Arsenic mobility in groundwater/surface water systems in carbonate-rich Pleistocene glacial drift aquifers (Michigan)

Within the Lower Peninsula of Michigan, groundwaters from the Marshall Formation (Mississippian) contain As derived from As-rich pyrites, often exceeding the World Heath Organization drinking water limit of 10 μg/L. Many Michigan watersheds, established on top of Pleistocene glacial drift derived from erosion of the underlying Marshall Formation, also have waters with elevated As. The Huron River watershed in southeastern Lower Michigan is a well characterized hydrogeochemical system of glacial drift deposits, proximate to the Marshall Fm. subcrop, which hosts carbonate-rich groundwaters, streams, and wetlands (fens), and well-developed soil profiles. Aqueous and solid phase geochemistry was determined for soils, soil waters, surface waters (streams and fens) and groundwaters from glacial drift aquifers to better understand the hydrogeologic and chemical controls on As mobility. Soil profiles established on the glacial drift exhibit enrichment in both Fe and As in the oxyhydroxide-rich zone of accumulation. The amounts of Fe and As present as oxyhydroxides are comparable to those reported from bulk Marshall Fm. core samples by previous workers. However, the As host in core samples is largely unaltered pyrite and arsenopyrite. This suggests that the transformation of Fe sulfides to Fe oxyhydroxides largely retains As and Fe at the oxidative weathering site. Groundwaters have the highest As values of all the waters sampled, and many were at or above the World Health limit. Most groundwaters are anaerobic, within the zones of Fe³⁺ and As(V) reduction. Although reduction of Fe(III) oxyhydroxides is the probable source of As, there is no correlation between As and Fe concentrations. The As/Fe mole ratios in drift groundwaters are about an order of magnitude greater than those in soil profiles, suggesting that As is more mobile than Fe. This is consistent with the dominance of As(III) in these groundwaters and with the partitioning of Fe²⁺ into carbonate cements. Soil waters have very low As and Fe contents, consistent with the stability of oxyhydroxides under oxidizing vadose conditions. When CO₂ charged groundwaters discharge in streams and fens, dissolved As is effectively removed by adsorption onto Fe-oxides or carbonate marls. Although Fe does not display conservative behavior with As in groundwaters, a strong positive correlation exists between As and Sr concentrations. As water–rock interactions proceed, the As/Fe and Sr/Ca ratios would be expected to increase because both As and Sr behave as incompatible elements. Comparisons with groundwater chemistries from other drift-hosted aquifers proximate to the Marshall sandstone are consistent with these relations. Thus, the Sr content of carbonate-rich groundwaters may provide useful constraints on the occurrence, origin and evolution of dissolved As in such systems.     

Silicate and carbonate weathering in the drainage basins of the Ganga-Ghaghara-Indus head waters: Contributions to major ion and Sr isotope geochemistry

The role of silicate and carbonate weathering in contributing to the major cation and Sr isotope geochemistry of the headwaters of the Ganga-Ghaghara-Indus system is investigated from the available data. The contributions from silicate weathering are determined from the composition of granites/ gneisses, soil profiles developed from them and from the chemistry of rivers flowing predominantly through silicate terrains. The chemistry of Precambrian carbonate outcrops of the Lesser Himalaya provided the data base to assess the supply from carbonate weathering. Mass balance calculations indicate that on an average ∼ 77% (Na + K) and ∼ 17% (Ca + Mg) in these rivers is of silicate origin. The silicate Sr component in these waters average ∼40% and in most cases it exceeds the carbonate Sr. The observations that (i) the⁸⁷Sr/⁸⁶Sr and Sr/Ca in the granites/gneisses bracket the values measured in the head waters; (ii) there is a strong positive correlation between⁸⁷Sr/⁸⁶Sr of the rivers and the silicate derived cations in them, suggest that silicate weathering is a major source for the highly radiogenic Sr isotope composition of these source waters. The generally low⁸⁷Sr/⁸⁶Sr (< 0.720) and Sr/Ca (∼ 0.2 nM/ μM) in the Precambrian carbonate outcrops rules them out as a major source of Sr and⁸⁷Sr/⁸⁶Sr in the headwaters on a basin-wide scale, however, the high⁸⁷Sr/⁸⁶Sr (∼ 0.85) in a few of these carbonates suggests that they can be important for particular streams. The analysis of⁸⁷Sr/⁸⁶Sr and Ca/Sr data of the source waters show that they diverge from a low⁸⁷Sr/⁸⁶Sr and low Ca/Sr end member. The high Ca/Sr of the Precambrian carbonates precludes them from being this end member, other possible candidates being Tethyan carbonates and Sr rich evaporite phases such as gypsum and celestite. The results of this study should find application in estimating the present-day silicate and carbonate weathering rates in the Himalaya and associated CO₂ consumption rates and their global significance.     

Determining CO2 consumption from elemental change in soil profiles developed on carbonate and silicate rocks

Acta Geochimica - To further understand the roles of carbonate and silicate rocks in regulating the atmosphere/soil CO2 level, the flux of CO2 consumed by the chemical weathering of silicate and...     

Growth mechanisms and geochemistry of carbonate concretions from the Cambrian Wheeler Formation (Utah,USA)

Carbonate concretions provide unique records of ancient biogeochemical processes in marine sediments. Typically, they form in organic‐rich mudstones, where a significant fraction of the bicarbonate required for carbonate precipitation is supplied from the decomposition of organic matter in the sediments. As a result, carbonates that comprise concretions are usually characterized by broad ranges in δ¹³C and include values that are significantly depleted relative to seawater. This article reports results from a physical, petrographic and geochemical analysis of 238 concretions from the Wheeler Formation (Cambrian Series 3), Utah, USA, which are unusual in several respects. Most prominently, they formed in organic‐poor mudstones (total organic carbon = 0·1 to 0·5%) and are characterized by a narrow range of δ¹³C that onlaps the range of contemporaneous seawater values. Subtle centre to edge trends in δ¹³C demonstrate that concretion precipitation was initiated by local chemical gradients set up by microbial activity in the sediments, but was sustained during growth by a large pool of inorganic bicarbonate probably derived from alkaline bottom waters. The large inorganic pool appears to have been important in facilitating rapid precipitation of the concretion matrix, which occurred via both displacive and replacive carbonate precipitation during early diagenesis. Stable isotope data from cogenetic pyrite (δ³⁴S) and silica (δ¹⁸O) phases provide insight into the evolution of biogeochemical processes during concretion growth, and suggest that concretions were formed almost entirely during sulphate reduction, with only minor modification thereafter. Concretions of the Wheeler Formation appear to represent an end‐member system of concretion formation in which rapid growth was promoted by ions supplied from sea‐water. As such, they offer insight into the spectrum of processes that may influence the growth of carbonate concretions in marine sediments.     

Early middle Pleistocene glacial sediments (780000-620000 BP) near Kansas City, northeastern Kansas and northwestern Missouri, USA

Two lithologically distinct tills are present near the pre-Illinoian glacial boundary in northeastern Kansas and northwestern Missouri. The tills are probably early middle Pleistocene (780 000-620 000 BP) based on normal polarity and their stratigraphic relationship to dated terraces. The upper till is sandier than the lower till and contains more expandable clay minerals and less illite than the lower till. Glaciofluvial and supraglacial sediments are preserved between the tills, yet palaeosols, or other evidence of an interglacial, are not present, suggesting that the tills were deposited during a single glaciation. Southeasterly and southwesterly trending striae and till fabric suggest that the glacial succession was deposited by at least two fluctuations (phases) of a lobe, which probably advanced down the axis of the present Missouri River lowland. These tills probably correlate to early middle Pleistocene tills in southwestern Iowa and eastern Nebraska, although it is possible that the lower till may correlate to even older tills in these areas.     

Determining mineral weathering rates based on solid and solute weathering gradients and velocities: application to biotite weathering in saprolites

Chemical weathering gradients are defined by the changes in the measured elemental concentrations in solids and pore waters with depth in soils and regoliths. An increase in the mineral weathering rate increases the change in these concentrations with depth while increases in the weathering velocity decrease the change. The solid-state weathering velocity is the rate at which the weathering front propagates through the regolith and the solute weathering velocity is equivalent to the rate of pore water infiltration. These relationships provide a unifying approach to calculating both solid and solute weathering rates from the respective ratios of the weathering velocities and gradients. Contemporary weathering rates based on solute residence times can be directly compared to long-term past weathering based on changes in regolith composition. Both rates incorporate identical parameters describing mineral abundance, stoichiometry, and surface area.

Weathering gradients were used to calculate biotite weathering rates in saprolitic regoliths in the Piedmont of Northern Georgia, USA and in Luquillo Mountains of Puerto Rico. Solid-state weathering gradients for Mg and K at Panola produced reaction rates of 3 to 6×10⁻¹⁷ mol m⁻² s⁻¹ for biotite. Faster weathering rates of 1.8 to 3.6×10⁻¹⁶ mol m⁻² s⁻¹ are calculated based on Mg and K pore water gradients in the Rio Icacos regolith. The relative rates are in agreement with a warmer and wetter tropical climate in Puerto Rico. Both natural rates are three to six orders of magnitude slower than reported experimental rates of biotite weathering.     

Regional variations in water quality and relationships to soil and bedrock weathering in the southern Sacramento Valley, California, USA

Regional patterns in ground- and surface-water chemistry of the southern Sacramento Valley in California were evaluated using publicly available geochemical data from the US Geological Survey’s National Water Information System (NWIS). Within the boundaries of the study area, more than 2300 ground-water analyses and more than 20,000 surface-water analyses were available. Ground-waters from the west side of the Sacramento Valley contain greater concentrations of Na, Ca, Mg, B, Cl and SO₄, while the east-side ground-waters contain greater concentrations of silica and K. These differences result from variations in surface-water chemistry as well as from chemical reactions between water and aquifer materials. Sediments that fill the Sacramento Valley were derived from highlands to the west (the Coast Ranges) and east (the Sierra Nevada Mountains), the former having an oceanic provenance and the latter continental. These geologic differences are at least in part responsible for the observed patterns in ground-water chemistry. Thermal springs that are common along the west side of the Sacramento Valley appear to have an effect on surface-water chemistry, which in turn may affect the ground-water chemistry.     

Mixing of hydrothermal water and groundwater near hot springs, Yellowstone National Park (USA): hydrology and geochemistry

Studies of hot springs have focused mainly on the properties of fluids and solids. Fewer studies focus on the relationship between the hot springs and groundwater/surface-water environments. The differences in temperature and dissolved solids between hot-spring water and typical surface water and groundwater allow interactions to be traced. Electromagnetic terrain (EMT) conductivity is a nonintrusive technique capable of mapping mixing zones between distinct subsurface waters. These interactions include zones of groundwater/surface-water exchange and groundwater mixing. Herein, hydrogeological techniques are compared with EMT conductivity to trace hot-spring discharge interactions with shallow groundwater and surface water. Potentiometric-surface and water-quality data determined the hydrogeochemistry of two thermally influenced areas in Yellowstone National Park, Wyoming (USA). Data from the sites revealed EMT conductivity contrasts that reflected the infiltration of conductive hot-spring discharge to local groundwater systems. The anomalies reflect higher temperatures and conductivity for Na⁺–Cl^?-rich hydrothermal fluids compared to the receiving groundwater. EMT conductivity results suggested hot springs are fed by conduits largely isolated from shallow groundwater; mixing of waters occurs after hot-spring discharge infiltrates groundwater from the surface and, generally, not by leakage in the subsurface. A model was proposed to explain the growth of sinter mounds.     

Seasonal variations in pore water and sediment geochemistry of littoral lake sediments (Asylum Lake, MI, USA)

Background  

Seasonal changes in pore water and sediment redox geochemistry have been observed in many near-surface sediments. Such changes have the potential to strongly influence trace metal distribution and thus create seasonal fluctuations in metal mobility and bioavailability.     

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California I: Interpreting rates and controls based on soil concentration-depth profiles

The spatial and temporal changes in element and mineral concentrations in regolith profiles in a chronosequence developed on marine terraces along coastal California are interpreted in terms of chemical weathering rates and processes. In regoliths up to 15 m deep and 226 kyrs old, quartz-normalized mass transfer coefficients indicate non-stoichiometric preferential release of Sr > Ca > Na from plagioclase along with lesser amounts of K, Rb and Ba derived from K-feldspar. Smectite weathering results in the loss of Mg and concurrent incorporation of Al and Fe into secondary kaolinite and Fe-oxides in shallow argillic horizons. Elemental losses from weathering of the Santa Cruz terraces fall within the range of those for other marine terraces along the Pacific Coast of North America.Residual amounts of plagioclase and K-feldspar decrease with terrace depth and increasing age. The gradient of the weathering profile b_s is defined by the ratio of the weathering rate, R to the velocity at which the profile penetrates into the protolith. A spreadsheet calculator further refines profile geometries, demonstrating that the non-linear regions at low residual feldspar concentrations at shallow depth are dominated by exponential changes in mineral surface-to-volume ratios and at high residual feldspar concentrations, at greater depth, by the approach to thermodynamic saturation. These parameters are of secondary importance to the fluid flux q_h, which in thermodynamically saturated pore water, controls the weathering velocity and mineral losses from the profiles. Long-term fluid fluxes required to reproduce the feldspar weathering profiles are in agreement with contemporary values based on solute Cl balances (q_h = 0.025-0.17 m yr⁻¹).During saturation-controlled and solute-limited weathering, the greater loss of plagioclase relative to K-feldspar is dependent on the large difference in their respective solubilities instead of the small difference between their respective reaction kinetics. The steady-state weathering rate under such conditions is defined as

     

Constraints on water chemistry by chemical weathering in the Lake Qinghai catchment, northeastern Tibetan Plateau (China): clues from Sr and its isotopic geochemistry

Lake water, river water, and groundwater from the Lake Qinghai catchment in the northeastern Tibetan Plateau, China have been analyzed and the results demonstrate that the chemical components and ⁸⁷Sr/⁸⁶Sr ratios of the waters are strictly constrained by the age and rock types of the tributaries, especially for groundwater. Dissolved ions in the Lake Qinghai catchment are derived from carbonate weathering and part from silicate sources. The chemistry of Buha River water, the largest tributary within the catchment, underlain by the late Paleozoic marine limestone and sandstones, constrains carbonate-dominated compositions of the lake water, being buffered by the waters from the other tributaries and probably by groundwater. The variation of ⁸⁷Sr/⁸⁶Sr ratios with cation concentrations places constraint on the Sr-isotopic compositions of the main subcatchments surrounding Lake Qinghai. The relative significance of river-water sources from different tributaries (possibly groundwater as well) in controlling the Sr distribution in Lake Qinghai provides the potential to link the influence of hydrological processes to past biological and physical parameters in the lake. The potential role of groundwater input in the water budget and chemistry of the lake emphasizes the need to further understand hydrogeological processes within the Lake Qinghai system.     

Tracing and dating recent chemical transfers in weathering profiles by trace-element geochemistry and U---U---Th disequilibria: the example of the Kaya lateritic toposequence (Burkina-Faso)

The paper presents a synthesis of the approach recently developed to constrain the nature and the age of recent element mobility in weathering profiles. The approach relies on a comparison of variations of trace elements and U-series disequilibria in weathering profiles. It is exemplified in the case of old lateritic profiles from the Kaya toposequence, Burkina Faso. Trace elements and ²³⁸U---²³⁴U---²³⁰Th disequilibria have been analysed in whole rock samples from two pits located in very contrasted topographical positions. Trace element data show that the whole toposequence is marked by an intense chemical remobilization, including uranium, from the cap to the lower part of the profiles. ²³⁸U---²³⁴U---²³⁰Th disequilibrium data outline that all the levels of the profiles are affected by recent U---Th fractionations, and that each level of the toposequence is marked by U gains and losses. The chronological approach developed in this paper leads to an age of about 400 kyr for the dismantling of the iron cap, and ages ranging from 0 to 400 kyr for U accumulation in the pink clay horizon of the profiles. The depth repartition of U accumulation in the profile implies that the remobilisation processes in this toposequence varied through time, on time constants similar to those of climatic variations. To cite this article: F. Chabaux et al., C. R. Geoscience 335 (2003).     

The fluvial geochemistry, contributions of silicate, carbonate and saline-alkaline components to chemical weathering flux and controlling parameters: Narmada River (Deccan Traps), India

The Narmada River in India is the largest west-flowing river into the Arabian Sea, draining through the Deccan Traps, one of the largest flood basalt provinces in the world. The fluvial geochemical characteristics and chemical weathering rates (CWR) for the mainstream and its major tributaries were determined using a composite dataset, which includes four phases of seasonal field (spot) samples (during 2003 and 2004) and a decade-long (1990-2000) fortnight time series (multiannual) data. Here, we demonstrate the influence of minor lithologies (carbonates and saline-alkaline soils) on basaltic signature, as reflected in sudden increases of Ca²⁺-Mg²⁺ and Na⁺ contents at many locations along the mainstream and in tributaries. Both spot and multiannual data corrected for non-geological contributions were used to calculate the CWR. The CWR for spot samples (CWR_spot) vary between 25 and 63 ton km⁻² year⁻¹, showing a reasonable correspondence with the CWR estimated for multiannual data (CWR_multi) at most study locations. The weathering rates of silicate (SilWR), carbonate (CarbWR) and evaporite (Sal-AlkWR) have contributed ∼38-58, 28-45 and 8-23%, respectively to the CWR_spot at different locations. The estimated SilWR (11-36 ton km⁻² year⁻¹) for the Narmada basin indicates that the previous studies on the North Deccan Rivers (Narmada-Tapti-Godavari) overestimated the silicate weathering rates and associated CO₂ consumption rates. The average annual CO₂ drawdown via silicate weathering calculated for the Narmada basin is ∼0.032 × 10¹² moles year⁻¹, suggesting that chemical weathering of the entire Deccan Trap basalts consumes approximately 2% (∼0.24 × 10¹² moles) of the annual global CO₂ drawdown. The present study also evaluates the influence of meteorological parameters (runoff and temperature) and physical weathering rates (PWR) in controlling the CWR at annual scale across the basin. The CWR and the SilWR show significant correlation with runoff and PWR. On the basis of observed wide temporal variations in the CWR and their close association with runoff, temperature and physical erosion, we propose that the CWR in the Narmada basin strongly depend on meteorological variability. At most locations, the total denudation rates (TDR) are dominated by physical erosion, whereas chemical weathering constitutes only a small part (<10%). Thus, the CWR to PWR ratio for the Narmada basin can be compared with high relief small river watersheds of Taiwan and New Zealand (1-5%) and large Himalayan Rivers such as the Brahmaputra and the Ganges (8-9%).     

Pleistocene basaltic volcanism of Kunashir Island (Kuril island arc): Mineralogy,geochemistry, and results of computer simulation

New mineralogical, geochemical, and isotope data in combination with numerical modeling were used to reconstruct the physicochemical and geodynamic conditions of the formation of Pleistocene basalts of Kunashir Island. Although they are petrologically close to the Holocene basalts of Tyatya Volcano, their eruption occurred during a brief period of island arc extension, which was accompanied by the high degree melting of mantle wedge asthenosphere. Numerous geological, petrological, and paleogeographical data testify that Pleistocene is an important stage in the geodynamic reorganization of the Kuril island arc. This stage was responsible for uplifting of the southern islands above sea level accompanied by catastrophic endogenous events, deformation, topographic reorganization of the large area of the Sea of Japan and adjacent land, and final folding stage in the West Sakhalin Mountains.     

河北承德偏硅酸矿泉水成因模式:岩石风化与水岩作用证据

【研究目的】承德地处京津冀水源涵养功能区,矿泉水资源丰富,研究其赋存分布与形成机制对矿泉水可持续利用与水源涵养优化具有重要意义。【研究方法】采用岩石地球化学和水化学分析、化学风化指数、矿物表面微观形态分析,同位素示踪等方法系统梳理了研究区地下水偏硅酸空间分异的影响因素,从岩石风化与水化学耦合角度探讨了偏硅酸矿泉水的成藏机制。【研究结果】结果表明：研究区常温水体偏硅酸含量达30 mg/L以上样品占比达5.16%,地热水偏硅酸平均含量达61.76 mg/L。偏硅酸矿泉水成藏受岩石风化和地质构造控制,风化酸性介质影响,水化学形成作用制约。风化敏感程度愈高,易风化矿物含量愈高的含水介质赋存地下水偏硅酸含量愈高。研究区硅酸盐岩总体处于初等化学风化——长石类矿物和辉石等镁铁质矿物风化形成高岭石、蒙脱石和伊利石阶段。构造深部幔源CO₂、工矿活动和人类生产生活输入的外源硫酸和硝酸共同参与岩石风化脱硅过程,偏硅酸矿泉水、地热水温泉出露处多为构造复合部位或主干断裂与次级断裂的交汇部位。【结论】承德市偏硅酸矿泉水成因模式可概化为构造断裂深循环淋溶型、风化裂隙浅循环淋溶型和层间孔隙裂隙-补给富集埋藏型3类。植被覆盖较好的玄武岩、火山碎屑岩、陆源碎屑岩流域山前宽缓沟谷与导水断裂交汇带,侵入岩导水导热断裂带、侵入岩与围岩接触带,花岗岩、片麻岩和陆源碎屑岩与碳酸盐岩接触带为偏硅酸矿泉水开采潜力区。创新点：（1）从岩石风化与水岩作用水化学耦合角度探讨了偏硅酸矿泉水的成藏机制;（2）系统总结了承德市偏硅酸矿泉水空间分布的影响因素与成因模式。     

Primary curvature in the Mid-Continent Rift: Paleomagnetism of the Portage Lake Volcanics (northern Michigan, USA)

Rocks of the North American Mid-Continent Rift (MCR) in the Keweenaw Peninsula of northern Michigan display a change in structural trend from east to west, varying in strike from 100° in the east to 35° farther west, before returning to a more east–west trend of 80° near Wisconsin. In general, curvature can be described either as of primary origin, meaning that the arc developed in its present curved state, or as of secondary origin, when the arc formed from an initially straighter geometry. A powerful tool in evaluating the origin and degree of curvature in any deformed belt is paleomagnetism, where coincident change in declination and strike is evidence for secondary curvature. Several paleomagnetic studies have been completed on rift-related sedimentary rocks, as well as lava flows, from the MCR in the Lake Superior region. Paleomagnetic directions for the sedimentary rocks vary much more in declination than in inclination, possibly reflecting a vertical axis rotation. If secondary rotation has affected the sedimentary rocks, then underlying volcanic rocks should also demonstrate a similar rotation.Thirty-one sites were collected from the Portage Lake Volcanics in the most highly curved part of the Keweenaw Peninsula in the Upper Peninsula of Michigan. Sites were chosen to maximize the variation in structural trend. Thermal demagnetization results showed two components in samples from most sites, a lower temperature A component (< 580 °C) as well as a higher temperature B component (> 580 °C). Both components were tested for primary remanence using a conglomerate test. The A component, carried by magnetite, passes the conglomerate test at a 95% confidence level, and is therefore considered a primary remanence. The B component, carried by hematite, fails at the 95% level and is considered a secondary magnetization. Most importantly, declination of the primary (A) magnetization between sites shows no correlation with strike, demonstrating that vertical axis rotations cannot explain the curvature of the Mid-Continent Rift. We conclude that curvature in the Lake Superior Region is a primary feature, likely reflecting a pre-existing zone of weakness that was exploited during rifting.     

Late quaternary glacial stades in the Cordillera Central,Colombia, based on glacial geomorphology,tephra–soil stratigraphy,palynology, and radiocarbon dating

Using data from glacial geomorphology, tephra–soil stratigraphy and mineralogy, palynology, and radiocarbon dating, a sequence of glacial and bioclimatic stades and interstades has been identified for the last ca. 50000 yr in the Ruiz-Tolima massif, Cordillera Central, Colombia. Six Pleistocene cold stades separated by warmer interstades occurred: before 48000, between 48000 and 33000, between 28000 and 21000, from ≥16000 to ca. 14000, ca. 13000–12400, and ca. 11000–10000 yr BP. Although these radiocarbon ages are minimum-limiting ages obtained from tephra layers on top of tills, the tills are not significantly older because most are bracketed by dated tephra sets in measured stratigraphic sections. Two minor moraine stages likely reflect glacier standstill during cold intervals ca. 7400 yr BP and slightly earlier. Finally, glaciers readvanced between the seventeenth and nineteenth centuries. In contrast to the ice-clad volcanoes of the massif, ca. 34 km² in area above an altitude of ca. 4800 m, the ice cover expanded to 1200 km² during the Last Glacial Maximum (LGM) and was still 800 km² during Late-glacial time (LGT). Glacier reconstructions based on the moraines suggest depression of the equilibrium line altitude (ELA) by ca. 1100 m during the LGM and 500–600 m during LGT relative to the modern ELA, which lies at ca. 5100 m in the Cordillera Central. Glaciers in this region apparently reached their greatest extent when the climate was cold and wet, e.g. during stades corresponding to Oxygen Isotope Stage 3; glaciers were still expanding during the LGM ca. 28000–21000 yr BP, but they shrank considerably after 21000 yr BP because of greatly reduced precipitation. © 1997 John Wiley & Sons, Ltd.     

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.     

Mobilization and redistribution of major and trace elements in two weathering profiles developed on serpentinites in the Lomié ultramafic complex, South-East Cameroon

The behaviour of major and trace elements have been studied along two serpentinite weathering profiles located in the Kongo-Nkamouna and Mang North sites of the Lomié ultramafic complex.The serpentinites are characterized by high SiO₂ and MgO contents, very low trace, rare earth and platinum-group element contents. Lanthanide and PGE contents are higher in the Nkamouna sample than in Mang North. Normalized REE patterns according to the CI chondrites reveal that: (i) all REE are below chondrites abundances in the Mang North sample; (ii) the (La/Yb)_N ratio value is higher in the Nkamouna sample (23.72) than in the Mang one (1.78), this confirms the slightly more weathered nature of the Nkamouna sample. Normalized PGE patterns according to the same CI chondrites reveal a negative Pt anomaly in the Mang sample. The Nkamouna sample is characterized by a flat normalized PGE pattern.All element contents increase highly from the parent rock to the coarse saprolite.In the weathering profiles, Fe₂O₃ contents decrease from the bottom to the top contrarily to Al₂O₃, SiO₂ and TiO₂. The contents of alkali and alkaline oxides are under detection limit.Concerning trace elements, Cr, Ni, Co, Cu, Zn and Sc decrease considerably from the bottom to the top while Zr, Th, U, Be, Sb, Sn, W, Ta, Sr, Rb, Hf, Y, Li, Ga, Nb and Pb increase towards the clayey surface soil. Chromium, Ni and Co contents are high in the weathered materials in particular in the saprolite zone and in the nodules.REE contents are high in the weathered materials, particularly in Nkamouna. Their concentrations decrease along both profiles. Light REE are more abundant than heavy REE. Normalized REE patterns according to the parent rock reveal positive Ce anomalies in all the weathered materials and negative Eu anomalies only at the bottom of the coarse saprolite (Nkamouna site). Positive Ce anomalies are higher in the nodular horizon of both profiles. An additional calculation method of lanthanide anomalies, using NASC data, confirms positive Ce anomalies ([Ce/Ce^*]_NASC = 1.15 to 60.68) in several weathered materials except in nodules ([Ce/Ce^*]_NASC = 0.76) of the upper nodular horizon (Nkamouna profile). The (La/Yb)_N ratios values are lower in the Nkamouna profile than in Mang site.PGE are more abundant in the weathered materials than in the parent rock. The highest contents are obtained in the coarse saprolite and in the nodules. The elements with high contents along both profiles are Pt (63–70 ppb), Ru (49–52 ppb) and Ir (41 ppb). Normalized PGE patterns show positive Pt anomalies and negative Ru anomalies.The mass balance evaluation, using thorium as immobile element, reveals that:

– major elements have been depleted along the weathering profile, except for Fe, Mn and Ti that have been enriched even only in the coarse saprolite;

– all the trace elements have been depleted along both profiles, except for Cr, Co, Zn, Sc, Cu, Ba, Y, Ga, U and Nb that have been enriched in the coarse saprolite;

– rare earth elements have been abundantly accumulated in the coarse saprolite, before their depletion towards the top of the profiles;

– platinum-group elements have been abundantly accumulated in the coarse saprolite but have been depleted towards the clayey surface soil.

Moreover, from a pedogenetical point of view, this study shows that the weathering profiles are autochtonous, except in the upper part of the soils where some allochtonous materials are revealed by the presence of zircon grains.