Determination of baseline element composition of lichens using samples from high elevations

The results of a survey aimed at providing baseline element composition of lichens from unpolluted or very low polluted areas are reported. Lichen samples collected at high elevation areas in Himalayas (Nepal), Mt. Kenya (Kenya) and the Alps (Italy) were analyzed for their trace element content, mostly by INAA, allowing for a multi-element analysis. The elemental composition of lichen samples was essentially influenced by natural occurrence, mainly airborne soil dust. However, also anthropogenic input determined by long-distance atmospheric transport of pollutants was involved for some highly volatile elements such as Br, Cd and Sb. To avoid the influence of soil contamination and air pollution, and obtain baseline concentrations to be used as reference (the "natural" elemental composition of lichens), the average of the lowest concentrations is suggested.     

Environmental distribution of uranium and other trace elements at selected Kosovo sites

This paper reports the results of a study using lichens as biomonitors to investigate the environmental distribution of uranium and other trace elements at selected Kosovo sites. The results suggested that the use of depleted uranium (DU) ammunitions in Kosovo did not cause a diffuse environmental contamination in such a way to have caused a detectable U enrichment in lichens. Also isotopic (235)U/(238)U measurements did not indicate the presence of DU particles in lichens. The present results also provided no indication of intense environmental contamination by the other trace elements analyzed, with the exception of Kosovska Mitrovica, where a diffuse environmental contamination by several heavy elements such as Pb, Zn, As and Cd was found.     

Historical and current atmospheric deposition to the epilithic lichen Xanthoparmelia in Maricopa County,Arizona

Spatial patterns of atmospheric deposition of trace elements to an epilithic lichen were assessed using a spatial grid of 28 field sites in 1998 throughout Maricopa County, Arizona, USA. In addition, samples of Xanthoparmelia spp. from Arizona State University lichen herbarium material (1975-1976) was utilized for a limited number of sites in order to explore temporal trends. The lichen material was cleaned, wet digested and analyzed by ICP-MS for a suite of elemental concentrations [antimony (Sb), cadmium (Cd), cerium (Ce), chromium (Cr), cobalt (Co), copper (Cu), dysprosium (Dy), europium (Eu), gadolinium (Gd), gold (Au), holmium (Ho), lead (Pb), lutetium (Lu), neodymium (Nd), nickel (Ni), palladium (Pd), platinum (Pt), praseodymium (Pr), samarium (Sm), scandium (Sc), silver (Ag), terbium (Tb), thulium (Tm), tin (Sn), uranium (U), ytterbium (Yb), yttrium (Y), and zinc (Zn)]. Cluster analysis and principal component analysis suggest three major factors, which, depending on regional aerosol fractionation, explain most of the variation in elemental signatures: (1) a group of widely distributed rare earth elements (2) a highly homogenous Co, Cr, Ni, and Sc component representing the influence of mafic rocks, and (3) anthropogenic emissions. Elemental concentrations in Maricopa County lichens were generally comparable to those reported for relatively unpolluted areas. Only highly urbanized regions, such as the greater Phoenix Metropolitan Area and the NW corner of the county, exhibited elevated concentrations for Zn, Cu, Pb, and Cd. Lead levels in lichens have fallen over the last 30 years by 71%, while Zn concentrations for some regions have increased by as much as 245%. From the spatial pattern of elemental deposition for Cd, Cu, Ni, Pr, Pb, and Cu, we infer that agriculture, mining, industrial activities, and traffic probably are the major air pollutant sources in Maricopa County.     

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.     

Ocean to continent transfer of atmospheric Se as revealed by epiphytic lichens

There is still a long-term debate concerning the relative contributions of naturally emitted and anthropogenic Se at the regional and local scales. Here, Se and heavy metal concentrations are reported for epiphytic lichens collected in coastal and inland areas from the USA, Canada and France for assessing atmospheric Se source. Correlations found between Se and Cl in lichens confirmed the major marine biogenic source for atmospheric Se. Continental samples do not show systematic relationships between Se and other metal (Pb, Cu, In …) contents, even for lichens collected in the vicinity of smelters or close to urban areas. Our results suggest that, although anthropogenic Se may be present, the marine biogenic Se source is a major contributor to atmospheric Se for our sampling locations. The contribution of naturally emitted atmospheric Se may be significant in urban and industrial areas and should be taken into account for further studies.     

Relationships between pesticides and organic carbon fractions in sediments of the Danshui River estuary and adjacent coastal areas of Taiwan

In order to understand the fate of pesticides in marine environments, concentrations of pesticides and different carbonaceous fractions were determined for surface sediments in the Danshui River and nearby coastal areas of Taiwan. The major compounds detected were tetrachlorobenzene, HCHs, chlordane, aldrin, DDDs, DDEs and DDTs. Total concentrations of pesticides in the sediments ranged from not detectable to 23 ng g(-1), with the maximum value detected near the discharge point of the marine outfall from the Pali sewage treatment plant. These results confirm that pesticides persist in estuarine and nearby coastal environments of the Danshui River well after their ban. Concentrations of total pesticides significantly correlate with concentrations of total organic carbon and black carbon in these sediments, suggesting that total organic carbon and black carbon regulate the distribution of trace organic pollutants in fluvial and coastal marine sediments.     

Essential and non-essential trace element concentrations in muscle and liver of a pregnant Munk’s pygmy devil ray (Mobula munkiana) and its embryo

During gestation, essential and non-essential trace elements are transferred from the pregnant females to embryos. This study aimed to determine and compare the concentrations of seven essential trace elements (Fe, Zn, Se, Cu, Mn, Cr, Co) and six non-essential trace elements (As, Cd, V, U, Tl, Ag) in the muscle and the liver of a Munk’s pygmy devil ray pregnant female, Mobula munkiana, and its embryo. Transfer evidence of essential and non-essential trace elements was detected in M. munkiana tissues. Arsenic was found in elevated concentrations in the pregnant female and the embryo tissues. Elevated levels of Cd, V, U, and Ag were found in the pregnant female liver, but were minimal in the embryo tissue. This is the first study to investigate maternal transfer of essential and non-essential trace elements in these species and their reproductive strategy.

     

Distribution and coassociations of trace elements in soft tissue and byssus of Mytilus galloprovincialis relative to the surrounding seawater and suspended matter of the southern part of the Korean Peninsula

The concentrations of Cd, Co, Cu, Cr, Fe, Hg, Mn, Ni, Pb, Sn, Ti and Zn were analyzed by AAS, ICP MS and AFS in soft tissues and byssal threads of Mytilus galloprovincialis from Masan Bay and Ulsan Bay, Korea. Spatial variations in metal concentrations were found. The levels of Cd, Pb, Hg, Cu, Zn, Co and Mn were very high in the mussels from Ulsan Bay (Sts. U1, U2) and comparable with elevated concentrations of these elements in Mytilus sp. reported to date for other geographical areas. Seasonal differences in some metal concentrations were also observed. These variations may be caused by factors such as: a large difference in seawater temperature, food supply for the mussel population and/or freshwater runoff of particulate metal to the coastal water and weight changes brought about by gonadal development and the release of sexual products. Pb, Cu, Zn, Co, Ni, Fe and Mn were more enriched in byssal threads than in the soft tissues, hence the byssus seems to be more sensitive in reflecting the availabilities of trace metals in the ambient waters. Concentrations of trace metals varied with respect to the size of mussels and season, depending on many factors like sexual development, and seawater temperature, etc. The levels of some trace metals in seawater, especially in suspended matter were correlated significantly with those in soft tissues and byssal threads. There were spatial variations in metal concentrations in the soft tissue and byssus attributed to different sources of trace elements located near the sampling sites. There were significant relationships between concentrations of some metals (Cd, Cu, Pb, and Zn) in mussel soft tissues and byssal threads and suspended matter. This suggests that M. galloprovincialis can be used as a sensitive biomonitor for the availabilities of trace elements in the coastal waters off Korea.     

Exposure assessment for trace elements from consumption of marine fish in Southeast Asia

Concentrations of 20 trace elements were determined in muscle and liver of 34 species of marine fish collected from coastal areas of Cambodia, Indonesia, Malaysia and Thailand. Large regional difference was observed in the levels of trace elements in liver of one fish family (Carangidae): the highest mean concentration was observed in fish from the Malaysian coastal waters for V, Cr, Zn, Pb and Bi and those from the Java Sea side of Indonesia for Sn and Hg. To assess the health risk to the Southeast Asian populations from consumption of fish, intake rates of trace elements were estimated. Some marine fish showed Hg levels higher than the guideline values by U.S. Environmental Protection Agency and Joint FAO/WHO Expert Committee on Food Additives (JECFA). This suggests that consumption of these fish may be hazardous to the people.     

Interannual patterns of variation in concentrations of trace elements in arms of Octopus vulgaris

Concentrations of essential (copper, iron, manganese, selenium, and zinc) and non-essential (arsenic, cadmium, mercury, and lead) trace elements were measured in arms of Octopus vulgaris. The cephalopods were sampled from commercial fishery landings at two sites on the Portuguese coast in spring 2002 and 2003. Mercury was determined using an Advanced Mercury Analyser Spectrophotometer (AMAS) and other trace elements were measured using inductively coupled plasma-atomic emission spectrometry (ICP-AES). Since high levels of arsenic were detected, identification of the forms present was carried out using high performance liquid chromatography (HPLC) followed by ICP-MS. Mean concentrations of trace elements analysed were in the following order: As > Zn > Fe > Cu > Cd > Pb > Se > Mn > Hg. The results of speciation of arsenic demonstrate that virtually all arsenic was in the arsenobetaine form, which is the less toxic form. The concentrations of several trace elements were generally high in samples from Viana in 2002. Cadmium concentrations were above the legal limit for human consumption in samples from Viana in 2002 and two of these animals also had lead concentrations that exceeded legal limits. Mercury appeared in all samples but levels were within legally defined safe limits. No relationship was detected between trace element concentrations and size or maturity of octopus.     

Evaluating the size distribution characteristics and sources of atmospheric trace elements at two mountain sites: comparison of the clean and polluted regions in China

Size-resolved trace metal concentrations at two background sites were assessed during a 1-year observation campaign, with the measurements performed in parallel at two mountain sites, where Mt. Dinghu (DHS) located in the rural region of Pearl River Delta (PRD) and Mt. Gongga (GGS) located in the Tibetan Plateau region. In total, 15 selected trace elements (Mg, Al, K, V, Mn, Fe, Cu, Zn, As, Mo, Ag, Cd, Ba, Tl, and Pb) in aerosol samples were determined using inductively coupled plasma mass spectrometry (ICPMS). The major metals in these two mountain sites were Fe, K, Mg, and Ca with concentrations ranging between 241 and 1452 ng/m³, 428 and 1351 ng/m³, 334 and 875 ng/m³, and 376 and 870 ng/m³, respectively, while the trace metals with the lowest concentrations were Mo, Ag, Cd, and Tl with concentrations lower than 4 ng/m³ in DHS and 2 ng/m³ in GGS. The pronounced seasonal variability in the trace elements was observed in DHS, with lower concentrations in spring and summer and relatively high in winter and autumn, whereas seasonal variance of trace elements is hardly observed in Mt. Gongga. The size distribution pattern of crustal elements of Al, Mg, K, Ba, and Fe was quite similar in DHS and GGS, which were mainly found in coarse particles peaked at 4.7–5.8 μm. In addition, V, Mo, Ag, and Tl were also concentrated in coarse particles, although the high enrichment factor (EF?>?100) of which suggested anthropogenic origin, whereas trace metals of Cd, Mn, Zn, As, Cu, and Pb concentrated in fine mode particles. Specifically, these trace metals peak at approximately 1.5 μm in DHS, while those in GGS peaked at diameter smaller than 0.3 μm, indicating the responsible for long-range transport from the far urban and industrialized areas. Multivariate receptor model combined with the enrichment factor results demonstrated that the trace elemental components at these two background sites were largely contributed from the fossil fuel combustion (55.4% in DHS and 44.0% in GGS) and industrial emissions factors (20.1% vs. 26.5%), which are associated with long distance transport from the coastal area of Southeast China and the Northwestern India, respectively, as suggested by the backward air mass trajectory analysis. Local sources from soil dust contributed a minor variance for trace elements in DHS (9.7%) and GGS (13.8%), respectively.

     

Risk to breeding success of waterbirds by contaminants in Hong Kong: evidence from trace elements in eggs

Concentrations of 17 trace elements (As, Se, Rb, Sr, Ag, Sb, Cs, Tl, Pb, V, Cr, Mn, Co, Cu, Zn, Cd, and Hg) were determined in eggs of little egrets (Egretta garzetta), black-crowned night herons (Nycticorax nycticorax) and bridled terns (Sterna anaethetus) from northwestern and northeastern coastal areas of Hong Kong. Results indicated significant differences among the three species. Eggs of little egrets and black-crowned night herons appeared to be good bioindicators for monitoring selected elements (As, Pb, Zn Cr, Cu, and V) due to consistent correlations between metal concentrations in eggs and those in coastal marine sediments. Based on limited toxicological information, the predicted no effect concentrations (PNECs) of Hg and Se in the bird eggs were estimated as 0.5 to 1.8 and 0.90 to 1.45 mug g(-1), dry wt., respectively. Hazard quotients (HQs) indicated that Hg and Se might pose some risk to certain waterbirds in Hong Kong.     

Influence of angular exposure and proximity to vehicular traffic on the diversity of epiphytic lichens and the bioaccumulation of traffic-related elements

This study investigated the influence of angular exposure and distance from vehicular traffic on the diversity of epiphytic lichens and the bioaccumulation of traffic-related elements in a town of central Italy. An Index of Lichen Diversity (ILD) was calculated on the street-facing and the opposite side of road-lining trees and in a urban park 250 m away, and the content of selected trace elements (Al, Ba, Ce, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V, and Zn) was determined in samples of the lichen Punctelia borreri (Sm.) Krog growing on tree bark, both on the exposed and opposite sides. ILD increases with distance from traffic emissions. However, at the site with vehicle traffic, non-nitrophilous lichens decreased while nitrophilous ones increased. The concentration of the traffic-related elements Ba, Cr, Cu, Mn, Sb, and Zn accumulated in thalli of P. borreri was higher on roadside trees than in trees from the urban park. ILD was not affected by the angular exposure to the road and the bioaccumulation of traffic-related elements was similar in lichens from the side of the bole exposed to traffic emissions and particulate resuspension and from the opposite side. The angular exposure in respect to the traffic source does not influence trace element accumulation. These results are important when using lichens for biomonitoring purposes, both for planning future studies and for the reliability of the interpretation of past surveys that do not report information about the angular exposure of the collected lichen material.     

Comparison of trace element concentrations in livers of diseased, emaciated and non-diseased southern sea otters from the California coast

Infectious diseases have been implicated as a cause of high rates of adult mortality in southern sea otters. Exposure to environmental contaminants can compromise the immuno-competence of animals, predisposing them to infectious diseases. In addition to organic pollutants, certain trace elements can modulate the immune system in marine mammals. Nevertheless, reports of occurrence of trace elements, including toxic heavy metals, in sea otters are not available. In this study, concentrations of 20 trace elements (V, Cr, Mn, Co, Cu, Zn, Rb, Sr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, Hg, Tl, Pb, and Bi) were measured in livers of southern sea otters found dead along the central California coast (n = 80) from 1992 to 2002. Hepatic concentrations of trace elements were compared among sea otters that died from infectious diseases (n = 27), those that died from non-infectious causes (n = 26), and otters that died in emaciated condition with no evidence of another cause of death (n = 27). Concentrations of essential elements in sea otters varied within an order of magnitude, whereas concentrations of non-essential elements varied by two to five orders of magnitude. Hepatic concentrations of Cu and Cd were 10- to 100-fold higher in the sea otters in this study than concentrations reported for any other marine mammal species. Concentrations of Mn, Co, Zn, and Cd were elevated in the diseased and emaciated sea otters relative to the non-diseased sea otters. Elevated concentrations of essential elements such as Mn, Zn, and Co in the diseased/emaciated sea otters suggest that induction of synthesis of metallothionein and superoxide dismutase (SOD) enzyme is occurring in these animals, as a means of protecting the cells from oxidative stress-related injuries. Trace element profiles in diseased and emaciated sea otters suggest that oxidative stress mediates the perturbation of essential-element concentrations. Elevated concentrations of toxic metals such as Cd, in addition to several other organic pollutants, may contribute to oxidative stress-meditated effects in sea otters.     

Multi-element composition of historical lichen collections and bark samples,indicators of changing atmospheric conditions

Thirty six element signatures were compared in historical Parmelia sulcata samples from the Natural History Museum herbarium collected over the period 1797–1967 with those recorded in the same species and tree bark sampled in 2000 from Burnham Beeches, lying 40 km west of London. Nineteen elements reached highest concentrations in herbarium samples, consistent with a pollution legacy and dust contamination in the herbarium. Healthy Parmelia sampled east and down-wind of London at a farm during peak SO₂ emissions in 1967 contained highest V, Ni, Zn, Cd, Se, Ge contents, supporting derivation from fuel combustion; the same sample was previously determined as having a low δ34S and high S and N contents. Lowest V, Co, Ni, Cu, Zn, Sn, Ba, Pb, Mo, Sb, Li, B, Cs, U, Th, Ga contents were recorded in a sample with a high δ34S and low S content collected in 1887 from a remote region from Ross-shire, Scotland. Se and Cd enrichment, never-the-less suggest a transboundary pollution influence. Lichen Pb concentrations from Burnham Beeches were amongst the lowest recorded in spite of lichens being collected close to roads. Herbarium samples help interpret changes in element deposition where few data exist, in spite of dust contamination.     

Trace metals in seagrass, algae and molluscs from an uncontaminated area in the Mediterranean

The concentrations of Cd, Cr, Cu, Pb and Zn were measured in specimens of four marine organisms--the seagrass Posidonia oceanica (L.) Delile, the brown algae Padina pavonica (L.) Thivy, and the two gastropod molluscs Monodonta turbinata Born and Patella caerulea L.--selected as possible cosmopolitan biomonitors of trace metals in the Mediterranean area. The organisms were collected at five coastal sites in Favignana Island (Sicily, Italy), an area virtually uninfluenced by anthropogenic activities. In order to gain a more complete picture of both the environmental conditions of the experimental area and the bioaccumulation patterns of the selected organisms, soluble and total metal concentrations were determined in coastal water samples collected at the same stations. The picture of bioavailable metal loads in the different sites of the selected area provided by the four species was rather univocal. An overall trend of increased metal concentrations at the station in which the local harbour is located was clear. On the other hand, the metal concentrations recorded at the 'clean' stations generally fall in the range of the lowest values available in the literature and may be considered as useful background levels to which to refer for intraspecific comparison within the Mediterranean area. Implications in biomonitoring of the observed accumulation patterns, especially in the different tissues of Posidonia oceanica, are discussed.     

The potential of lichens as long-term biomonitors of natural and artificial radionuclides

Lichens were used as biomonitors of Chernobyl fallout 137Cs, of cosmogenic 7Be and of radioactive members of the natural uranium and thorium decay chains. Samples were taken from two locations in France, including lichens sampled at different distances of a coal fired power plant and close to a uranium ore processing waste disposal site. All samples were analyzed gamma-spectrometrically after equilibrium concentrations of short-lived isotopes had been attained. Activity concentrations of the members of the uranium and thorium decay chains in Parmelia sulcata sampled 1994 decrease with distance from the plant, whereas in lichens taken at the waste disposal site a decrease with time was observed. Comparison of 7Be activity concentrations measured in lichens with atmospheric deposition rates confirms that P. sulcata can be used as a quantitative biomonitor of radioactive trace substances. Retention half-lives calculated with a simple one-compartment model are 2.6 +/- 1.2 years for cesium, which was detected in all samples even more than a decade after the Chernobyl accident, and of 0.7 (+/- 0.1) to 3.3 (+/- 0.7) years for lead. Consequences of our results for model identifiability and parameter estimation of a two-compartment model are discussed.     

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.     

Determination of trace elements and evaluation of their enrichment factors in Himalayan lichens

Within the framework of the Ev-K2-CNR research program of the Italian National Research Council a specific task project has been initiated for the identification of trace elements in lichens in remote high altitude areas. This is to evaluate the possibility of using lichens as biomonitors of trace elements of atmospheric pollution. In this preliminary study, more than 20 elements have been determined in some species of lichens collected at different altitudes (from 1300 to 5000 m) in the region of the Sagarmatha National Park (Nepal). Samples of superficial soils were also collected and analyzed to calculate the trace element enrichment factors (EF) using scandium as a normalizing element. Most of the trace elements were determined by instrumental neutron activation analysis (INAA), while lead and cadmium measurements were carried out with electrothermal atomic absorption spectroscopy (ET-AAS). The EF values as well as the elemental concentrations are reported and discussed.