Deep groundwater circulation and associated methane leakage in the northern Canadian Rocky Mountains

Concern over potential impact of shale gas development on shallow groundwater systems requires greater understanding of crustal scale fluid movement. We examined natural deeply circulating groundwater systems in northeastern British Columbia adjacent to a region of shale gas development, in order to elucidate origin of waters, depths of circulation, and controls on fluid flow. These systems are expressed as thermal springs that occur in the deformed sedimentary rocks of the Liard Basin. Stable isotope data from these springs show that they originate as meteoric water. Although there are no thermal anomalies in the region, outlet temperatures range from 30 to 56 °C, reflecting depth of circulation. Based on aqueous geothermometry and geothermal gradients, circulation depths up to 3.8 km are estimated, demonstrating connection of deep groundwater systems to the surface. Springs are also characterised by leakage of thermogenic gas from deep strata that is partly attenuated by methanotrophic microbial communities in the spring waters. Springs are restricted to anomalous structural features, cross cutting faults, and crests of fault-cored anticlines. On a regional scale they are aligned with the major tectonic features of the Liard Line and Larsen Fault. This suggests that while connection of surface to deep reservoirs is possible, it is rare and restricted to highly deformed geologic units that produce permeable pathways from depth through otherwise thick intervening shale units. Results allow a better understanding of potential for communication between deep shale gas units and shallow aquifer systems.     

Significant Li isotope fractionation in geochemically evolved rare element-bearing pegmatites from the Little Nahanni Pegmatite Group,NWT, Canada

Lithium isotope signatures of whole rock pegmatite samples and mineral separates from the rare element-bearing Little Nahanni Pegmatite Group, NWT, and whole rock samples from nearby granitic intrusions were measured. Correlation of the Li isotopic values from the pegmatite dikes with whole rock trace element geochemistry, mineralogy and primary textural evidence reflect mechanisms of Li isotopic fractionation during pegmatite formation. The heavier δ⁷Li signatures within the broad range measured from whole rock LNPG samples (? 0.94‰ to + 11.36‰) are related to the consolidation of the final ~ 15% melt fraction of a volatile-rich peraluminous magma in the late stages of magmatic fractionation. Rock-forming minerals (quartz, albite, spodumene and mica) display δ⁷Li signatures that indicate consolidation of the dikes under variable, non-equilibrium conditions. Lithium isotope signatures of relatively cool, highly evolved peraluminous magmas reflect the build-up of fluxes (e.g., H₂O and F) and provide a qualitative assessment of the state of mineral/melt chemical equilibrium.     

Chemical and Sr isotopic characterization of North America uranium ores: Nuclear forensic applications

This study reports major, minor, and trace element data and Sr isotope ratios for 11 uranium ore (uraninite, UO_2+x) samples and one processed uranium ore concentrate (UOC) from various U.S. deposits. The uraninite investigated represent ores formed via different modes of mineralization (e.g., high- and low-temperature) and within various geological contexts, which include magmatic pegmatites, metamorphic rocks, sandstone-hosted, and roll front deposits. In situ trace element data obtained by laser ablation-ICP-MS and bulk sample Sr isotopic ratios for uraninite samples investigated here indicate distinct signatures that are highly dependent on the mode of mineralization and host rock geology. Relative to their high-temperature counterparts, low-temperature uranium ores record high U/Th ratios (>1000), low total rare earth element (REE) abundances (<1 wt%), high contents (>300 ppm) of first row transition metals (Sc, Ti, V, Cr, Mn, Co, Ni), and radiogenic ⁸⁷Sr/⁸⁶Sr ratios (>0.7200). Comparison of chondrite normalized REE patterns between uraninite and corresponding processed UOC from the same locality indicates identical patterns at different absolute concentrations. This result ultimately confirms the importance of establishing geochemical signatures of raw, uranium ore materials for attribution purposes in the forensic analysis of intercepted nuclear materials.     

Diatom-inferred depth models in 8 Canadian boreal lakes: inferred changes in the benthic:planktonic depth boundary and implications for assessment of past droughts

Assessment of past drought in boreal regions, a region predicted to be strongly affected by climate warming, can provide insights into future availability of water. However, limited instrumental data and paleoclimatic data are available for this assessment. To address this lack of data in the boreal region of northwest Ontario, a regional study of lakes in the Winnipeg River Drainage Basin was initiated. Diatom-inferred (D-I) depth models were developed based on surface samples collected along a depth gradient within 8 small boreal lakes. Weighted-averaging and modern analog approaches provided robust within-lake depth models for each of the study lakes, with bootstrapped r² values ranging from 0.90 to 0.98, and root-mean-squared-errors of prediction (RMSEP) between 1.1 and 2.5 m. Large differences in the estimated depth optima for three representative, but common diatom species across our 8 study lakes suggested that within-lake calibration datasets are more appropriate for inferring past drought based in depth models than a regional multi-lake calibration dataset, and that light and related variables are controlling factors governing the maximum depth of benthic taxa. A down-core application of the D-I depth models on a near-shore core from Meekin Lake, retrieved near the present-day ecotone between the benthic and planktonic diatom assemblages indicated highly similar trends in inferred depth (r = 0.96). The models have significant correlations with other metrics of changes in depth including diatom species richness (r = 0.74–0.78) and evenness (r = 0.76–0.8), thereby allowing a check on the strength and direction of the depth inferences down-core. Near-shore cores located near the benthic:planktonic transition is a sensitive region that can provide estimates of past droughts in lakes where such inferences have been difficult to estimate.     

Iron isotope composition of the suspended matter along depth and lateral profiles in the Amazon River and its tributaries

Samples of suspended matter were collected at different locations, seasons, depths and lateral profiles in the Amazon River and three of its main tributaries, the Madeira, the Solimões and the Negro rivers. Their iron isotope compositions were studied in order to understand the iron cycle and investigate the level of isotopic homogeneity at the river cross-section scale. Samples from four depth profiles and three lateral profiles analyzed show suspended matter δ⁵⁷Fe values (relative to IRMM-14) between −0.501 ± 0.075‰ and 0.196 ± 0.083‰ (2SE). Samples from the Negro River, a blackwater river, yield the negative values. Samples from other stations (whitewater rivers, the Madeira, the Solimões and the Amazon) show positive values, which are indistinguishable from the average composition of the continental crust (δ⁵⁷Fe_IRMM-14 ∼ 0.1‰). Individual analyses of the depth and lateral profiles show no significant variation in iron isotope signatures, indicating that, in contrast to certain chemical or other isotopic tracers, one individual subsurface sample is representative of river deeper waters. This also suggests that, instead of providing detailed information on the riverine iron cycling, iron isotopes of particulate matter in rivers will rather yield a general picture of the iron sources.     

Hydrochemical signatures of deep groundwater circulation in a part of the Himalayan foreland basin

Groundwater samples were analyzed from 71 springs and wells as part of a larger study in a region of compressional tectonic regime. The study site covers the Peshawar basin and surroundings in the Himalayan foreland of Pakistan. The northern portion is mountainous and the water table is discontinuous in different intermontane valleys, with abundant springs (with normal and anomalous temperatures and composition). The southern part is divided into isolated basins with a number of drilled (“deep”) and dug (“shallow”) wells. Hydrochemical signatures of elevated strontium (Sr), SiO₂, boron (B)—and the geothermometric signatures—all indicate a deep circulation of the emerging groundwater. Moreover, for several of the sample sites, water chemical compositions, measured spring and water well temperatures, and reservoir temperatures calculated for spring waters, all point to origin from deep horizons within the basin. Remarkable proximity of all the thermal and hydrochemical anomalies to major faults suggests that the waters ascended along these faults from greater depths. The area is a natural western extension of the Himalayan Geothermal Belt described in earlier literature for the eastern and central Himalayas.     

Noble gas,CFC and other geochemical evidence for the age and origin of the Bath thermal waters,UK

The city of Bath is a World Heritage site and its thermal waters, the Roman Baths and new spa development rely on undisturbed flow of the springs (45 °C). The current investigations provide an improved understanding of the residence times and flow regime as basis for the source protection. Trace gas indicators including the noble gases (helium, neon, argon, krypton and xenon) and chlorofluorocarbons (CFCs), together with a more comprehensive examination of chemical and stable isotope tracers are used to characterise the sources of the thermal water and any modern components. It is shown conclusively by the use of ³⁹Ar that the bulk of the thermal water has been in circulation within the Carboniferous Limestone for at least 1000 years. Other stable isotope and noble gas measurements confirm previous findings and strongly suggest recharge within the Holocene time period (i.e. the last 12 kyr). Measurements of dissolved ⁸⁵Kr and chlorofluorocarbons constrain previous indications from tritium that a small proportion (<5%) of the thermal water originates from modern leakage into the spring pipe passing through Mesozoic valley fill underlying Bath. This introduces small amounts of O₂ into the system, resulting in the Fe precipitation seen in the King’s Spring. Silica geothermometry indicates that the water is likely to have reached a maximum temperature of between 69–99 °C, indicating a most probable maximum circulation depth of ∼3 km, which is in line with recent geological models. The rise to the surface of the water is sufficiently indirect that a temperature loss of >20 °C is incurred. There is overwhelming evidence that the water has evolved within the Carboniferous Limestone formation, although the chemistry alone cannot pinpoint the geometry of the recharge area or circulation route. For a likely residence time of 1–12 kyr, volumetric calculations imply a large storage volume and circulation pathway if typical porosities of the limestone at depth are used, indicating that much of the Bath-Bristol basin must be involved in the water storage.     

Solid phase characterization and metal deportment in a mussel shell bioreactor for the treatment of AMD,Stockton Coal Mine,New Zealand

The Stockton Coal Mine, located on the West Coast of New Zealand, is evaluating the use of a mussel shell bioreactor (MSB) to treat acidic metalliferous runoff from acid forming overburden. This novel approach is similar in concept to vertical flow wetlands (VFWs) and successive alkalinity producing systems (SAPS). The MSB system is a trapezoidal pit 2 m deep, 35 m long, 3–10 m wide with 60° angle sides. During operation it contained 160 tonnes (240 m³) of mussel shell material and was saturated with a 100–200 mm water cap. Influent flowed through the reactor at a mean rate of 0.3 L s⁻¹ resulting in a hydraulic retention time (HRT) of ≈6 days. The prototype MSB was in operation for a total of 1027 days, from June 2009 through March 2012, and effectively sequestered 99.7% of Al, 99.3% of Fe, 98.8% of Ni, 98.4% Tl and 99.3% of Zn, as determined from a previous evaluation of MSB performance. The MSB also effectively neutralized acidity, which resulted in an increase in influent pH from 2.8 to 6.9 in the effluent. Based on an examination of several excavated pits, five distinct reaction zones developed within the MSB. The reaction zones consisted of an allochthonous sediment layer (0–330 mm), an oxidized iron-rich ocherous layer (at 330–350 mm depth), an aluminum layer (at 350–600 mm depth) with geochemical variations throughout (350–500 mm and 500–600 mm); and a chemically reduced bottom shell layer (at 600–1100 mm). Representative samples were collected from each layer and analyzed using a combination of geochemical and physical methods to assess the stability of the secondary minerals and trace metal deportment within the MSB. Major elements Fe, Al, Ni, Tl, and Zn where preferentially associated with particular layers within the MSB. Elevated concentrations of Fe (110,000 mg kg⁻¹) were observed in the allochthonous sediment and ocherous precipitate layers, while Al (27,816 mg kg⁻¹), Ni (55 mg kg⁻¹), and Zn (655 mg kg⁻¹) were elevated within the aluminum and lower reduced depths within the MSB. Trace Tl (21 mg kg⁻¹) showed varying concentrations throughout the MSB, but was strongly correlated to lower layers of the system. Microbial biofilms were observed within the reduced portions of the shell layers often proximal to bacterial shaped sulfides. The geochemical assessment of the MSB presented in this study is the first of its kind for a MSB, and supports the argument that this system is another viable option for passive treatment of AMD.     

Detailed compositional analysis of gas seepage at the National Carbon Storage Test Site,Teapot Dome,Wyoming, USA

A baseline determination of CO₂ and CH₄ fluxes and soil gas concentrations of CO₂ and CH₄ was made over the Teapot Dome oil field in the Naval Petroleum Reserve No. 3 (NPR-3) in Wyoming, USA. This was done in anticipation of experimentation with CO₂ sequestration in the Pennsylvanian Tensleep Sandstone underlying the field at a depth of 1680 m.The baseline data were collected during the winter, 2004 in order to minimize near-surface biological activity in the soil profile. The baseline data were used to select anomalous locations that may be the result of seeping thermogenic gas, along with background locations. Five 10-m holes were drilled, 3 of which had anomalous gas microseepage, and 2 were characterized as “background.” These were equipped for nested gas sampling at depths of 10-, 5-, 3-, 2-, and 1-m depths. Methane concentrations as high as 170,000 ppmv (17%) were found, along with high concentrations of C₂H₆, C₃H₈, n-C₄H₁₀, and i-C₄H₁₀. Much smaller concentrations of C₂H₄ and C₃H₆ were observed indicating the beginning of hydrocarbon oxidation in the anomalous holes. The anomalous 10-m holes also had high concentrations of isotopically enriched CO₂, indicating the oxidation of hydrocarbons. Concentrations of the gases decreased upward, as expected, indicating oxidation and transport into the atmosphere. The ancient source of the gases was confirmed by ¹⁴C determinations on CO₂, with radiocarbon ages approaching 38 ka within 5 m of the surface.Modeling was used to analyze the distribution of hydrocarbons in the anomalous and background 10-m holes. Diffusion alone was not sufficient to account for the hydrocarbon concentration distributions, however the data could be fit with the addition of a consumptive reaction. First-order rate constants for methanotrophic oxidation were obtained by inverse modeling. High rates of oxidation were found, particularly near the surface in the anomalous 10-m holes, demonstrating the effectiveness of the process in the attenuation of CH₄ microseepage. The results also demonstrate the importance of CH₄ measurements in the planning of a monitoring and verification program for geological CO₂ sequestration in sites with significant remaining hydrocarbons (i.e. spent oil reservoirs).     

Evidence of local sourcing of sulfur and gold in an Archaean sediment-hosted gold deposit

Determining the source of sulfur in an ore deposit is key to understanding the nature of the ore forming processes. The Neoarchaean Paulsens sediment-hosted gold deposit (∼1 Moz @ 7.6 g/t) located in the Pilbara Craton of Western Australia exhibits many of the characteristics of Phanerozoic shale hosted gold deposits (e.g. Huijiabao Trend, Northern Carlin Trend and Sukhoi Log), in that 1) black shales are the dominant host rock, 2) gold is hosted in pyrite as both free gold and dissolved gold in the lattice of the pyrite, and 3) multiple generations of pyrite have formed due to a variety of geological processes. In this contribution we utilised Secondary Ion Mass Spectrometer (SIMS) to measure the in-situ quadrupole (³²S, ³³S, ³⁴S and ³⁶S) sulfur isotope compositions of the different generations of pyrite. Our results indicate that the both diagenetic and hydrothermal pyrite generations display similar and anomalous Δ³³S signatures (up to +0.4‰). Further, the Δ³³S-Δ³⁶S arrays in the hydrothermal pyrite generations lie on a slope which is similar to that of the diagenetic pyrite. These data support the hypothesis that the sulfur in the ore zones came from the host Hardey Formation black shales.We also performed trace element analyses of syn-sedimentary and early diagenetic pyrite from the Hardey Formaiton using Nano Secondary Ion Mass Spectrometry (NanoSIMS), Electron Probe Microanalysis (EPMA) and Laser Ablation-inductively coupled plasma-mass spectrometry (LA-ICPMS), all of which show that the syn-sedimentary and early diagenetic pyrite contain high concentrations of many trace elements (As, Ni, Co, Cu, Ag, Se, Te, Bi), including up to 1.5 ppm Au. These metals contents are also abundant in the several generations of mineralised hydrothermal pyrite and form clear patterns of growth associated with couple dissolution reprecipitation reactions. These findings clearly indicate that the fluid that transported the Au must have also been enriched in the base and precious metals that are contained in the early, syn-diagenesis pyrite.Data from this study clearly support the hypothesis that in some sediment-hosted gold systems, all the sulfur and gold required to form the deposit are sourced from the local sedimentary package. By using the presence of anomalous mass independent sulfur isotope signatures as chemically conservative and indelible tracers, it is possible to fingerprint the source of sulfur in a wide range of mineral systems, thus enhancing predictive exploration strategies at the regional to camp scales.     

Hydrochemistry and environmental isotopes of spring water and their relation to structure and lithology identified with remote sensing methods in Wadi Araba,Egypt

Springs located at the historical sites of Wadi Araba (Eastern Desert of Egypt) and emerging from the escarpments of the Northern and Southern Galala Plateaus were investigated. A combination of methods, including hydrochemistry, stable and radioisotope composition, and structural analyses based on satellite data, provided information about the structure of the subsurface and the derived groundwater flow paths. Satellite images reveal karst features within the northern plateau, e.g. conical landforms. Karstic caves were documented along both escarpments. Chemical analysis of floodwater from Wadi Araba indicates higher concentrations of terrestrial salts compared to floodwaters from central and southern parts of the desert. δ¹⁸O and δ²H signatures in spring waters resemble those of floodwater and fall on the global meteoric water line, confirming their fast infiltration with minor influence of evaporation. The aquifer feeding the springs of the Northern Galala Plateau has low retention and the springs dry out quickly, even after heavy rainfall. Contrastingly, ³H activities in springs emerging from the Southern Galala Plateau refer to much slower subsurface passage. With respect to ³H content (3.8 TU) in recent flood waters, the spring water at Southern Galala Plateau contains about 40% recently recharged groundwater. However, its largest spring—the St. Antony spring—discharges water with a radiocarbon age of about 15,000 years. In combination with this spring’s constant and high discharge over a period of several months, that age estimate suggests a large reservoir with moderate to high retention.

     

‘PALEOVAN’, International Continental Scientific Drilling Program (ICDP): site survey results and perspectives

Lake Van is the fourth largest terminal lake in the world (volume 607 km³, area 3570 km², maximum depth 460 m), extending for 130 km WSW–ENE on the Eastern Anatolian High Plateau, Turkey. The sedimentary record of Lake Van, partly laminated, has the potential to obtain a long and continuous continental sequence that covers several glacial–interglacial cycles (ca 500 kyr). Therefore, Lake Van is a key site within the International Continental Scientific Drilling Program (ICDP) for the investigation of the Quaternary climate evolution in the Near East (‘PALEOVAN’). As preparation for an ICDP drilling campaign, a site survey was carried out during the past years. We collected 50 seismic profiles with a total length of ～850 km to identify continuous undisturbed sedimentary sequences for potential ICDP locations. Based on the seismic results, we cored 10 different locations to water depths of up to 420 m. Multidisciplinary scientific work at positions of a proposed ICDP drill site included measurements of magnetic susceptibility, physical properties, stable isotopes, XRF scans, and pollen and spores. This core extends back to the Last Glacial Maximum (LGM), a more extended record than all the other Lake Van cores obtained to date. Both coring and seismic data do not show any indication that the deepest part of the lake (Tatvan Basin, Ahlat Ridge) was dry or almost dry during past times. These results show potential for obtaining a continuous undisturbed, long continental palaeoclimate record. In addition, this paper discusses the potential of ‘PALEOVAN’ to establish new results on the dynamics of lake level fluctuations, noble gas concentration in pore water of the lake sediment, history of volcanism and volcanic activities based on tephrostratigraphy, and paleoseismic and earthquake activities.     

Minor and trace elements in bornite and associated Cu-(Fe)-sulfides: A LA-ICP-MS studyBornite mineral chemistry

In situ laser ablation inductively-coupled mass spectroscopy (LA-ICP-MS) has been used to provide a baseline dataset on the minor element contents in hypogene bornite and accompanying Cu-sulfides from 12 deposits with emphasis on syn-metamorphic Cu-vein systems in Norway, and skarn, porphyry and epithermal systems in SE Europe.Bornite contains significant concentrations of both Ag and Bi, especially in the vein and skarn deposits studied and has the potential to be a major Ag-carrier in such ores. Concentrations of up to >1 wt.% of both elements are documented. Measured concentrations appear to be independent of whether discrete Ag- and/or Bi-minerals are present within the analyzed sulfide. Where bornite and chalcocite (or mixtures of Cu-sulfides) coexist, Ag is preferentially partitioned into chalcocite over co-existing bornite and Bi is partitioned into the bornite. Bornite is a relatively poor host for Au, which mimics Ag by being typically richer in coexisting chalcocite. Most anomalous Au concentrations in bornite can be readily tracked to micron- and submicron-scale inclusions, but bornite and chalcocite containing up to 3 and 28 ppm Au in solid solution can be documented. Selenium and Te concentrations in bornite may be as high as several thousand ppm and correlate with the abundance of selenides and tellurides within the sample. Selenium distributions show some promise as a vector in exploration, offering the possibility to track a fluid source. Bornite and chalcocite are poor hosts for a range of other elements such as Co, Ni, Ga and Ge, etc. which have been reported to be commonly substituted within sulfides. Hypogene bornite and chalcocite may have significantly different trace element geochemical signatures from secondary (supergene) bornite.     

Microscopic oxygen isotopic homogeneity/heterogeneity in the matrix of the Vigarano CV3 chondrite

Two-dimensional ¹⁸O/¹⁶O isotopic analysis of the Vigarano matrix was conducted by secondary ion-imaging using a novel two-dimensional ion-imager. Quantitative oxygen-isotope images (isotopographs) of the Vigarano matrix show that ¹⁶O-rich micrograins are scattered within ¹⁶O-poor matrix. This heterogeneous O-isotopic distribution indicates that matrix is composed of different O-isotopic components that formed in different locations and/or at different times. However, the O-isotopic composition of groundmass in the matrix is the same as the bulk isotopic composition of the matrix within ±5‰ uncertainty. The spatial resolution and isotopic precision of our technique should allow submicron-size objects (>0.2 μm) with extreme O-isotopic anomalous characteristics (δ¹⁸O_SMOW ∼250‰) to be detectable in isotopographs. Because the mean grain size of the matrix is ∼0.2 μm, the inability to detect such O-isotopic anomalous objects indicates that isotopically anomalous micrograins (e.g., presolar grains) are extremely rare in the Vigarano matrix and that most objects in the matrix were formed in the solar nebula or in the parent body.     

CO<Subscript>2</Subscript> emissions from a municipal site for final disposal of solid waste in Gualeguaychu,Entre Rios Province,Argentina

This paper estimates CO₂ fluxes in a municipal site for final disposal of solid waste, located in Gualeguaychu, Argentina. Estimations were made using the accumulation chamber methods, which had been calibrated previously in laboratory. CO₂ fluxes ranged from 31 to 331 g m⁻² day⁻¹. Three different populations were identified: background soil gases averaging 46 g m⁻² day⁻¹, intermediate anomalous values averaging 110 g m⁻² day⁻¹ and high anomalous values averaging 270 g m⁻² day⁻¹. Gas samples to a depth of 20 cm were also taken. Gas fractions, XCO₂ < 0.1, XCH₄ < 0.01, XN₂ ~0.71 and XO₂ ~0.21, δ¹³C of CO₂ (−34 to −18‰), as well as age of waste emplacement, suggest that the study site may be at the final stage of aerobic biodegradation. In a first approach, and following the downstream direction of groundwater flow, alkalinity and δ¹³C of dissolved inorganic carbon (−15 to 4‰) were observed to increase when groundwater passed through the disposal site. This suggests that the CO₂ generated by waste biodegradation dissolves or that dissolved organic matter appears as a result of leachate degradation.     

Aluminum-dependent trace element partitioning in clinopyroxene

As technical advances have dramatically increased our ability to analyze trace elements, the need for more reliable data on the compositional dependence of trace element partitioning between minerals and melt has become increasingly important. The late-Cretaceous Carmacks Group of south central Yukon comprises a succession of primitive high-Mg ankaramitic lavas characterized by shoshonitic chemical affinities and containing large complexly zoned clinopyroxene phenocrysts. The compositional zonation of the clinopyroxene phenocrysts is characterized by relatively Fe-rich (Mg^# = Mg/(Mg + Fe) = 0.85), but mottled, cores surrounded by mantles of cyclically-zoned clinopyroxene whose Mg^# varies repeatedly between 0.9 and 0.80. These cyclically zoned clinopyroxene mantles appear to record the repeated influx and mixing of batches of primitive with more evolved magma in a deep sub-crustal (∼1.2 GPa) magma chamber(s). Laser ablation ICP-MS was used to analyze the trace element variation in these zoned clinopyroxenes. The results indicate more than a threefold variation in the absolute concentrations of Th, Zr, rare earth elements (REE), and Y within individual clinopyroxene phenocrysts, with no apparent change in the degree of REE or high field strength element (HFSE) fractionation. The variation in absolute abundances of trace elements correlates closely with the major element composition of the clinopyroxene, with the most enriched clinopyroxene having the lowest Mg^# and highest Al contents. The problem is that the amount of crystal fractionation required to explain the major element variation (∼20%) in these clinopyroxene phenocrysts cannot explain the increase in the abundance of the incompatible trace elements, which would require more than 70% crystal fractionation, if constant partition coefficients are assumed. The anomalous increase in incompatible trace elements appears to reflect an increase in their partition coefficients with increasing Al^IV in the clinopyroxene; with an increase in Al₂O₃ from 1.5 to 4.0 wt.% during ∼20% crystal fractionation over a temperature decrease of ∼100°C being associated with more that a threefold increase in the partition coefficients of Th, Zr, REE, and Y. The magnitude of these increases may indicate that the substitution of these trace elements into clinopyroxene is better modeled in some natural systems by a local charge balance model, rather than the distributed charge model that better replicates the results of annealed experiments. These findings indicate that the effect of Al on the partition coefficients of incompatible trace elements in clinopyroxene may be under appreciated in natural magmatic systems and that the application of experimentally determined clinopyroxene partition coefficients to natural systems must be done with caution.     

Geochemistry of basal Cambrian black shales and cherts from the Northern Tarim Basin,Northwest China: Implications for depositional setting and tectonic history

Black shales and thin-bedded cherts in the basal Cambrian are widespread worldwide and they carry important information on the formation of sedimentary basins and on the tectonic history. We studied the geochemical signatures of the early Cambrian black shales and bedded cherts from the Northern Tarim Basin, China, with the objectives of understanding the depositional setting of these rocks and inferring the tectonic history in the region. Twenty two black shales, ten cherts, and two nodular phosphorites were collected from two outcrops at Xiaoerbulake and Sugaitebulake in the Northern Tarim Basin, spanning vertical sections of 8.8 and 7.5 m, respectively. A suite of techniques, including field investigations, X-ray diffraction, electron microscopy, trace element, rare earth element (REE), and isotope geochemistry, were employed to characterize the geochemical signatures of these rocks. Field evidence indicates that the black shales and bedded cherts are over- and underlain by dolomites, suggesting a shallow marine depositional environment. Mineralogical and trace element data suggest that the Tarim black shales and cherts were deposited in a suboxic continental shelf environment, and hydrothermal activity may have extracted certain trace elements from mafic continental crust and concentrated them in the sedimentary basin. REE characteristics for the cherts are very similar to those that are known to be deposited in pelagic ocean floor settings, suggesting that the hydrothermal fluids may be derived from the infant southern Tianshan Ocean in the north of the Tarim Basin. Os isotope signatures at the time of deposition (¹⁸⁷Os/¹⁸⁸Os_i = 1.1–2.7) are typical of crustal signatures, and the radiogenic Os isotope signatures rule out the mantle as a possible source of Os and other metals. A positive correlation between ¹⁸⁷Os/¹⁸⁸Os and ε_Nd is consistent with upper crust-derived basin sediments that contain a variable contribution of hydrothermal fluids possibly derived from ancient mafic continental crust. These trace element, REE, and isotope systematics collectively suggest that incorporation of hydrothermal fluids derived from ancient, mafic continental crust combined with deposition in relatively reducing conditions may have controlled the chemical and isotopic compositions of these rocks. We infer that the hydrothermal fluid was carried to the continental shelf by upwelling during the initial stages of formation of the southern Tianshan Ocean, where the fluid interacted with thinned, mafic crustal basement lithologies and was subsequently incorporated into the black shales and bedded cherts in the Northern Tarim Basin. This study provides important geochemical evidence for the creation of the Tianshan Ocean, which is a result of break-up of the Rodinia Supercontinent during the early Cambrian.     

Pyritization of trace metals in estuarine sediments and the controlling factors: a case in Jiaojiang Estuary of Zhejiang Province,China

Three undisturbed sediment samples were collected from the intertidal zone of the Jiaojiang Estuary of Zhejiang Province, China. The sediments were found to contain remarkably low concentrations of organic carbon (<0.6%) and acid volatile sulfide (AVS) (<30 μmol g⁻¹). The availability of these two substrates likely constrained sulfate reduction and pyritization of several trace metals, respectively. This was especially true at one station where AVS concentrations in the upper 20 cm averaged less than 0.05 μmol g⁻¹. Although the depth dependence of the degree of trace metal pyritization was generally consistent with expectations based on redox conditions, depth profiles of reactive-metal and pyrite-metal concentrations in several cases revealed more complex behavior and a positive correlation between reactive-metal concentrations and pore water metal concentrations.     

Arsenic and other drinking water quality issues,Muzaffargarh District,Pakistan

In 49 samples of groundwater, sampled in Muzaffargarh District of south-western Punjab, central Pakistan, concentrations of As exceeded the World Health Organisation provisional guideline value, and United States Environmental Protection Agency (USEPA) Maximum Contaminant Level (MCL), of 10 μg L⁻¹ in 58% of samples and reached up to 906 μg L⁻¹. In this semi-arid region canal irrigation has lead to widespread water-logging, and evaporative concentration of salts has the potential to raise As concentrations in shallow groundwater well above 10 μg L⁻¹. In fact, in rural areas, concentrations stay below 25 μg L⁻¹ because As in the oxic shallow groundwater, and in recharging water, is sorbed to aquifer sediments. In some urban areas, however, shallow groundwater is found to contain elevated levels of As. The spatial distribution of As-rich shallow groundwater indicates either direct contamination with industrial or agricultural chemicals, or some other anthropogenic influence. Geochemical evidence suggests that pollutant organics from unconfined sewage and other sources drives reduction of hydrous ferric oxide (HFO) releasing sorbed As to shallow groundwater. The situation is slightly less clear for seven wells sampled which tap deeper groundwater, all of which were found with >50 μg L⁻¹ As. Here As concentrations seem to increase with depth and differing geochemical signatures are seen, suggesting that As concentrations in older groundwater may be governed by different processes. Other data on parameters of potential concern in drinking water are discussed briefly at the end of the paper.     

Geochemical constraint on origin and evolution of solutes in geothermal springs in western Yunnan,China

Geothermal resources are very rich in Yunnan, China. However, source of dissolved solutes in geothermal water and chemical evolution processes remain unclear. Geochemical and isotopic studies on geothermal springs and river waters were conducted in different petrological-tectonic units of western Yunnan, China. Geothermal waters contain Ca–HCO₃, Na–HCO₃, and Na (Ca)–SO₄ type, and demonstrate strong rock-related trace elemental distributions. Enhanced water–rock interaction increases the concentration of major and trace elements of geothermal waters. The chemical compositions of geothermal waters in the Rehai geothermal field are very complicated and different because of the magma chamber developed at the shallow depth in this area. In this geothermal field, neutral-alkaline geothermal waters with high Cl, B, Li, Rb Cs, As, Sb, and Tl contents and acid–sulfate waters with high Al, Mn, Fe, and Pb contents are both controlled by magma degassing and water–rock interaction. Geothermal waters from metamorphic, granite, and sedimentary regions (except in the Rehai area) exhibit varying B contents ranging from 3.31 mg/L to 4.49 mg/L, 0.23 mg/L to 1.24 mg/L, and <0.07 mg/L, respectively, and their corresponding δ¹¹B values range from −4.95‰ to −9.45‰, −2.57‰ to −8.85‰, and −4.02‰ to +0.06‰. The B contents of these geothermal waters are mainly controlled by leaching host rocks in the reservoir, and their δ¹¹B values usually decrease and achieve further equilibrium with its surrounding rocks, which can also be proven by the positive δ¹⁸O-shift. In addition to fluid–rock reactions, the geothermal waters from Rehai hot springs exhibit higher δ¹¹B values (−3.43‰ to +1.54‰) than those yielded from other areas because mixing with the magmatic fluids from the shallow magma. The highest δ¹¹B of steam–heated waters (pH 3.25) from the Zhenzhu spring in Rehai is caused by the fractionation induced by pH and the phase separation of coexisting steam and fluids. Given the strong water–rock interaction, some geothermal springs in western Yunnan show reservoir temperatures higher than 180 °C, which demonstrate potential for electricity generation and direct-use applications. The most potential geothermal field in western Yunnan is located in the Rehai area because of the heat transfer from the shallow magma chamber.