Organic carbon isotope ratios (δ13C) of Arctic Amerasian Continental shelf sediments

Organic matter origins are inferred from carbon isotope ratios ('¹³C) in recent continental shelf sediments and major rivers from 465 locations from the north Bering-Chukchi-East Siberian-Beaufort Sea, Arctic Amerasia. Generally, there is a cross-shelf increase in '¹³C, which is due to progressive increased contribution seaward of marine-derived organic carbon to surface sediments. This conclusion is supported by the correlations between sediment '¹³C, OC/N, and '¹⁵N. The sources of total organic carbon (TOC) to the Amerasian margin sediments are primarily from marine water-column phytoplankton and terrigenous C₃ plants constituted of tundra taiga and angiosperms. In contrast to more temperate regions, the source of TOC from terrigenous C₄ and CAM plants to the study area is probably insignificant because these plants do not exist in the northern high latitudes. The input of carbon to the northern Alaskan shelf sediments from nearshore kelp community (Laminaria solidungula) is generally insignificant as indicated by the absence of high sediment '¹³C values (-16.5 to -13.6‰) which are typical of the macrophytes. Our study suggests that the isotopic composition of sediment TOC has potential application in reconstructing temporal changes in delivery and accumulation of organic matter resulting from glacial-interglacial changes in sea level and environments. Furthermore, recycling and advection of the extensive deposits of terrestrially derived organic matter from land, or the wide Amerasian margin, could be a mechanism for elevating total CO₂ and pCO₂ in the Arctic Basin halocline.     

Uranium depositional controls at the Prairie Flats surficial uranium deposit, Summerland, British Columbia

A hydrological and geochemical investigation of the Prairie Flats surficial uranium deposit in Summerland, BC was undertaken to identify the principal controls on uranium deposition. A network of piezometers was installed and used to measure the hydraulic conductivities of the host sediments as well as the general flow direction and aqueous geochemistry of the resident groundwaters. Two hydrostratigraphic units were identified: a peat and clay unit overlying a sand and gravel unit. Measured hydraulic conductivities were on the order of 10^-7 and 10^-5 m/s, respectively, and the vertical hydraulic gradients indicate significant groundwater discharge upward into the peat and clay unit. Prairie Flats groundwaters are neutral to alkaline in pH, enriched in Ca²⁺ and HCO₃^-, and have dissolved uranium concentrations ranging from 10 to nearly 1,000 µg/l. Groundwater flow and geochemistry data were used to estimate the flux of uranium in groundwater at the site. A major fraction of the uranium is taken up by adsorption to organics. There is also evidence for subsequent desorption by the formation of soluble complexes with bicarbonate. Uranium that is not held by adsorption is most likely precipitated as uraninite, UO_2(c). Reducing conditions in the peat and clay unit (Eh<0.1 V) relative to the underlying sand and gravel unit (Eh>0.2 V) may explain the high concentrations of uranium nearer ground surface. The current flux of uranium into the flats is significantly smaller than that calculated from the size and age of the deposit, which may be an indication of changing rates of deposition in response to varying climatic and hydrogeologic conditions over time.     

北京平原包气带典型沉积物对NH+4 N吸附特性研究

采用批实验方法,研究了北京平原典型沉积物对NH+4 N的吸附规律。结果表明颗粒越细的沉积物,达到吸附反应平衡所需的时间越长,对NH+4 N的吸附量也越大;NH+4 N初始浓度在0~50 mg/L范围内,Henry、Langmuir、Freundlich吸附等温模式均能较好地描述北京平原典型沉积物对NH+4 N的吸附特性。沉积物对NH+4 N的吸附量随初始浓度的增加而增加;沉积物的颗粒越细,Henry吸附系数K越大,单位质量沉积物的饱和吸附量也越大;沉积物中TOC含量对沉积物的NH+4 N吸附行为有一定的控制作用,永定河、潮白河沉积物TOC值与Henry吸附系数K的相关系数R2分别为050,076;沉积物对NH+4 N的饱和吸附量随着土水比的增加而减少,通过乘幂的方式拟合不同土水比下的饱和吸附量,得出了北京平原包气带沉积物对NH+4 N的饱和吸附量;相同岩性条件下,特别是细颗粒沉积物中,潮白河沉积物对NH+4 N的吸附能力较永定河沉积物强,而同一流域内,中、下游沉积物的吸附能力较上游强。     

Assessment of organic pollutants in coastal sediments, UAE

Twenty-five stations were selected along the UAE coastal region to delineate the distribution and to determine the source of total petroleum hydrocarbon (TPH), total organic carbon (TOC), total Kjeldhal nitrogen (TKN), polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). The concentrations of TPH ranged between 46 and 223 mg/kg and the level of TOC was in the range from 0.044 to 17.8 wt%, while TPAHs occupied the range of 5–102.2 μg/kg. On the other hand, TPCBs showed values between 60 and 205 μg/kg and TKN ranged from 104 to 1,073 mg/kg. The present study shows that the distribution of organic compounds in UAE sediments were within safe limits comparing with previous studies. The present study revealed that TOC can be used as an indicator of oil pollution in heavily oiled sediments. The highest values of TOC, TPH, TPAHs and TPCBs related to the stations covered in fine sand due to adsorption properties and the large surface areas of the grains. The evaporation of low-boiling point compounds from surface layers leads to the enrichment of sediments with a thick residual. Al Sharjah-1 exhibited the highest values of TPH and TOC at Ras Al-Khaima-5, Umm Al-Quwen-1 and Dubai-1, while the highest values of TPAHs were at KhorFakkan-9, the highest value of TPCBs was at Ajman-2, and the highest values of TKN were at KhorFakkan-1, KhorFakkan-6 and Dubai-1.     

Changes in the deposition of terrestrial organic matter on the Laptev Sea shelf during the Holocene: evidence from stable carbon isotopes

Stable carbon isotope ratios in the organic fraction of surface sediments from the Laptev Sea shelf were analyzed in order to study the modern distribution pattern of terrestrial organic matter. The '¹³C_org signature of the surface sediments range from -26.6‰ near the coastal margin to -22.8‰ in the north towards the outer shelf. Characterizing the possible sources of organic matter by their '¹³C_org signature reveals that the terrestrial influence reaches further north in the eastern than in the western Laptev Sea. Downcore records of the '¹³C_org, measured on three AMS ¹⁴C-dated cores from water depths between 46 and 77 m, specify the spatial and temporal changes in the deposition of terrestrial organic matter on the Laptev Sea shelf during the past 12.7 ka. The major depositional changes of terrestrial organic matter occurred between 11 and 7 ka and comprised the main phase of the southward retreat of the coastline and of the river depocenters due to the postglacial sea level rise.     

Coupled evolution of back-arc and island arc-like mafic crust in the late-Neoproterozoic Agardagh Tes-Chem ophiolite, Central Asia: evidence from trace element and Sr–Nd–Pb isotope data

. We report major-element, trace-element and isotopic data of volcanic rocks from the late-Neoproterozoic (570 Ma) Agardagh Tes-Chem ophiolite in Central Asia, south-west of Lake Baikal (50.5°N, 95°E). The majority of samples are high-alumina basalts and basaltic andesites having island-arc affinities. They were derived from an evolved parental magma (Mg#̾.60, Cr~180 ppm, Ni~95 ppm) by predominantly clinopyroxene fractionation. The parental magma developed from a primary mantle melt by fractionation of about 12% of an olivine+spinel assemblage. The island-arc rocks have high abundances of incompatible trace elements (light rare-earth element abundances up to 100 times chondritic, chondrite-normalised (La/Yb)_n=14.6-5.1) and negative Nb anomalies (Nb/La=0.37-0.62), but low Zr/Nb ratios (7-14). Initial )_Nd values are around +5.5, initial Pb isotopic compositions are ²⁰⁶Pb/²⁰⁴Pb=17.39-18.45, ²⁰⁷Pb/²⁰⁴Pb=15.49-15.61, ²⁰⁸Pb/²⁰⁴Pb=37.06-38.05. Enrichment of large-ion lithophile elements within this group is significant (Ba/La=11-130). Another group of samples consists of back-arc basin-related volcanic rocks. They are most likely derived from the same depleted mantle source as the island-arc rocks, but underwent higher degrees of melting (8-15%) and are not influenced by slab components. They have lower abundances of incompatible trace elements, flat rare-earth element patterns [(La/Yb)_n=0.6-2.4] and higher )_Nd values (+7.8 to +8.5). Negative Nb anomalies are absent (Nb/La=0.81-1.30), but Zr/Nb is high (21-48). At least three components are necessary to explain the geochemical evolution of the volcanic rocks: (1) an enriched (ocean island-like) component characterised by a high Nb concentration (up to 30 ppm), an absent negative Nb anomaly, a low Zr/Nb ratio (~6.5), a low )_Nd value (around 0), and radiogenic ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb; (2) a back-arc basin component similar to N-MORB with a flat rare-earth element pattern and a high )_Nd value (around +8.5); and (3) an island-arc component from a mantle source which was modified by the downgoing slab. Crystal fractionation superimposed on mixing and source contamination by subducted sediments is suitable to explain the observed geochemical data. The most likely geodynamic environment to produce these characteristics is a young, intra-oceanic island-arc system and an associated back-arc basin.     

Mobilisation of traffic-derived trace metals from road corridors into coastal stream and estuarine sediments,Cairns, northern Australia

This investigation revealed the presence of traffic-derived metals within road, stream and estuarine sediments collected from a coastal catchment, northern Australia. Studied road sediments displayed variable total metal concentrations (median Cd, Cu, Pb, Pd, Pt, Ni and Zn values: 0.19, 42.6, 67.5, 0.064, 0.104, 36.7 and 698 mg/kg, respectively). The distinctly elevated Zn values are due to abundant tyre rubber shreds (as verified by SEM-EDS and correlation analysis). By comparison to the road sediments, background stream sediments taken upstream from roads have relatively low median Pb, Pd, Pt and Zn concentrations (7.3 mg/kg Pb, 0.01 mg/kg Pd, 0.012 mg/kg Pt, 62 mg/kg Zn). Stream and estuarine sediment samples collected below roads have median values of 21.8 mg/kg Pb, 0.014 mg/kg Pd, 0.021 mg/kg Pt and 71 mg/kg Zn, and exhibit ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios that appear on a mixing line between the isotopically distinct background stream sediments and the road sediments. Thus, mobilisation of dusts and sediments from road surfaces has resulted in relatively elevated Pb, Pd, Pt and Zn concentrations and non-radiogenic Pb isotope ratios in local coastal stream and estuarine sediments. The investigation demonstrates that traffic-derived metals enter coastal stream and estuary sediments at the fringe of the Great Barrier Reef lagoon.     

Organic matter and nutrients in an altered subtropical marsh system,Chiricahueto, NW Mexico

Seven sediment push-cores were extracted from Chiricahueto, a marsh affected by urban, industrial and agricultural wastes. Concentrations of total phosphorus (300-1,620 µg g^-1), organic carbon (4-39 mg g^-1) and total nitrogen (0.5-4.5 mg g^-1) in the sediments showed an exponential decrease with depth, related to the decomposition of organic matter (OM). Between 20 and 40% of OM initially deposited is degraded at the sediment-water interface under oxic conditions. Another fraction (40-60%) of non-refractory OM is decomposed within the sediments by oxidants other than oxygen. Likewise, the preservation of OM (<20%) was estimated as burial concentrations of C, N and P linked to organic compounds. The C/N ratios, '¹³C and '¹⁵N suggested that the major source of OM to the sediments derives from marine phytoplankton. The allochthonous sources of OM were overprinted by the high flux of marine autochthonous OM. However, an indirect terrestrial influence is recognised, in which high nutrient load derived from agricultural, domestic and industrial activities promoted high productivity.     

Mercury contamination chronologies from Connecticut wetlands and Long Island Sound sediments

Sediment cores were used to investigate the mercury deposition histories of Connecticut and Long Island Sound. Most cores show background (pre-1800s) concentrations (50-100 ppb Hg) below 30-50 cm depth, strong enrichments up to 500 ppb Hg in the core tops with lower Hg concentrations in the surface sediments (200-300 ppb Hg). A sediment core from the Housatonic River has peak levels of 1,500 ppb Hg, indicating the presence of a Hg point source in this watershed. The Hg records were translated into Hg contamination chronologies through ²¹⁰Pb dating. The onset of Hg contamination occurred in ~1840-1850 in eastern Connecticut, whereas in the Housatonic River the onset is dated at around 1820. The mercury accumulation profiles show periods of peak contamination at around 1900 and at 1950-1970. Peak Hg* (Hg*= Hg measured minus Hg background) accumulation rates in the salt marshes vary, dependent on the sediment character, between 8 and 44 ng Hg/cm² per year, whereas modern Hg* accumulation rates range from 4-17 ng Hg/cm² per year; time-averaged Hg* accumulation rates are 15 ng Hg/cm² per year. These Hg* accumulation rates in sediments are higher than the observed Hg atmospheric deposition rates (about 1-2 ng Hg/cm² per year), indicating that contaminant Hg from the watershed is focused into the coastal zone. The Long Island Sound cores show similar Hg profiles as the marsh cores, but time-averaged Hg* accumulation rates are higher than in the marshes (26 ng Hg/cm² a year) because of the different sediment characteristics. In-situ atmospheric deposition of Hg in the marshes and in Long Island Sound is only a minor component of the total Hg budget. The 1900 peak of Hg contamination is most likely related to climatic factors (the wet period of the early 1900s) and the 1950-1970 peak was caused by strong anthropogenic Hg emissions at that time. Spatial trends in total Hg burdens in cores are largely related to sedimentary parameters (amount of clay) except for the high inventories of the Housatonic River, which are related to Hg releases from hat-making in the town of Danbury. Much of the contaminated sediment transport in the Housatonic River Basin occurs during floods, creating distinct layers of Hg-contaminated sediment in western Long Island Sound. The drop of about 40% in Hg accumulation rates between the 1960s and 1990s seems largely the result of reduced Hg emissions and to a much lesser extent of climatic factors.     

In-situ hafnium and lead isotope analyses of detrital zircons from the Devonian sedimentary basin of NE Greenland: a record of repeated crustal reworking

An intramontane collapse basin developed within the hanging wall above the large-scale extensional Fjord Regional Detachment of NE Greenland in middle to late Devonian times. The continental clastic sediments within the basin are derived locally from Laurentian source rocks, which makes them well suited for a study of the crustal evolution of the source terrain. This is the first integrated in-situ Pb and Hf isotope study to be presented, and zircon data on a selected sandstone from the basin are combined with Sm-Nd whole-rock data on sand/siltstones. Nd whole-rock ages of two samples of sandstones and a siltstone are 2.0-2.1 Ga. Peak frequencies of zircon ²⁰⁷Pb/²⁰⁶Pb ages at 1,764-1,912 Ma, and ¹⁷⁶Hf/¹⁷⁷Hf values at 0.28142-0.28163 (t_DM=2.47 to 2.06) for the sandstone suggest the generation of a considerable volume of juvenile continental crust in the ultimate zircon provenance at 1.9-2.0 Ga. The Hf isotopic compositions of Archaean zircons in the sandstone are distinct from those of the source materials of Proterozoic protocrust at 1.9-2.0 Ga, but zircons with elevated Hf-t_DM ages of up to 2.47 Ga can be related to a component of Archaean crust or reworked Archaean material in the ultimate zircon source area. Zircon ²⁰⁷Pb/²⁰⁶Pb ages are also recorded at 1,480-1,572, 1,318 and 1,014 Ma (Grenvillian). The Hf isotope compositions of these zircons are consistent with reworking of the Proterozoic protocrust at these times, with little or no juvenile input. The Proterozoic zircons form two distinct groups defined by ¹⁷⁶Yb/¹⁷⁷Hf>0.05055 and ¹⁷⁶Yb/¹⁷⁷Hf<0.03301, and the latter group overlaps with Yb-Hf isotope data on the Archaean zircons. The two groups may represent zircons derived from evolved granites and intermediate to mildly felsic rocks, respectively. The repeated reworking of the continental crust also comprised erosion and deposition of sediments in the Proterozoic (the Krummedal sequence and the Eleonore Bay Supergroup, EBS) and intrusion of Caledonian anatectic granites in the EBS, which both represent provenance components to the Devonian sediments. No discrete Caledonian Pb-Pb zircon ages are recorded, but Caledonian magmatism may be represented by strongly discordant zircons which form arrays with a lower intercept age at ca. 400 Ma and an upper intercept at 1,600-2,000 Ma. One undated zircon records a ¹⁷⁶Hf/¹⁷⁷Hf ratio of 0.282218, higher than that of the Proterozoic protocrust in Caledonian/late-Caledonian times (380-450 Ma) which may represent a Caledonian mantle contribution.     

Interrelationship of TOC,As, Fe,Mn, Al and Si in shallow alluvial aquifers in Chapai-Nawabganj,Northwestern Bangladesh: implication for potential source of organic carbon

Two boreholes and ten piezometers in the Ganges flood plain were drilled and installed for collecting As-rich sediments and groundwater. Groundwater samples from the Ganges flood plain were collected for the analysis of cations (Ca²⁺, Mg²⁺, K⁺, Na⁺), anions (Cl⁻, NO₃ ⁻, SO₄ ²⁻), total organic carbon (TOC), and trace elements (As, Mn, Fe, Sr, Se, Ni, Co, Cu, Mo, Sb, Pb). X-ray powder diffraction was performed to characterize the major mineral contents of aquifer sediments and X-ray fluorescence (XRF) to analyze the major chemical composition of alluvial sediments. Results of XRF analysis clearly show that fine-grained sediments contain higher amounts of trace element because of their high surface area for adsorption. Relative fluorescence index (15–38 QSU) of humic substance in groundwater was measured using spectrofluorometer, the results revealed that groundwater in the Ganges flood plain contains less organic matter (OM). Arsenic concentration in water ranges from 2.8 to 170 μg/L (mean 50 μg/L) in the Ganges flood plain. Arsenic content in sediments ranges from 2.1 to 14 mg/kg (mean 4.58 mg/kg) in the flood plains. TOC ranges from 0.49 to 3.53 g/kg (mean 1.64 g/kg) in the Ganges flood plain. Arsenic is positively correlated with TOC (R ² = 0.55) in sediments of this plain. Humic substances were extracted from the sediments from the Ganges flood plain. Fourier transform infrared analysis of the sediments revealed that the plain contains less humic substances. The source of organic carbon was assigned from δ¹³C values obtained using elemental analysis-isotope ratio mass spectrometry (EA-IRMS); the values (−10 to −29.44‰) strongly support the hypothesis that the OM of the Ganges flood plain is of terrestrial origin.     

Major ion chemistry of Renuka Lake and weathering processes, Sirmaur District, Himachal Pradesh, India

Renuka Lake in the Lesser Himalaya, Himachal Pradesh is in a valley surrounded by mountains comprised of highly crumpled, shattered, crushed, folded and dislocated rocks consisting of carbonaceous shales-slates often pyrite-ferrous, limestone, quartzites, boulder beds, etc. A detailed and systematic study of the major ion chemistry of the lake, clay mineral composition of the bed and core sediments and the Pb²¹⁰ isotope estimation in the latter was conducted. The chemistry is dominated by carbonate weathering and (Ca + Mg) and (HCO₃ + SO₄) accounts for about 90% of the cations and anions. The SO₄ content is almost the same as the HCO₃. The low contribution of (Na + K) to the total cations and the (Ca + Mg) and HCO₃ data tends to indicate that silicate weathering has not been the potential source of major ions to the lake waters. This difference may be related to the increasing susceptibility to weathering of carbonate over silicate rocks exposed in the catchment and also seepage of water at the bottom. The high sulphate content in waters is derived from dissolution of pyrite-ferrous reduced black shales, which constitute a significant lithology in the catchment. The chemical index of alteration (CIA) value in core sediments is on an average 76, which is comparable with average shale (70-75) and the rate of sedimentation 3.3 mm/year based on measurement of Pb²¹⁰, indicating a fairly high weathering rate in the catchment. Illite is the dominant clay mineral (52-90%) in the bed and core sediments, chlorite constitutes 7-48% and the kaolinite-chlorite mixed silicate layer is l-2%. This is consistent with the shale-slate, sandstone lithology in the valley.     

Basalt and Sediment Geochemistry and Magma Petrogenesis in a Transect from Oceanic Island Arc to Rifted Continental Margin Arc: the Kermadec--Hikurangi Margin, SW Pacific

Sediment mixing and recycling through a subduction zone canbe detected in lead isotopes and trace elements from basaltsand sediments from the Kermadec-Hikurangi Margin volcanic arcsystem and their coupled back-arc basins. Sr, Nd and Pb isotopesfrom the basalts delineate relatively simple, almost overlapping,arrays between back-arc basin basalts of the Havre Trough-NgatoroBasin (⁸⁷Sr/⁸⁶Sr = 0.70255; _Nd=+9.3; ²⁰⁶Pb/²⁰⁴Pb = 18.52; ²⁰⁸Pb/²⁰⁴Pb= 38.18), island arc basalts from the Kermadec Arc togetherwith basalts from Taupo Volcanic Zone (⁸⁷Sr/⁸⁶Sr 0.7042; _Nd= +5; ²⁰⁶Pb/²⁰⁴Pb= 18.81; ²⁰⁸Pb/²⁰⁴Pb = 38.61), and sedimentsderived from New Zealand's Mesozoic (Torlesse) basement (⁸⁷Sr/⁸⁶Sr 0.715; _Nd —4; ²⁰⁶Pb/²⁰⁴Pb 18.86; ²⁰⁸Pb/²⁰⁴Pb 38.8).Basalts from the arc front volcanoes have high Cs, Rb, Ba, Th,U and K, and generally high but variable Ba/La, Ba/Nb ratios,characteristic of subduction-related magmas, relative to typicaloceanic basalts. These signatures are diluted in the back-arcbasins, which are more like mid-ocean ridge basalts. Strongchemical correlations in plots of SiO₂ vs CaO and loss on ignitionfor the sediments (finegrained muds) are consistent with mixingbetween detrital and biogenic (carbonate-rich) components. Otherdata, such as Zr vs CaO, are consistent with the detrital componentcomprising a mixture of arc- and continent-derived fractions.In chondrite-normalized diagrams, most of the sediments havelight rare earth element enriched patterns, and all have negativeEu anomalies. The multielement diagrams have negative spikesat Nb, P and Ti and distinctive enrichments in the large ionlithophile elements and Pb relative to mantle. Isotopic measurementsof Pb, Sr and Nd reveal restricted fields of Pb isotopes butwide variation in Nd and Sr relative to other sediments fromthe Pacific Basin. Rare K-rich basalts from Clark Volcano towardthe southern end of the oceanic Kermadec Island Arc show unusualand primitive characteristics ( 2% K₂O at 50% SiO₂, Ba 600p.p.m., 9–10% MgO and Ni > 100 p.p.m.) but have highlyradiogenic Sr, Nd and Pb isotopes, similar to those of basaltsfrom the continental Taupo Volcanic Zone. These oceanic islandarc basalts cannot have inherited their isotope signatures throughcrustal contamination or assimilation—fractional crystallizationtype processes, and this leads us to conclude that source processesvia bulk sediment mixing, fluid and/or melt transfer or somecombination of these are responsible. Although our results showclear chemical gradients from oceanic island arc to continentalmargin arc settings (Kermadec Arc to Taupo Volcanic Zone), overlapbetween the data from the oceanic and continental sectors suggeststhat the lithospheric (crustal contamination) effect may beminimal relative to that of sediment subduction. Indeed, itis possible to account for the chemical changes by a decreasenorthward in the sediment flux into the zone of magma genesis.This model receives support from recent sediment dispersal studiesin the Southern Ocean which indicate that a strong bottom current(Deep Western Boundary Current) flows northward along the easterncontinental margin of New Zealand and sweeps continental derivedsediment into the sediment-starved oceanic trench system. Thetrace element and isotopic signatures of the continental derivedcomponent of this sediment are readily distinguished, but alsodiluted in a south to north direction along the plate boundary. KEY WORDS: subduction zone basalts; sediments; Sr-, Nd-, Pb-isotopes; trace elements ^*Present address: School of Earth Sciences, University of Melbourne, Parkville, Vic. 3052, Australia.     

Geochemical distribution of arsenic in waters,sediments and weathered gold mineralized rocks from Iron Quadrangle,Brazil

The Iron Quadrangle has been the scenery of the most important gold production in Brazil. It is estimated that during the three centuries of gold mining in the Iron Quadrangle, at least 390,000 t of arsenic was discharged into the drainage system. This study presents geochemical data for the three river basins in the region, with focus on surface water and stream sediment monitoring. Samples of primary and oxidized sulfide ores as well as of tailings and groundwater from the major gold mines were also studied. The highest As concentrations in water and stream sediments occur in the vicinity of mining areas. In surface water, up to 300 g As/l were found whereas the As contents in stream sediments were in the range of 20 to 4,000 mg/kg. The As³⁺/As⁵⁺ concentration ratios obtained for some water samples range from 1.10^у to 4.10^ф. The As mobility associated with ore-deposit weathering could be traced in some closed gold mines by observation of in-situ pyrite and arsenopyrite oxidation, precipitation of scorodite and gippsite, As adsorption onto goethite, and final liberation of As into underground and surface waters. This process is likely to produce large volumes of mine effluents containing total As and trivalent As up to 1,960 and 60 g/l, respectively. River sediments and tailings pile samples were submitted to a leaching procedure showing maximal arsenic release from 1 to 4% of the original total As in the samples. There are potential risks for As hazards in some areas induced by, for instance, the dispersion of old tailings by flooding, occupation of poisoned soils for settlements, and occasional consumption of contaminated surface and groundwater.     

Tin–polymetallic sulfide deposits in the eastern part of the Dachang tin field (South China) and the role of black shales in their origin

The Dafulou and Huile vein and stratabound cassiterite-sulfide deposits and sheeted ore veins at the Kangma cassiterite-sulfide deposit are located in the eastern part of the Dachang tin field. These deposits are hosted in a sedimentary sequence containing significant concentrations of organic matter in the form of Lower Devonian calcareous black shales and hornfels. These rocks together with the younger intrusion of Longxianggai granite (91DŽ Ma) actively participated in the formation of Sn-polymetallic deposits. The following three major stages have been distinguished in stratiform and vein-type orebodies at Dafulou, Huile and Kangma: stage I (cassiterite, pyrrhotite, arsenopyrite, tourmaline, carbonate), stage II - main sulfide stage (quartz, cassiterite, arsenopyrite, pyrrhotite, sphalerite, stannite, pyrite, carbonates) and stage III (native Bi, galena, electrum, sulfosalts). Stage IV (post-ore), recognized at Huile is represented by barren carbonates and zeolites. Whole rock geochemistry has revealed that at Dafulou, Bi and Cu correlate strongly with S, whereas V and Pb correlate well with C_org (organic carbon). The similar distribution patterns of selected elements in average slightly mineralized low-Ca black shales indicate a fluid composition similar for all deposits studied. Studies of graphitization of the organic matter in black shales adjacent to orebodies indicate that d₍₀₀₂₎ and FWHM (full width in half maximum)/peak height values gradually decrease in the following sequence: Dafulou deposit M Kangma deposit M Huile deposit. The pyrolysate of wall rocks at the Dafulou deposit is relatively enriched in asphaltenes and maltenes (55.6-72.0% of the pyrolysate) comparable with pyrolysate obtained from more distal black shales (19.2-28.5%). Typical GC-MS spectra of pyrolysate from distal black shales are dominated by alkanes in the n-C15 to n-C25 range, aromatic molecules being represented mostly by alkyl-naphthalenes. In contrast, only traces of aliphatic hydrocarbons in the n-C14 to n-C18 range and elemental sulfur were identified in pyrolysates from pyrrhotitized wall rocks. The earliest fluid inclusions of the studied system occur in the quartz-tourmaline-cassiterite assemblage of stage I at Dafulou. These inclusions are H₂O-CO₂-CH₄-rich, with 10 to 20 vol% of aqueous phase. P-T conditions of the trapping of inclusions are estimated to be up to 400 °C and 1.3 to 2.0 kbar (between 5.0 and 7.5 km under lithostatic pressure). In contrast, the presence of a low density gaseous CO₂-CH₄ phase indicates relatively low pressures during the formation of the breccia-type quartz-calcite-cassiterite-sulfide mineralization (stage II), when P-T conditions probably reached approx. 380 to 400 °C and 0.6 kbar (up to 6 km under hydrostatic pressure). Fluid inclusion data and oxygen isotope thermometry indicate that cassiterite-sulfide ores of the main sulfide stage (stage II) formed from aqueous-carbonic fluid (CO₂/CH₄ =ᄺ) at temperatures of up to 390 °C at Dafulou and in a temperature range of 250 to 360 °C at Huile and 260 to 370 °C at Kangma. The '³⁴S values of sulfides from Dafulou range mostly between -1 and -6‰, whereas sulfides from the Kangma and Huile deposits are characterized by more negative '³⁴S values (between -8 and -11‰, and between -9 and -12‰, respectively). These data suggest that bacteriogenic sulfides of black shales were a dominant source of reduced sulfur for epigenetic (vein and replacement) mineralization. Oxygen isotopic compositions of five quartz-cassiterite pairs from Dafulou and Huile show a relatively narrow range of calculated oxygen isotope temperatures (250-320 °C, using the equation of Alderton 1989) and high '¹⁸O_fluid values between +8 and +10‰ (SMOW), which are in agreement with fluid derivation from and/or high temperature equilibration with the Longxianggai granite. The carbon and oxygen isotope composition of carbonates reflects variable carbon sources. Stage I calcite is characterized by narrow ranges of '¹³C (-7.0 to -9.5‰ PDB) and '¹⁸O (+15.0 to +17.5‰ SMOW). This calcite shows ubiquitous deformation, evidenced by intense development of twins. Fluid compositions calculated at 330 °C for the Dafulou and Huile deposits and at 270-300 °C for the Kangma deposit ('¹⁸O_fluid between +10.0 and +11.5‰ SMOW, '¹³C_fluid between -5.5 and -7.5‰ PDB), agree with fluid derivation from and/or equilibration with the peraluminous, high-'¹⁸O Longxianggai granite and suggest a significant influence of contact metasedimentary sequences (carbon derived from decomposition and/or alteration of organic matter of calcareous black shales). The '¹³ C values of organic matter from the Lower to Upper Devonian host rocks at the Dafulou deposit (-24.0 and -28.0‰) fit with a marine origin from algae. However, organic matter adjacent to the host rock-ore contact displays a slight enrichment in ¹³C. The organic carbon from the Huile and Kangma deposits is even more ¹³C enriched (-24.6 to -23.5‰). The most heavy '¹³ C values (-16.5‰) were detected in hornfels sampled at the contact of the Upper Devonian sediments with the Longxianggai granite. The '¹³C data broadly correlate with the degree of structural ordering (degree of graphitization) of organic matter, which indicates that both variables are related to thermal overprint.     

Strontium Isotope Geochemistry and Petrogenesis of the Early Tertiary Lava Pile of the Isle of Skye, Scotland, and other Basic Rocks of the British Tertiary Province: an Example of Magma--Crust Interaction

Most of the flows in the Palaeocene lava pile remnant of Skyeare members of the Skye Main Lava Series (SMLS), comprisingtransitional basalts and two associated suites of evolved lavas.The first suite evolves through Fe-rich hawaiites and mugearitesto benmoreites, and the second suite evolves through Fe-poorintermediates to trachytes. Ca-rich, alkali-poor olivine tholeiites(the Preshal Mhor magma type) occur as sparse flows in the stratigraphicallyhighest parts of the lava pile remnant and are abundant in thedyke swarm transecting it. Initial ⁸⁷Sr/⁸⁶Sr ratios rangingfrom 0.70308 to 0.70571 in 45 SMLS samples show no significantcorrelation with degree of zeolitization (H₂O⁺), silica saturation,or ⁸⁷Rb/⁸⁶Sr. A moderately good negative correlation with totalSr confirms published Pb-isotope evidence of interaction withancient, sialic crust. Details of the (⁸⁷Sr/⁸⁶Sr)_l versus Srpattern are consistent with previous hypotheses that the SMLSbasalt-benmoreite suite evolved at a depth near the Moho, whilstthe low-Fe trend to trachyte resulted from near-surface basaltfractionation. (⁸⁷Sr/⁸⁶Sr)_l values ranging from 0.70307 to 0.70621 for PreshalMhor basalts show a strong positive correlation with total Sr,consistent with a model of extensive fractionation within theupper crust of a mantle-derived low ⁸⁷Sr/⁸⁶Sr-low Sr magma,which became progressively contaminated with comparatively radiogeniccrustal Sr. The lowest measured (⁸⁷Sr/⁸⁶Sr)_l values of 0.70307and 0.70308, for a Preshal Mhor basalt and for an SMLS basaltrespectively, are consistent with the hypothesis that thesetwo magma types were produced by successive phases of partialmelting from a single volume of upper mantle. (⁸⁷Sr/⁸⁶Sr)_l values for additional miscellaneous basaltic lavas,dykes and major intrusives from Skye and from nearby Isle ofMull exhibit considerable variability within the range 0.7038to 0.7072, whilst three basaltic dykes from Northern Englandare in the range 0.7089 to 0.7123. The latter values overlapwith published (⁸⁷Sr/⁸⁶Sr)_l values for some of the granitesin the Tertiary Province of northwest Scotland and indirectlyremove objections based on Sr-isotopic arguments to the genesisof the granites by fractionation of basalt contaminated withcrustal Sr, but neither prove this nor disprove large-scalecrustal partial fusion.     

Rare earth element diffusion in diopside: influence of temperature, pressure, and ionic radius, and an elastic model for diffusion in silicates

Volume diffusion rates for five rare earth elements (La, Ce, Nd, Dy, and Yb) have been measured in single crystals of natural diopside at pressures of 0.1 MPa to 2.5 GPa and temperatures of 1,050 to1,450 °C. Polished, pre-annealed crystals were coated with a thin film of rare earth element oxides, then held at constant temperature and pressure for times ranging from 20 to 882 h. Diffusion profiles in quenched samples were measured by SIMS (secondary ion mass spectrometry) depth profiling. At 1 atm pressure, with the oxygen fugacity controlled near the quartz-fayalite-magnetite buffer, the following Arrhenius relations were obtained for diffusion normal to (001) (diffusion coefficient D in m²/s): log₁₀D_Yb=(-4.64ǂ.42)-(411ᆠ kJ/mol/2.303RT); log₁₀D_Dy=(-3.31ǃ.44)-(461ᆽ kJ/mol/2.303RT); log₁₀D_Nd=(-2.95DŽ.64)-(496ᇡ kJ/mol/2.303RT); log₁₀D_Ce=(-4.10ǃ.08)-(463ᆳ kJ/mol/2.303RT); log₁₀D_Lu=(-4.22DŽ.66)-(466ᇢ kJ/mol/2.303RT). Diffusion rates decrease significantly with increasing ionic radius, with La a factor of ~35 slower than Yb. The relationship between diffusivity and ionic radius is consistent with a model in which elastic strain plays a critical role in governing the motion of an ion through the crystal lattice. Activation volumes for Yb and Ce diffusion, at constant temperature and oxygen fugacity, are 9.0DŽ.0 cm³/mol and 8.9Dž.2 cm³/mol, respectively, corresponding to an order of magnitude decrease in diffusivity as pressure is increased from 0 to 3 GPa at 1,200 °C. Diffusion of Nd is such that grain-scale isotopic equilibrium in the mantle can be achieved in ~1 My under conditions near the peridotite solidus (~1,450 °C at 2.5 GPa). The equilibration time is much longer under P, T conditions of the lithospheric mantle or at the eclogite solidus (~1 Gy at 1.5 GPa and 1,150 °C). Because of the relatively strong decrease in diffusivity with pressure (two orders of magnitude between 2.5 and 15 GPa along an adiabatic temperature gradient), Nd transport in clinopyroxene will be effectively frozen at pressures approaching the transition zone, on time scales less than 100 My. Rare earth element diffusion rates are slow enough that significant disequilibrium uptake of REE by growing clinopyroxene phenocrysts may be preserved under natural conditions of basalt crystallization. The relative abundances and spatial distributions of REE in such crystals may provide a sensitive record of the cooling and crystallization history of the host lava.     

Origin of arsenic in the groundwater of the Rioverde basin, Mexico

Groundwater in the semiarid Rioverde basin in the northern part of Mexico was investigated with respect to major and minor elements including arsenic, as well as As(III) and As(V). The total arsenic concentrations varied from less than 5 to 50 g/L. The in situ arsenic determination method produced reliable results with deviations from -5.6 to 2.2 g/L compared to laboratory HGAAS. Since arsenic and barium were found to be inversely correlated, it was suspected that precipitation of barium arsenate controlled arsenic solubility. Thermodynamically modeling by means of PHREEQC indicated that BaHAsO₄·H₂O (not BaAsO₄) might be a limiting phase, however only at higher concentrations than those determined in this study. Increased arsenic groundwater concentrations were found with lacustrine sediments and decreased concentrations with fluvial Quaternary sediments. Increased total arsenic concentrations correlate with increased As(III) concentrations in the groundwater of the lacustrine sediments.     

Geochemistry of Pyramid Lake sediments: influence of anthropogenic activities and climatic variations within the basin

In 1998, a 59-cm sediment box core (PLB98-2) was taken from the deepest part of Pyramid Lake (water depth =106 m), Nevada. Age control for PLB98-2 was provided using a variety of approaches. Dried sediment samples were leached with 10% ultra-pure nitric acid and analyzed for their elemental concentrations using standard ICP techniques. The variations in elemental concentrations can be divided into two periods: one prior to European settlement and one influenced by anthropogenic activities. The concentrations of K, Al, Na, Zn, and Mn all began to increase after pre-European manipulation of the watershed in ~1860, which indicates the increasing soil erosion in the watershed was due to deforestation and development. The highest concentrations of these elements and lithogenic elements such as P, Mg, Fe, Cu, Ba, and Si occurred during the flood event of the 1990s. The Pb enrichment times are similar to what has been observed in estuaries draining the western Sierra Nevada, but the Pb enrichments in Pyramid Lake are much less. The Ca, TOC, TIC, Sr, and Ba concentrations show a strong association that is closely related to drought-wet variations of climate and the construction of Derby Dam for water diversions in the early 1900s. Se concentrations vary with the '¹⁸O of the carbonate in the sediments. Although the '¹⁸O "leads" the other species and Truckee River discharge by a few years, it is an excellent indicator of the hydrological change of Pyramid Lake, which is related to climate changes and human activities. From ~1920, Mn and Mo vary inversely in the sediments. In general, the Mo concentrations varies directly with the organic carbon content of the sediments from 1910 to ~1980, suggesting enhanced removal of Mo during times of increased productivity in the lake, and anoxic conditions at the sediment/water interface. This coincides with low lake levels. The elemental composition of the sediments in Pyramid Lake clearly reflect the timing of important anthropogenic activities and climatic variations that have taken place within the watershed over the past 240 years.     

Stability of Al- and F-rich titanite in metacarbonate: petrologic and isotopic constraints from a polymetamorphic eclogitic marble of the internal Sesia Zone (Western Alps)

Al- and F-rich titanite (3.862O₃ <9.33 wt%, 0.931(F, OH)₁Ti_-1O_-1 substitution within single crystals, particularly at grain boundaries with omphacite and/or phengite. In-situ ion microprobe U-Pb analysis of titanite domains that have various Al and F contents yielded apparent ²⁰⁶Pb/²³⁸U ages scattering between 283 and 153 Ma. Chemical and petrological data are indispensable to interpret this complex age distribution, and the good correlation between ²⁰⁶Pb/²³⁸U ratios and Al content indicates that the Al- and F-rich titanite was formed during pre-Alpine metamorphism (𔕑ᆟ Ma). Progressively younger ages are obtained in domains with decreasing Al and F content, suggesting that partial chemical re-equilibration was responsible for the incomplete isotopic resetting during Alpine metamorphism. Petrological and U-Pb data show that Al- and F-rich titanite should be used with caution to infer high-pressure conditions in polymetamorphic carbonate systems.