Trace element contents and C-O isotope geochemistry of the different originated magnesite deposits in Lake District (Southwestern Anatolia), Turkey

Vein-stockwork magnesite in the Madenli area, sedimentary huntite-magnesite in the A?a??t?rtar area, and lacustrine hydromagnesite in the Salda Lake area are located in the Bey?ehir-Hoyran and Lycian nappe rocks around Isparta and Burdur, Southwest Anatolia. The aim of this study is to understand trace element contents and carbon-oxygen isotope ratios in different originated magnesite, magnesite bearing huntite, and hydromagnesite deposits. Also, the element contents and isotope ratios of the magnesite occurrences are to compare with each other and similar magnesite occurrences in Turkey and world. It is found that the Madenli magnesite occurrences in the ?arkikaraa?aç ophiolites, A?a??t?rtar magnesite bearing huntite deposits in the lacustrine rocks of the Miocene-Pliocene, and the Salda hydromagnesite deposits in lacustrine basin on the Ye?ilova ophiolites. The paragenesis contains a common carbonate mineral magnesite, less calcite, serpentine, smectite, dolomite, and talc in the Madenli magnesite occurrences, mostly huntite and locally magnesite, dolomite, calcite, illite, quartz, and smectite in the A?a??t?rtar huntite-magnesite occurrences, and only hydromagnesite mineral in the Salda Lake hydromagnesite occurrences. Vein and stockwork Madenli magnesite deposits were recognized by higher total iron oxide concentrations (mean 1.10 wt%) than sedimentary A?a??t?rtar magnesite bearing huntite (mean 0.13 wt%) and lacustrine Salda hydromagnesite (mean 0.22 wt%) deposits. It is suggested that high Fe content (up to 5%) in the magnesite associated with ultramafic rocks than those from sedimentary environments (≤1% Fe). Based on average Ni, Co, Ba, Sr, As and Zr contents in the magnesite deposits, average Ni (134.63 ppm) and Co (15.19 ppm) contents in the Madenli magnesite and Salda hydromagnesite (36.85 ppm for Ni, 3.15 ppm for Co) have higher values than A?a??t?rtar huntite + magnesite (7.67 ppm for Ni and 0.89 ppm for Co). Average Ni-Co contents of these deposits can have close values depending on ophiolite host rock. Average Ba values of the Madenli (108.09 ppm) and A?a??t?rtar (115.88 ppm) areas are higher than those of Salda hydromagnesite (13.15 ppm). Sediment-hosted A?a??t?rtar magnesite-huntite deposits have the highest Sr contents (mean 505.81 ppm) as reasonably different from ultrabasic rock-related Madenli magnesite (mean 38.76 ppm) and Salda hydromagnesite (mean 36.70 ppm). The highest Sr content of sedimentary A?a??t?rtar deposits reveals that Sr is related to carbonate rocks. As and Zr contents have the highest average values (As 52.76 ppm and Zr 9.67 ppm) in the A?a??t?rtar deposits different from Madenli magnesite (As 0.54 ppm and Zr 1.67 ppm) and Salda hydromagnesite (As 0.5 ppm and Zr 2.58 ppm) deposits. High As and Zr concentrations in the A?a??t?rtar magnesite-huntite deposits may come from volcanic rocks in near country rocks. The δ ¹³C (PDB) isotope values vary between ?10.1 and ?11.4‰ in the Madenli magnesite, 7.8 to 8.8‰ for huntite, 1.7 to 8.3‰ for huntite + magnesite and 4.0‰ for limestone + magnesite in the A?a??t?rtar huntite-magnesite deposits, and 4.4 to 4.9‰ for Salda Lake hydromagnesite. The sources of the CO₂ are hydrothermal solutions, meteoric waters, groundwater dissolved carbon released from fresh water carbonates and marine limestone, soil CO₂, and plant C3 in the Madenli magnesite, and may be deep seated metamorphic reactions in limestone and shales of rich in terms of organic matter. The sources of CO₂ in A?a??t?rtar huntite and Salda hydromagnesite were meteoric water, groundwater dissolved inorganic carbon, fresh water carbonates, and marine limestone. The δ ¹⁸O (SMOW) isotope composition ranges from 26.8 to 28.1‰ in the Madenli magnesite, 30.4 to 32.4‰ for huntite and 29.8 to 35.5‰ for huntite + magnesite and 26.9‰ for limestone + magnesite in the A?a??t?rtar area, and 36.4 to 38.2‰ in the Salda Lake hydromagnesite. The Salda Lake hydromagnesite has heavier oxygen isotopic values than others. The sources of oxygen in the Madenli magnesite deposits are hydrothermal solutions, meteoric water, freshwater carbonates, and marine limestone, but the sources of oxygen of the A?a??t?rtar magnesite-huntite are meteoric water, fresh water carbonates, and marine limestone. The Salda Lake hydromagnesite has very high δ¹⁸O isotope values indicating a strong evaporitic environment. Magnesium (Mg⁺²) and silica are released by disintegration of very weathered-serpentinized ultrabasic rocks of all magnesite deposits and from partly dolomite and dolomitic limestone in the A?a??t?rtar magnesite bearing huntite deposits. In the A?a??t?rtar area, calcium (Ca⁺²) for huntite mineralization is provided by surrounding carbonate rocks. Based on isotopic data, host rocks, petrographic properties of the Madenli magnesite can be described as an ultramafic-associated hydrothermal vein mineralization corresponding to “Kraubath type” deposits, but A?a??t?rtar ve Salda Lake deposits are sedimentary mineralization (lacustrine/evaporitic) corresponding to “Bela Stena type” deposits. The estimated temperature using average δ¹⁸O isotope values is about 33.51 °C for Madenli magnesite, 48.33 °C for A?a??t?rtar huntite-magnesite, and 25 °C for Salda hydromagnesite. Based on isotope data, we can be say that the Madenli magnesite, A?a??t?rtar magnesite-huntite, and Salda hydromagnesite occur at low to moderate-low temperature water and alkaline (pH 8.5–10.5) under surface or near-surface conditions.     

Hydromagnesite replacement of biomineralized aragonite in a new location of Holocene stromatolites, Lake Walyungup, Western Australia

Holocene stromatolites are described from Lake Walyungup, a coastal hyposaline lake in south-western Australia. At summer low water, this groundwater-fed depression comprises two permanent shallow water bodies and an ephemeral southern pool, set within an areally extensive littoral zone of variably cemented carbonate crust. Up to 5 m of organic-rich carbonate mud has been deposited within each of these basins in less than 7000 years. Stromatolites rim the water bodies with individual columns up to 2 m tall. Stromatolite-capped tepee structures in subparallel alignment are widespread in the littoral crust, suggesting a linkage between stromatolite growth and zones of groundwater discharge. Lake Walyungup stromatolites, regardless of external morphology and setting, are coarsely laminated and have aragonitic mesoclot microfabrics. These microfabrics are similar to those from lithified portions of active thrombolitic microbialites from nearby Lake Clifton. Hydromagnesite is a minor to subdominant phase (up to 47 wt%) of the carbonate mineral assemblage in Lake Walyungup. It occurs mainly in the littoral zone as a diagenetic replacement of precursor aragonite, particularly within the mesoclot fabric of stromatolites, but also in sediments (strandline and dune sand, crusts) derived mainly from erosion of stromatolites. In contrast with nonreplaced and impermeable inorganic aragonitic cements, stromatolite mesoclots are microper- meable. Micropermeability is inferred to facilitate hydromagnesite diagenesis. Dolomite is also present in minor amounts as a pore fill in stromatolites, and as a subdominant to dominant (up to 100 wt%) phase in thin, mudcracked micrite layers within the crust package. The layered dolomite may be precipitated directly from the lake water. Major element abundance of the lake water is: Na⁺ > Mg²⁺ » K⁺ > Ca²⁺ for cations, and Cl^? » SO₄^2? ≈ HCO₃^? > CO₃^2? for anions. Compared to other nearby coastal lakes, Lake Walyungup has a high pH (> 9·0), and an extremely high molar Mg/Ca ratio of > 90. Groundwater in the area has a Mg/Ca ratio generally less than 1. The unusual Mg/Ca ratio in Lake Walyungup is partially a result of in-lake processes with additional minor contribution of Mg²⁺ sourced from basal marine sand because no Mg-rich bedrock source has been found in the region.     

A depositional model for hydromagnesite–magnesite playas near Atlin,British Columbia,Canada

This study formulates a comprehensive depositional model for hydromagnesite–magnesite playas. Mineralogical, isotopic and hydrogeochemical data are coupled with electron microscopy and field observations of the hydromagnesite–magnesite playas near Atlin, British Columbia, Canada. Four surface environments are recognized: wetlands, grasslands, localized mounds (metre‐scale) and amalgamated mounds composed primarily of hydromagnesite [Mg₅(CO₃)₄(OH)₂·4H₂O], which are interpreted to represent stages in playa genesis. Water chemistry, precipitation kinetics and depositional environment are primary controls on sediment mineralogy. At depth (average ≈ 2 m), Ca–Mg‐carbonate sediments overlay early Holocene glaciolacustrine sediments indicating deposition within a lake post‐deglaciation. This mineralogical change corresponds to a shift from siliciclastic to chemical carbonate deposition as the supply of fresh surface water (for example, glacier meltwater) ceased and was replaced by alkaline groundwater. Weathering of ultramafic bedrock in the region produces Mg–HCO₃ groundwater that concentrates by evaporation upon discharging into closed basins, occupied by the playas. An uppermost unit of Mg‐carbonate sediments (hydromagnesite mounds) overlies the Ca–Mg‐carbonate sediments. This second mineralogical shift corresponds to a change in the depositional environment from subaqueous to subaerial, occurring once sediments ‘emerged’ from the water surface. Capillary action and evaporation draw Mg–HCO₃ water up towards the ground surface, precipitating Mg‐carbonate minerals. Evaporation at the water table causes precipitation of lansfordite [MgCO₃·5H₂O] which partially cements pre‐existing sediments forming a hardpan. As carbonate deposition continues, the weight of the overlying sediments causes compaction and minor lateral movement of the mounds leading to amalgamation of localized mounds. Radiocarbon dating of buried vegetation at the Ca–Mg‐carbonate boundary indicates that there has been ca 8000 years of continuous Mg‐carbonate deposition at a rate of 0·4 mm yr^?1. The depositional model accounts for the many sedimentological, mineralogical and geochemical processes that occur in the four surface environments; elucidating past and present carbonate deposition.     

Biologically induced mineralization of dypingite by cyanobacteria from an alkaline wetland near Atlin,British Columbia,Canada

Background  

This study provides experimental evidence for biologically induced precipitation of magnesium carbonates, specifically dypingite (Mg₅(CO₃)₄(OH)₂·5H₂O), by cyanobacteria from an alkaline wetland near Atlin, British Columbia. This wetland is part of a larger hydromagnesite (Mg₅(CO₃)₄(OH)₂·4H₂O) playa. Abiotic and biotic processes for magnesium carbonate precipitation in this environment are compared.     

Rare earth element and strontium isotope geochemistry in Dujiali Lake,central Qinghai-Tibet Plateau,China: Implications for the origin of hydromagnesite deposits

Rare earth element (REE) and strontium isotope data (⁸⁷Sr/⁸⁶Sr) are presented for hydromagnesite and surface waters that were collected from Dujiali Lake in central Qinghai-Tibet Plateau (QTP), China. The goal of this study is to constrain the solute sources of hydromagnesite deposits in Dujiali Lake. All lake waters from the area exhibit a slight LREE enrichment (average [La/Sm]_PAAS = 1.36), clear Eu anomalies (average [Eu/Eu*]_PAAS = 1.31), and nearly no Ce anomalies. The recharge waters show a flat pattern (average [La/Sm]_PAAS = 1.007), clear Eu anomalies (average [Eu/Eu*] _PAAS = 1.83), and nearly no Ce anomalies (average [Ce/Ce*]_PAAS = 1.016). The REE+Y data of the surface waters indicate the dissolution of ultramafic rock at depth and change in the hydrogeochemical characteristics through fluid-rock interaction. These data also indicate a significant contribution of paleo-groundwater to the formation of hydromagnesite, which most likely acquired REE and Sr signatures from the interaction with ultramafic rocks. The ⁸⁷Sr/⁸⁶Sr data provide additional insight into the geochemical evolution of waters of the Dujiali Lake indicating that the source of Sr in the hydromagnesite does not directly derive from surface water and may have been influenced by both Mg-rich hydrothermal fluids and meteoric water. Additionally, speciation modeling predicts that carbonate complexes are the most abundant dissolved REE species in surface water. This study provides new insights into the origins of hydromagnesite deposits in Dujiali Lake, and contributes to the understanding of hydromagnesite formation in similar modern and ancient environments on Earth.     

Methane‐related microbial gypsum calcitization in stromatolites of a marine evaporative setting (Münder Formation,Upper Jurassic,Hils Syncline,north Germany)

Fossil stromatolites may reveal information about their hydrochemical palaeoenvironment, provided that assignment to a specific microbial community and a corresponding biogeochemical mechanism of formation can be made. Tithonian stromatolites of the Münder Formation at Thüste, north Germany, have traditionally been considered as formed by intertidal cyanobacterial communities. However, thin sections of the stromatolites show elongated angular traces of former gypsum crystals in a dense arrangement, but no algal or cyanobacterial filament traces. Moreover, high Fe²⁺ and Mn²⁺ contents, oxygen‐isotope and sulphur‐isotope ratios of carbonate‐bound sulphates, and sulphurized hydrocarbon biomarkers of the stromatolitic carbonate indicate that CaCO₃ precipitation occurred near the oxic–anoxic interface as a result of intensive bacterial sulphur cycling rather than photosynthetic activity. Furthermore, anaerobic oxidation of methane by Archaea may have driven CaCO₃ precipitation in deeper parts of the biofilm community, as reflected by high concentrations of squalane with a strongly negative δ¹³C in conjunction with evaporite pseudomorphs showing extremely low δ¹³C_Carb ratios. Consequently, the Thüste stromatolites are now interpreted as having initially formed by gypsum impregnation of biofilms. Subsequently, early Mg‐calcitic calcitization within the biofilms occurred because of combined bacterial iron, manganese and sulphate reduction, with an increasing contribution of anaerobic oxidation of methane with depth. This model plausibly explains the prominent preservation of signals derived from oxygen‐independent metabolic pathways, whereas virtually no geochemical record exists for an aerobic community that may, nevertheless, have prevailed at the stromatolite surface. Photic‐zone stromatolites with a prominent signal of anaerobic oxidation of methane may be common in, and indicative of, oxygen‐depleted sulphate‐bearing environments with high rates of methane production, conditions that possibly were fulfilled at the Archaean to Proterozoic transition.     

The hydromagnesite playas of Atlin, British Columbia, Canada: A biogeochemical model for CO2 sequestration

Anthropogenic greenhouse gas emissions may be offset by sequestering carbon dioxide (CO₂) through the carbonation of magnesium silicate minerals to form magnesium carbonate minerals. The hydromagnesite [Mg₅(CO₃)₄(OH)₂·4H₂O] playas of Atlin, British Columbia, Canada provide a natural model to examine mineral carbonation on a watershed scale. At near surface conditions, CO₂ is biogeochemically sequestered by microorganisms that are involved in weathering of bedrock and precipitation of carbonate minerals. The purpose of this study was to characterize the weathering regime in a groundwater recharge zone and the depositional environments in the playas in the context of a biogeochemical model for CO₂ sequestration with emphasis on microbial processes that accelerate mineral carbonation.Regions with ultramafic bedrock, such as Atlin, represent the best potential sources of feedstocks for mineral carbonation. Elemental compositions of a soil profile show significant depletion of MgO and enrichment of SiO₂ in comparison to underlying ultramafic parent material. Polished serpentinite cubes were placed in the organic horizon of a coniferous forest soil in a groundwater recharge zone for three years. Upon retrieval, the cube surfaces, as seen using scanning electron microscopy, had been colonized by bacteria that were associated with surface pitting. Degradation of organic matter in the soil produced chelating agents and acids that contributed to the chemical weathering of the serpentinite and would be expected to have a similar effect on the magnesium-rich bedrock at Atlin. Stable carbon isotopes of groundwater from a well, situated near a wetland in the southeastern playa, indicate that  12% of the dissolved inorganic carbon has a modern origin from soil CO₂.The mineralogy and isotope geochemistry of the hydromagnesite playas suggest that there are three distinct depositional environments: (1) the wetland, characterized by biologically-aided precipitation of carbonate minerals from waters concentrated by evaporation, (2) isolated wetland sections that lead to the formation of consolidated aragonite sediments, and (3) the emerged grassland environment where evaporation produces mounds of hydromagnesite. Examination of sediments within the southeastern playa–wetland suggests that cyanobacteria, sulphate reducing bacteria, and diatoms aid in producing favourable geochemical conditions for precipitation of carbonate minerals.The Atlin site, as a biogeochemical model, has implications for creating carbon sinks that utilize passive microbial, geochemical and physical processes that aid in mineral carbonation of magnesium silicates. These processes could be exploited for the purposes of CO₂ sequestration by creating conditions similar to those of the Atlin site in environments, artificial or natural, where the precipitation of magnesium carbonates would be suitable. Given the vast quantities of Mg-rich bedrock that exist throughout the world, this study has significant implications for reducing atmospheric CO₂ concentrations and combating global climate change.     

Major ion geochemistry of shallow groundwater in the Qinghai Lake catchment, NE Qinghai-Tibet Plateau

Conventional hydrochemical techniques and statistical analyses were applied to better understand the solute geochemistry and the hydrochemical process of shallow groundwater in the Qinghai Lake catchment. Shallow groundwater in the Qinghai Lake catchment is slightly alkaline, and is characterized by a high ion concentrations and low water temperature. The total dissolved solids (TDS) in most of the samples are <1,000?mg/L, i.e. fresh water and depend mainly on the concentration of SO₄ ^2?, Cl^? and Na⁺. Groundwater table is influenced directly by the residents?? groundwater consumption. Most of the groundwaters in the Qinghai Lake catchment belong to the Ca²⁺(Na⁺) ?CHCO₃ ^? type, while the Qinghai Lake, part of the Buha (BHR) and the Lake Side (LS) samples belong to the Na⁺?CCl^? type. The groundwater is oversaturated with respect to aragonite, calcite and dolomite, but not to magnesite and gypsum. Solutes are mainly derived from strong evaporite dissolution in Daotang, BHR and LS samples and from strong carbonate weathering in Hargai and Shaliu samples. Carbonate weathering is stronger than evaporite dissolution with weak silicate weathering in the Qinghai Lake catchment. Carbonate weathering, ion exchange reaction and precipitation are the major hydrogeochemical processes responsible for the solutes in the groundwater in the Qinghai Lake catchment. Most of the shallow groundwaters are suitable for drinking. More attention should be paid to the potential pollution of nitrate, chloride and sulfide in shallow groundwater in the future.     

The crystallization of magnesite from aqueous solution

It has been suggested that the highly hydrated character of the Mg²⁺ ion in aqueous solution is responsible for the often encountered difficulty of precipitating stable, anhydrous phases of magnesium carbonate and calcium-magnesium carbonate. In an effort to investigate this, a study of magnesite crystallization kinetics was undertaken, utilizing the reaction of hydromagnesite plus CO₂ to yield magnesite at 126°C. The reactions were characterized by prolonged initial quiescent periods prior to the onset of detectable crystallization. The length of the initial period was found to vary with Mg concentration, pCO₂ and ionic strength. Contrary to classical kinetics, the reaction studied was inhibited by increased Mg concentration. Ionic strength and pCO₂ acted as positive catalysts.     

Geochemical baseline of major anions and heavy metals in groundwaters and drinking waters around the urban areas of Kerman city, southeastern Iran

In order to investigate the environmental geochemistry of groundwaters in the urban areas of Kerman city, 50 samples of natural groundwaters, urban groundwaters and drinking waters were collected. High values of salinity (5.8???), electrical conductivity (10,270???S/cm), total dissolved solids (TDS) (5,140?mg/kg), fluorine (4.9?mg/kg), chlorine (3,974?mg/kg), bromine (1.6?mg/kg) and sulfate (4,306?mg/kg) in the northern part of the studied area are caused by dissolution of evaporate bed rocks and Quaternary salt plains. Low values of salinity (0.5???), electrical conductivity (973???S/cm), TDS (486?mg/kg), fluorine (0.8?mg/kg), chlorine (297?mg/kg), bromine (0.25?mg/kg) and sulfate (262?mg/kg) are only reported in the southern part of the Kerman city. High values of nitrate (NO₃ ^?) range from 134 to 725?mg/kg and nitrite (NO₂ ^?) content is variable between 0.04 to 23.45?mg/kg. These values indicate mixing of groundwaters with wastewaters. The heavy metal values in groundwaters around the Kerman city show 20.5???g/kg Cu, 5.88???g/kg Mo, 16.2???g/kg Pb, 70???g/kg Zn, 11.6???g/kg Cr, 1.99???g/kg Co, 4.13???g/kg Ni, respectively. Furthermore, the natural aquifers of Kerman city contain 24???g/kg Cu, 8.15???g/kg Mo, 18.25 Pb, ??g/kg, 193???g/kg Zn, 14.7???g/kg Cr, 3.97???g/kg Co and 7.45???g/kg Ni, respectively. The results demonstrate that the main sources of contamination are related to the natural evaporates, mixing of groundwaters with wastewaters and constructional materials in the area.     

Impact of lake‐level changes on the formation of thermogene travertine in continental rifts: Evidence from Lake Bogoria,Kenya Rift Valley

Travertine is present at 20% of the ca 60 hot springs that discharge on Loburu delta plain on the western margin of saline, alkaline Lake Bogoria in the Kenya Rift. Much of the travertine, which forms mounds, low terraces and pool‐rim dams, is sub‐fossil (relict) and undergoing erosion, but calcite‐encrusted artefacts show that carbonate is actively precipitating at several springs. Most of the springs discharge alkaline (pH: 8·3 to 8·9), Na‐HCO₃ waters containing little Ca (<2 mg l^?1) at temperatures of 94 to 97·5°C. These travertines are unusual because most probably precipitated at temperatures of >80°C. The travertines are composed mainly of dendritic and platy calcite, with minor Mg‐silicates, aragonite, fluorite and opaline silica. Calcite precipitation is attributed mainly to rapid CO₂ degassing, which led to high‐disequilibrium crystal morphologies. Stratigraphic evidence shows that the travertine formed during several stages separated by intervals of non‐deposition. Radiometric ages imply that the main phase of travertine formation occurred during the late Pleistocene (ca 32 to 35 ka). Periods of precipitation were influenced strongly by fluctuations in lake level, mostly under climate control, and by related changes in the depth of boiling. During relatively arid phases, meteoric recharge of ground water declines, the lake is low and becomes hypersaline, and the reduced hydrostatic pressure lowers the level of boiling in the plumbing system of the hot springs. Any carbonate precipitation then occurs below the land surface. During humid phases, the dilute meteoric recharge increases, enhancing geothermal circulation, but the rising lake waters, which become relatively dilute, flood most spring vents. Much of the aqueous Ca²⁺ then precipitates as lacustrine stromatolites on shallow firm substrates, including submerged older travertines. Optimal conditions for subaerial travertine precipitation at Loburu occur when the lake is at intermediate levels, and may be favoured during transitions from humid to drier conditions.     

Heterogeneous Mg isotopic composition of the early Carboniferous limestone: implications for carbonate as a seawater archive

Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from seawater. Mg isotopes are significantly (up to 5‰) fractionated during carbonate precipitation by preferential incorporation of ²⁴Mg, while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of ²⁶Mg. Thus, the marine Mg cycle could be reflected by seawater Mg isotopic composition (δ²⁶Mg_sw), which might be recorded in marine carbonate. However, carbonates are both texturally and compositionally heterogeneous, and it is unclear which carbonate component is the most reliable for reconstructing δ²⁶Mg_sw. In this study, we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous Huangjin Formation in South China. Based on petrographic studies, four carbonate components were recognized: micrite, marine cement, brachiopod shell, and mixture. The four components had distinct δ²⁶Mg: (1) micrite samples ranged from ?2.86‰ to ?2.97‰; (2) pure marine cements varied from ?3.40‰ to ?3.54‰, while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range (?3.27‰ to ?3.75‰); (3) values for the mixture component were ?3.17‰ and ?3.49‰; and (4) brachiopod shells ranged from ?2.20‰ to ?3.07‰, with the thickened hinge area enriched in ²⁴Mg. Due to having multiple carbonate sources, neither the micrite nor the mixture component could be used to reconstruct δ²⁶Mg_sw. In addition, the marine cement was homogenous in Mg isotopes, but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ²⁶Mg_sw. Furthermore, brachiopod shells had heterogeneous C and Mg isotopes, suggesting a significant vital effect during growth. Overall, the heterogeneous δ²⁶Mg of the Huangjin limestone makes it difficult to reconstruct δ²⁶Mg_sw using bulk carbonate/calcareous sediments. Finally, δ²⁶Mg_sw was only slightly affected by the faunal composition of carbonate-secreting organisms, even though biogenic carbonate accounts for more than 90% of marine carbonate production in Phanerozoic oceans and there is a wide range (0.2‰–4.8‰) of fractionation during biogenic carbonate formation.     

Influence of microbial photosynthesis on tufa stromatolite formation and ambient water chemistry, SW Japan

Photosynthetic influences on tufa stromatolite formation and ambient water chemistry were investigated at two well-studied streams depositing tufa in Southwestern Japan (Shirokawa and Shimokuraida). The tufa stromatolites in both streams are composed of fine-grained calcite crystals showing annual lamination, and colonized by a number of filamentous cyanobacteria as well as non-phototrophic bacteria. Microelectrode measurements of pH, O₂, and Ca²⁺ near the stromatolite surface (the diffusive boundary layer; DBL) revealed that the investigated tufa stromatolites are formed by photosynthesis-induced CaCO₃ precipitation (PCP): cyanobacterial photosynthesis induces calcite precipitation under light conditions, while respiration of cyanobacteria and non-phototrophic bacteria inhibits precipitation in the dark. The bulk water chemistry at the lower sites of the investigated streams showed the daytime decreases of Ca²⁺ concentration and alkalinity that was expected for significant influence of PCP, while the other expected change, increased pH, was not observed. In order to examine this discrepancy, a novel approach using semi-in situ microelectrode measurements was applied to perform precise quantitative calculations. The calculation results demonstrated that the observed Ca²⁺ concentration and alkalinity decreases were caused by PCP, and that the concomitant pH increase was expected to be under the detection level of a conventional pH meter. Although the amount of PCP is supposed to be significantly affected by light intensity, observations in Shimokuraida revealed that the amount of PCP on cloudy day nonetheless accounted for about 80% of that on sunny day. Despite the significant role of PCP for tufa stromatolite formation, PCP accounted for only about 10% of the precipitated calcite in the investigated streams, which indicates that tufa stromatolites, the characteristic deposits in the streams, are responsible for only a small portion of calcite precipitation, and the rest is considered to precipitate inorganically at biofilm-free substrates.     

Fluid history of UHP metamorphism in Dabie Shan, China: a fluid inclusion and oxygen isotope study on the coesite-bearing eclogite from Bixiling

This paper characterizes late Holocene basalts and basaltic andesites at Medicine Lake volcano that contain high pre-eruptive H₂O contents inherited from a subduction related hydrous component in the mantle. The basaltic andesite of Paint Pot Crater and the compositionally zoned basaltic to andesitic lavas of the Callahan flow erupted approximately 1000 ¹⁴C years Before Present (¹⁴C years b.p.). Petrologic, geochemical and isotopic evidence indicates that this late Holocene mafic magmatism was characterized by H₂O contents of 3 to 6 wt% H₂O and elevated abundances of large ion lithophile elements (LILE). These hydrous mafic inputs contrast with the preceding episodes of mafic magmatism (from 10,600 to ∼3000 ¹⁴C years b.p.) that was characterized by the eruption of primitive high alumina olivine tholeiite (HAOT) with low H₂O (<0.2 wt%), lower LILE abundance and different isotopic characteristics. Thus, the mantle-derived inputs into the Medicine Lake system have not always been low H₂O, primitive HAOT, but have alternated between HAOT and hydrous subduction related, calc-alkaline basalt. This influx of hydrous mafic magma coincides temporally and spatially with rhyolite eruption at Glass Mountain and Little Glass Mountain. The rhyolites contain quenched magmatic inclusions similar in character to the mafic lavas at Callahan and Paint Pot Crater. The influence of H₂O on fractional crystallization of hydrous mafic magma and melting of pre-existing granite crust beneath the volcano combined to produce the rhyolite. Fractionation under hydrous conditions at upper crustal pressures leads to the early crystallization of Fe-Mg silicates and the suppression of plagioclase as an early crystallizing phase. In addition, H₂O lowers the saturation temperature of Fe and Mg silicates, and brings the temperature of oxide crystallization closer to the liquidus. These combined effects generate SiO₂-enrichment that leads to rhyodacitic differentiated lavas. In contrast, low H₂O HAOT magmas at Medicine Lake differentiate to iron-rich basaltic liquids. When these Fe-enriched basalts mix with melted granitic crust, the result is an andesitic magma. Since mid-Holocene time, mafic volcanism has been dominated primarily by hydrous basaltic andesite and andesite at Medicine Lake Volcano. However, during the late Holocene, H₂O-poor mafic magmas continued to be erupted along with hydrous mafic magmas, although in significantly smaller volumes. Received: 4 January 1999 / Accepted: 30 August 1999     

Rapid development of negative Ce anomalies in surface waters and contrasting REE patterns in groundwaters associated with Zn–Pb massive sulphide deposits

Ground and surface waters collected from two undisturbed Zn–Pb massive sulphide deposits (the Halfmile Lake and Restigouche deposits) and active mines in the Bathurst Mining Camp (BMC), NB, Canada were analysed for the rare earth elements (REE). REE contents are highly variable in waters of the BMC, with higher contents typical of waters with higher Fe and lower pH. There are significant differences between ground- and surface waters and between groundwaters from different deposits. The REE contents of surface waters are broadly similar within and between deposit areas, although there are spatial variations reflecting differences in pH and redox conditions. Surface waters are characterised by strong negative Ce anomalies ([Ce/Ce*]_NASC as low as 0.08), produced by oxidation of Ce³⁺ to Ce⁴⁺ and preferential removal of Ce⁴⁺ from solution upon leaving the shallow groundwater environment. Groundwaters and seeps typically lack significant Ce anomalies reflecting generally more reducing conditions in the subsurface environment and indicating that Ce oxidation is a rapid process in the surface waters. Deeper groundwaters at the Halfmile Lake deposit are characterised by REE patterns that are similar to the host lithologies, whereas most groundwaters at the Restigouche deposit have LREE-depleted patterns compared to NASC. Halfmile Lake deposit groundwaters have generally lower pH values, whereas Restigouche deposit groundwaters show greater heavy REE-complexation by carbonate ions. Shallow waters at the Halfmile Lake and Stratmat Main Zone deposits have unusual patterns which reflect either the adsorption of light REE onto colloids and fracture-zone minerals and/or precipitation of REE–phosphate minerals. Middle REE-enrichment is typical for ground- and surface waters and is highest for neutral pH waters. The labile portion of stream sediments are generally more middle REE-enriched than total sediment and surface waters indicating that the REE are removed from solution by adsorption to Fe- and Mn-oxyhydroxides in the order middle REE≥light REE>heavy REE.     

Geochemical evolution of groundwater in carbonate aquifers in Taiyuan, northern China

Thirty-nine samples of both cold and thermal karst groundwater from Taiyuan, northern China were collected and analyzed with the aim of developing a better understanding of the geochemical processes that control the groundwater quality evolution in the region’s carbonate aquifers. The region’s karst groundwater system was divided into three geologically distinct sub-systems, namely, the Xishan Mountain karst groundwater subsystem (XMK), the Dongshan Mountain karst groundwater subsystem (DMK) and the Beishan Mountain karst groundwater subsystem (BMK). Hydrochemical properties of the karst groundwaters evolve from the recharge zones towards the cold water discharge zones and further towards the thermal water discharge zones. In the XMK and the DMK, the hydrochemical type of the groundwater evolves from HCO₃-Ca·Mg in the recharge - flow-through zone, to HCO₃·SO₄-Ca·Mg/SO₄·HCO₃-Ca·Mg in the cold water discharge zone, and further to SO₄-Ca·Mg in the thermal water discharge zone. By contrast, the water type changes from HCO₃-Ca·Mg to HCO₃·SO₄-Ca·Mg in the BMK, with almost invariable TDS and temperatures all along from the recharge to the discharge zone. The concentrations of Sr, Si, Fe, F⁻ and of some trace elements (Al, B, Li, Mn, Mo, Co, Ni) increase as groundwater temperature increases. Different hydrogeochemical processes occur in the three karst groundwater sub-systems. In the XMK and the DMK, the geochemical evolution of the groundwater is jointly controlled by carbonate dissolution/precipitation, gypsum dissolution and dedolomitization, while only calcite and dolomite dissolution/precipitation occurs in the BMK without dedolomitization. The hydrogeochemical data of the karst groundwaters were used to construct individual geochemical reaction models for each of the three different karst groundwater sub-systems. The modeling results confirm that dedolomization is the major process controlling hydrochemical changes in the XMK and the DMK. In the thermal groundwaters, the dissolution rates of fluorite, siderite and strontianite were found to exceed those of the cold karst groundwater systems, which can explain the higher concentrations of F⁻, Fe and Sr²⁺ that are found in these waters.     

Microbe–mineral interactions: early carbonate precipitation in a hypersaline lake (Eleuthera Island, Bahamas)

Microbialites (benthic microbial carbonate deposits) were discovered in a hypersaline alkaline lake on Eleuthera Island (Bahamas). From the edge towards the centre of the lake, four main zones of precipitation could be distinguished: (1) millimetre‐sized clumps of Mg‐calcite on a thin microbial mat; (2) thicker and continuous carbonate crusts with columnar morphologies; (3) isolated patches of carbonate crust separated by a dark non‐calcified gelatinous mat; and (4) a dark microbial mat without precipitation. In thin section, the precipitate displayed a micropeloidal structure characterized by micritic micropeloids (strong autofluorescence) surrounded by microspar and spar cement (no fluorescence). Observations using scanning electron microscopy (SEM) equipped with a cryotransfer system indicate that micrite nucleation is initiated within a polymer biofilm that embeds microbial communities. These extracellular polymeric substances (EPS) are progressively replaced with high‐Mg calcite. Discontinuous EPS calcification generates a micropeloidal structure of the micrite, possibly resulting from the presence of clusters of coccoid or remnants of filamentous bacteria. At high magnification, the microstructure of the initial precipitate consists of 200–500 nm spheres. No precipitation is observed in or on the sheaths of cyanobacteria, and only a negligible amount of precipitation is directly associated with the well‐organized and active filamentous cyanobacteria (in deeper layers of the mat), indicating that carbonate precipitation is not associated with CO₂ uptake during photosynthesis. Instead, the precipitation occurs at the uppermost layer of the mat, which is composed of EPS, empty filamentous bacteria and coccoids (Gloeocapsa spp.). Two‐dimensional mapping of sulphate reduction shows high activity in close association with the carbonate precipitate at the top of the microbial mat. In combination, these findings suggest that net precipitation of calcium carbonate results from a temporal and spatial decoupling of the various microbial metabolic processes responsible for CaCO₃ precipitation and dissolution. Theoretically, partial degradation of EPS by aerobic heterotrophs or UV fuels sulphate‐reducing activity, which increases alkalinity in microdomains, inducing CaCO₃ precipitation. This degradation could also be responsible for EPS decarboxylation, which eliminates Ca²⁺‐binding capacity of the EPS and releases Ca²⁺ ions that were originally bound by carboxyl groups. At the end of these processes, the EPS biofilm is calcified and exhibits a micritic micropeloidal structure. The EPS‐free precipitate subsequently serves as a substrate for physico‐chemical precipitation of spar cement from the alkaline water of the lake. The micropeloidal structure has an intimate mixture of micrite and microspar comparable to microstructures of some fossil microbialites.     

Geochemistry and anthropogenic inputs of metals in a tropical lake in Venezuela

Lake Valencia is a tropical lowland lake in north-central Venezuela. Lake bottom sediments were collected from 25 locations in April, 1988. At 2 locations water pH, conductivity, dissolved O₂ and temperature were measured at successive depths. After drying, 5 sediment samples were sieved into 5 mechanical fractions. Each was extracted with 1 M HNO₃ and analysed for AI, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb and Zn. The <63 μm fraction of all samples was similarly analysed. Water temperatures declined with depth (1°C/25 m) from approximately 26°C. Conductivity varied little with depth but dissolved O₂ contents indicated anoxic conditions < 25 m. Water pH (8.8–9.4) was consistent with high dissolved carbonates. There was little consistent relationship between grain size and sediment metal contents. Approximate baseline metal contents were calculated from 21 of 25 samples. The average composition of the sediments corresponded to an ideal mixture of shales/carbonate rocks as 0.5–0.7/0.5-0.3. Five samples from alluvial fans near the mouths of rivers traversing urban-industrial zones had compositions different from the other sediments. Generally, Ph, Zn, Ni, Cd and Cu were anthropogenically enriched by factors of 2–16. The major sources of pollutants were identified as domestic and industrial activities affecting the rivers that traverse the lakeside cities of Maracay and Valencia. Sodium, Mg, Ca, Mn and CO₃⁻ showed natural enrichment arising from carbonate precipitation following a physical mixing of 2 sedimentary components (biogenic carbonate and terrigenous material). Low geochemical mobility of metallic elements in neutral-basic and reducing waters, a processes of bury and mixture of sediments and precipitation of carbonate result in only 10% of the lake area being affected by contamination. Isoline plots of elements in the bottom sediments supported a hypothesis that material mixing, physical transport and carbonate precipitation are the main controls of spatial distribution patterns.