The performance of moss, grass, and 1- and 2-year old spruce needles as bioindicators of contamination: a comparative study at the scale of the Czech Republic

Moss (Pleurozium schreberi), grass (Avenella flexuosa), and 1- and 2-year old spruce (Picea abies) needles were collected over the territory of the Czech Republic at an average sample density of 1 site per 290 km². The samples were analysed for 39 elements (Ag, Al, As, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, Hg, K, La, Li, Mg, Mn, Mo, Na, Nd, Ni, Pb, Pr, Rb, S, Sb, Se, Sn, Sr, Th, Tl, U, V, Y and Zn) using ICP-MS and ICP-AES techniques (the major nutrients Ca, K, Mg and Na were not analysed in moss). Moss showed by far the highest element concentrations for most elements. Exceptions were Ba (spruce), Mn (spruce), Mo (grass), Ni (spruce), Rb (grass) and S (grass). Regional distribution maps and spatial trend analysis were used to study the suitability of the four materials as bioindicators of anthropogenic contamination. The highly industrialised areas in the north-west and the far east of the country and several more local contamination sources were indicated in the distribution maps of one or several sample materials. At the scale of the whole country moss was the best indicator of known contamination sources. However, on a more local scale, it appeared that spruce needles were especially well suited for detection of urban contamination.     

Biogeochemical cycles for the chemical elements in Nymphaea odorata ait. and the aphid Rhopalosiphum nymphaeae (L.) living in Linsley Pond

A hydrogeochemical study to determine the abundance of the chemical elements in the water of Linsley Pond, North Branford, Conn., U.S.A., was initiated in 1965. As the investigation progressed, it became clear that the aquatic macrophytes, associated sediments, and the soils and rocks of the basin had to be examined chemically in order to elucidate the biogeochemical cycle of the elements in the water. This aspect of the study concerns the elemental chemical composition of Nymphaea odorata Ait. and the aphid Rhopalosiphum nymphaeae (L.) feeding on its leaves. Thirty-five elements were detected in the water but fifty-four were found in this water-lily and its aphid. Those not encountered in lake water concentrated twenty-fold were Cs, Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb, Ge, Zr, Hf, Th, As, Nb and Se. The water-lily, the aphid, the lake sediment and the soils and rocks of the basin all contained detectable quantities of the rare earths, though beyond Sm only those of even atomic number were encountered. The aphids contained more Na, Li, Cs, Ba, Zn, Al, Ga, Si, Ge, Pb, Ti, Hf, P, Bi, S, Se, Cr, Mo, I, Fe, Co, Ni, Mn, Y, La, Ce, Pr and Sm than the leaves upon which they feed. The water-lily leaves contain more Ag, Ca, Mg, Cd, Hg, B, Sn, Zr, Th, Cl, Br, Nd and Sc than the aphids. The amount of Be, Gd, Dy, Er, Yb, K, Rb, Cu, Sr, As, V and F is essentially the same in the insects as in the leaves which support them. Pertinent comparative data from other sources are also presented.     

The influence of a city on element contents of a terrestrial moss (Hylocomium splendens)

Forty terrestrial moss (Hylocomium splendens) samples were collected along a 120-km-long south-north transect running through Norway's largest city Oslo. Concentrations of 29 chemical elements (Ag, Al, Au, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, La, Mg, Mn, Mo, Na, Ni, P, Pb, Pt, S, Sb, Sr, Th, Ti, and Zn) and values for loss on ignition (475 degrees C) are reported. Silver (Ag), Al, Au, Bi, Cd, Co, Cr, Cu, Fe, Mo, Ni, Pb, Pt, Sb, Th, Ti, and Zn all show a characteristic Oslo peak when element concentrations are plotted against location of the sample site along the transect. Gold (Au) and Pt show the greatest relative enrichment of all elements in the city (ca. 10x "background"). Titanium (Ti), which is related to local minerogenic dust rather than anthropogenic emissions, shows a significant peak in Oslo. Loss on ignition, a measure of the amount of organic material in a sample, shows a negative peak in Oslo and at sites close to a known dust source. Input of fine dust thus appears to dominate many of the observed element concentrations in moss. The concentrations of Na are clearly influenced by the input of marine aerosols and show decreasing concentrations from south (near Oslo Fjord) to north (inland). The major plant nutrients Ca, K, Mg, P and S, as well as Hg, are the few elements displaying no spatial dependency along the transect. Element concentrations reach background variation levels at a distance of 20-40 km from the city centre.     

小秦岭大湖金矿区深部矿体原生晕特征及其找矿应用

矿床原生晕地球化学轴向分带是深部矿体预测的重要依据。金成矿成晕具有多期多阶段叠加特点,本文通过对大湖矿区矿体原生晕元素进行统计分析和空间分布特征研究,总结了大湖矿区金矿体的原生晕理想模型:即前缘晕元素组合为As、Sb,近矿晕元素组合为Bi、Au、Ag、Mo、Pb、Cu,矿尾晕元素组合为Mn、Zn、V、Co、Ni。根据原生晕特征进行成矿预测,经过工程验证,在8线发现4层金矿体,在4线发现1层金矿体,取得了较好的找矿效果,为小秦岭金矿田其他矿区的深部找矿勘探提供了参考。     

The water quality of the River Carnon, west Cornwall, November 1992 to March 1994: the impacts of Wheal Jane discharges

In January 1992, there was a major pollutant event for the River Carnon and downstream with its confluence to the River Fal and the Fal estuary in the west Cornwall. This incident was associated with the discharge of several million gallons of highly polluted water from the abandoned Wheal Jane tin mine that also extracted Ag, Cu and Zn ore. Later that year, the Centre for Ecology and Hydrology (CEH; then Institute of Hydrology) Wallingford undertook daily monitoring of the River Carnon for a range of major, minor and trace elements to assess the nature and the dynamics of the pollutant discharges. These data cover an 18-month period when there remained major water-quality problems after the initial phase of surface water contamination. Here, a summary is provided of the water quality found, as a backdrop to set against subsequent remediation. Two types of water-quality determinant grouping were observed. The first type comprises the determinants B, Cs, Ca, Li, K, Na, SO4, Rb and Sr, and their concentrations are positively correlated with each other but inversely correlated with flow. This type of water-quality determinant shows variations in concentration that broadly link to the normal hydrogeochemical processes within the catchment, with limited confounding issues associated with mine drainage. The second type of water-quality determinant comprises Al, Be, Cd, Ce, Co, Cu, Fe, La, Pb, Pr, Nd, Ni, Si, Sb, U, Y and Zn, and concentrations for all this group are positively correlated. The determinants in this second group all have concentrations that are negatively correlated with pH. This group links primarily to pollutant mine discharge. The water-quality variations in the River Carnon are described in relation to these two distinct hydrogeochemical groupings.     

Heavy metal behaviour during the activated sludge process I. Extent of soluble and insoluble metal removal

The extent of removal of Ag, Bi, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Tl and Zn and their distribution between the soluble and insoluble phases in the influent, and effluent of the activated sludge process has been studied using a pilot-scale plant operated at sludge ages of 3, 6, 9 and 12 days. Molybdenum, Tl, Co, Mn and Ni were >50% soluble in the influent settled sewage. The mean removals of the former two metals were <3% and the latter three were 35 and 50%. Silver, Bi, Cd, Cr, Cu, Pb and Zn were all <35% soluble in the influent and had substantial removals of >75%. Solubilities were greater in the effluent than the influent with the exception of Mn. The observed overall removals of Ag, Bi, Co, Ni, Pb, Tl and Zn were almost entirely due to insoluble metal removal; Cd, Cr and Cu removals had a significant contribution from soluble metal removal. Overall Mn removal appeared to be solely due to soluble metal removal.     

Drinking water quality in the Ethiopian section of the East African Rift Valley I--data and health aspects

Drinking water samples were collected throughout the Ethiopian part of the Rift Valley, separated into water drawn from deep wells (deeper than 60 m), shallow wells (<60 m deep), hot springs (T>36 degrees C), springs (T<32 degrees C) and rivers. A total of 138 samples were analysed for 70 parameters (Ag, Al, As, B, Ba, Be, Bi, Br, Ca, Cd, Ce, Cl, Co, Cr, Cs, Cu, Dy, Er, Eu, F, Fe, Ga, Gd, Ge, Hf, Hg, Ho, I, In, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, NO(2), NO(3), Pb, Pr, Rb, Sb, Se, Si, Sm, Sn, SO(4), Sr, Ta, Tb, Te, Th, Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr, temperature, pH, conductivity and alkalinity) with ion chromatography (anions), spectrometry (ICP-OES and ICP-MS, cations) and parameter-specific (e.g. titration) techniques. In terms of European water directives and WHO guidelines, 86% of all wells yield water that fails to pass the quality standards set for drinking water. The most problematic element is fluoride (F), for which 33% of all samples returned values above 1.5 mg/l and up to 11.6 mg/l. The incidence of dental and skeletal fluorosis is well documented in the Rift Valley. Another problematic element may be uranium (U)-47% of all wells yield water with concentrations above the newly suggested WHO maximum acceptable concentration (MAC) of 2 microg/l. Fortunately, only 7% of the collected samples are above the 10 microg/l EU-MAC for As in drinking water.     

Element levels in birch and spruce wood ashes: green energy?

Production of wood ash has increased strongly in the last ten years due to the increasing popularity of renewable and CO(2)-neutral heat and energy production via wood burning. Wood ashes are rich in many essential plant nutrients. In addition they are alkaline. The idea of using the waste ash as fertiliser in forests is appealing. However, wood is also known for its ability to strongly enrich certain heavy metals from the underlying soils, e.g. Cd, without any anthropogenic input. Concentrations of 26 chemical elements (Ag, As, Au, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, La, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Sr, Ti, and Zn) in 40 samples each of birch and spruce wood ashes collected along a 120 km long transect in southern Norway are reported. The observed maximum concentrations are 1.3 wt.% Pb, 4.4 wt.% Zn and 203 mg/kg Cd in birch wood ashes. Wood ashes can thus contain very high heavy metal concentrations. Spreading wood ashes in a forest is a major anthropogenic interference with the natural biogeochemical cycles. As with the use of sewage sludge in agriculture the use of wood ashes in forests clearly needs regulation.     

浙江省燕山期花岗岩化学元素丰度及特征

本研究从浙江省87个燕山期花岗岩体中系统采集了189件样品,采用等离子体光谱法等11种分析方法,获得了Ag、As、Au、B、Ba、Be、Bi、Br、Cd、Cl、Co、Cr、Cs、Cu、F、Ga、Ge、Hf、Hg、I、In、Li、Mn、Mo、N、Nb、Ni、P、Pb、Rb、S、Sb、Sc、Se、Sn、Sr、Ta、Te、Th、Ti、Tl、U、V、W、Zn、Zr、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y、SiO₂、Al₂O₃、TFe₂O₃、MgO、CaO、K₂O、Na₂O共68项主量、微量、稀土元素值以及TC、pH的实测数据,计算了扬子板块东缘与华南造山带燕山期花岗岩的化学元素丰度。岩石地球化学特征显示,这些花岗岩为高硅、富碱、弱过铝质的高钾钙碱性花岗岩,具有较强的Eu负异常,富集Rb、Th、U、K,亏损Sr、Ba、P、Ti、Nb、Ta等元素的特征,其普遍富铝和低MgO含量的岩石化学特征,指示它们的岩浆源区以壳源为主。     

Trace element concentrations in blood of harbor seals (Phoca vitulina) from the Wadden Sea

Concentrations of 23 elements (Be, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Mo, Pd, Cd, Sn, Pt, Pb) were evaluated in whole blood samples of live harbor seals (Phoca vitulina) from two different locations in the Wadden Sea, the Lorenzenplate in Germany, and the Danish island R?m?. Elemental blood levels were compared to data from literature of seals, other marine mammals and humans. While homeostatically controlled elements showed no differences, concentrations of As, Cr, Mn, Mo, Se, and V were higher than human levels. Furthermore, animals from both locations showed significant geographical differences in whole blood concentrations of Al, Mn, Cu, and Pt. These findings could be explained by differences in feeding areas. The element pattern was not affected by gender. In conclusion, these findings indicate an impact of the environment on biochemical blood parameters of the harbor seals. The significant differences of elements in blood samples of two groups of seals, which were associated with geographical variations of prey support the use of element pattern in blood as tool for investigation of environmental impact on seals.     

青海五龙沟矿集区典型金矿床深部盲矿预测构造叠加晕模型

五龙沟地区是青海省昆中构造成矿带的重要组成部分,该区金矿床严格受构造带控制,为典型蚀变岩型金矿床。区内典型金矿床地球化学和构造叠加晕特征研究表明:矿床具有Au、Ag、Cu、Pb、Zn、As、Sb、Bi、Hg、W、Mo、B、Co、Ni、V等多元素组合特点,主要金矿体赋矿构造带原生晕轴向分带规律表现为金矿体前缘指示元素为As、Sb、Hg、B,近矿指示元素为Au、Ag、Cu、Pb、Zn,尾晕指示元素为Bi、Mo、Mn、Co。在总结构造叠加晕预测标志基础上,建立了盲矿预测的构造叠加晕模型,通过赋矿构造带构造叠加晕特征研究,进一步圈定了深部找矿靶位。     

Determination of 14 elements in Taiwanese bones

The objective of this study was to measure the concentration of 14 elements in human bone and investigate the affecting factors. This study aims to establish a database of elements in Taiwanese bone. Seventy-seven bone samples were taken from 70 subjects who were undertaking various bone surgeries from a medical center in central Taiwan. Bone samples were pretreated using microwave digestion and then, after determining the optimal conditions for analysis, fourteen elements were analyzed using Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES). Results showed that Ca had the highest concentration, followed by Mg and Zn. The lowest concentrations were of Mn, followed by Cd and Co. There was a positive correlation between the frequency of seafood intake and presence of all the 14 elements in human bone. There were several elements that had positive inter-correlation: As with Co; Al, Ag and Ca; Ni with Co, Mn and Al; Co with Al, Ag and Ca; Mn with Cr and Cu; Cr with Cu; Mg with Ca; Al with Ag and Ca; Ag with Ca; and also Zn with Mg. There were no significant differences found between concentrations of elements and etiology of bone disease and age. The authors suggest that further studies be conducted to establish a normal value of elements in human bone in Taiwan. This will greatly benefit the understanding of the relationship between disease pattern and elements in human bone.     

Metal concentrations in a shallow groundwater aquifer underneath petrochemical complex

Duplicate groundwater samples were collected from 104 monitoring wells (piezometers) from shallow aquifers underneath an industrial city in the Eastern Province of Saudi Arabia. Concentrations of Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Ti, V, Zn, Ca, Mg, K, Na, Cl, SO₄, alkalinity, salinity, total dissolved salts, and pH were determined in these samples. Analysis of variance showed significantly (p < 0.05) wide variations in the concentrations of the above parameters. The contour maps of metal concentrations indicated that these variations were related to important landmarks in the study area. The results of correlation analyses suggest that geographical as well as chemical factors may influence metal distribution in the groundwater samples. To investigate the geographical effects, the analytical data were normalized (element/Cl ratios were calculated) for chemical variability. As expected, contour mapping of the ratio data of element/Cl of Na, Ca, Mg, K, SO₄, alkalinity, salinity, total dissolved salts, and Sr vary in a relatively small range and did not show a particular geographical trend. The groundwater sample from the industrial-dust area contained higher ratios between concentrations of Cl and Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, and Zn. These observations clearly suggest an extraneous contamination source, probably industrial dust, in the area. Another geographical area where metal (As, Cd, Cu, Mo, Ni, Ti,and V)/Cl ratios were found to be large was in the vicinity of an oil-refinery. Groundwater samples collected from the vicinity of a fertilizer plant and green-belt area contained relatively higher ratios of Al, Cd, Cr, Co, and Ni. The results of this study suggest that leachate from the industrial dust, leakage from the oil refinery and fertilizer plant, and drainage of irrigation water are some of the important pollution sources in the industrial city.     

Heavy metal pollution of soils affected by the Guadiamar toxic flood

Total heavy metal concentrations were determined in soil samples of seven selected areas along the Guadiamar river valley affected by the toxic flood, after removal of the deposited sludge. Mean total concentrations of nine elements (As, Au, Bi, Cd, Cu, Pb, Sb, Tl and Zn) out of the 23 (As, Au, Ba, Be, Bi, Cd, Co, Cr, Cu, In, Mn, Mo, Ni, Pb, Sb, Sc, Sn, Th, Tl, U, V, Y and Zn) analysed were higher in sludge-covered soils than in unaffected soils. Mean values of total As, Au, Pb, Sb, Tl and Zn in sludge-affected soils were higher than the upper limits for normal soils world-wide. Mean concentrations of Bi, Cd and Cu were within these ranges, although some individual values exceeded the upper limits. In all sampling areas, severe heavy metal pollution was observed in the superficial layers (0-20 cm) of most of the affected soils, which decreased downward in the soil profile. Generally, in soils with more than 25% of clay, concentration of heavy metals below the 20-cm depth decreased to values close to those of the background level of the Guadiamar valley soils, while in coarser soils, heavy metal pollution penetrated below this depth, being noticeable down to a depth of at least 50-80 cm.     

Enhanced methods for assessment of the trace element composition of Iron Age bone

Modern, ultra-trace, analytical methods, coupled with magnetic sector ICP-MS (HR-ICP-MS), were applied to the determination of a large suite of major and trace elements in Iron Age bones. The high sensitivity and un-paralleled signal-to-noise characteristics of HR-ICP-MS enabled the accurate measurement of Ag, Al, As, Ba, Ca, Cd, Ce, Co, Cr, Cu, Fe, La, Li, Mg, Mn, Ni, P, Pb, Pt, Rb, Sr, U, V, and Zn in small bone sections (<75 mg). Critically, the HR-ICP-MS effectively addressed molecular interferences, which would likely have compromised data generated with quadrupole-based ICP-MS instruments. Contamination and diagenetic alteration of ancient bone are grave concerns, which if not properly addressed, may result in serious misinterpretation of data from bone archives. Analytical procedures and several chemical and statistical methods (Principal Components Analysis - PCA) were studied to assess their utility in identifying and correcting bone contamination and diagenetic alteration. Uncertainties in bone (femur) sampling were characterized for each element and longitudinal variation was found to be the dominant source of sampling variability. However the longitudinal variation in most trace elements levels was relatively modest, ranging between 9 and 17% RSD. Bone surface contamination was evaluated using sequential acid leaching. Calcium-normalized metal levels in brief, timed, dilute nitric acid leaches were compared with similarly normalized interior core metal levels to assess the degree of surface enrichment. A select group of metals (Mn, Co, Ni, Ag, Cd, and Pt) were observed to be enriched by up to a factor of 10 in the bone surface, indicating that that these elements may have a higher contamination component. However, the results of sequential acid leaching experiments indicated that the single acid leaching step was effective in removing most surface-enriched contaminants. While the leaching protocol was effective in removing contaminants associated with the bone surface, there remained potentially significant residual levels of soil-sourced contaminant tracers within the leached bone. To address this issue a mathematical procedure, based on metal/aluminum ratios, was developed to correct-for the soil-contaminant metal pools. Soil correction fractions for the primary anthropogenically mobilized metals evaluated were greatest for Pb (13.6%) followed by As (4.4%), Ag (3.9%), and Cd (0.94%). Although median soil corrections were typically low, many samples did require a much larger correction, thus both bone cleaning and soil corrections may be necessary to realize accurate endogenous bone elemental data. The results of the PCA analysis were remarkably consistent with outcomes from the chemical and elemental ratio protocols evaluated in the study, and suggest that loadings on certain factors will be helpful in screening for soil-biased samples and in identifying diagenetically altered bone. Application of these contamination evaluation and correction tools was made possible by the high-quality, multi-element, datasets produced by HR-ICP-MS. Large variations in bone core concentrations between the 80 Iron Age specimens examined were observed for all the primary trace elements and in many of the supporting elements, even after correction for major contaminant components.     

内蒙古甲乌拉铅锌银矿床构造地球化学研究与找矿预测

内蒙古甲乌拉铅锌银矿床是大型火山-次火山热液脉状铅锌银金属矿床,经多年的开采,矿山面临着深部找矿问题。本次研究通过对2号矿体、3号矿体、2-44号矿体构造地球化学研究,建立了各矿体银铅锌矿化元素组合特征及不同成矿阶段矿体元素组合特征。研究认为甲乌拉矿床成矿期分为3个阶段,其第一阶段元素组合为As、Sb、Pb、Zn、Ag、Cu、Cd;第二阶段为As、Sb、Pb、Zn、Ag、Cu、Au、Ga、Cd;第三阶为Pb、Ag、Cd。成矿元素水平分带及垂直分带特征表明热液的来源可能为构造的南西深部,在此基础上,建立矿区近矿晕(Pb、Zn、Cu、Ag)、前晕(As、Sb、Hg、B)、尾晕(Bi、Mo、Mn、Co、Ni)的构造地球化学找矿标志,在2号矿体深部圈定找矿靶区3处,为深部探矿工程部署提供依据,实现甲乌拉铅锌银矿找矿新突破。     

Heavy metals and essential elements in livers of the polar bear (Ursus maritimus) in the Canadian Arctic

Polar bear (Ursus maritimus) livers (67) from six Management Zones in the western and central Canadian Arctic were analysed for 22 elements. Several, Ba, Be, Co, Mo, Ti, V and Zr, were near the detection limit in all cases. Baseline data were obtained for the remaining elements, Ag, As, Ca, Cd, Cu, Fe, Hg, K, Mg, Mn, Na, P, Se, Sr and Zn. No statistically significant effect of age, sex or geographical location was found for any of the elements, except Cd, Hg and Se, for which age and geographical location effects were found. The frequency distribution of Zn levels was bimodal. The second peak in the distribution appeared to be related to elevated levels of Cu. The average level of Cu was 104 mg kg-1 (dry wt.), higher than other marine mammals. Average levels of Cd were significantly higher in the eastern zones, but were always less than 1.0 mg kg-1 (dry wt.), significantly lower than their prey species. This may be due to the preference of polar bears for eating seal skin and fat which is low in Cd. Mercury levels tended to be higher in the western zones bordering the Beaufort Sea, which may be related to a higher proportion of bearded seal in their diet. Mean Hg levels ranged from 20 mg kg-1 in the eastern zones were related to age by the expression: Hg (mg kg-1 dry wt.) = 15.7 + 8.0 Age (years). Mercury levels in the most northerly zone near Melville Island were very high: Hg (mg kg-1 dry wt.) = 18.4 + 27.5 Age (years). Levels of Hg and Se were very highly correlated, with a molar ratio of 1.27:1, Hg/Se.     

Adsorption of trace metals on aluminium oxide: A simulation of processes in freshwater systems by close approximation to natural conditions

The interaction of the trace metals Cu, Co, Zn, Ni, Pb and Cd with aluminium hydroxide precipitated in-situ from homogeneous solution was studied. Using total concentrations of 10⁻⁴ M Al, 10⁻⁷ M Zn, Cu, Co, Ni and 10⁻⁸ M Pb and Cd a removal of Zn, Cu, Pb, Cd from solution occurred together with Al, while Co and Ni concentrations in solution remained unchanged. The binding of Cu, Pb and Zn, Cd is in agreement with the effect predicted by using published (resp. evaluated for Zn and Cd), values for stability constants of surface complexes on preformed Al₂O₃-suspension. The different behaviour of these elements and of Co and Ni is expected from the hydrolysis and adsorption tendencies. The experimental conditions correspond to natural conditions in lake waters, where due to the pH-dependent solubility of aluminium hydroxide, in-situ precipitation may occur and cause the scavenging of trace elements.     

A pilot study on the content and the release of Ni and other allergenic metals from cheap earrings available on the Italian market

The capability of alloys used in cheap jewellery to release metal ions on contact with the skin causing allergic contact dermatitis (ACD) is generally acknowledged. To reduce the diffusion of the Ni-induced ACD the Council Directive 94/27/EC [Council Directive 94/27/EC of 30 June 1994. Official Journal L 188, 22/07/1994, 1.] limited the total Ni content in alloys and its release rate in artificial sweat. In this work, three different aspects were explored: i) the frequency of skin sensitization to Ni-containing earrings in patients before and after the introduction of the Directive's limit; ii) metal composition of alloys by X-ray analysis; iii) metal leaching in artificial sweat followed by Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICP-MS) quantification. Well-known allergenic metals, as Ni, Cr and Co, and possible emergent allergens, as Al, Ag, Au, Cd, Cu, Fe, Ir, Mn, Pb, Pd, Pt, Rh, Sn, V and Zn, were studied. Results showed that the frequency of allergy due to earrings did not decrease after the introduction of the Ni limit: in 1994 and in 2005 patients positive to Ni patch tests were 54.3% and 53.5%, respectively. The earring components analyzed were Fe-based or alloys of Cu/Zn or Fe/Cr/Ni, plated with a thin film of precious metal (Ag, Au) which, in several cases, was combined with a Ni layer beneath. Five out of 10 items were not in compliance with the Ni Directive 94/27/EC having a total Ni content >0.05%. In three cases the release of Ni concentrations was higher than the safe sensitizing limit given by the above mentioned Regulation (i.e., <0.5 microg/cm(2)/week). The release of Cu and Zn was very variable among the different pieces (Cu: 0.134-30.9 microg/cm(2)/week; Zn: 0.141-160 microg/cm(2)/week); two objects released high amounts of Fe (358 and 586 microg/cm(2)/week) and one released considerable Mn (21 microg/cm(2)/week). Lead was released from 70% of the objects, while Ag, Al, Cd, Co, Cr and Sn from ca. 30% of the items and concentrations of these elements were well below 0.5 microg/cm(2)/week. Vanadium was released by only one item whereas Au, Ir, Pd, Pt and Rh were never leached.     

Variations in heavy metal concentrations in the moss species Abietinella abietina (Hedw.) Fleisch. according to sampling time,within site variability and increase in biomass

Concentrations of Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mo, Ni, Pb, V and Zn were analysed in the moss Abietinella abietina (Hedw.) Fleisch. to estimate atmospheric heavy metal depositions. Samples were taken at five comparable sites within a radius of 25 m four times during the year 2000 (July 3rd, August 3rd, September 7th, October 3rd). The samples were taken by means of a PVC-tube (r=10 cm) and could therefore be related to aboveground growth and aerial deposition. The investigation showed significant differences between the various sampling times for concentrations of all heavy metals in total but not between concentrations of a single metal. For Cu, Hg, Mo, Pb and Zn temporal variation (=variation between the four times of sampling) was larger than spatial variation (=variation of concentrations between sub-samples at a single sampling time). Growth rates of the mosses differed significantly between sampling times, which reflects the low precipitation at the beginning of the season. Biomass increase, dust and precipitation influenced the metal concentrations. The calculation of deposition rates, which takes growth rates into account, showed significant differences between the various sampling times for Al, Cd, Cr, Cu and Ni, which is controversial to the results obtained from concentrations of these elements. Additionally, the calculation of atmospheric deposition rates showed a constant increase of metal depositions throughout the investigated period, which can not be seen by considering the concentrations only.