Atmospheric Deposition of Trace Elements in Romania Studied by the Moss Biomonitoring Technique

The first systematic study in Romania of atmospheric pollution from heavy metals and other toxic elements based on moss analysis was undertaken as a Romanian–Russian–Norwegian collaboration, primarily in order to assess the general state of heavy metal pollution in Romania. An additional goal was to contribute to the European heavy metals in mosses survey, conducted under the auspices UNECE ICP Vegetation which reports to the Working Group of Effects of the Long-range Transboundary Air Pollution Convention. Samples of the moss species Hypnum cupressiforme, Hylocomium splendens and Brachytechium salebrosum and B. rutabulum were collected during the period 1995–2001. A total of 40 elements were determined using NAA and AAS. The total concentrations of arsenic, cadmium, copper, nickel, vanadium and zinc are presented in the form of contour maps. Generally, the observed concentrations in Romania are markedly higher than those observed in most other countries of Europe using the moss technique.     

Biomonitoring of Atmospheric Heavy Metal Deposition by Mosses in the Vicinity of Industrial Sites

At four industrial regions, heavy metal concentrations and calculated depositions were investigated by sampling and analysing mosses. In each region, a special spatial pattern of heavy metal concentrations was detected, reflecting the industrial processes. Metals most likely originating from the industrial sites showed an exponential decrease of concentrations and depositions with increasing distance from the pollution source. The exponential deposition pattern was in some cases modified by a series of natural factors, like the main direction of winds or orographic conditions. The distance at which deposition dropped to background values was up to 20 km. Beside the fact that the moss-metho is a useful tool for deposition measurement in the vicinity of stationary sources, some improvements for using this method are discussed, highlighting factors such as a proper calculation of deposition from concentrations, or the better knowledge of correlations between heavy metal concentrations in mosses and effects on human health.     

Field and Laboratory Exposures of Two Moss Species to Low Level Metal Pollution

Moss transplants of the species Rhytidiadelphus squarrosus and Pleurozium schreberi were used as active biomonitoring organisms as a part of a monitoring study to assess the impact of metals associated with ambient particles on mosses at roadsides.The moss samples were exposed at a semi-urban and roadside site for 3 months for subsequent analysis of metal concentration (Cu, Pb and Zn). This field experiment was carried out to investigate the accumulation of the metals over a period of 0, 4, 8 and 12 weeks at the two sites. The metal concentration in the moss samples generally increased with the length of exposure and was higher at the roadside site. The two species, however, showed slightly different accumulation patterns. In addition to the metal analysis chlorophyll concentrations were analysed as a measure of stress response in the moss samples of the above mentioned field exposures. The chlorophyll concentrations of exposed mosses showed no or only weak correlations to the concentration of the three metals measured in the moss, which suggests that other conditions have a greater influence on the chlorophyll concentration.The effect of a single metal on the moss was studied in laboratory experiments exposing R. squarrosus to the metals copper, lead and zinc at concentrations based on the above field data. At the concentrations used there was a significant reduction in the chlorophyll a concentration after exposure to copper.     

Continental origin and industrial sources of trace metals in the Northwest Atlantic troposphere

Trace metals (Mn, Fe, Ni, Cu, Zn, Cd, Pb and stable lead isotopes) have been analyzed in precipitation and total aerosols collected in the northwest Atlantic troposphere in April and November 1989. According to stable lead isotope signatures we encountered two main air mass sources, Mediterranean easterlies (206Pb/207Pb=1.131) and US westerlies (206Pb/207Pb=1.195–1.205). The phasing out of leaded gasoline has been invoked to explain the decrease of the 206Pb/207Pb ratios from 1.22 to 1.20 for the past 10 years in North America. Based on trajectory analyses, intermediate 206Pb/207Pb ratios are explained by a mixing of pure US westerlies with Canadian air masses (206Pb/207Pb=1.190–1.195) or Mediterranean air masses (206Pb/207Pb=1.18–1.19). Isentropic trajectories are very useful in explaining the variability of trace metal concentrations, a result of the fluctuating transport range of anthropogenic aerosols to remote marine areas of the North Atlantic. Lead concentrations appear to be closely correlated to the air mass transport patterns as defined from the meteorological analyses. For instance oceanic air masses transported over remote marine areas for more than three days were characterized by lead concentrations 2 to 10 times lower (Pb=0.5 to 2 ng/scm) than coastal air masses (Pb=3 to 10 ng/scm).Anthropogenic trace metal concentrations are generally in good agreement with the air mass signatures which display Pb and Cu, Ni, Zn concentrations higher than 2 and 10 ng/scm respectively in aerosol samples for the US source. Trace metal elemental ratios and soil enrichment factors were used to define industrial sources. Aerosol originating from the US exhibits the distinct industrial signature of Cu/Ni production and coal-oil combustion, while steel metallurgy could account for more than 50% of the overall Mn input into the Northwest Atlantic ocean.     

Trace Metals in Mosses in the Estonian Oil Shale Processing Region

Electric energy production and most heavy industry in Estonia are concentrated in the north-eastern part of the country. Thermoelectric power plants (total maximal capacity over 3 GW), cement and chemical industries are fueled by Kukersite oil shale, mined nearby. The mineral part of oil shale is rich in trace metals that can accumulate in the local ecosystem. Samples of epigeic mosses Pleurozium schreberi and Hylocomium splendens were taken in 1992, 1997 and 2002 from sites 1 km to 30 km from the main air pollution sources and analysed for Cd, Cr, Cu, Fe, Ni, Pb, V and Zn. For background data collection, analogous measurements within the national monitoring programme were used. Raster maps of concentrations were generated from the measurements, using the Kriging algorithm. These maps were compared with the model-estimated (AEROPOL model) maps of fly ash and cement dust deposit from the past. The concentration of trace metals in mosses is highly (Cr, Fe, Ni, V) or moderately (Cd, Cu, Pb, Zn) affected by the airborne emissions of the oil shale industry. During the past decade the uptake of the first group of elements in the industrial zone has decreased 3–4 times in proportion to emissions.     

Integrative Monitoring Analysis Aiming at the Detection of Spatial and Temporal Trends of Metal Accumulation in Mosses

Goal and Scope. The UNECE heavy metals in Mosses Surveys provide data on the accumulation of metals in naturally growing mosses throughout Europe. Using Germany as an example, this article concentrates on the elaboration and application of methods of data analysis that are necessary for a comprehensive interpretation of spatial and temporal trends in metal accumulation.Methods and Results. The sampling of mosses, and the chemical analysis of Cr, Cu, Fe, Ni, Pb, Ti, V and Zn in 1990, 1995 and 2000 are summarized briefly. The variogram analyses detect distinct autocorrelation structures in the sample data which may consequently be estimated for all sites in Germany without monitoring metal accumulation by means of ordinary kriging. A procedure for the geostatistical detection of spatial outliers was developed and applied and, after the elimination of the spatial outliers, several measurements were seen to indicate an adequate quality of the geostatistical estimations. The cluster analyses of the z-transformed estimation data result in a nominal multi-element index that indicates regional metal accumulation types over time. Percentile statistics serve for computation of an ordinal, scaled, multi-element accumulation index which is spatially differentiated over time in terms of multivariate, statistically defined ecoregions. The integrative statistical analysis reveals, from 1990 to 2000, that the metal accumulation declines up to 80% in some of the ecoregions. Hot spots of metal accumulation are mapped and interpreted by means of metadata analysis.Conclusions. Dot maps depict the spatial structure of the metal accumulation without spatial bias. This information, detailed with respect to metal species and space, should be generalized for better supporting the interpretation. The combination of geostatistical analysis and estimation, percentile and multivariate statistics is suitable for the calculation of indices that serve for a comprehensive mapping of metal accumulation in the ecoregions over time, for quantifying the bias of the surface estimation, and for mapping spatial outliers and hot spots of metal accumulation.     

Regional model for formation,dynamics and Long-range transport of atmospheric aerosol: Study of atmospheric aerosol properties in Europe

This paper provides performance evaluation of the EMEP (Cooperative Programme for the Monitoring and Evaluation of the Long-range Transmission of Air Pollutants in Europe) model, formulated in [1], and presents model calculation results. A satisfactory agreement is found between calculated and observed PM₁₀ and PM_2.5 concentrations (i.e., particulate matter with diameters smaller than 10 and 2.5 μm) and their chemical composition for different parts of Europe for the years 2001–2004. The model manages to reproduce observed regional gradients of background PM₁₀ and PM_2.5, with spatial correlations being 0.70 and 0.80, respectively, while the temporal correlation coefficients between modeled and measured daily PM vary mostly between 0.4 and 0.8 at EMEP sites. The agreement between calculated and observed aerosol number concentrations is worse than for mass concentrations. Model calculated PM₁₀ and PM_2.5 concentrations and chemical composition in Europe for the year 2004 are presented, as well as their interannual variations in the period 2000–2004. Further, contributions of different sources to PM₁₀ and PM_2.5 are estimated. Model results show that in 2004, background PM₁₀ and PM_2.5 exceeded EU critical levels and WHO recommended guidelines in a number of European regions. They also show that the transboundary transport contributes considerably to PM pollution in the European countries.     

河南省某高校校园土壤重金属污染及其防治

在河南省某高校校区内的规模绿地上采集21个土壤样品,在郊区农田采集2个对照样品。按照国家标准方法,测定了土壤Cu、Zn、Ni、Pb和Cr的含量。结果发现:校园土壤中Ni、Zn和Cr发生了不同程度的富积;土壤重金属含量空间变异明显;校园土壤普遍发生了Zn污染,平均污染分指数达2.48,中度和重度污染样点占总样点的57.14%;绝大部分样点的综合污染指数均大于1,其中轻度污染样点13个,中度污染样点5个,重度污染样点2个。根据校园土壤的实际,应从严格控制污染物排放、翻土和客土改良、增施有机肥料、植物修复等方面防治校园土壤重金属污染。     

Calibration of Four Species of Tillandsia as Air Pollution Biomonitors

Many organisms have been used as bioindicators of atmospheric contamination, with moss and lichen species being the most common. However, studies using epiphytic vascular species of Tillandsia have shown a good correlation between the presence of pollutants and the bioindicator's response. Therefore, the aim of our investigation was to calibrate and compare the response of four Tillandsia species of Argentina to ascertain whether they could be used as atmospheric contamination biomonitors. For this, we analysed the correlation between the levels of heavy metals in total atmospheric deposition samples and: a) their rate of enrichment; b) the physiological response of the plant samples. Tillandsia samples collected from a non contaminated area in the province of Córdoba were transplanted to four areas in the capital city with different sources of pollution (industrial or traffic emissions). They were exposed for a period of 3 to 6 months after which the concentrations of Pb, Ni, Fe, Zn, Cu and S as well as the physiological parameters of foliar damage were determined. Simultaneously samples of total atmospheric deposition were also taken.The highest level of metal enrichment was found in T. capillaris followed by T. tricholepis, T. permutata and T. retorta. Also, the use of a foliar damage index proved to be effective and could be a useful tool to evaluate different levels of atmospheric quality in these species. The rate of heavy metal deposition was higher in the industrial area for all metals except for Zn whose values were higher in areas with high levels of traffic.     

Heavy metals in aerosol samples from the Eastern Pamirs collected 2004–2006

This study measured the concentration of heavy metal elements in atmospheric aerosol samples collected between July 2004 and April 2006 at a remote site on Mt. Muztagata (38°17'N, 75°01'E, 4430 m), in the Eastern Pamirs. Inductively coupled plasma mass spectroscopy (ICP–MS) results show that the air at Muztagata contains low concentrations of As and heavy metal elements (Cr, Ni, Cu, Zn, Cd, Pb, and Bi), comparable with those in the Arctic — far lower than in heavily populated or industrialized areas. Observed enrichment factor (EF) values greater than 10 for those elements suggest partly anthropogenic sources. Seasonal variations in the concentrations of Zn, Cd, Pb, Bi, and As resemble those of crustal Al, with greater concentrations during the summer but lower ones in winter. Our results reveal that the background atmosphere in remote inner Asia is only weakly affected by anthropogenic pollution, and demonstrate that high heavy metal concentrations occur during summer but with greater EF values during the winter. The air mass back-trajectory analyses suggest that pollution from West Asia, Central Asia, and South Asia are the main possible source areas that contribute to the heavy metals in aerosols at Muztagata.     

Trace gases and PM2.5-bound metal abundance over a tropical urban environment,South India

Pre and Post-Monsoon levels of ambient SO₂, NO₂, PM_2.5 and the trace metals Fe, Cu, etc. were measured at industrial and residential regions of the Kochi urban area in South India for a period of two years. The mean PM_2.5, SO₂ and NO₂ concentrations across all sites were 38.98?±?1.38 µg/m³, 2.78?±?0.85 µg/m³ and 11.90?±?4.68 µg/m³ respectively, which is lower than many other Indian cities. There was little difference in any on the measured species between the seasons. A few sites exceeded the NAAQS (define acronym and state standard) and most of the sites exceeded WHO (define acronym and state standard) standard for PM_2.5. The average trace metal concentrations (ng/m³) were found to be Fe (32.58)?>?Zn (31.93)?>?Ni (10.13)?>?Cr (5.48)?>?Pb (5.37)?>?Cu (3.24). The maximum concentration of trace metals except Pb were reported in industrial areas. The enrichment factor, of metals relative to crustal material, indicated anthropogenic dominance over natural sources for the trace metal concentration in Kochi’s atmosphere. This work demonstrates the importance of air quality monitoring in this area.

     

Contraction and convergence of in-use metal stocks to meet climate goals

The foundations of modern society are based on metals, yet their production is currently placing considerable strain on the Earth’s carrying capacity. Here, we develop a century-long scenario for six major metals (iron, aluminum, copper, zinc, lead, and nickel) harmonized with climate goals, with the goal of establishing science-based targets. We show that for the metal sector to contribute proportionally to emission reductions targets of the industrial sector, global in-use metal stocks need to converge from the current level of around 4 t/capita to about 7 t/capita. This will require today’s high-income countries to contract their per capita stock from current levels of about 12 t/capita to make room for growth in countries that are presently classified as middle- and low-income countries. In such a contraction and convergence scenario, primary production of all six metals will peak by 2030, and secondary production will surpass primary production by at least 2050. Consequently, cumulative ore requirements over the 21st century will remain below currently identified resources, implying that natural ore extraction will be limited by emissions budgets before existing resources can be depleted. Importantly, realizing such system changes will require urgent and concerted international efforts involving all countries, but specific responsibilities will vary according to income level. Namely, wealthy countries will need to use existing metal stocks more intensively and for longer periods to reduce stock replacement demand, while poor countries will need to develop long-lasting and material-efficient infrastructure to curtail stock expansion demand in the first half of the 21st century.     

Air Pollution Studies in Central Russia (Tver and Yaroslavl Regions) Using the Moss Biomonitoring Technique and Neutron Activation Analysis

Data of 34 elements, including heavy metals, halogens, rare earth elements, U, and Th in 139 moss samples, collected in Central Russia in 2000–2002 in the Tver and Yaroslavl regions and in the northern part of the Moscow region, are presented. Factor analysis with VARIMAX rotation was applied to identify possible sources of the elements determined in the mosses. The seven resulting factors represent crust, vegetation and anthropogenic components. Some of the factors were interpreted as being associated with ferrous smelters (Fe, Zn, Sb, Ta); combination of non-ferrous smelters and other industries (Mn, Co, Mo, Cr, Ni, W); an oil-refining plant, and oil combustion at the thermal power plant (V, Ni). The geographical distribution patterns of the factor scores are also presented. Dependency equations of elemental content in mosses versus distance from the source were derived.     

Biomonitoring of Element Deposition Using Mosses in the 2000 French Survey: Identifying Sources and Spatial Trends

In the year 2000, the elemental composition of mosses collected from 528 French sites has been studied as part of the 2000 European Moss Survey. Five moss species were collected: Scleropodium purum (56%), Pleurozium schreberi (18%), Hypnum cupressiforme (18%), Thuidium tamariscinum (4.5%.) and Hylocomium splendens (3.5%). Mosses were kept whole for analysis, including green and brownish parts. Summary statistics on element concentrations (Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Na, Ni, P, Pb, Rb, Sr, V and Zn), and comparisons made with data from the other 27 participating European countries are shown here. The sources of these elements are identified using calculations of enrichment factors (EF) and principal component analysis (PCA). Finally, the spatial distribution in France of 10 elements is also shown, using maps underscoring areas showing highest concentration levels for each metal.     

中亚五国局地暴雨及其环流特征

采用NCEP/NCAR全球逐日格点再分析资料,分析了中亚五国暴雨的落区特征,归纳了不同落区暴雨环流形势的天气学特点。结果表明：中亚五国暴雨次数较少,局地性强。暴雨三个相对集中的区域分别为哈萨克斯坦西部、北部和东部。中亚五国暴雨的环流可分为11个环流型。中亚五国暴雨的影响系统主要为东欧低值系统东南伸,西西伯利亚低值系统西南伸,以及中纬度西风带上东移的短波。伊朗脊是控制中亚五国降水的主要天气系统。中亚五国降水主要有3个水汽源地,分别是地中海,大西洋和北冰洋。     

Sulphur atmospheric deposition in areas with different anthropogenic loads in Belarus

This article presents some results of an investigation of sulphur atmospheric deposition in areas with different anthropogenic loads in Belarus. Through sampling and chemical analysis of precipitation, new data about sulphate concentrations in precipitation and atmospheric deposition of sulphur in different conditions, including regional background conditions, a large industrial city and a zone affected by point source of sulphur emission, were obtained. Comparison of the chemical composition of precipitation at three sampling locations has shown that the local emission of sulphur compounds has a minor influence on local sulphur deposition. This data points to the dominant role of transboundary transfer of sulphur in contamination and acidification of the environment in Belarus.     

Heavy Metal Accumulation in the Lichen Evernia prunastri Transplanted at Urban, Rural and Industrial Sites in Central Italy

The lichen Evernia prunastri has been employed for biomonitoring the atmospheric deposition of heavy metals at urban, rural and industrial sites in Central Italy. Lichen samples have been collected in a control site 1500 m a. s. l. (Parco Nazionale dAbruzzo, Central Italy) and subsequently transplanted at urban site (Cassino city center), at rural location 7 km away from Cassino (S. Elia Fiumerapido) and at industrial location (Piedimonte S. Germano) surrounding an automobile factory. Once defined the surface of impact relevant to this work, the lichen samples were transplanted at the four cardinal points of each site. Studies of bioaccumulation of Pb, Cd, Cr, Cu and Zn in lichen samples were performed five times at regular intervals between November 2000–December 2001. Microwave digestion of the samples and graphite furnace atomic absorption spectrometry were employed for the heavy metal determinations. Suitable certified reference materials (CRM) were used for validation of the analytical methodology. Results showed the ability of Evernia prunastri to accumulate the heavy metals under study. As expected, the area chosen as control site showed significantly (Friedman test, cluster analysis) lower impact in comparison to the other sites and the rural site showed smaller impact than the urban and the industrial sites.     

Lichen as quantitative biomonitors of atmospheric heavy metals deposition in Central India

Three different growth forms of lichens belonging to six species; Phaeophyscia hispidula, Parmotrema praesorediosum (foliose); Caloplaca subsoluta, Diploschistes candidissmus (crustose) and Peltula euploca, Phylliscum indicum (squamulose) were studied comparatively for the biomonitoring of Al, Cd, Cr, Cu, Fe, Ni and Zn in Mandav city in central India. Based on the anthropogenic activities three sites were selected for lichen collection. To identify the sources of heavy metal pollution, their concentration was analyzed in thallus as well as in their respective substrates. The thallus of studied lichens showed higher concentration of metals such as Cd, Cr, Ni and Zn, while most of the metals were absent or present in negligible amount in substrates (Fe, Al, Cu), which proves that the accumulated metals were air borne. The foliose lichens (P. hispidula and P. praesorediosum) found highly significant in metal accumulation at each sites followed by crustose and squamulose forms. Lichen samples collected from site 2, adjacent to road side accumulated maximum quantities of Zn, Ni, Cd and Cr whereas the city centre (Site 1) had maximum concentrations of Fe, Cu and Al. The site 3 situated away from the city had lowest amount of all the metals. The analysis of variance and LSD indicated that the metal concentrations among lichen species as well as between substratum is significant at p < 0.05% and P < 0.01% level respectively.     

南京江北地区菜地土壤重金属污染特征及评价

在南京市浦口和大厂的五大主要功能区（工业区、交通干线、居民区、蔬菜生产基地和风景区）分别布置采样点,共采集了75个菜地耕层土壤样品,以Cd、Cu、Pb和Zn等典型污染重金属元素的全量数据为基础,运用经典统计分析、综合污染指数和地统计分析相结合的方法对土壤重金属污染进行评价。结果表明,Cd、Cu和Zn分别超出其南京地区土壤背景值的5．42、1．84和1．14倍,Pb未超出。不同功能区菜地土壤的重金属全量水平存在明显差异,其中工业区菜地土壤的重金属污染较为严重。对于Cd和Cu,单因子污染指数大于1的样点数达100％,Zn为52％,Pb为2．67％。研究区内菜地土壤重金属的综合污染指数为4．12,属于中度污染。Cu的空间相关性很弱,Cd、Pb和Zn具有中等的空间结构性;四种重金属的空间相关尺度较为接近。Cd、Cu和Zn的单因子污染指数具有相似的空间分布,总体呈现出南高北低的带状递减趋势,且高峰值具有空间分布的趋同性,而Pb的单因子污染指数分布呈现西北和东南两端高,中间较低的趋势。综合污染指数的空间分布显示,研究区大部分菜地土壤处于中度重金属污染水平,钢铁生产厂周边的斑块状区域重金属污染更加严重。     

Monitoring of Short-Term Heavy Metal Deposition by Accumulation in Epiphytic Lichens (Hypogymnia Physodes (L.) Nyl.)

Many lichens are very sensitive to air pollution due to their symbiotic nature. However, they are generally less sensitive to toxic effects of trace elements; therefore they can be used as accumulator organisms for estimating concentrations of these elements in the environment. Heavy metal accumulation in lichens is a commonly used bioindication method for assessing heavy metal ambient levels. An active biomonitoring method was used for the determination of short-term accumulation of zinc, lead, arsenic and cadmium by epiphytic lichens transplanted at different localities in Slovenia polluted by heavy metals. The atomic absorption spectrophotometry method was used for the determination of heavy metal content in lichen thalli. The content of heavy metals in lichens collected in the background area with clean air (Rogla, Pohorje Mountains) was used as the reference value. Lichens were transplanted from Rogla using the branch transplantation technique for a period of 6 months in the surroundings of Slovenian thermal power plants (Velenje, otanj, Zavodnje, Veliki Vrh, Vnajnarje, and Dobovec) and close to the lead and zinc ore smelter at erjav. The monthly accumulation of heavy metals was comparable within years at selected locations. Heavy metal pollution was the highest at erjav despite of remediation of lead and zinc ore smelter. The monthly accumulation of all four heavy metals was statistically significantly higher in lichens exposed at erjav than at other localities.