

An intensive 1-month atmospheric sampling campaign was conducted concurrently at eight monitoring sites in central Illinois, USA, from June 9 to July 3, 2011 to assess spatial patterns in wet and dry deposition of mercury and other trace elements. Summed wet deposition of mercury ranged from 3.1 to 5.4 μg/m² across sites for the total study period, while summed dry deposition of reactive mercury (gaseous oxidized mercury plus particulate bound mercury) ranged from 0.7 to 1.6 μg/m², with no statistically significant differences found spatially between northern and southern sites. Ratios of summed wet to summed dry mercury deposition across sites ranged from 2.2 to 4.9 indicating that wet deposition of mercury was dominant during the study period. Volume-weighted mean mercury concentrations in precipitation were found to be significantly higher at northern sites, while precipitation depth was significantly higher at southern sites. These results showed that substantial amounts of mercury deposition, especially wet deposition, occurred during the study period relative to typical annual wet deposition levels. Summed wet deposition of anthropogenic trace elements was much higher, compared to summed dry deposition, for sulfur, selenium, and copper, while at some sites summed dry deposition dominated summed wet deposition for lead and zinc. This study highlights that while wet deposition of Hg was dominant during this spring/summer-season study, Hg dry deposition also contributed an important fraction and should be considered for implementation in future Hg deposition monitoring studies.     

Annual input fluxes and source identification of trace elements in atmospheric deposition in Shanxi Basin: the largest coal base in China

Industrialization and urbanization have led to a great deterioration of air quality and provoked some serious environmental concerns. One hundred and five samples of atmospheric deposition were analyzed for their concentrations of 13 trace elements (As, Cd, Cu, Fe, Al, Co, Cr, Hg, Mn, Mo, Pb, Se, and Zn) in Shanxi Basin, which includes six isolate basins. The input fluxes of the trace elements in atmospheric deposition were observed and evaluated. Geostatistical analysis (EF, PCA, and CA ) were conducted to determine the spatial distribution, possible sources, and enrichment degrees of trace elements in atmospheric deposition. Fe/Al and K/Al also contribute to identify the sources of atmospheric deposition. The distribution of trace elements in atmospheric deposition was proved to be geographically restricted. The results show that As, Cd, Pb, Zn, and Se mainly come from coal combustion. Fe, Cu, Mn, Hg, and Co originate mainly from interactions between local polluted soils and blowing dust from other places, while the main source of Al, Cr, and Mo are the soil parent materials without pollution. This work provides baseline information to develop policies to control and reduce trace elements, especially toxic elements, from atmospheric deposition. Some exploratory analytical methods applied in this work are also worth considering in similar researches.     

Use of mosses to study atmospheric deposition of trace elements: contributions from investigations in Norway

This paper presents essential features of biomonitoring work carried out in the author's laboratory during more than 25 years using various analytical techniques for the determination of over 50 elements. A substantial part of this work concerns large-scale deposition surveys in Norway using the moss Hylocomium splendens, where five nationwide surveys have been carried out since 1977. Considerable efforts have also been spent on intercalibration of different species of mosses and transformation of concentrations in moss to absolute deposition rates. Other significant activities include establishment of recommended values for moss reference samples, source apportionment of lead in mosses by stable isotope ratios and monitoring of local metal deposition around factories. Experience from this work has facilitated a critical evaluation of the contribution from sources other than atmospheric deposition to the elemental composition of the moss, as well as factors leading to depletion of elements in the moss. Recent work indicates that mosses may also be suitable for the monitoring of persistent halogenated organic pollutants and ¹³⁷Cs deposition.     

Relation between forest vegetation, atmospheric deposition and site conditions at regional and European scales

Several monitoring programs have been set up to assess effects of atmospheric deposition on forest ecosystems. The aim of the present study was to evaluate effects on the understorey vegetation, based on the first round of a regional (the Netherlands) and a European forest monitoring program. A multivariate statistical analysis showed surprisingly similar results for both data sets; the vegetation appeared to be largely determined by the ‘traditional’ factors soil, climate, and tree species, but there was a small but statistically significant effect of atmospheric deposition. The effects of deposition include a slight shift towards nitrophytic species at high N deposition in the European network, and towards acidophytic species at high S-deposition in the Dutch network. The relatively small effect of atmospheric deposition is understandable in view of the very large natural variation in environmental conditions. Time series of both vegetation and environment are needed to assess deposition effects in detail.     

Historical deposition of mercury and selected trace elements to high-elevation National Parks in the Western U.S. inferred from lake-sediment cores

Atmospheric deposition of Hg and selected trace elements was reconstructed over the past 150 years using sediment cores collected from nine remote, high-elevation lakes in Rocky Mountain National Park in Colorado and Glacier National Park in Montana. Cores were age dated by ²¹⁰Pb, and sedimentation rates were determined using the constant rate of supply model. Hg concentrations in most of the cores began to increase around 1900, reaching a peak sometime after 1980. Other trace elements, particularly Pb and Cd, showed similar post-industrial increases in lake sediments, confirming that anthropogenic contaminants are reaching remote areas of the Rocky Mountains via atmospheric transport and deposition. Preindustrial (pre-1875) Hg fluxes in the sediment ranged from 5.7 to 42 μg m^?2 yr^?1 and modern (post-1985) fluxes ranged from 17.7 to 141 μg m^?2 yr^?1. The average ratio of modern to preindustrial fluxes was 3.2, which is similar to remote lakes elsewhere in North America. Estimates of net atmospheric deposition based on the cores were 3.1 μg m^?2 yr^?1 for preindustrial and 11.7 μg m^?2 yr^?1 for modern times. Current-day measurements of wet deposition range from 5.0 to 8.6 μg m^?2 yr^?1, which are lower than the modern sediment-based estimate of 11.7 μg m^?2 yr^?1, perhaps owing to inputs of dry-deposited Hg to the lakes.     

Relationship between epiphytic lichens, trace elements and gaseous atmospheric pollutants

A study was conducted to determine the joint effect of gaseous atmospheric pollutants and trace elements on epiphytic lichens. We used our data to test the hypothesis that lichens are generally insensitive to toxic effects of trace elements, and can therefore be used as accumulator organisms to estimate concentrations of these elements in the environment. In a field study in The Netherlands the abundance of epiphytic lichen species was estimated, and their supporting bark was collected. Concentrations of a range of trace elements were determined in the bark, and concentrations of atmospheric trace gases were estimated at the sites of collection. Multivariate statistics were used to determine the relation between the abundance of the species and pollutant concentrations. Atmospheric SO2 and NO2 appeared to be the most important factors determining lichen biodiversity. Nearly all species were sensitive to these compounds. The effect of the other trace elements was very slight; only Sb had a significantly negative effect on the abundance of a few species. It is concluded that lichens can safely be used as accumulator organisms in pollution studies, provided that concentration in lichen thalli reflect atmospheric concentrations.     

Evaluation of trace elements contamination in cloud/fog water at an elevated mountain site in Northern China

Totally 117 cloud/fog water samples were collected at the summit of Mt. Tai (1534 m a.s.l.)—the highest mountain in the Northern China Plain. The results were investigated by a combination of techniques including back trajectory model, regional air quality and dust storm models, satellite observations and Principal Component Analysis. Elemental concentrations were determined by Inductively Coupled Plasma Mass Spectrometry, with stringent quality control measures. Higher elemental concentrations were found at Mt. Tai compared with those reported by other overseas studies. The larger proportions and higher concentrations of toxic elements such as Pb and As in cloud/fog water compared with those in rainwater at Mt. Tai suggests higher potential hazards of cloud/fog water as a source of contamination in polluted areas to the ecosystem. Peak concentrations of trace elements were frequently observed during the onset of cloud/fog events when liquid water contents of cloud/fog water were usually low and large amount of pollutants were accumulated in the ambient air. Inverse relationship between elemental concentrations and liquid water contents were only found in the samples with high electrical conductivities and liquid water contents lower than 0.3 g m⁻³. Affected mainly by the emissions of steel industries and mining activities, air masses transported from south/southwest of Mt. Tai were frequently associated with higher elemental concentrations. The element Mn is attributed to play an important role in the acidity of cloud/fog water. The composition of cloud/fog water influenced by an Asian dust storm event was reported, which was seldom found in the literature.     

Active moss biomonitoring of trace elements with Sphagnum girgensohnii moss bags in relation to atmospheric bulk deposition in Belgrade, Serbia

Active biomonitoring with wet and dry moss bags was used to examine trace element atmospheric deposition in the urban area of Belgrade. The element accumulation capability of Sphagnum girgensohnii Russow was tested in relation to atmospheric bulk deposition. Moss bags were mounted for five 3-month periods (July 2005-October 2006) at three representative urban sites. For the same period monthly bulk atmospheric deposition samples were collected. The concentrations of Al, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, and Pb were determined by instrumental neutron activation analyses and atomic absorption spectrometry. Significant accumulation of most elements occurred in the exposed moss bags compared with the initial moss content. High correlations between the elements in moss and bulk deposits were found for V, Cu, As, and Ni. The enrichment factors of the elements for both types of monitor followed the same pattern at the corresponding sites.     

Temporal distribution and potential sources of atmospheric mercury measured at a high-elevation background station in Taiwan

Measurements of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM), and particulate mercury (PHg) have been conducted at Lulin Atmospheric Background Station (LABS) in Taiwan since April 2006. This was the first long-term free tropospheric atmospheric Hg monitoring program in the downwind region of East Asia, which is a major Hg emission source region. Between April 13, 2006 and December 31, 2007, the mean concentrations of GEM, RGM, and PHg were 1.73 ng m^?3, 12.1 pg m^?3, and 2.3 pg m^?3, respectively. A diurnal pattern was observed for GEM with afternoon peaks and nighttime lows, whereas the diurnal pattern of RGM was opposite to that of GEM. Spikes of RGM were frequently observed between midnight and early morning with concurrent decreases in GEM and relative humidity and increases in O₃, suggesting the oxidation of GEM and formation of RGM in free troposphere (FT). Upslope movement of boundary layer (BL) air in daytime and subsidence of FT air at night resulted in these diurnal patterns. Considering only the nighttime data, which were more representative of FT air, the composite monthly mean GEM concentrations ranged between 1.06 and 2.06 ng m^?3. Seasonal variation in nighttime GEM was evident, with lower concentrations usually occurring in summer when clean marine air masses prevailed. Between fall and spring, air masses passed the East Asian continent prior to reaching LABS, contributing to the elevated GEM concentrations. Analysis of GEM/CO correlation tends to support the argument. Good GEM/CO correlations were observed in fall, winter, and spring, suggesting influence of anthropogenic emission sources. Our results demonstrate the significance of East Asian Hg emissions, including both anthropogenic and biomass burning emissions, and their long-range transport in the FT. Because of the pronounced seasonal monsoon activity and the seasonal variation in regional wind field, export of the Asian Hg emissions to Taiwan occurs mainly during fall, winter, and spring.     

Ambient concentrations and dry deposition fluxes of trace elements in Izmir,Turkey

Dry deposition samples were collected using a smooth surrogate surface at the Kaynaklar Campus of the Dokuz Eylul University in Izmir, Turkey. Concurrently ambient aerosol samples were collected. All samples were analyzed for anthropogenic and crustal trace elements. The average trace element concentrations and fluxes measured in this study were generally higher than those reported previously for urban and rural areas. The contribution of local terrestrial and anthropogenic sources were also investigated using enrichment factors (EFs) calculated relative to the local soil. Relatively lower EFs for ambient samples and high ambient concentrations indicated that the local soil was polluted and contributed significantly to ambient trace element concentrations. Deposition samples had higher EFs than the air samples. The EF sequences of trace elements were also different for deposition and ambient samples, probably due to the fact they have different mass median diameters and deposition velocities. The overall dry deposition velocities for trace elements calculated by dividing the particulate fluxes measured with the surrogate surfaces by ambient concentrations ranged from 0.6 (Al) to 6.2 cm s⁻¹ (Fe). The agreement between the experimental dry deposition velocities determined in this study and the previously reported ones using similar techniques for trace elements was good.     

Atmospheric dry deposition fluxes of trace elements measured in Bursa, Turkey

Trace element dry deposition fluxes were measured using a smooth, greased, knife-edge surrogate surface (KSS) holding greased Mylar strips in Bursa, Turkey. Sampling program was conducted between October 2002 and June 2003 and 46 dry deposition samples were collected. The average fluxes of crustal metals (Mg, Ca, and Fe) were one to four orders of magnitude higher than the fluxes of anthropogenic metals. Trace element fluxes ranged from 3 (Cd) to 24,230 (Ca) microg m(-2) d(-1). The average trace element dry deposition fluxes measured in this study were similar to those measured in other urban areas. In addition, ambient air samples were also collected simultaneously with flux samples and concentrations of trace elements, collected with a TSP sampler, were between 0.7 and 4900 ng m(-3) for Cd and Ca, respectively. The overall trace element dry deposition velocities, calculated by dividing the fluxes to the particle phase concentrations ranged from 2.3+/-1.7 cm s(-1) (Pb) to 11.1+/-6.4 cm s(-1) (Ni). These values are in good agreement with the values calculated using similar techniques. The anthropogenic and crustal contributions were estimated by employing enrichment factors (EFs) calculated relative to the average crustal composition. Low EFs for dry deposition samples were calculated. This is probably due to contamination of local dust and its important contribution to the collected samples.     

Source apportionment and deposition of dustfall-bound trace elements around Tabriz,Iran

Environmental Science and Pollution Research - The monthly and spatial variations of atmospheric dustfall (DF) and their elemental components were determined. The DF sampling was performed using...     

Wash effect of atmospheric trace metals wet deposition and its source characteristic in subtropical watershed in China

In order to better understand air pollution in deve-loping regions, such as China, it is important to investigate the wet deposition behavior of atmospheric trace metals and its sources in the subtropical watershed. This paper studies the seasonal change of trace metal concentrations in precipitation and other potential sources in a typical subtropical watershed (Jiazhuhe watershed) located in the downstream of the Yangtze River of China. The results show that typical crustal elements (Al, Fe) and trace element (Zn) have high seasonal variation patterns and these elements have higher contents in precipitation as compared to other metals in Jiazhuhe watershed. In addition, there is no observed Pb in base flow in this study, and the concentration magnitudes of Al, Ba, Fe, Mn, Sr, and Zn in base flow are significantly higher than that of other metals. During different rainfall events, the dynamic export processes are also different for trace metals. The various trace metals dynamic export processes lead to an inconsistent mass first flush and a significant accumulative variance throughout the rainfall events. It is found that in this region, most of the trace metals in precipitation are from anthropogenic emission and marine aerosols brought by typhoon and monsoon.

     

Ten years of atmospheric methane observations at a high elevation site in Western China

In this paper, the continuous (1994–2001) and discrete air sample (1991–2001) measurements of atmospheric CH₄ from the Waliguan Baseline Observatory located in western China (36°17′N, 100°54′E, 3816 m asl) are presented and characterized. The CH₄ time series show large episodic events on the order of 100 ppb throughout the year. During spring, a diurnal cycle with average amplitude of 7 ppb and a morning maximum and late afternoon minimum is observed. In winter, a diurnal cycle with average amplitude of 14 ppb is observed with an afternoon maximum and morning minimum. Unlike most terrestrial observational sites, no obvious diurnal patterns are present during the summer or autumn. A background data selection procedure was developed based on local horizontal and vertical winds. A selected hourly data set representative of “baseline” conditions was derived with approximately 50% of the valid hourly data. The range of CH₄ mixing ratios, annual means, annual increases and mean annual cycle at Waliguan during the 1992–2001 were derived from discrete and continuous data representative of “baseline” conditions and compared to air samples collected at other Northern Hemisphere sites. The range of CH₄ monthly means of 1746–1822 ppb, average annual means of 1786.7±10.8 ppb and mean annual increase of 4.5±4.2 ppb yr⁻¹ at Waliguan were inline with measurements from sites located between 30° and 60°N. There were variations observed in the CH₄ annual increase patterns at Waliguan that were slightly different from the global pattern. The mean CH₄ annual cycle at Waliguan shows an unusual pattern of two gentle peaks in summer and February along with two small valleys in early winter and spring and a mean peak-to-peak amplitude of 11 ppb, much smaller than amplitudes observed at most other mid- and high-northern latitude sites. The Waliguan CH₄ data are strongly influenced by continental Asian CH₄ emissions and provide key information for global atmospheric CH₄ models.     

Coarse atmospheric aerosol: size distributions of trace elements

A sampler, employing nine single stage impactors placed in parallel within a portable wind tunnel, has been used to determine the metal content of coarse atmospheric aerosol. The wind tunnel maintains a constant flow environment for the collectors housed inside it, so that representative sampling conditions are achieved compared to the varied ambient wind conditions. At a flow rate of 8 m s⁻¹ the 50% cut-off diameters of the impactors ranged from 7.8 to 38.8 μm. Measurements were conducted at a rural and urban site near Colchester in south east England. The samplers were analysed by PIXE for P, K, Ca, Fe, Ti, Mn, Cu, V, Co, Cr, Br, Zn, Ni, Sc and Pb. It is found that the sampler can be employed to quantitatively characterise the elemental mass size distribution for aerosol larger than 10 μm. The results indicate that a small fraction of the above earth and trace elements’ metal mass is present in particles greater than 10 μm. This fraction for earth metals (Ca, K, Ti) is comparatively greater in the rural site than the urban site, while for trace metals (Mn, V, Cu, Cr) this fraction constitutes a more significant part of the coarse mass at the urban site. Trace element concentrations were of a similar order of magnitude to earlier literature reports. Although the number of measurements was limited it can be concluded that the size distributions obtained were characteristic of an unpolluted area.