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1.
The Mapocho river, which crosses downtown Santiago, is one of the most important rivers in contact with a population of about six million inhabitants. Anthropogenic activities, industrialization, farming activities, transport, urbanization, animal and human excretions, domestic wastes and copper mining have affected the river, contaminating it and its sediments with heavy metals. Concentration and distribution of Cu, Zn, Pb and Cd were studied with the purpose of determining their bioavailability and their relation with the characteristics of the sediments. Freshly deposited seasonal sediments were collected from 0–8 cm depths from 6 locations (S1 to S6) along the 30-km long channel length, in the four seasons of year on the following dates: May 2001 (D1, autumn); August 2001 (D2, winter); October 2001 (D3, spring) and January 2002 (D4, summer). The dried samples were sifted to obtain the < 63-μm sediment fraction, since it has been shown that large amounts of heavy metals are bound in the fine-grained fraction of the sediment. Cu and Zn were analyzed by atomic absorption spectrophotometry and Pb and Cd by square wave anodic stripping voltammetry. The highest concentrations of Cu (2850 μg g− 1) were found in the northern part of the river (S1, average D1–D4), near the mountains and a copper mine, and then decreased downstream to 209 μg g− 1 (S6). Total Zn showed an irregular variation, with higher values at S1 (1290 μg g− 1) and high values in some winter sampling (1384 μg g− 1 S4, S5–D2). Pb showed different trends, increasing from S1 to S6 (17 to 61 μg g− 1), with the highest values in the summer samples (83 μg g− 1, S4–S6, D4), and total Cd increased slightly from mean values of 0.2 and 0.5 μg g− 1. Partition into five fractions was made using Tessier's analytical sequential extraction technique; the residue was treated with aqua regia for recovery studies, although this step is not part of the Tessier procedure. The results show that Cu, Zn and Pb in the sediments were dependent on the sampling places along the river, and variation in two years was low (D1–D4). The highest values of total organic matter, carbonate and conductivity were found in S6, which has the smallest size particles, while at S1 the sediments were predominantly sand and contain larger amounts of silica. Cu associated with carbonate decreased gradually from 58% (1771 μg g− 1, S1) to 16% (32 μg g− 1, S6); Cu bonded to reducible fraction was almost constant (33% to 37%), and Cu associated with oxidizable fraction increased from 7% (S1) to 34% (S6), but copper content was lower (214 to 68 μg g− 1). Zn had a similar fractionation profile. However, Pb bound to oxidizable fraction did not show significant percent variation along the river (20% to 19%), but the amount bounded was 4 to 12 μg g− 1. The residual fraction increased from 24% to 41% (5 to 25 μg g− 1, S1 to S6). The distribution of Cd in the sediment was almost independent of the sampling stations and was bound to carbonate, reducible and residual fraction in similar proportion. Cu and Zn at S1 were mainly bound to carbonates and reducible phases with 91% and 73% (2779 and 965 μg g− 1, respectively), and with a change in the pH and/or the redox potential of the sediment–water system, these contaminants could easily enter the food chain. In S6 the amount of Cu and Zn in these phases was 50% and 53% (100 to 313 μg g− 1, respectively).  相似文献   

2.
Marine black shales of the Lower Cambrian Niutitang Formation in southern China host Mo–Ni–platinum group elements (PGE) mineralization confined to a phosphate- and pyrite-rich stratiform body (max. 20-cm thick). The H/C atomic ratio, carbon isotopic composition, FTIR spectra of bulk organic matter, and spectra of extractable part of organic matter indicate similar sources and thermal evolution of organic matter in barren and mineralized black shales.The morphology and relative abundance of organic particles in barren and mineralized shales are different. In barren black shales, organic particles comprise only elongated bodies and laminae 2–10 μm across or elongated larger bodies (> 10 μm) with Rmax = 2.96–5.21% (Type I particles). Mineralized black shales contain Type I particles in rock matrix (90–95 vol%), small veinlets or irregular organic accumulations (Type II particles, 1–5 vol%) that display weak to well developed mosaic texture and a variable reflectance (Rmax = 3.55–8.65%), and small (< 1 to 5 μm) rounded or irregular Type III organic particles (1–4 vol%) distributed within phosphate nodules and sulphide rip-up clasts. Type III particles show similar reflectance as particles of Type I in rock matrix. Type I particles are interpreted as remnants of in situ bacterially reworked organic matter of cyanobacteria/algal type, Type II as solidified products or oil-derived material (migrabitumen), and Type III particles as remnants of original organic matter in phosphatized or sulphidized algal/microbial oncolite-like bodies. Equivalent vitrinite reflectances of Type I and III particles in barren and mineralized rocks are similar and correspond to semi-anthracite and anthracite. Micro-Raman spectra of organic particles in rocks display a wide belt in the area of 1600 cm− 1 (G belt) and approximately the same belt in the area of 1350 cm− 1 (D belt). The ratio of integrated areas of the two belts correlate with Rmax values.The Mo–Ni–PGE mineralized body is interpreted as to represent a remnant of phosphate- and sulphide-rich subaquatic hardground supplied with organic material derived from plankton and benthic communities as well as with algal/microbial oncolite-like bodies that originated in wave-agitated, shallow-water, nearshore environment.  相似文献   

3.
Concentrations of Au, Ag, As, Cd and Sb in aquatic bryophytes collected from the Dolgellau Mineral Belt, North Wales, U.K. are reported. One aquatic liverwort, Scapania undulata (L) Dum. and two mosses, Fontinalis squamosa Hedw. and Racomitrium aciculare (Hedw.) Brid. were collected from sites upstream and downstream of the recently reopened Gwynfyndd Au mine. There was little inter-species variation in metal contents for these three bryophytes, but Scapania undulata appeared the most sensitive to changes in water concentrations of Ag, As and Sb. Gold concentrations varied little between the contaminated and control sites. Concentrations in the range < 4–18 ng Aug g−1 D.W. were typical background levels, while bryophytes collected immediately below the mine contained 6–45 ng Au g−1. Silver and Sb both showed more pronounced ( 5–10 fold) elevations above control concentrations in samples collected downstream of the mine. Background concentrations for these elements were 5–85 ng Ag g−1 and 0.15–1.3 μg Sb g−1.Arsenic concentrations downstream of the mine (160–1080 μg g−1) greatly exceeded the background range of 9–32 μg g−1. It is suggested, therefore, that As may be an ideal ‘pathfinder’ element when prospecting for auriferous deposits using aquatic bryophytes.  相似文献   

4.
Douglas fir trees and associated soils were sampled from the slopes of a small ( 4 km2) drainage basin in northeastern Washington to investigate the biogeochemical response to locally uraniferous groundwater. Uranium is preferentially incorporated in needles and twigs compared to larger branches or the trunk. The U concentration in needle ash ranges from 0.2 to 5.8 μg g−1 (ppm) and shows no correlation with the U concentration in associated soils. Rather, the distribution of anomalously uraniferous douglas fir (>1.0μg g−1 U in needle ash) appears to be controlled by observed or readily inferred pathways of near-surface groundwater movement in the drainage. These pathways include: (1) general downslope movement of subsurface runoff; (2) increased flux of near-surface groundwater near the toe of an alluvial fan; and (3) emergence of uraniferous (100–150 ng ml−1 [ppb] groundwater in the vicinity of a slope spring. The data also indicate the presence of near-surface uraniferous groundwater along a structurally controlled zone that parallels the north-south strike of the valley, and that includes the slope spring. The results suggest that biogeochemical sampling may be used to supplement more direct, but more limited, measurements of groundwater quality and flow regime in areas of near-surface contaminated groundwater.  相似文献   

5.
The geochemistry of Sepetiba Bay was studied in four sediment cores using a multi-element approach. Two cores were sampled in the more contaminated eastern part of the bay and two cores were sampled in the western region. The aim was to determine whether less common elements like the rare earths or the actinides are associated with contaminant metals like zinc in the Bay. Samples were analysed by instrumental neutron activation analysis that permits the quantification of total concentrations of metals (Ba, Co, Cr, Cs, Fe, Hf, Rb, Sc, Zn), rare earth elements (Ce, Eu, La, Lu, Sm and Yb), actinides (Th, U), non-metals and semi-metals (As, Br). Organic carbon and total sulphur were also analysed. The results show very strong zinc contamination in the top layers (more than 1000 μg g−1) and background concentrations in the bottom (15 μg g−1). Elements like chromium which would be expected to be released by the heavy industries of Sepetiba Bay, did not show a contamination profile, and concentrations remained close to those of natural environments. No evidence of any association between the zinc and other potential contaminant elements could be identified in this work.  相似文献   

6.
The amount of Cu and Fe associated with humic acids was estimated in five sediment cores from a tropical coastal lagoon (Piratininga Lagoon, Rio de Janeiro, Brazil). Core samples were analysed for humic acid contents, total Fe and Cu content. Fe and Cu associated with humic acids were also measured. Results show amounts of humic acids ranging from 0.7 to 21.7% of the dry weight of sediment (average 4.6%, standard deviation 4.4%). Concentrations of Fe and Cu ranged from 0.3 to 6.0% (average 2.2%, S.D. 1.2%) and from <1.0 to 65.0 μg g−1 (average 28.6 μg g−1, S.D. 16.4 μg g−1), respectively. The results of strongly bound metals show that while humic acids are the main carrier for Cu, Fe does not seems to be significantly associated with this organic matter.  相似文献   

7.
Molybdenum-rich black shales from the Cambrian of south China contain sulfide beds with >2 wt.% Mo, >2 wt.% Ni and 200–700 mg/T each for Au, Pt and Pd. Similar deposits occur in Canada. In the U.S. Midwest, Paleozoic black shales contain an extensive Mo anomaly and sporadic enrichments for Pt group elements, suggesting the presence of Ni-Mo-PGE-Au sulfide deposits like those being mined in China.  相似文献   

8.
The aim of this study is to estimate the C loss from forest soils due to the production of dissolved organic C (DOC) along a north–south European transect. Dissolved organic matter (DOM) was extracted from the forest soils incubated at a controlled temperature and water content. Soils were sampled from forest plots from Sweden to Italy. The plots represent monocultures of spruce, pine and beech and three selected chronosequences of spruce and beech spanning a range of mean annual temperature from 2 to 14 °C. The DOM was characterized by its DOC/DON ratio and the C isotope composition δ13C. The DOC/DON ratio of DOM varied from 25 to 15 after 16 days of incubation and it decreased to between 16 and 10 after 126 days. At the beginning of incubation the δ13C values of DOC were 1‰ or 2‰ less negative than incubated soils. At the end of the experiment δ13C of DOC were the same as soil values. In addition to DOC production heterotrophic respiration and N mineralization were measured on the incubated soils. The DON production rates decreased from 30 to 5 μgN gC−1 d−1 after 16 days of incubation to constant values from 5 to 2 μgN gC−1 d−1 after 126 days at the end of experiment. The DIN production rates were nearly constant during the experiments with values ranging from 20 to 4 μgN gC−1 d−1. DOC production followed first-order reaction kinetics and heterotrophic respiration followed zero-order reaction kinetics. Kinetic analysis of the experimental data yielded mean annual DOC and respiration productions with respect to sites. Mean annual estimates of DOC flux varied from 3 to 29 g of C m−2 (1–19 mg C g−1 of available C), corresponding to mean DOC concentrations from 2 to 85 mg C L−1.  相似文献   

9.
The occurrence and distribution of polycyclic musks in the Lippe River system (a tributary of the Rhine River, Germany) was investigated in order to observe the dynamic transport and partitioning of these compounds between aqueous and particulate phases after their discharge into the river by sewage effluents. 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyrane (HHCB), 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), 6-acetyl-1,1,2,3,3,5-hexamethylindane (AHMI) and 4-acetyl-1,1-dimethyl-6-tert.-butylindane (ADBI) concentrations were determined in 19 water and surface sediment samples which were taken from a longitudinal section of the river. HHCB and AHTN were present in each of the water samples at concentrations ranging from <10 to 180 ng l−1 and <10 to 70 ng l−1, respectively. The load of dissolved HHCB and AHTN was calculated on the basis of compound concentrations in water and the corresponding river runoff data and ranged from 3 to 293 g day−1 and from 1 to 108 g day−1, respectively. Increasing loads of HHCB and AHTN along the river reflect a high input of sewage effluents to the densely populated areas along the central part of the river. Decreasing loads at the lower reaches indicate that in the corresponding river sections the rate of removal of musks was higher than the rate of input. Degradation and/or adsorption to particulate matter are processes that might explain this phenomenon. Consequently, high concentrations of HHCB and AHTN were detected in surface sediments from the Lippe River (from 5 to 191 μg kg−1 and from 2 to 1399 μg kg−1, respectively). HHCB/AHTN ratios in sediment samples were lower (average 1.2) than in water samples (average 2.9), suggesting the preferential adsorption of AHTN to particulate matter.  相似文献   

10.
Surface sediments from the subtropical Pearl River estuary and adjacent South China Sea were investigated by molecular organic geochemical methods to determine the composition, distribution and origin of extractable lipids (n-alkanes, n-alkanols and sterols). The absolute and organic C normalized concentrations of total alkane, n-alkanol, and sterol ranged from 0.16 to 2.67 μg g−1 and 0.9 to 12.3 μg g−1 OC, 24.4 to 427.3 ng g−1 and 63.2 to 1966.7 ng g−1 OC, and 9.0 to 493.5 ng g−1 and 58.4 to 1042.4 ng g−1 OC, respectively. The spatial distributions of these biomarkers indicated that terrestrial-derived molecular biomarkers such as long-chain n-alkanes, n-alkanols and plant-derived sterols were higher at the river mouth and along the coastline, suggesting that a higher proportion of terrestrial particulate organic matter was deposited there. Relatively lower amounts of marine-derived biomarkers such as short-chain n-alkanes, algal sterols at the river mouth reflected the lower primary productivity due to high turbidity. The spatial patterns of these biomarkers were partially related to the estuarine processes and conditions, evidencing an increased terrestrial signal from the Pearl River mouth to the inner estuary, and enhanced marine conditions further offshore.  相似文献   

11.
Big sagebrush — a cold-desert species that dominates the terrain over large parts of western United States — was sampled along several traverses that crossed thermally metamorphosed limestone, phyllitic shale, and schist of the Middle and Upper Cambrian Preble Formation that host skarn-, disseminated gold and silver-, and hot springs gold-type mineral occurrences. Patterns of detectable levels of gold (8 to 28 ppb or ng g−1) in ash of new growth were consistent with areas affected by known or suspected gold mineralization. Soils collected along one of the traverses where a selenium-indicator plant was common contained no gold above background levels of 2ppb, but were consistently high in As, Sb, and Zn, and several samples were unusually high in Se (maximum 11 ppm or μg g−1). Sagebrush along this traverse contained Li at levels above norms for this species. We also found a puzzling geochemical anomaly at a site basinward from active hot springs along a range-front fault scarp. Sagebrush at this site contained a trace of gold and an unusually high concentration of Cd (13 ppm) and the soil had anomalous concentrations of Cd and Bi (3.2 and 6 ppm, respectively). The source of this anomaly could be either metal-rich waters from an irrigation ditch or leakage along a buried fault. Despite the limited nature of the study, we conclude that gold in sagebrush could be a cost-effective guide to drilling locations in areas where the geology seems favorable for disseminated and vein precious metals.  相似文献   

12.
Large sections of the Abitibi volcanic belt of Archean age are covered by thick glacial and glacio-lacustrine overburden. To increase our knowledge of the geology and the economic potential of the basement, approximately 5000 ground-water samples were collected from wells, springs and drill holes over an area of about 20 000 km2. Samples were collected at intervals varying from 150 to 500 m in settled areas. They were analysed for: Cu, Zn, Pb, Ni, Co, Cd, Cr, Mn, Fe, Mo, Hg, As, U, Na, K, Ca, Mg, Li, F, and Cl− and pH.Several types of regional and local geochemical patterns were identified. However, since the apparent dispersion distance of trace elements from a point source is usually less than 1 km in ground waters, the local zones of geochemical activity having an area less than 15 km2 are considered of greatest interest for exploration. The large regional patterns and geochemical complexes which consist of clusters of grouped, overlapping, and superimposed regional and local patterns are presumed to be related to particular geological or metallogenic contexts.The elements with the highest frequency of occurrence in the 240 identified local zones of geochemical activity are As, Ni and U which occur in more than 30% of these zones; they are closely followed by the groups Co, Cu, Mo and Zn, Hg, Pb, F− which occur respectively in more than 25% and 20% of the zones. Element associations in these zones can be broken down into three major groups: the trace metals (Cu, Zn, Pb, Co, Cd, Mo), the major and associated elements (Na, K, Ca, Mg, Li, F−, Cl−) and the elements As, U and Ni which occur with elements of either of the first two groups.Ground-water samples were also collected in 21 mines. The results of this study suggest that the best indicator elements for base metal deposits are As, Mo and F, whereas As, Ni, F− or Cl− and Mn are the best indicators of gold deposits.The results of the ground-water survey have identified numerous new areas to explore. Anomalous concentrations of at least two of the best indicators occur in more than 33% of the 240 local zones of geochemical activity.  相似文献   

13.
For a period of 2 a, pore water composition in a heavily contaminated river floodplain soil was monitored in situ. Pore water samples were collected 12 times over all seasons in a profile ranging from aerobic to sulphidic redox conditions, and As, Cd, Cr, Cu, Pb, Zn, Mn, Fe, Ca, Cl, SO4, DOC, IOC and pH were determined. The variability of pH, IOC, DOC and Ca was found to be rather small during the year and within the profile (rsd < 0.04, 0.16, 0.24 and 0.22, respectively). The temporal variability of the metal and As concentrations was small, too, whereas changes with depth were distinct. Under sulphidic conditions, concentrations were below 1 μg L−1 (Cd, Cu, Pb) or 10 μg L−1 (Zn, As). The data set was compared with results from a geochemical model that was fully parameterised from literature data and included equilibrium speciation, sorption and mineral dissolution. The general pattern of the solid–solution partitioning of Cd, Cu, Zn and As in the profile was predicted well by mechanistic geochemical modelling on the basis of solid phase composition. Metals strongly bound to organic matter such as Cd and Cu were predicted better than metals mainly present within a mineral. Detailed information regarding the presence of colloidal Fe and Mn in pore water might improve the prediction of the solid–solution partitioning of a number of metals. The study also indicates that the chemical behaviour of Pb is still not understood sufficiently.  相似文献   

14.
M. Doi  G. Warren  M.E. Hodson   《Applied Geochemistry》2005,20(12):2207-2216
Ochre is an unwanted waste product that accumulates in wetlands and streams draining abandoned coal and metal mines. A potential commercial use for ochre is to remediate As contaminated soil. Arsenic contaminated soil (605 mg kg−1) was mixed with different ochres (A, B and C) in a mass ratio of 1:1 and shaken in 20 mL of deionised water. After 72 h As concentration in solution was ca. 500 μg kg−1 in the control and 1–2.5 μg kg−1 in the ochre treated experiments. In a second experiment soil:ochre mixtures of 0.05–1:1 were shaken in 20 mL of deionised water for 24 h. For Ochres A and C, as solution concentration was reduced to ca. 1 μg kg−1 by 0.2–1:1 ochre:soil mixtures. For Ochre B, as concentration only reached ca. 1 μg kg−1 in the 1:1 ochre:soil mix. Sorption of As was best modelled by a Freundlich isotherm using As sorption per mass of goethite in the ochre (log K = 1.64, n = 0.79, R2 = 0.76, p 0.001). Efficiency of ochre in removing As from solution increased with increasing total Fe, goethite, citrate dithionite extractable Fe and surface area.  相似文献   

15.
A reversal of the conventional carbon isotope relationship, “terrestrial-lighter-than-marine” organic matter, has been documented for two Pennsylvanian (Desmoinesian) cyclothemic sequence cores from the Midcontinent craton of the central United States. “Deep” water organic-rich phosphatic black shales contain a significant proportion of algal-derived marine organic matter (as indicated by organic petrography, Rock-Eval hydrogen index and ratios) and display the lightest δ13C-values (max −27.80‰ for kerogen) while shallower water, more oxic facies (e.g. fossiliferous shales and limestones) contain dominantly terrestrial organic matter and have heavier δ13Ckerogen-values (to −22.87‰ for a stratigraphically adjacent coal). δ13C-values for extract fractions were relatively homogeneous for the organic-rich black shales with the lightest fraction (often the aromatics) being only 1‰, or less, more negative than the kerogen. Differences between extract fractions and kerogens were much greater for oxic facies and coals (e.g. saturates nearly 5‰ lighter than the kerogen).A proposed depositional model for the black shales calls upon a large influx of nutrients and humic detritus to the marine environment from the laterally adjacent, extremely widespread Pennsylvanian (peat) swamps which were rapidly submerged by transgression of the epicontinental seas. In this setting marine organisms drew upon a CO2-reservoir which was in a state of disequilibrium with the atmosphere, being affected by isotopically light “recycled-CO2” derived from the decomposition of peaty material in the water column and possibly from the anoxic diagenesis of organic matter in the sediments.  相似文献   

16.
Re-Os data and PGE concentrations as well as Mo concentrations and isotope data are reported for suites of fine clastic sediments and black shales from the Barberton Greenstone Belt, South Africa (Fig Tree and Moodies Groups, 3.25-3.15 Ga), the Belingwe Greenstone Belt, Zimbabwe (Manjeri Formation, ca. 2.7 Ga) and shales from the Witwatersrand, Ventersdorp and Transvaal Supergroups, South Africa ranging from 2.95 to 2.2 Ga. Moderately oxidizing conditions are required to mobilize Re and Mo in the environment, Mo fractionation only occurs in solution, and these parameters thus have potential use as paleoredox proxies for the early Earth.PGE + Re abundance patterns of Barberton Greenstone Belt sediments are uniform and very similar in shape to those of komatiites. This indicates (1) that the PGE came from a source of predominantly ultramafic composition and, (2) that PGE were transported and deposited essentially in particulate form. Sediments from the younger Belingwe Greenstone Belt show more fractionated PGE + Re patterns and have Re/Os ratios 10 to 100× higher than those of Barberton sediments. Their PGE abundance patterns and Re/Os ratios are intermediate between those of the mid-Archean shales and Neoproterozoic to Recent black shales. They reflect scavenging of Re from solution in the sedimentary environment.δ98/95Mo values of black shales of all ages correlate with their concentrations. The Barberton Greenstone Belt samples have ∼1-3 ppm Mo, similar to a granitoid-basaltic source. This Mo has δ98/95Mo between −1.9 and −2.4‰ relative to present day mean ocean water molybdenum, MOMO and is thus not isotopically fractionated relative to such a source. Similar to the PGE this indicates transport in solid form. Sediments from the Belingwe Greenstone Belt show in part enhanced Mo concentrations (up to 6 ppm) and Mo isotope fractionation (δ98/95Mo up to −1.4‰ relative to MOMO). The combined PGE + Re and Mo data show mainly reducing conditions in the mid-Archean and suggest that by 2.7 Ga, the atmosphere and oceans had become more oxidizing.Substantially younger samples from the Transvaal Supergroup (to ca. 2.2 Ga) surprisingly have mainly low Mo concentrations (around 1 ppm) and show no significant Mo isotope fractionation relative to the continental source. Among possible explanations for this are a return to reducing atmospheric conditions after 2.7 Ga, reservoir effects, or Mo removal by sulfide precipitation following sulfate reduction in early Proterozoic oceans.  相似文献   

17.
Radiocaesium (137Cs) dispersion and Cs+ fixation were studied in the sediments collected from the lagoon systems of “Ria de Aveiro”. The Cs+ sorption was tested for the fine mica grains and for the < 2 μm clay fractions extracted from silty clays. The Cs+ exchange is found strongly onto mica-rich fractions than smectite-rich fractions. The distribution coefficient increases if the silty material is constituted by rich-mica clay fractions or if the non-clay minerals are removed from the silty-clay material. The samples studied behave as multisite ion exchange, where Cs+ engages in ion-exchange reactions with hydrated cations on planar sites on expansible layer silicates. Higher concentrations of the 137Cs were found associated with mica-rich silty clays. The 137Cs ranges from 3.2 to 3.9 Bq kg− 1 in the < 38 μm fractions and from 2.9 to 3.3 Bq kg− 1 in the < 64 μm fractions.  相似文献   

18.
The Ediacaran and early Cambrian black shales are widespread across the South China Craton (Yangtze and Cathaysia blocks). However, the trace element distribution patterns of the Ediacaran and early Cambrian black shales in the Cathaysia Block are still unclear. In this study, thirty-four black shale samples in the Lechangxia Group (Ediacaran) and thirteen black shale samples in the lower Bacun Group (early Cambrian) from Guangning area, western Guangdong Province, South China, were analyzed for major and trace elements concentrations. Compared to the upper continental crust, the Ediacaran black shales exhibit strongly enriched Se, Ga, and As with enrichment factor values (EF) higher than 10, significantly enriched Bi and Rb (10>EF>5), weakly enriched Mo, Ba, Cs, V, In, Be, Tl, and Th (5>EF>2), normal U, Cr, Cd, Sc, Pb, Cu, and Li (2>EF>0.5), and depleted Ni, Zn, Sr, and Co. Early Cambrian black shales display strongly enriched Se, Ga, and As, significantly enriched Ba, Bi, and Rb, weakly enriched Mo, Cs, Cd, V, U, Be, In, and Tl, normal Sc, Th, Cr, Li, Cu, Ni, and Pb and depleted Co, Zn, and Sr. Moreover, Se is the most enriched trace element in the Ediacaran and early Cambrian black shales: concentrations vary from 0.25 to 30.09 ppm and 0.54 to 5.01 ppm, and averaging 4.84 and 1.72 ppm, with average EF values of 96.87 and 34.32, for the Ediacaran and early Cambrian shales respectively. The average concentration of Se in the Ediacaran black shales is 2.8 times higher than that of early Cambrian black shales. Se contents in the Ediacaran and early Cambrian black shales exhibit significant variation (P = 0.03). Provenance analysis showed that Se contents of both the Ediacaran and early Cambrian black shales were without detrital provenance and volcanoclastic sources, but of hydrothermal origin. The deep sources of Se and the presence of pyrite may explain the higher Se contents in the Ediacaran black shales. Similar with the Se-rich characteristics of the contemporaneous black shales in the south Qingling Mountain and Yangtze block, the Ediacaran and early Cambrian black shales in Guangning area, Cathaysia, are also enriched in Se, which may provide a clue for looking for the selenium-rich resources in western Guangdong Province.  相似文献   

19.
Extensive measurements of dissolved Re and major ion abundances in the Yamuna River System (YRS), a major tributary of the Ganga, have been performed along its entire stretch in the Himalaya, from its source near the Yamunotri Glacier to its outflow at the foothills of the Himalaya at Saharanpur. In addition, Re analysis has been made in granites and Precambrian carbonates, some of the major lithologies of the drainage basin. These data, coupled with those available for black shales in the Lesser Himalaya, allow an assessment of these lithologies’ contributions to the Re budget of the YRS.The Re concentrations in the YRS range from 0.5 to 35.7 pM with a mean of 9.4 pM, a factor of ∼4 higher than that reported for its global average concentration in rivers. Dissolved Re and ΣCations∗ (= Na∗+K+Ca+Mg) are strongly correlated in the YRS, indicating that they are released to these waters in roughly the same proportion throughout their course. The Re/ΣCations∗ in most of these rivers are one to two orders of magnitude higher than the (Re/Na+K+Mg+Ca) measured in granites of the Yamuna basin. This leads to the conclusion that, on average, granites/crystallines make only minor contributions to the dissolved Re budget of the YRS on a basin-wide scale, though they may be important for rivers with low dissolved Re. Similarly, Precambrian carbonates of the Lesser Himalaya do not seem to be a major contributor to dissolved Re in these rivers, as their Re/(Ca+Mg) is much less than those in the rivers. The observation that Re concentrations in rivers flowing through black shales and in groundwaters percolating through phosphorite-black shale-carbonate layers in phosphorite mines are high, and that Re and SO4 are significantly correlated in YRS, seems to suggest that the bulk of the dissolved Re is derived from black shale/carbonaceous sediments. Material balance considerations, based on average Re of 30 ng g−1 in black shales from the Lesser Himalaya, require that its abundance in the drainage basin of the YRS needs to be a few percent to yield average Re of 9.4 pM. Furthermore, the positive correlation between Re and ΣCations∗ would require that these Re-rich sediments (e.g., black shales) and Re-poor lithologies (e.g., crystallines, Precambrian carbonates) contribute Re and cations in roughly the same proportion throughout the drainage basin. The available data on the abundance and distribution of black shales in the basin are not adequate to test if these requirements can be met.The annual fluxes of dissolved Re at the base of the Himalaya from the Yamuna are ∼150 mol at Batamandi and ∼100 mol at Saharanpur, compared to ∼120 mol from the Ganga at Rishikesh. The total flux from the Yamuna and the Ganga account for ∼0.4% of the global riverine Re flux, much higher than their contribution to global water discharge. This is also borne out from the mobilization rate of Re: ∼1 to 3 g km−2 y−1 in the Ganga and Yamuna basins in the Himalaya, compared to the global average of ∼0.1 g km−2 y−1.Black shale weathering can also significantly influence the budgets of Os and U in rivers and CO2 in rivers and the atmosphere. Using dissolved Re in rivers as a proxy, it is estimated that ∼(6-9) × 108 kg y−1 of black shales are being weathered in the Ganga and Yamuna basins in the Himalaya. Weathering of such amounts of black shales can account for the reported concentrations of Os and U in these rivers. Furthermore, if the weathering results in the conversion of organic carbon in the black shales to CO2, it would release ∼2 × 105 mol of CO2 km−2 y−1 in the Yamuna and Ganga basins in the Himalaya, comparable to the CO2 consumption from silicate weathering.  相似文献   

20.
The redox-sensitive geochemical behavior of uranium permits the use of Th/U ratios as a geochemical proxy for the oxidation state of the atmosphere during deposition. Due to the effects of post-depositional uranium mobility on Th/U ratios during events involving oxygenated fluids, direct measurements of Th/U ratios are often misleading even for drill core samples. Because both of these elements radioactively decay and produce lead isotopes, the Pb isotope composition may reflect the depositional Th/U ratio, although the Th/U ratios induced by changes shortly after deposition may not be distinguished from the true depositional Th/U ratios. In order to effectively evaluate the time-integrated Th/U ratio (κa), values for the initial depositional Pb isotope composition must be determined or accepted from the models for the whole Earth.While the timing for the rise of atmospheric oxygen is reasonably well constrained now, its effect on continental weathering and ocean redox state remains poorly constrained and debated. The ca. 2.15 Ga Sengoma Argillite Formation of Botswana contains organic-rich shales deposited during the Great Oxidation Event. The slope of the 207Pb/204Pb–206Pb/204Pb array of shales from the Sengoma Argillite Formation corresponds to a Pb–Pb age that is within analytical error of the depositional age and is, therefore, inferred to be the time by which the time-integrated thorogenic and uranogenic lead growth started. The time-integrated lead growth corresponds to an average κa of 2.63 (± 0.62, 1σ) for the organic-rich shales of the Sengoma Argillite Formation. This is lower than Th/U ratios measured in Archean shale suites or estimated for the Archean–Proterozoic average upper continental crust [Taylor, S.R. and McLennan, S.M., 1985. The Continental Crust: Its Composition and Evolution. Blackwell, Oxford, 312 pp.], which indicates that these samples were enriched in uranium with respect to thorium (and perhaps lead) at the time of deposition. In the modern ocean, sediments are enriched in uranium under reducing conditions by reduction of the water-soluble uranyl ion, which is delivered to the ocean by oxidative weathering of continental crust. To evaluate the potential mobility of Th, U, and Pb during post-depositional processes, the concentrations of the rare earth elements (REE) were also determined. Interelement ratios of the largely immobile REE (in this study, La/Nd and Gd/Er) can be used as a proxy for the Th/U ratio, as the geochemical behavior of the lanthanide and actinide elements is similar under a variety of conditions. Furthermore, close similarity in the chondrite-normalized REE patterns and small range in La/Nd and Gd/Er ratios in studied samples indicate that variations in κa values are not likely to have been controlled by mixing of one or more REE-, Th-, and U-rich heavy minerals from the multiple detrital sources. Our study of shales from the ca. 2.15 Ga Sengoma Argillite Formation indicates that decoupling of U from Th, most likely related to the oxidative continental weathering, began by 2.15 Ga, at the latest.  相似文献   

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