Monitoring atmospheric metal pollution: a review of the use of mosses as indicators

This article reviews the literatureon the use of mosses for monitoring atmospheric metalpollution. It discusses the nature of mosses, themechanisms for moss uptake of metals from the air andwet precipitation, the various forms in which mossesare used for this purpose, and cases in which mosseshave been used for monitoring local hot spots ofpollution, and regional patterns of metal pollution.Also highlighted are the questions of uptake of metalsfrom the substrates, interspecies differences, and acomparison of the effectiveness of mosses with otherindicator materials, among other issues.     

Analysis of selected biomonitors to evaluate the suitability for their complementary use in monitoring trace element atmospheric deposition

The biomonitoring properties of oak tree bark compared with the epiphytic moss Hypnum cupressiforme and the influence of the tree bark, as its growth substrate, on the content of heavy metals in moss were investigated. Samples of the epiphytic moss H. cupressiforme and oak tree bark (Quercus spp.) were collected in Eastern Romania at a total of 44 sampling sites. Parallel moss and bark samples were collected from the same sides of the trunk circumference. V, Cr, Ni, Cu, Zn, As, Mo, Cd, In, Tl, Sn, Pb, and Bi were determined by ICP-MS. Principal component analysis was used to identify possible sources of metals in bark and moss. Six factors explaining 87 % of the total variance in the data set were chosen. The main factors represent long-range atmospheric transport of elements (Zn, Cd, (Pb), Bi, (Mo), (Tl)), local emissions from industrial sources (As, Cr, Ni, V), road traffic (Pb, Zn) and agricultural activities (Cu, (Zn)). The element concentrations in moss and bark samples are of the same order of magnitude. For almost all the elements, higher concentrations were obtained in moss. Significant correlations between concentrations in moss and bark samples were obtained for 7 of the 13 elements: V, Ni, Cu, Zn, Cd, In, and Bi, all typical anthropogenic pollutants. The use of tree bark for monitoring purposes might be an alternative in areas where there is a scarcity of mosses.     

Biomonitoring of polycyclic aromatic hydrocarbons in urban and industrial environments of the Western Black Sea Region,Turkey

This research was carried out in the cities of Zonguldak and Eregli, which have been characterized as urban and industrial environments of the Western Black Sea Region, Turkey, in order to assess the contamination of polycyclic aromatic hydrocarbons (PAHs) using mosses as biomonitors. The methodology involved the collection of moss samples (Hypnum cupressiforme), ultrasonic extraction with dichloromethane, cleanup using silica gel and analysis by liquid chromatography with ultraviolet detection. The total PAH concentrations ranged from 78.1 to 1693.5 ng g^?1 in Zonguldak and from 15.2 to 275.1 ng g^?1 in Eregli. The total PAH concentration in Eregli was about six times lower than that in Zonguldak, revealing the importance of switching from coal to natural gas in residential heating. The diagnostic ratios and the correlation analysis have indicated that coal combustion and traffic emissions were the major PAH sources at both sites. The contour maps were constructed for the determination of spatial distributions of total PAHs, and it was shown for Zonguldak as well as for Eregli that the PAH pollution was much more predominant in highly populated regions. Moving away from the city centres, a gradual decrease in PAH pollution rates was observed.     

Assessment of the impact of petroleum and petrochemical industries to the surrounding areas in Malaysia using mosses as bioindicator supported by multivariate analysis

Biomonitoring of multi-element atmospheric deposition using terrestrial moss is a well-established technique in Europe. Although the technique is widely known, there were very limited records of using this technique to study atmospheric air pollution in Malaysia. In this present study, the deposition of 11 trace metals surrounding the main petroleum refinery plant in Kerteh Terengganu (eastern part of peninsular Malaysia) has been evaluated using two local moss species, namely Hypnum plumaeforme and Taxithelium instratum as bioindicators. The study was also done by means of observing whether these metals are attributed to work related to oil exploration in this area. The moss samples have been collected at 30 sampling stations in the vicinity of the petrochemical industrial area covering up to 15 km to the south, north, and west in radius. The contents of heavy metal in moss samples were analyzed by energy dispersive x-ray fluorescence technique. Distribution of heavy metal content in all mosses is portrayed using Surfer software. Areas of the highest level of contaminations are highlighted. The results obtained using the principal components analysis revealed that the elements can be grouped into three different components that indirectly reflected three different sources namely anthropogenic factor, vegetation factor, and natural sources (soil dust or substrate) factor. Heavy metals deposited mostly in the distance after 9 km onward to the western part (the average direction of wind blow). V, Cr, Cu, and Hg are believed to have originated from local petrochemical-based industries operated around petroleum industrial area.     

The potential of elemental and isotopic analysis of tree bark for discriminating sources of airborne lead contamination in the UK

Samples of tree bark, which accumulate airborne material, were collected from seven locations in the UK to provide an indication of the magnitude and source of lead pollution. Measurement of the Pb content and 206/207Pb stable isotope ratio by inductively coupled plasma mass spectrometry revealed significant differences between the sites. The concentration of Pb varied over almost four orders of magnitude from 7.2 to 9,600 micrograms g-1, the maximum values being found near a 'secondary' Pb smelter. The 206/207Pb isotope ratios varied from 1.108 +/- 0.002 to 1.169 +/- 0.001. The lowest Pb concentrations and highest isotope ratios were detected in bark samples from the Scilly Isles, reflecting the low-level of industry and road traffic. In contrast, samples obtained from a city centre (Sheffield) and near a motorway (M1) contained 25-46 micrograms g-1 Pb and recorded the lowest 206/207Pb ratios. Higher concentrations in the vicinity of a coal-fired power station recorded a 206/207Pb ratio of 1.14, suggesting a significant contribution from fly-ash. The relative contribution of lead from petrol (206/207Pb = 1.08) and other sources such as coal (206/207Pb = 1.18) were thus estimated using mass balance equations. Tree bark near the lead smelter recorded an intermediate 206/207Pb ratio of 1.13 reflecting the processing of material of mixed origin.     

Speciation of nickel in Canadian subbituminous and bituminous feed coals, and their ash by-products

The nickel species in the feed coals and ash by-products from seven Canadian power plants (including one with a fluidized bed combuster) burning local subbituminous and bituminous coals with sulfur contents ranging from 0.22 to 3.6% have been examined using nickel XANES spectroscopy. XANES spectroscopy of Ni in coal and coal derived ash is complicated by a poor signal : noise ratio due to fluorescence of the much more abundant iron in the coal. Nevertheless, it has proved possible to show that the Ni environment in coals varies from largely oxidic species to mixtures of Ni-containing oxide and sulfide species. The nickel in one oxidized coal appears to be present as nickel sulfate. Nickel in all bottom and fly ash samples examined appears also to be present largely in oxygen anion environments. With the exception of one fly ash sample, for which the Ni exhibited spectral features similar to those for Ni(2+) in spinel or oxide phases, the nickel in the bottom and fly ash samples appears to exist largely as Ni(2+) in environments similar to those reported for Ni in silicate glasses. The data obtained indicate that the presence of potentially carcinogenic nickel sulfides in ash by-products from combustion of these coals is unlikely.     

Environmental indicators for long-range atmospheric transported heavy metals based on national moss surveys

Environmental indicators for long-range atmospheric transported heavy metals have been developed. The indicators are based on data for Pb and Cd from national moss surveys which are performed regularly in Norway. The interpolation programme kriging has been used to transform the data from irregular grids to regular grids. Contour maps have been produced, and areas above estimated background levels for Pb and Cd in mosses have been calculated. The indicators are used to characterise the atmospheric deposition of long-range atmospheric transported heavy metals and monitor the changes with time.     

Evolution of water chemistry in natural acidic environments in Yangmingshan,Taiwan

In Yangmingshan National Park, located in the northern part of the Taiwan Island, there is a very rare area where fish (Channa asiatica) live in spite of acid environments. The origin of the acid in local acid ponds and rivers and the evolution of the water chemistry are discussed on the basis of sulfur stable isotope ratios and chemical equilibria. One of the sources of the acid is sulfuric acid, which is derived from the oxidation of hydrogen sulfide in volcanic gas gushing out from fumaroles around the area and from acid deposition supplied from Taipei City. It is also derived from the oxidation of pyrite: the sulfur stable isotope ratios of delta 34S of +1@1000 to +4@1000 (relative to CDT) of sulfate in acid pond waters (pH 3-4) could be related to those of hydrogen sulfide in volcanic gas, pyrite in local pond sediments and soils, and sulfate in rain water. One acid source is sulfuric and hydrochloric acids arising in springs from geothermal activity: the delta 34S values were characterised by +13@1000 to +17@1000 sulfate-S, which was provided by a disproportionation reaction of sulfur dioxide in the depths. Another acid source could be the oxidation of iron(II). Under acidic conditions, the water-rock reaction gives rise to high concentrations of aluminium and iron. While flowing down surface streams, iron(II) is oxidised to iron(III) and then hydrolysed to cause further acidification under oxic conditions. The concentrations of iron and aluminium are controlled by redox and dissolution equilibria.     

Airborne organic micropollutant concentrations in mosses and humus as indicators for local versus long-range sources

The concentrations of HCB, PCB, and PAH in epiphytic mosses (Hylocomium splendens and Pleurozium schreberi) and forest humus were used to study the atmospheric exposure of conferous forests in a region in central Sweden. Air concentrations of HCB and PCB were monitored around an expected source. Moss contamination was used as a short-term exposure indicator, and humus contamination was assumed to indicate long-term exposure to HCB, PCB, and PAH.The level of HCB in mosses (0.4–1.7 ng/g, by dry weight, DW) complied well with background values. The levels of PCB measured as a sum of 7 identified PCB-congeners varied between 2–28 ng/g DW, with the highest levels in moss from the western part of the region, and decreasing concentrations from west to east. Around an expected PCB source in the southeastern part of the region the concentrations of PCB declined with increasing distance from the source area. The identified PAH concentrations in mosses varied between 39 and 730 ng/g DW. The PAH content in the mosses consisted mainly of nonvolatile PAH while the more volatile PAH were below the detection limit. The levels of HCB in humus were slightly more than in mosses (0.4–3.3 ng/g DW), and complied well with the background values. Sum PCB in the humus varied between 2 and 28 ng/g DW. The PAH in the humus were mainly nonvolatile PAH. The PAH concentrations in humus varied between 99 and 2600 ng/g DW. The air concentrations of PCB around the expected source (radius <1.5 km) were higher than background levels, and most likely caused the raised levels of PCB measured in the moss nearby.     

Nitrogen multitemporal monitoring through mosses in urban areas affected by mud volcanoes around Mt. Etna, Italy

Nitrogen emissions were assessed by using mosses as bioindicators in a densely inhabited area affected by mud volcanoes. Such volcanoes, locally called Salinelle, are phenomena that occur around Mt. Etna (Sicily, Italy), and are interpreted as the surface outflow of a hydrothermal system located below Mt. Etna, which releases sedimentary fluids (hydrocarbons and Na-Cl brines) along with magmatic gases (mainly CO₂ and He). To date, N emissions from such mud volcanoes have been only quantitatively assessed, and no biomonitoring campaigns are reported about the cumulative effects of these emissions. This study analyzed N concentrations in moss, water and soil samples, collected in a 4-year monitoring campaign. The bryophyte Bryum argenteum, a species widely adopted in surveys of atmospheric pollution, was used as a biological indicator. N concentrations in biomonitors showed relatively low values in the study sites. However, the results of this study suggest that N emissions from Salinelle may have an impact on surrounding ecosystems because N values in moss and water showed a significant correlation. N oxides, in particular, contribute to acidification of ecosystems, thus multitemporal biomonitoring is recommended, especially in those areas where N emitting sources are anthropogenic and natural.     

云南省宣威市和富源县空气和土壤中多环芳烃污染水平研究

宣威市和富源县位于我国云南省东北部,是全世界肺癌发病率最高的地区之一。当地居民在不通风的房间内燃烧烟煤做饭或取暖造成了严重的室内空气污染。研究表明,长期暴露在燃煤造成的污染物中是导致两地居民肺癌持续高发的主要原因,多环芳烃是最可疑的致病因子之一。2008年1月,分别用聚胺脂泡沫和玻璃纤维滤膜采集了当地9个点位室内、室外空气中气相和颗粒物相中的多环芳烃,同时采集了对应点位的土壤样品。通过对样品的分析,考察了当地空气和土壤中多环芳烃的污染水平、特征以及来源。结果证明,当地空气和土壤中存在严重的多环芳烃污染,室内污染显著高于室外,然而随着当地工业的发展室外污染同样不可忽视,主成分分析结合比值法证明,当地室内外多环芳烃的主要污染源来自于煤炭的燃烧。对空气颗粒物和土壤中多环芳烃浓度进行了比较,对土壤中多环芳烃的来源进行了验证。     

铅锌冶炼厂周边土壤铅源的铅同位素示踪

以某铅锌冶炼厂周边土壤为研究对象,通过对其原料及周边土壤中铅含量的检测,结果显示：该冶炼厂周边土壤铅质量比在22.73mg/kg～126.51mg/kg之间,平均值为42.68mg/kg,是当地土壤铅背景值的1.85倍.采用铅质量比空间分布分析和同位素混合模型计算分析了冶炼厂周边土壤中铅的可能来源,分析表明：土壤铅质量比的空间分布及铅同位素比值与冶炼厂的焦化原料煤相近,焦化原料煤对周边土壤铅污染贡献最大.     

Polycyclic aromatic hydrocarbons (PAHs) in the air of Chinese cities

Polycyclic aromatic hydrocarbons (PAHs) were determined in the air of 37 cities and 3 rural locations across China during the winter, spring, summer and autumn of 2005, using polyurethane foam (PUF) disks as passive air samplers (PAS). Winter and autumn concentrations in cities exceeded spring and summer values. Concentrations were amongst the highest in the world; seasonally averaged autumn/winter values in some cities in the north and north-west of China exceeded proposed European Union air quality standards. Several factors, acting in combination, influenced air concentrations. A significant negative correlation was found between average annual city concentrations and the annual average temperature, while winter time PAH concentrations correlated with estimated coal consumption. The highest total PAH concentrations and loadings of high molecular weight compounds generally occurred in major cities located on higher land (500-2000 m), where relatively cold winters and higher coal consumption occurs. Lower values occurred in cities located in the south and east China and along the coastal regions. Molecular markers indicated incomplete combustion of fossil fuels dominated the urban air and gave evidence for photo-decomposition of selected compounds.     

Verifying emission factors and national POPs emission inventories for the UK using measurements and modelling at two rural locations

Different approaches are used to verify the adequacy of emission factors (EFs) and their use in emission inventories of persistent organic pollutants (POPs). The applicability of EFs was tested using atmospheric dispersion modelling to predict atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and resulting toxic equivalents (SigmaTEQ) and particulate matter <10 microm (PM(10)) in two rural locations in northern England (UK). The modelling was based on general assumptions of fuel composition, consumption and heating needs to simulate emissions of POPs from the domestic burning of coal and wood where ambient measurements were made in the winter of 1998. The model was used to derive the local contribution to ambient air concentrations, which were estimated independently based on comparative air measurements. The results support the hypothesis that in both villages, the majority of PAHs and the lower chlorinated PCDFs were locally released. The situation for PCBs and polychlorinated naphthalenes (PCNs) was different. While the EFs show the release of both compound groups from the domestic burning of coal and wood, the ambient levels of these "legacy POPs" in the villages were still clearly dominated by other sources. Rural areas relying mainly on fossil fuels can exceed the proposed UK ambient air quality standard for benzo[a]pyrene during winter. The measured EFs were then used to estimate the importance of the domestic burning of coal and wood to national emission inventories for these compound classes. Extrapolations to the UK suggest that the domestic burning of pure wood and coal were minor emitters for chlorinated POPs but contributed strongly to PAH and PM(10) levels in 2000. Finally, the UK's national POPs emission inventories based on source inventories and EF, as used here, were compared to estimates derived using the increase in atmospheric concentration of selected POPs.     

An Analogy on Assessment of Urban Air Pollution in Turkey Over the Turn of the Millennium (1992–2001)

Rapid industrialization and urbanization in Turkey, especially over the last twenty five years, has provided better living standards to its residents, but it also caused a decrease in environmental quality. In late 1970's, air quality monitoring activities were started in some major cities by individual researchers in Turkey. It was just around the 1990's that a countrywide program on continuous air pollution monitoring in major province centers and selected large towns was launched. The impact of air pollution on people depend on various factors, such as existence and magnitude of coal powered energy generation plants, type of urban heating and their efficiency, and the numbers and specifications of vehicles. In this study, current Turkish urban air quality over the turn of the Millennium (1992–2001) is studied in the light of the country's worst cities in terms of outdoor air quality, the number of upper respiratory diseases, sinusitis, bronchitis, and pneumonia cases in these provinces reported by the state medical treatment facilities in 2001. The population that is under outdoor urban air pollution hazard was computed. A comparative analysis between the provinces that use natural gas and others that use fossil fuels was also completed in order to project monetary gains if the studied provinces will transform their indoor heating and industrial operations to be run by natural gas or other cleaner energy sources. If natural gas use in air polluted urban centers could be realized in the near future, approximately 212 to 350 million US dollars per annum could to be saved just by reducing health related problems caused by outdoor air pollution.     

Global methane emissions from the world coal industry

The Coal Industry Advisory Board (CIAB) of the International Energy Agency (IEA) estimated the total methane emissions from worldwide mining, treatment and storage of coal to be approximately 25 million tonnes/year for 1990. Slightly more than one million tonnes of methane are utilized by the industry. Thus, the net annual discharge to the atmosphere is 24 million tonnes. Methane emissions data were available for the U.S., the U.K., former U.S.S.R., Australia, China, Germany, Poland and Czechoslovakia. Methane emissions for India and S. Africa were estimated from a linear correlation between the average depth of mining and specific methane emissions derived from the available data for the eight countries. These ten largest coal producing countries represented nearly 90% of world coal production in 1990. Total methane emissions for the world coal industry were calculated by prorating the methane emissions from these ten countries in proportion to coal production.The reported values represent the best international data available at present. The net total emissions of 24 million tonnes/year are substantially less than some previously reported indirect estimations and constitute only 4 to 6% of the global methane emissions.     

Heavy metal deposition in moss samples from East and South Marmara Region, Turkey

A survey of atmospheric heavy metal deposition in the east and south Marmara region, Turkey was carried out in September 2004. For this purpose, moss samples (Hypnum cupressiforme) were collected in a systematic network of 125 sites. Concentrations of the elements (Al, B, Ba, Ca, Cd, Fe, Co, Cr, Cu, K, Li, Mn, Na, Ni, Pb, Sr, Mg, Ti, and Zn) in the moss were used as an indication of the level of air pollution in the region. Significant differences in heavy metal concentrations, especially for Pb, Cd, Cu, and Zn, were recorded in the moss samples collected around industrialized and heavily populated cities (Istanbul, Bursa, Band?rma, Kocaeli, Biga-?an) and in an abandoned lead-mining area (Bal?kesir-Balya). A map of the spatial distribution of each element in the region was plotted, and enrichment factors were calculated. VARIMAX principal component analysis was applied to the data obtained, and five different components were obtained. The results showed that Pb, Cu, Cd, and Zn derived from anthropogenic and industrial sources while other elements came mostly from natural sources.     

燃煤电厂周边大气重金属污染特征及来源解析

为探究燃煤电厂周边大气环境中重金属的污染特征与来源,对广东某山区燃煤电厂周边地区环境和污染源的重金属进行测定,分析其污染特征,采用因子分析法和Pb同位素示踪法对环境中的重金属进行来源解析。结果表明,研究区域室内积尘中重金属浓度水平明显高于土壤重金属,污染空间分布与当地气象条件相关。环境空气TSP中重金属主要来自2个污染源,Cd、Pb、As主要来自电厂燃煤,Ca、Mn、Al、Mg主要来自土壤扬尘。TSP、降尘、积尘样品所含的Pb均与电厂采集的煤、炉渣、粉煤灰样品所含的Pb具有同源性,与其他污染源同源性不明显,说明研究区域大气中Pb污染主要来自电厂燃烧所排放的烟尘,其他污染源影响不大。     

Effect of 30 years of road traffic abandonment on epiphytic moss diversity

Road traffic emits a cocktail of pollutants that can influence the vegetation and plant diversity in neighboring areas. However, the recovery potential of bryophytes after traffic abandonment is still little explored. In addition, the effects of the main pollutants of road verges, such as metals and salinity, on moss flora need to be investigated. In our study, we compared the moss richness and diversity in two closely related veteran tree allees of high conservation importance. The allees in Gry?ów and Lubrza, Poland, were chosen because of their similarity in age, geographical location, type of surrounding areas, and tree species. The only difference was that the trees in Gry?ów had not been exposed to direct road pollution for almost 30 years. The moss richness and diversity differed significantly between the sites. Altogether, 20 moss species were recorded on 229 trees, 17 species in Gry?ów (abandoned road), and 13 in Lubrza (busy road). We found considerable differences between moss cover on the road-facing and opposite sides of tree trunks. In Lubrza, mosses on the road-facing side were very scarce. The moss cover in Gry?ów was highly balanced between trunk sides as well as among trunk heights. Typical epiphytic species such as Bryum moravicum, Dicranoweisia cirrata, Leskea polycarpa, and Orthodicranum tauricum preferred the Gry?ów tree stands, where they were present in numbers almost twice as high as that at Lubrza. The study shows that constructing a bypass road could be an effective conservation measure for veteran tree protection with their epiphytic moss flora.     

Changes in the heavy metal and nutrient contents of dried feather mosses during long-term storage

This study measured heavy metal and nutrient concentrations of two feather mosses during the periods of dry storage. Samples (Hylocomium splendens, Pleurozium schreberi) were collected in the nationwide moss surveys carried out on the permanent sample plots of the 8th Finnish National Forest Inventory in 1985–86, 1990, 1995 and 2000. A small amount of each moss sample was analyzed soon after collection, and the remainder was dried and stored at the Paljakka environmental specimen bank (ESB). The 108 stored samples from 27 plots were reanalyzed in 2008. Concentrations of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) and nutrients (Ca, K, Mg, P) were determined and compared for each survey year. Overall, Fe, Pb and Cr concentrations decreased, and Cu concentrations increased significantly during storage. The greatest decrease was observed in samples from plots where their initial concentrations were the highest. Changes in the concentrations of Cd, Ni and Zn were less pronounced. The loss of heavy metals is likely due to drying when cell membranes rupture and some of the surface material is lost. K, P and, to some extent, Mg concentrations increased during storage, whereas Ca did not change significantly. Nutrient increase is probably due to their movement from older to younger growths during the initial phase of drying. Ca is mostly bound to cell walls and is not easily released. Results emphasize the importance of establishing the intended use of a stored moss prior to sampling, in order to select and optimize an appropriate storage technique.