Atmospheric pollution for trace elements in the remote high-altitude atmosphere in central Asia as recorded in snow from Mt. Qomolangma (Everest) of the Himalayas

A series of 42 snow samples covering over a one-year period from the fall of 2004 to the summer of 2005 were collected from a 2.1-m snow pit at a high-altitude site on the northeastern slope of Mt. Everest. These samples were analyzed for Al, V, Cr, Mn, Co, Ni, Cu, Zn, As, Rb, Sr, Cd, Sb, Pb, and Bi in order to characterize the relative contributions from anthropogenic and natural sources to the fallout of these elements in central Himalayas. Our data were also considered in the context of monsoon versus non-monsoon seasons. The mean concentrations of the majority of the elements were determined to be at the pg g(-1) level with a strong variation in concentration with snow depth. While the mean concentrations of most of the elements were significantly higher during the non-monsoon season than during the monsoon season, considerable variability in the trace element inputs to the snow was observed during both periods. Cu, Zn, As, Cd, Sb, and Bi displayed high crustal enrichment factors (EF(c)) in most samples, while Cr, Ni, Rb, and Pb show high EF(c) values in some of the samples. Our data indicate that anthropogenic inputs are potentially important for these elements in the remote high-altitude atmosphere in the central Himalayas. The relationship between the EF(c) of each element and the Al concentration indicates that a dominant input of anthropogenic trace elements occurs during both the monsoon and non-monsoon seasons, when crustal contribution is relatively minor. Finally, a comparison of the trace element fallout fluxes calculated in our samples with those recently obtained at Mont Blanc, Greenland, and Antarctica provides direct evidence for a geographical gradient of the atmospheric pollution with trace elements on a global scale.     

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.     

Speciation of selected trace elements in three Ethiopian Rift Valley Lakes (Koka, Ziway, and Awassa) and their major inflows

The Ethiopian Rift Valley Lakes (ERVLs) are water resources which have considerable environmental, economic and cultural importance. However, there is an increasing concern that increasing human activities around these lakes and their main inflows can result in increased contamination of these water bodies. Information on total concentrations of some trace elements is available for these lakes and their inflows; however, data on the trace element speciation is lacking. Therefore, the objective of this study was to determine the low molecular mass (LMM) trace element species and also, evaluate the influence of flooding episodes on the LMM trace element fractions. At-site size and charge fractionation system was used for sampling of water from the lakes Koka, Ziway and Awassa and their main inflows during the dry and wet seasons. The results showed that chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), and lead (Pb) in Lake Koka and its inflows as well as in Lake Ziway were predominantly present as HMM (high molecular mass, i.e., > 10 kDa) forms, while arsenic (As), selenium (Se), cadmium (Cd) were more mobile during the dry season. In Lake Awassa, all except Cr and Mn were predominantly found as LMM species (low molecular mass, i.e. < 10 kDa) which can be attributed to the high concentrations of LMM DOC (dissolved organic carbon). During the wet season, results from the Lake Koka and its inflows showed that all trace elements were predominantly associated with HMM forms such as colloids and particles, demonstrating that the mobility of elements was reduced during the wet season. The colloidal fraction of elements such as Cr, Ni, and Cd was also correlated with dissolved Fe. As the concentration of LMM trace element species are very low, the mobility, biological uptake and the potential environmental impact should be low.     

Determination of mineral and trace elements in some medicinal herbs and their infusions consumed in Turkey

Fourteen mineral and trace elements (Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sr and Zn) were determined in the herbs and their infusions consumed for medical purposes in Turkey such as chamomile (Matricaria chammomile L.), fennel (Foeniculum vulgare), linden (Tilia vulgaris), nettle (Urtica dioical), rosehip (Fr.Rosa caninae), sage (Salvia officinalis) and senna tea (Cassia anqustifolia). Microwave digestion procedure was applied under optimized conditions for dissolution of medicinal herbs. Element concentrations in the medicinal herbs and their infusions were determined by FAAS and ICP-AES. The accuracy and precision were verified against a GBW 07605 Poplar leaves and Tea certified reference material. The mineral and trace element content of medicinal herbs and their infusions showed a wide variability. However, distribution of the elements in the infusions is not high and it is nil especially for Cd, Co, Cr and Pb.     

Trace element concentrations in hair of healthy Chinese centenarians

Trace element concentrations, as indicators of micronutrient status of healthy centenarians, have not been widely analyzed. This study aimed to assess trace element concentrations in the hair of healthy centenarians. The effects of gender and age on element concentrations were also investigated. Eleven trace elements (Al, Ba, Cd, Cr, Cu, Fe, Mo, Pb, Se, Sr and Zn) in the scalp hair of 107 healthy Chinese centenarians were examined. The overall reference values (RVs) in mg/kg for the hair concentrations of trace elements in centenarians were as follows: Al, 14.95; Ba, 2.68; Cd, 0.06; Cr, 0.59; Cu, 6.21); Fe, 19.37; Mo, 0.50; Pb, 4.64; Se, 0.37; Sr, 4.84; and Zn, 154.37. Data analysis found that only Cu and Zn concentrations show a normal distribution, and there is no significant difference between males and females in any element except Zn. However, the levels of Al, Cd, Cr, Fe, Mo, Pb decrease and the levels of Ba, Cu, Se, Sr, Zn increase with age in the centenarian cohort. Results also revealed that sufficient Zn and Se concentrations as well as low exposure to heavy metals pollution contribute to the longevity of centenarians. The results imply the possibility of manipulating trace element concentrations, especially Zn and Se concentrations in tissues, as a means for therapeutic modality in geriatric disease.     

Subcellular and body distributions of 17 trace elements in the variegated scallop Chlamys varia from the French coast of the Bay of Biscay

Seventeen elements were analysed in the organs and tissues of the variegated scallop Chlamys varia, from the Atlantic coast of France. Concentration levels were determined in scallops of different sizes sampled in contaminated (La Rochelle Bay) and clean (Re Island) sites. Greater concentrations of Ag, Al, Ce, Cr, La, Mo, Nd, Ti, and V were found in the digestive gland while As, Cd, Co, Cu, Mn, Ni, Pb, and Zn were the highest in the kidneys. In the digestive gland, most of the metals were found in the insoluble fraction while As, Co, Cd, Mo, Ni, and V appeared to be mostly bound to soluble compounds. Among tissues, the adductor muscle always displayed the lowest trace element concentrations. According to size, Ag and Cd showed significantly higher concentrations in larger individuals, while Co and Zn were higher in the smallest ones. According to the sampling area, most of the metals, Ag, Al, Ce, Co, Cu, La, Mn, Nd, Pb, and Zn, showed significantly higher concentrations in La Rochelle Bay compared to the Re Island, reflecting differing inputs from industrial, domestic and harbour activities. However, Cr, Mo, Ni, Ti, and V concentrations did not display significant differences between sites and As and Cd were significantly higher at the Re Island. This study highlighted the ability of the variegated scallop C. varia to concentrate numerous trace elements to high levels, even those reported as poorly bioavailable for marine biota, such as rare earth elements.     

Trophodynamics of mercury and other trace elements in a pelagic food chain from the Baltic Sea

Mercury (Hg) and 13 other trace elements (Al, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, As, Cd, and Pb) were measured in phytoplankton, zooplankton, mysis and herring in order to examine the trophodynamics in a well-studied pelagic food chain in the Baltic Sea. The fractionation of nitrogen isotopes (δ¹⁵N) was used to evaluate food web structure and to estimate the extent of trophic biomagnification of the various trace elements. Trophic magnification factors (TMFs) for each trace element were determined from the slope of the regression between trace element concentrations and δ¹⁵N. Calculated TMFs showed fundamental differences in the trophodynamics of the trace elements in the pelagic food chain studied. Concentrations of Al, Fe, Ni, Zn, Pb and Cd showed statistically significant decreases (TMF < 1) with increasing trophic levels and thus these trace elements tropically dilute or biodilute in this Baltic food chain. Cu, As, Cr, Mn, V, Ti and Co showed no significant relationships with trophic levels. Hg was unique among the trace elements studied in demonstrating a statistically significant increase (TMF > 1) in concentration with trophic level i.e. Hg biomagnifies in this Baltic food chain. The estimated TMF for Hg in this food chain was comparable to TMFs observed elsewhere for diverse food chains and locations.     

Assessment of daily intake of trace elements due to consumption of foodstuffs by adult inhabitants of Rio de Janeiro city

Concentrations of Al, Cd, Cr, Cu, Mn, Ni, Pb, U and Zn were determined in vegetables (leafy vegetables, fruit, root, grain and cereal), derived products (sugar, coffee, manioc flour, wheat flour, corn flour, and pasta) and animal products (meat, fish, milk) most frequently consumed by adult inhabitants of Rio de Janeiro city. A total of 90 samples were analyzed using inductively coupled plasma mass spectrometry (ICPMS) as the principal method following sample dissolution by dry and wet ashing. Generally, highest contributions for the intake of micronutrients (Cu, Mn, Ni and Zn) arise from bean, rice and wheat flour consumption. Meat, cow milk and the flours, wheat and manioc, are major sources of Al, Cd, Pb and U intake. The daily intake of nine elements via foodstuffs was estimated as: 3.4x10(-4) mg of U, 1.8x10(-3) mg of Cd, 2.8x10(-2) mg of Pb, 2.3x10(-2) mg of Cr, 8.9x10(-2) mg of Ni, 1.12 mg of Cu, 2.5 mg of Mn, 3.5 mg of Al and 4.8 mg of Zn. The intake of toxic elements ranged between 2.7% (Cd) and 30% (U) of the provisional tolerable daily intake and reference dose values indicating that food consumption is, at present, no critical factor for the uptake of these toxic metals, in the population studied here. Concerning micronutrients, the recommended values of daily intake of Cu and Mn are conveniently supplied by the diet; however, for Cr and Zn they are lower than the recommend daily allowance. Due to high metal concentrations and consumption rates, black bean is the foodstuff that provided the highest ingestion rates of Cu, Mn, Ni and Zn (36-60% of the reference dose), being therefore a very important source of micronutrient supply.     

The use of lichen (Cetraria nivalis) and moss (Rhacomitrium lanuginosum) as monitors for atmospheric deposition in Greenland

Concentrations of Pb, Cd, Hg, Zn, Cu, Cr, Ni, As, V, Al and Fe are reported from soil, humus, moss (Rhacomitrium lanuginosum) and lichen (Cetraria nivalis) sampled at four locations in Greenland. For Al, Fe, Cr and V the levels in soil were highest followed by humus and R. lanuginosum and with the lowest levels in C. nivalis. The same was true for Pb, Cu and Ni but without as great a difference between medias. For Cd and Hg, the lowest levels were found in soil. For Zn and As, the media with highest levels differed between locality. Data were examined by a principal component analysis. Three principal components explained 87% of the total variation. The dominant elements in the first component were Fe, Al, V, Ni, Cr, Cu and Pb. This component is interpreted as a soil dust factor. The concentrations in R. lanuginosum and C. nivalis of these elements are believed to be highly influenced by soil dust. Pb concentrations in moss and lichen may also be influenced by other sources as Pb also had some correlation's with the third component. Zn and Cd and to a lesser extent. As were the dominant elements in the second component. The third component was highly dominated by Hg with a lesser influence of Pb and As, Zn, Cd and Hg concentrations in R. lanuginosum and C. nivalis are believed to be influenced by other sources than soil dust which may be long-range atmospheric transport. In general, both the within locality and the between locality variability in the values of the three components decreased in the order soil, humus, R. lanuginosum and C. nivalis. The lichen C. nivalis is looked at as an indicator with greater potential for monitoring atmospheric deposition of elements than the moss R. lanuginosum.     

Heavy-metal pollution of sediments from Szczecin Lagoon and the Gdansk Basin, Poland

Concentrations of Al, V, Mn, Fe, Co, Cu, Ni, Zn, Sr, Mo, Cd, Sb, Pb, Th, U, REE, Na, K, Mg, Ca, Si, P, S, Ti, Cr and Ba were determined in the <63 microm fraction of bottom sediments of the Szczecin Lagoon and the Gdansk Basin, Baltic Sea, by ICP-MS, ICP-AES and XRF methods. Sediment samples from the Szczecin Lagoon displayed somewhat higher concentrations of P, Mn, Cr, Cu and possibly Cd, Pb and Zn in those collected in October 1997 after the exceptional flooding of the Oder River than in those collected in December 2000. The data suggest that the flood resulted in the enhanced transport of redox-sensitive and anthropogenic elements in the Oder River and their subsequent redeposition mainly in the western part of Szczecin Lagoon. The sediments of the Szczecin Lagoon also appear to be the most polluted with heavy metals within the Polish Exclusive Economic Zone (EEZ) of the Baltic Sea. Cd, Pb, Zn and Cu are anthropogenically enriched in top layers of sediment cores from the Gdansk Basin, but the decrease of these elements with depth in the core is not systematic. The rare earth element (REE) patterns in sediments from both these areas do not appear to have been greatly modified during transport from their source into the southern Baltic. Factor analysis (FA) of the compositional data shows that sediments from Szczecin Lagoon can be divided into three main groups depending on their composition. It is concluded that clay minerals and organic matter build aggregates and flocs, which effectively concentrate trace metals and sink down to form a 'fluffy layer'.     

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.     

Effects of experimental CO2 leakage on solubility and transport of seven trace metals in seawater and sediment

The impact of CO₂ leakage on solubility and distribution of trace metals in seawater and sediment has been studied in lab scale chambers. Seven metals (Al, Cr, Ni, Pb, Cd, Cu, and Zn) were investigated in membrane-filtered seawater samples, and DGT samplers were deployed in water and sediment during the experiment. During the first phase (16 days), “dissolved” (< 0.2 µm) concentrations of all elements increased substantially in the water. The increase in dissolved fractions of Al, Cr, Ni, Cu, Zn, Cd and Pb in the CO₂ seepage chamber was respectively 5.1, 3.8, 4.5, 3.2, 1.4, 2.3 and 1.3 times higher than the dissolved concentrations of these metals in the control. During the second phase of the experiment (10 days) with the same sediment but replenished seawater, the dissolved fractions of Al, Cr, Cd, and Zn were partly removed from the water column in the CO₂ chamber. DNi and DCu still increased but at reduced rates, while DPb increased faster than that was observed during the first phase. DGT-labile fractions (Me_DGT) of all metals increased substantially during the first phase of CO₂ seepage. DGT-labile fractions of Al, Cr, Ni, Cu, Zn, Cd and Pb were respectively 7.9, 2.0, 3.6, 1.7, 2.1, 1.9 and 2.3 times higher in the CO₂ chamber than that of in the control chamber. Al_DGT, Cr_DGT, Ni_DGT, and Pb_DGT continued to increase during the second phase of the experiment. There was no change in Cd_DGT during the second phase, while Cu_DGT and Zn_DGT decreased by 30% and 25%, respectively in the CO₂ chamber. In the sediment pore water, DGT labile fractions of all the seven elements increased substantially in the CO₂ chamber. Our results show that CO₂ leakage affected the solubility, particle reactivity and transformation rates of the studied metals in sediment and at the sediment-water interface. The metal species released due to CO₂ acidification may have sufficiently long residence time in the seawater to affect bioavailability and toxicity of the metals to biota.     

Sediment reference concentrations of seldom monitored trace elements (Ag, Be, In, Ga, Sb, Tl) in four Swedish boreal lakes--comparison with commonly monitored elements

This paper presents reference and recent acid-leachable concentrations of some seldom monitored trace elements (SMTE; Ag, Be, Ga, In, Sb and Tl) in sediments from four boreal oligotrophic lakes in a south to north transect in Sweden. For comparison commonly monitored trace elements (As, Cd, Co, Cr, Cu, Ni, Pb and Zn) are included as well as those of relevance for redistribution processes (Al, Ca, Fe, Mg and Mn). Pore water pH and the corresponding solid/solution distribution coefficients (Kd) indicated that redistribution of the elements due to acidification is minor. The depth of impact was defined as the level in the sediment where the mean values became constant on successive exclusion of metal concentrations in overlying strata. Reference concentrations were calculated below the depth of impact. The present concentration changes are estimated by the ratio between the average concentration above the depth of impact and the reference concentration. Reference concentration ranges for the SMT-elements are (mg/kg, dry wt.): Ag 0.16-0.66; Be 1.6-3.7; Ga 2.0-5.1; In 0.05-0.22; Sb 0.05-0.11 and Tl 0.17-0.70. The concentration ratios for these elements ranged in the two most southern lakes from 1.5 to 4.5 and in the two northern ones from 0.6 to 1.6. A high correlation between Kd for the SMT-elements, and iron, except for Sb and Tl, infer that the biogeochemistry of iron is quantitatively important for the accumulation of these elements. The reference concentration ranges for the commonly monitored trace elements are (mg/kg, dry wt.): As 7.0-29.6; Cd 0.33-0.98; Co 5.7-23.8; Cr 15.2-26.1; Cu 27.6-58.4; Ni 5.4-20.8; Pb 44-96. The corresponding concentration ratios were 1.2-18 (second highest 3.9) in the two most southern lakes and 0.8-1.6 in the two northern ones. Declining ratios were found from south to north, most obvious for cobalt and zinc. The copper ratios did not show a regional pattern, partly because of the impact from old mine waste. Increased concentrations of Ag, Be, Ga, In, Sb and Tl in recent sediments up to 4.5 times the reference levels in combination with the geographical pattern infer an elevated loading of these elements.     

Trace elements in foods and meals consumed by students attending the faculty cafeteria

The content and intake of some trace elements (Pb, Cd, Ni, Hg, Cr) in meals, consumed by students attending the Faculty Cafeteria, were assessed. The study was carried out over 6 days of the 2nd week of February, 1993 and in three consecutive days of the second week of May. In those periods 10453 and 4055 students attended the cafeteria, respectively. After recording the ingredients and the preparation and cooking methods, some edible portions of foods and dishes were collected, homogenised, lyophilised and kept in polyethylene bottles until analysis. We found few differences in food content and dietary intake of some (Ni and Cr) but not all trace elements between February and May. Higher levels of Pb, Cd, Ni, Cr were present in bread (21.5+/-14.0, 5.6+/-0.02, 55.6+/-1.7 and 66.9+/-0.1 microg/100 g of edible portion, respectively), followed by meat, filled pasta and cheese, whereas lower values were observed in vegetables and fruit. The highest Hg content was recorded in the pasta group. Among the most frequently consumed foods and meals, the highest levels of P, Pb, Cr, Hg, Ni were found in bread, meat and pasta. The calculation of mean trace element intake, corrected for leftovers, showed pasta, bread and meat as the main sources of Pb, Cd, Ni, Hg and Cr over the two periods. The estimated potential tolerated weekly intake (PTWI) resulted high for Pb and Cd and low for Hg. Finally, a large variability in trace element content between raw and cooked foods was observed. These results give valuable information on trace element content of foods to be used for preparation of meals at the Faculty cafeteria in different seasons.     

Natural attenuation processes in two water reservoirs receiving acid mine drainage

Characteristics of water profiles and sulphide formation processes in sediments were studied in two water reservoirs affected by acid mine drainage in order to investigate the mechanisms controlling the physical and chemical processes that, under favourable conditions, act to reduce the toxicity, mobility and concentration of metals and metalloids in the water column. Water columns and pore-waters from sediments were analysed for Fe species, trace elements (As, Cd, Co, Cu, Mn, Ni, Pb, Zn, Cr), sulphide, sulphate and bicarbonate. Inorganic reduced sulphur compounds (acid volatile sulphur, pyrite sulphur and elemental sulphur) and reactive Fe were determined in the sediments. A sequential extraction was also performed. Both reservoirs behave like holomictic and monomictic lakes, with a summer thermal stratification that disappears during winter. pH values between 4 and 7 can be observed along the water columns. Pore-water concentrations of up to 25 mg/l of Fe, 4 mg/l of Al, 1.3 mg/l of Zn, 170 µg/l of Pb, 11 µg/l of As, etc. have been found. The results suggest that toxic elements such as Cu, Zn, Co, Pb, Cr, As, etc. are mainly found in the bioavailable fraction which is the most hazardous for the environment. The calculated degree of sulphidization (DOS) and degree of pyritization (DOP) values indicates that removal of trace elements from anoxic pore-waters occurs by coprecipitation and/or adsorption on newly formed Fe sulphides (framboidal pyrite), attenuating the contamination. However oxidation of the sediments during turnover periods also occurs, which releases toxic elements back into the water column.     

Mineral content in legumes and nuts: contribution to the Spanish dietary intake

We evaluated the levels of essential elements as Cu, Cr, Fe and Zn, and toxic elements as Al, Ni, Pb and Cd in a total of 40 samples of different legumes and 56 samples of different nuts, that are widely consumed in Spain. These elements were determined in the samples mineralized with HNO(3) and V(2)O(5), using electrothermal atomic absorption spectrometry (ETAAS) as the analytical technique. Reliability of the procedure was checked by analysis of a certified reference material. No matrix effects were observed and aqueous standard solutions were used for calibration. In legumes, the levels ranged from 1.5-5.0 microg Cu/g, 0.05-0.60 microg Cr/g, 18.8-82.4 microg Fe/g, 32.6-70.2 microg Zn/g, 2.7-45.8 microg Al/g, 0.02-0.35 microg Ni/g, 0.32-0.70 microg Pb/g and not detectable-0.018 microg Cd/g. In nuts, the levels ranged from 4.0-25.6 microg Cu/g, 0.25-1.05 microg Cr/g, 7.3-75.6 microg Fe/g, 25.6-69.0 microg Zn/g, 1.2-20.1 microg Al/g, 0.10-0.64 microg Ni/g, 0.14-0.39 microg Pb/g, and not detectable-0.018 microg Cd/g. A direct statistical correlation between Cu-Cr, Zn-Al and Cr-Ni (P<0.05), and Al-Pb (P<0.001), has been found. The growing popularity of these products in recent years on the basis of its nutritional properties and beneficial effects, requires additional data and a periodical control. In addition, the present findings are of potential use to food composition tables.     

Relationships among total recoverable and reactive metals and metalloid in St. Lawrence River sediment: bioaccumulation by chironomids and implications for ecological risk assessment

The availability and bioaccumulation of metals and metalloids, and the geochemical interactions among them, are essential to developing an ecological risk assessment (ERA) framework and determining threshold concentrations for these elements. The purpose of this study was to explore the relationships among total recoverable and reactive metals and metalloid in sediment and their bioaccumulation by chironomids. In the fall of 2004 and 2005, 58 stations located in the three fluvial lakes of the St. Lawrence River and its largest harbour area in Montreal, Canada, were sampled. Nine total recoverable and reactive metals (Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) and one metalloid (As) were measured in whole sediment using two extraction methods: HCl/HNO(3) and HCl 1N, respectively. The bioaccumulation of six metals (Cd, Cr, Cu, Ni, Pb and Zn) and As by chironomids was evaluated in a subset of 22 stations. Strong collinearities were observed between some total recoverable or reactive metal concentrations in sediment; two principal clusters, including collinear metals, were obtained. The first one included metals of mainly geological origin (Al, Cr, Fe, Mn, Ni), while the second one included As, Cd, Cu, Pb and Zn, which likely derive mainly from point sources of anthropogenic contamination. Each element also showed strong collinearity between their total recoverable and reactive forms (0.65< or =r < or =0.97). We can conclude that both chemical forms are equivalent for use in statistical models needed to explain biological responses and also in screening risk assessment. However, these relationships are not always proportional. Lower availability percentages were observed for Cd, Cu and Zn in the highly mixed-contaminated area of the Montreal Harbour, even though concentrations in sediment were higher. We observed a significant correlation (0.50< or =r < or =0.56) between concentrations in chironomids and concentrations of both total recoverable and reactive Cr and Pb in sediment. Arsenic was an exception, with accumulation by chironomids being highly related to reactive sediment concentrations. Finally, we observed variable influences of explanatory factors (e.g. sediment grain size, Al, Fe, Mn, S, TOC), depending on which metal or metalloid was being predicted in chironomids. In this context, it is difficult to choose a universal predictive method to explain the bioaccumulation of specific metals, and more research is still needed into normalization procedures that consider a combination of explanatory factors.     

Elemental composition of ancient Japanese bones

Excavated bones (rib) obtained from 50 sites in Japan were measured by ICP atomic emission spectrometry and atomic absorption spectrometry for concentration of 19 elements, including Al, B, Ca, Cd, Cr, Co, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, Sr, Ti, V and Zn. One hundred and forty-one specimens were classified into five groups according to Japanese prehistoric and historic eras (Jomon, Yayoi, Kofun, Kamakura and Muromachi, and Edo). The elements, with concentrations which showed no significant change with era were Al, B and Cr. Average concentrations of Ca were in the range 2-2.5 X 10(-1) g g-1 and those of P ranged from 1.1 to 1.3 X 10(-1) g g-1, indicating a well-preserved bone mineral matrix. The Ca/P ratio (mol/mol) was lowest in the Edo group--1.48 as compared with 1.54-1.66 in the other groups. Among the elements which showed changes with era were Pb, Fe, Co and Mn, all of which showed remarkably elevated concentrations in the Edo group. In addition to this unique elemental composition of Edo bones, samples from the Kofun era showed a completely different composition from those of other periods, i.e. they had the highest concentrations of Cd, Zn and Mg, and the lowest concentrations of Cu, K, Ni and Sr. The cause of the elevated Pb concentration in Edo bones is discussed in relation to human activities which may have led to environmental Pb pollution.     

Trace elements in stream bed sediments from agricultural catchments (Gascogne region, S-W France): Where do they come from?

The Gascogne region (SW of France) is cultivated for more than 75% of the area. 83 samples of stream bed sediments were collected in three main Gascogne river basins (Gers, Save and Touch, left tributaries of the Garonne river) to evaluate the impact of agricultural practices on trace elements behavior. Eight potential harmful elements (PHE) (Cr, Co, Ni, Cu, Zn, As, Cd and Pb), four reference elements for normalization (Sc, Cs, Al and Fe) and four major elements (Mn, Ca, Mg and P) were considered. The average trace element concentrations in the fine fractions (< 63 µm) are in the decreasing order: Zn > Cr > Ni > Pb > Cu > Co > As > Sc > Cs > Cd. Geochemical investigations and an original approach combining regression analysis and chemical sequential extraction allowed to select the most adequate reference material (regional molasse) and reference element (Cs) for normalization procedure. The enrichment factor (EF) is generally lower than 2.5, particularly for Cr, Ni, Cu, As, Zn; however, 23% of the sampling stations are more contaminated (2.5 < EF < 4.5), particularly for Cd, Pb and Co. The PHE in the Gascogne river sediments are mainly originated from natural weathering processes; nevertheless, anthropogenic contribution could represent up to 34% of the total sediment content. For lead, geochemical and isotopic methods gave very similar anthropogenic contributions (24% and 22%, respectively).The enrichment of Cu, Pb, Zn, Co, As, Ni, Cr was mainly related to global and local atmospheric deposition of industrial emissions and gasoline combustion, and was associated to forested catchments. All PHE's are controlled by clay and oxi-hydroxides minerals. Cd was the only PHE enriched downstream cultivated catchments and this enrichment was linked to Ca and P. This indicates a major origin of Cd from fertilizer inputs and a main control by carbonate minerals.     

Inputs of trace elements in agricultural soils via phosphate fertilizers in European countries

Mineral fertilizers are sources of diffuse metal enrichment of agricultural soils. A survey of phosphate fertilizers (blends or raw) sold on the European market was undertaken to quantify metal input via fertilizers in European agricultural soils. A total of 196 phosphate fertilizer samples from 12 European countries were analyzed for trace metals. Analytical quality was controlled with a certified rock phosphate sample. The average metal concentrations (mg kg(-1)) in the fertilizers were 14.8 (Ni), 7.4 (Cd), 166 (Zn), 2.9 (Pb), 7.6 (As), and 89.5 (Cr). The trace metal concentrations were positively correlated with the P concentrations confirming that the rock phosphate was the major source of these elements. Lowest metal concentrations were generally found in samples from Scandinavian countries. At average P use, the trace metal input via fertilizers was similar to or even larger than the metal input via atmospheric deposition in European agricultural soils for Cd, As, and Cr, whereas the reverse was true for Zn, Ni, and Pb. The input of Cd in European agricultural soils has decreased from previously estimated values and the soil Cd mass balance was close to steady state on an average basis.