Atmospheric trace element deposition: principal component analysis of ICP-MS data from moss samples

Data from a Norwegian survey on atmospheric deposition, including 33 elements in 495 moss samples collected in 1990, are presented. The biomonitor moss used was Hylocomium splendens, and the analyses were carried out by ICP-MS. Principal component analysis is used to identify possible sources of the elements determined in the mosses. Dominant factors represent long-range atmospheric transported elements (Bi, Pb, Sb, Mo, Cd, V, As, Zn, Tl, Hg, Ga), windblown mineral particles (Y, La, Al, Li, U, Th, Ga, Fe, V, Cr), local emission sources (Ni, Cu, Co, and As; Zn, Cd, and Hg; Fe, Cr, and Al), transport from the marine environment (Mg, B, Na, Sr, Ca), and contribution from higher plants (Cs, Rb, Ba, Mn). Comparison of the results with similar surveys from 1977 and 1985 show a decreasing contribution of most long-range transported elements to southern Norway.     

Influence of extreme pollution on the inorganic chemical composition of some plants.

Leaves of nine different plant species (terrestrial moss: Hylocomium splendens and Pleurozium schreberi, blueberry: Vaccinium myrtillus, cowberry: Vaccinium vitis-idaea, crowberry: Empetrum nigrum, birch: Betula pubescens, willow: Salix spp., pine: Pinus sylvestris, and spruce: Picea abies) have been collected from up to nine catchments (size 14-50 km2) spread over a 1,500,000 km2 area in northern Europe. Additional soil samples were taken from the O-horizon and the C-horizon at each plant sample site. All samples were analysed for 38 elements (Ag, Al, As, B, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, S, Sb, Sc, Se, Si, Sn, Sr, Th, Tl, U, V, Y, Zn, and Zr) by ICP-MS, ICP-AES or CV-AAS (Hg) techniques. One of the 9 catchments was located directly adjacent (5-10 km S) to the nickel smelter and refinery at Monchegorsk, Kola Peninsula, Russia. The high levels of pollution at this site are reflected in the chemical composition of all plant leaves. However, it appears that each plant enriches (or excludes) different elements. Elements emitted at trace levels, such as Ag, As and Bi, are relatively much more enriched in most plants than the major pollutants Ni, Cu and Co. The very high levels of SO2 emissions are generally not reflected by increases in plant total S-content. Several important macro-(P) and micro-nutrients (Mn, Mg, and Zn) are depleted in most plant leaves collected near Monchegorsk.     

Distribution patterns of PAHs and trace elements in mosses Hylocomium splendens (Hedw.) B.S.G. and Pleurozium schreberi (Brid.) Mitt. from different forest communities: a case study, south-central Poland

Twenty samples of the moss species Hylocomium splendens and Pleurozium schreberi were collected at 10 sites of the Holy Cross Mountains (south-central Poland) and analyzed for 16 polycyclic aromatic hydrocarbons and 33 elements. The ring sequence of PAHs in the moss samples is: 4 (92-1040 ng x g(-1))>3 and 5 (21-272 ng x g(-1))>6 (<5-131 ng x g(-1)). H. splendens accumulates PAHs more effectively than P. schreberi, and therefore the former may be regarded as a better bioindicator of PAHs. No correlation was found between concentrations of PAHs and elements. However, both H. splendens and P. schreberi shows different bioaccumulative capabilities depending on the plant communities. The mosses growing in the dry pine forest Cladonio-Pinetum reveal higher levels of Fe, Na, Sr, Ti, Cr, Mo, Ni, V and higher mean concentrations of summation operator16 PAHs, whereas those from the continental coniferous forest Querco roboris-Pinetum are highlighted by elevated levels of B, Ca, K, Mg, Mn, P, Rb and Sb and lower mean concentrations of summation operator16 PAHs. These differences seem to be brought about by a higher biodiversity of the second forest type and its higher productivity that favors more effective cycling of elements.     

Testing the Bergerhoff method to determine the bulk deposition loads of 49 elements

The suitability of the simple and rather cheap Bergerhoff method for the determination of bulk deposition loads of 49 elements was tested. The method is suitable for the following elements: Ag, Al, As, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, Ge, In, K, La, Li, Mg, Mn, Mo, Na, Nb, Ni, Pb, Rb, S, Sb, Sc, Se, Sn, Sr, Th, Ti, Tl, V, W, Y and Zn provided that for some of these elements one does not get total recovery with HNO₃-digestion. This, nevertheless, supplies sufficient information for most concerns. Analytical problems were encountered for the following elements: U and Te concentrations in our samples were close to the blanks; P and Ta were highly variable within the sampling areas; B, Hf and Zr leached out of the glass of the digestion vessels; Hg is highly volatile.Field studies at three background sites in Switzerland, two on the northern side of the Alps and one in the southern Alps, showed higher burdens of element emissions in the latter, partly because of higher precipitation, and partly because of higher concentrations in the dust. An anthropogenic influence can be inferred for Ag, Bi, Cd, Cu, Hg, Mo, Pb, Sb, Te, W and Zn and probably also for As, P, S (with associated Se) and Sn.     

Changes in the atmospheric deposition of minor and rare elements between 1975 and 2000 in south Sweden, as measured by moss analysis

Elements emitted to the atmosphere are partly exported to more remote areas and contribute to the regional and territorial deposition rates. This study is based on the principle that carpet-forming bryophytes (pleurocarpic mosses) absorb elements and particles from rain, melting snow and dry deposition. We compare the concentrations of 60 elements in carpets of the forest moss Pleurozium schreberi sampled in 1975 and 2000 within a sparsely inhabited area dominated by forest and bogland in south Sweden. As an average for all the 60 elements, the median concentration was 2.7 times higher in 1975 than in 2000. The greatest difference was measured for Pb, although In, Bi, Ge, V, Sn, As and Ag had more than 5 times higher concentrations in 1975 than in 2000. Somewhat lower 1975/2000 concentration ratios (3.0-3.8) were measured for U, Sb, Cd, W, Ga, Fe, Li, and Be. The rare-earth elements (Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), except Eu as well as Th, Ni, Al, Ti, Hf, Nb, and Zr, had concentration ratios around the average (2.5-2.8). Possible causes of these changes are discussed. We conclude that reductions in anthropogenic dust emissions during recent decades have decreased the atmospheric deposition over northern Europe of most elements in the periodical system, as previously reported for a limited number of transition and heavy metals. Changes in the deposition of soil dust would be of minor importance to the decreased deposition rates.     

Analysis of essential and non-essential trace elements in the organs of a mother–fetus pair of spotted seals (Phoca largha) from the Sea of Japan

Environmental Science and Pollution Research - Concentrations of 22 essential and non-essential trace elements (Be, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, Sb, Ba, Tl, Pb, Th, U, and...     

Element concentrations in the forest moss Hylocomium splendens: variation associated with altitude, net primary production and soil chemistry.

Net primary production (NPP) of the forest moss Hylocomium splendens increased significantly along an elevational gradient in the southern Alps of Italy. Extracellularly bound metals (Al, Ca, Co, Cr, Fe, Ni, Mo, Ni, Pb) showed declining concentrations in moss tissue with increasing altitude, presumably because the amount of exchange sites on the cell wall increases less than total biomass. Concentrations of intracellular elements did not vary (Cd, Cu, Mg, Na, Zn), or even increased (K) with altitude. The observed patterns were always independent of precipitation amount and soil concentrations of exchangeable elements. A higher soil nutrient status only enhanced K uptake by the moss. We concluded that variations in moss NPP, associated with elevational gradients, may significantly affect estimates of atmospheric deposition based on moss analysis in mountainous regions.     

Biological fluxes conversion and SXRF experiment with a new active biomonitoring tool for atmospheric metals and trace element deposition

A new active biomonitoring tool, keeping alive mosses for 2 months, had demonstrated the buffering action of the water presence on the biological activity of three moss species (chlorophyll fluorescence induction method on Pleurozium schreberi, Scleropodium purum, Eurhynchium praelongum). The two more resistant mosses were exposed on four different sites with parallel exposure of monthly bulk collectors during three successive periods of 2 months. The coarse and sedimentable particles of bulk collectors were separated into different size classes (> 1 mm; 1000-200 microm; 200-40 microm; 40-20 microm). Dry depositions and mosses were analysed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) for a stock (microg g(-1)- fluxes (microg m(-2) t(-1)) conversion. The "moss plate" allowed relative site (Ba, Cs, Sb, Sr, U) and species (Pb, Sb, Ti, V) comparisons. Two months were enough for a significant enrichment (Ba, Cd, Pb, Sb, Ti, U, V). Good explicative models were elaborated for Ba, Pb, Sb and Ti (r2 > 70%) including categorical (sites, moss species) and quantitative variables (fluxes of particles size classes). Entire and intact shoots of Scleropodium purum were analysed by detected synchrotron radiation induced X-ray fluorescence (SXRF). The in vivo distribution of the multi-elemental short term enrichment along the moss stem was mainly localized in the plant older parts (Pb, Ti, Cl, Se).     

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.     

Comparison of trace element accumulation in Baikal seals (Pusa sibirica), Caspian seals (Pusa caspica) and northern fur seals (Callorhinus ursinus)

Concentrations of 18 trace elements (V, Cr, Mn, Co, Cu, Zn, Se, Rb, Sr, Zr, Mo, Ag, Cd, Sb, Cs, Hg, Tl and Pb) were determined in liver, kidney, muscle and hair of Baikal seals, Caspian seals and northern fur seals. All the three species showed the highest concentrations of Hg, V, Mn, Se and Ag in liver, Cd, Co and Tl in kidney, and Cs in muscle among the soft tissues examined. The highest burdens of Zn, Rb and Cs were observed in muscle, Mo and Ag in liver, and Sb and Pb in hair in all the three species. Concentrations of non-essential elements, Rb, Cd, Cs and Hg, showed significant positive correlations among liver, kidney and muscle, whereas correlation coefficients for essential elements, Mn, Co, Cu, Zn and Se, between the three tissues were generally low for all the species, suggesting that homeostasis controls the concentrations of essential elements but not the non-essential elements in the tissues of these animals. Significant age-dependent increase was found in the concentrations of V, Se and Ag in liver and Hg in liver and kidney of all the three species. Hair concentrations showed significant positive correlations with Zn levels in liver and kidney and Hg in muscle for Caspian seals, Hg in liver and kidney for Baikal seals, and Pb in liver for northern fur seals. Furthermore, regression analysis using the data in the present study and in the literature showed significant positive correlations between Hg levels in hair, and liver, kidney and muscle for various species of pinnipeds. These results indicate the possibility of using hair samples for monitoring these trace elements in pinnipeds.     

Comparison between the accumulation capacity of four lichen species transplanted to a urban site

The capacity to accumulate trace elements from the atmosphere of the lichens Hypogymnia physodes, Parmelia sulcata, Pseudevernia furfuracea and Usnea gr. hirta transplanted to an urban site of N Italy was compared. Twenty-nine elements (Al, As, Br, Ca, Cd, Ce, Cl, Co, Cr, Cs, Cu, Fe, Hg, I, K, La, Mg, Mn, Ni, Pb, Rb, Sb, Sc, Se, Sm, Th, Ti, V, Zn) were analyzed by Instrumental Neutron Activation Analysis (INAA) and Electro-Thermal Atomic Absorption Spectroscopy (ET-AAS). The ratio between the concentrations of each element in exposed samples to that of control samples (exposed-to-control ratio and EC ratio) was used to investigate the accumulation rates of lichen thalli. The results showed that in general elements did not exhibit well defined trends, but rather showed fluctuations, and indicated that H. physodes, P. furfuracea and U. gr. hirta have a similar accumulation capacity, while that of P. sulcata is lower.     

Critical remarks on the use of terrestrial moss (Hylocomium splendens and Pleurozium schreberi) for monitoring of airborne pollution

Duplicate samples of the two terrestrial moss species Hylocomium splendens and Pleurozium schreberi, which are widely used to monitor airborne heavy metal pollution, have been collected from eight catchments spread over a 1,500,000 km2 area in northern Europe. These were analysed for a total of 38 elements by inductively coupled plasma-mass spectrometry, inductively coupled plasma-atomic emission spectrometry and cold vapour-atomic absorption spectometry techniques. Results show that the moss species can be combined without interspecies calibration for regional mapping purposes. For the majority of elements the observed within-catchment variation is large--big composite samples over a large area should thus be collected when moss is to be used for monitoring purposes. For the majority of elements the input of dust governs moss chemistry. For a reliable 'contamination' signal over a sizeable area a major source is needed. Some elements show a dependence on climate/vegetation zone. In coastal areas the input of marine aerosols will alter the chemical signal obtained from moss samples.     

Response of mosses to the heavy metal deposition in Poland--an overview

Concentrations of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) in Pleurozium schreberi (Brid.) Mitt., a common moss species, were used to indicate relative levels of atmospheric deposition in Poland in the years 1975-1998. Spatial and temporal differences in the heavy metal concentrations in mosses were found. The highest concentration of heavy metals was recorded in the moss samples from the southern, most industrialised part of the country, and the lowest from north-eastern Poland. A significant decrease of heavy metals over 20 years (1975-1998) was found.     

Trace element contamination of Norwegian Lake sediments

Concentrations of Sb, Hg, Bi, Cd, Mo, As, Co, Ni, Cr, Cu, V, Pb and Zn in surface and preindustrial sediments from 210 lakes in Norway were used for studying modern atmospheric depositions of these elements. Surface sediments had considerably higher concentrations of Sb, Hg, Bi, Cd, As, Pb than preindustrial sediments. The differences decreased with latitude and altitude. A multivariate analysis including the trace elements and the major constituents (organic matter, Si, Al, Fe and Mn) of surface sediments suggested the following relationships: Sb, Hg, Bi, As, and Pb formed a group with strong associations to organic matter. Ni, Cr and Cu formed a second group, weakly associated to the inorganic sediment fraction (Si and Al). Zn and Cd formed a third group with weak associations to organic matter. Co was associated to Mn, whereas Mo and V showed no important covariations with any other trace elements or major components.     

Geographical variations of major and trace elements in East Antarctica

Surface snow samples have been analyzed for a total of 37 elements including Na, Mg, Al, K, Ca, Fe, Ba, Cd, Fe, Cd, Cr, Cu, Ga, Li, Mn, Pb, Se, Sr, V, Zn, As, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Th by inductively coupled plasma mass spectroscopy (ICP-MS). Rare earth elements in surface snow were evaluated after preconcentration of the samples in a class 1000 clean room. These samples were collected between 1991–1993 during the oversnow traverses along a 2200 km route in East Queen Maud Land, Antarctica. They include one at Dome Fuji Station (77°32′S, 24°08′E; 3810 m a.s.l.) built on the top of the second highest dome. In coastal area, fallout flux for Na, Mg, Sr and Cu or more weakly for Ca and Ba shows an apparent decrease according to the distance from the coast. On the other hand, fallout flux for Co, Ni and Cd shows an increase at 2500–3000 m or >3500 m above sea level. For Mn, Se, Zn and As, it shows a combined pattern of these two types. For Al, V and Pb, a constant profile with an intermittent peaks along this route was indicated. These geographical distributions of fallout flux for each element could reflect polar stratospheric precipitation or long-range tropospheric transport from the southern hemisphere. In the present study, concentrations of rare earth elements in Antarctic surface snow at sub-ppt level are first reported. A clear rare earth pattern is noticed in the Antarctic samples and rare earth ratios are also valuable to estimate anthropogenic emissions to the Antarctica.     

Some mineral constituents of Parasol Mushroom (Macrolepiota procera)

This article reports background concentrations of Ag, Ba, Cd, Co, Cr, Cs, Cu, Ga, Hg, Mn, Mo, Pb, Rb, Sb, Sr, Se, Tl, V and Zn in caps and stalks of M. procera collected from four spatially distant sites across Poland. The elements were determined using inductively coupled plasma-mass spectrometry (ICP-MS), hydride generation atomic absorption spectrometry (HG-AAS) or a cold vapor atomic absorption spectrometry (CV-AAS). Copper, zinc, rubidium, selenium, chromium and cobalt were the most abundant amongst elements determined in this mushroom. Some elements (Cu, Zn, Rb, Se, Pb, Hg, Cd, Mo) occurred at greater concentrations in the caps than stalks of M. procera and some (Ag, Ba, Sr, V, Tl) dominated in the stalks, while for some other this proportion was similar or varied (Mn, Cr, Co, Ga, Sb, Cs) depending on the sampling site. For elements such as copper, zinc, rubidium as well as selenium some spatial similarity in distribution and/or concentration values both in caps and stalks was noted. Cadmium and lead content in caps of M. procera was usually below the European Union tolerance limit value of 2.0 and 3.0 microg/g dw set for cultivated mushrooms, respectively. These two toxic metals have been found in elevated concentration in M. procera from unpolluted stands outside of Poland as reported by some authors, which implies the possibility of relatively high background levels in this species.     

Arsenic and Mn levels in Isaza (Gymnogobius isaza) during the mass mortality event in Lake Biwa, Japan

The present study measured the concentrations of 25 elements (Li, Mg, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, Hg, Tl, Pb and Bi) in the whole body of Isaza which is an endemic fish species to Lake Biwa, Japan, and compared the values in the specimens from the mass mortality Isaza (MMI) and normal fresh Isaza (NFI). The mean levels of Mn and total As (T-As) were relatively higher in MMI than in NFI. In the T-As, highly toxic inorganic As was detected in MMI. Moreover we found Mn and As concentrations in surface sediment were extremely high and temporally increased. From all these results, we could infer that the dissolution of Mn and As from surface sediment of Lake Biwa might have been one of the cause for the mass mortality of Isaza.     

Environmental specimen bank samples of Pleurozium schreberi and Hylocomium splendens as indicators of the radiation environment at the surface

Pleurozium schreberi (Brid.) Mitt. and Hylocomium splendens (Hedw.) Schimp. samples from the Finnish Environmental Specimen Bank were used to study the UV-B-absorbing compounds as potential screens of the past radiation environment. The first series from southern and central Finland consisted of samples collected from 18 P. schreberi or H. splendens dominated sites in 1985 and 1995. The second series from four H. splendens dominated sites (two in southern and two in northern Finland) and two P. schreberi dominated sites (one southern and one northern) were from the years 1985, 1990, 1995 and 2000. In the first series, the moss surface area of the analyzed specimens (5 +/- 0.2 mg DW) was smaller in 1995 (40% of both species collected in June) than in 1985 (40% of P. schreberi and 55% of H. splendens collected in September). The methanol-extractable UV-B-absorbing compounds of P. schreberi in 1985 and 1995 measured as absorbance at 10 nm intervals at 280-360 nm per mg DW revealed a negative correlation with reconstructed UV-radiation data. In the second series, the UV-B-absorbing compounds per specific surface area (surface area mm2 per DW) showed significant differences between the years. The highest values in both species were obtained in 1990. In H. splendens, a difference between the southern and northern samples was observed. The preliminary study encouraged the use of environmental specimen bank samples to indicate changes in surface radiation conditions.     

Air dispersion of heavy metals in the vicinity of the As-Sb-Tl abounded mine and responsiveness of moss as a biomonitoring media in small-scale investigations

A systematic study was carried out to investigate air deposition and to explore the natural distribution and enrichment (contamination) with trace elements in the small area (cca. 13 km²) of an antimony-arsenic-thallium mineralization outcrop at an abandoned mine “Allchar.” The mine is located on the northwestern part of Ko?uf Mount, Republic of Macedonia. The locality of Allchar is unique in its mineral composition; besides a very intriguing mineral, lorandite, there are 45 other minerals, some of which are rare. The distribution of 53 elements (with special attention to As, Sb, and Tl) were detected in 69 moss samples from eight various species collected from this area. Moss samples were analyzed following microwave digestion by inductively coupled plasma–mass spectrometry and inductively coupled plasma–atomic emission spectrometry. It was found that the atmospheric deposition for As in the moss samples on or around the Allchar mine is >6.5 times higher and for Tl is 19 times higher compared to values for the samples from the rest of the Allchar area. By the application of multivariate cluster and R-mode factor analyses (FA), five geochemical associations were determined. Cluster and R-mode FA were used to identify and characterize element associations, and five associations of elements were determined by the method of multivariate statistics. F1 (Co, Cr, Fe, Sc, Li, V, Ga, Y, Ni, Mn, Al, La-Lu, Cu, Ge, Be, Bi, and Hf); F2 (As, Tl, Sb, and Mg); F3 (Rb, Cs, and Mo); F4 (Sr, Ba, Hf, Zr, La-Lu, and Bi), and F5 (Cd, Zn, Ag, and Cu).     

Accumulation of Hg and other heavy metals in the Javan mongoose (Herpestes javanicus) captured on Amamioshima Island, Japan

Concentrations of 22 elements (Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, Sb, Cs, Ba, Tl, total Hg (T-Hg), Pb) and organic Hg (O-Hg) were examined in the liver, kidney and brain of the Javan mongoose (Herpestes javanicus) and in liver of the Amami rabbit (Pentalagus furnessi) from Amamioshima Island in Japan. Relatively high levels of T-Hg levels (from 1.75 to 55.5 microg g-1 wet wt.) were found in the Javan mongoose. As for a comparison of hepatic T-Hg concentrations between the two areas, there was no significant difference between the Javan mongoose in Amamioshima and those in the Okinawa islands. In addition, T-Hg levels in the livers of the Amami rabbit were the same as in the livers of other herbivorous mammals. Taken together, it suggested that T-Hg accumulation in the livers of the Javan mongoose was not affected by the environment but by a specific physiological mechanism. The comparison of Hg and other heavy metal accumulations between terrestrial mammals (13 species, 61 individuals) including the Javan mongoose and marine mammals (18 species, 508 individuals) were also discussed.