贵州中三叠统上部垄头组的沉积性质——再论其钙结壳的成因

钙结壳是土壤层之下的岩石在出露地表渗流带环境内受大气雨水的溶解,并通过上覆土壤层的淋滤而成的产物。由于雨水的不断的溶解,使原始的岩石或沉积物发生破裂,从而形成各种大小的砾块或砾石。随着雨水不断的溶解,雨水逐渐增加 CaCO_3的含量。这些富含碳酸钙的雨水,当它流到位于潜水面之上的下渗流带时,就在土壤层之下、原来岩石之上沉积了特殊的、层纹状方解石胶结物。它们往往覆盖岩石表面或沿着砾石的外缘、呈包覆状沉积,从而形成典型的层纹状钙结壳。渗滤豆粒的外皮也属于层纹状钙结壳的性质,这些外皮有向下方加厚的趋势,这表明渗流带的含碳酸钙的雨水,受重力作用影响下,具有往下悬垂现象,类似于洞穴内的钟乳石。豆粒之间的相互衔接呈多边形构造,也表明它是受重力作用而形成的构造。     

The Great Barrier Reef: a 700 000 year diagenetic history

A deep borehole through Ribbon Reef 5 in the Great Barrier Reef off north‐eastern Australia has identified a variety of cements, including epitaxial, radial prismatic and spherular aragonite, together with blocky, prismatic and fibrous calcite. These cements are discontinuously arranged within the sequence that consists predominantly of grainstones but locally includes clotted muddy and filamentous textures that may be of microbial origin. Calcite cements vary in morphology with groups of crystals that include acute scalenohedral, rhombohedral and flattened concordant terminations; these show varying densities of inclusions that locally define growth zones and in some terminations divide in the manner of ‘split crystals’ to form fibrous fringes. Morphological changes in calcite are inferred to reflect changes in water chemistry and crystal growth rates at the time of growth, allied to their relationship to the palaeo‐water table, and linked in turn to changes in sea‐level. Neomorphism and dissolution are widespread and variations in the severity of both imply response to the degree of undersaturation of pore waters that at times were probably balanced within very narrow limits. A total of 10 depositional units are identified. Those units at the base of the borehole reflect deposition and diagenesis within a marine environment. The influence of meteoric waters, indicated by stable isotopes, is first apparent at the top of Unit 1 and in Unit 2 (184 to 155 m below sea floor). Petrographic evidence of vadose conditions appears at the tops of Unit 3 (131 to 99 m below sea floor). Units 4 to 8, all deposited under marine conditions, provide isotopic evidence of meteoric or mixing‐zone waters and petrographic indicators of vadose conditions, typically at the top of the units. Evidence indicates that in Unit 5 the water table was mobile and Units 6a, 6b, 7 and 8, all characterized by ultraviolet fluorescent cements, are capped by sub‐aerial erosion surfaces. Unit 9 (the Holocene) reflects the recent re‐establishment of marine conditions. The extent of alteration of the entire sequence reflects the substantial and pervasive influence of meteoric waters. This effect is interpreted as a result of a greater rainfall and river flow from the mainland during early and late stages of interstadial periods. The study reflects progress in the ability to recognize the diagenetic signal generated by sea‐level change. However, whereas the isotopic results reflect the changing relationships between vadose and phreatic zones in groundwater systems beneath successive emergent surfaces, their correspondence with petrographic features is expressed only weakly and commonly lacks the systematic sequential overprinting implied by the distribution of cathodoluminescent zones of cements in many ancient limestones.     

Mechanisms controlling acid neutralization and metal mobility within a Ni-rich tailings impoundment

Low-quality pore waters containing high concentrations of dissolved H⁺, SO₄, and metals have been generated in the East Tailings Management Area at Lynn Lake, Manitoba, as a result of sulfide-mineral oxidation. To assess the abundance, distribution, and solid-phase associations of S, Fe, and trace metals, the tailings pore water was analyzed, and investigations of the geochemical and mineralogical characteristics of the tailings solids were completed. The results were used to delineate the mechanisms that control acid neutralization, metal release, and metal attenuation. Migration of the low-pH conditions through the vadose zone is limited by acid-neutralization reactions, resulting in the development of distinct pore-water pH zones at depth; the neutralization reactions involve carbonate (pH ⩾ 5.7), Al-hydroxide (pH ⩾ 4.0), and aluminosilicate solids. As the zone of low-pH pore water expands, the pH will then be primarily controlled by less soluble solids, such as Fe(III) oxyhydroxides (pH < 3.5) and the relatively more recalcitrant aluminosilicates (pH ⩾ 1.3). Precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxides and hydroxysulfates control the concentrations of dissolved Fe(III). Concentrations of dissolved SO₄ are principally controlled by the formation of gypsum and jarosite. Geochemical extractions indicate that the solid-phase concentrations of Ni, Co, and Zn are associated predominantly with reducible and acid-soluble fractions. The concentrations of dissolved trace metals are therefore primarily controlled by adsorption/complexation and (or) co-precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxide and hydroxysulfate minerals. Concentrations of dissolved metals with relatively low mobility, such as Cu, are also controlled by the precipitation of discrete minerals. Because the major proportion of metals is sequestered through adsorption and (or) co-precipitation, the metals are susceptible to remobilization if low-pH or reducing conditions develop within the tailings.     

Controls on the chemistry of springs at Teels Marsh,Mineral County,Nevada

Evaporative process plays a dominant role in determining the water chemistry of the springs at Teels Marsh, a closed basin in western Nevada. Analysis of the spring waters indicates that calcium, magnesium, sulfate, and silica are removed from solution during dry periods, even though groundwater is undersaturated with respect to gypsum, amorphous silica, and sepiolite. The removal mechanism is precipitation of authigenic phases such as gypsum above the water table, in the vadose zone.In episodes of rain and snowfall in which none of the waters enters the phreatic zone, ions in the rain and snow accumulate near the ground surface. This accumulation of material, together with the sparse rain and snowfall, inhibits chemical weathering of silicate minerals. Only at high elevations in the basin is there sufficient fluxing of water through the alluvium for silicate weathering to make a significant contribution to the sodium content of the springs. When a sufficiently heavy rainfall occurs, salts are partially dissolved and the ions transported to the permanent groundwater. The kinetics of dissolution of secondary phases in the vadose zone exert an important control on the composition of the springs.     

Modification to the crystal structure of chlorite during early stages of its dissolution

Early stage processes of Mg-rich chlorite (clinochlore) dissolution were examined, focusing especially on the structural modification at grain edges during dissolution. Focused ion beam transmission electron microscopy sample preparation was applied to crystals dissolved in a flow-through reaction system at pH 3.0 and 25°C for 31 days. The obtained Si and Mg dissolution rates are −11.49 and −11.14 (logR, mol/(m²/s)), respectively, implying dissolution is non-stoichiometric. TEM-EDX analyses of dissolved samples reveal the development of 20–50-nm thick amorphous zone at an outermost rim with a chemical gradient of Mg, lower towards the solid surface, and Si enrichment in this amorphous zone. Crystalline material is partially interwoven with amorphous one at the interface between the amorphous and crystalline regions. These results indicate that the amorphous zone was produced by selective leaching of cations except for Si. Chlorite dissolution may proceed via the formation and thickening of leached layer as a by-product of release to solution of Si at slightly slower rate than Mg.     

Transport of trace elements under different seasonal conditions: Effects on the quality of river water in a Mediterranean area

Concentrations of total and dissolved elements were determined in 35 water samples collected from rivers in Sardinia, a Mediterranean island in Italy. The overall composition did not change for waters sampled in both winter and summer (i.e., January at high-flow condition and June at low-flow condition), but the salinity and concentrations of the major ions increased in summer. Concentrations of elements such as Li, B, Mn, Rb, Sr, Mo, Ba and U were higher in summer with only small differences between total and dissolved (i.e., in the fraction <0.4 μm) concentrations. The fact that these elements are mostly dissolved during low flow periods appears to be related to the intensity of water–rock interaction processes that are enhanced when the contribution of rainwater to the rivers is low, that is during low-flow conditions. In contrast, the concentrations of Al and Fe were higher in winter during high flow with total concentrations significantly higher than dissolved concentrations, indicating that the total amount depends on the amount of suspended matter. In waters filtered through 0.015 μm pore-size filters, the concentrations of Al and Fe were much lower than in waters filtered through 0.4 μm pore-size filters, indicating that the dissolved fraction comprises very fine particles or colloids. Also, Co, Ni, Cu, Zn, Cd and Pb were generally higher in waters collected during the high-flow condition, with much lower concentrations in 0.015 μm pore-size filtered waters; this suggests aqueous transport via adsorption onto very fine particles. The rare earth elements (REE) and Th dissolved in the river waters display a wide range in concentrations (∑REE: 0.1–23 μg/L; Th: <0.005–0.58 μg/L). Higher REE and Th concentrations occurred at high flow. The positive correlation between ∑REE and Fe suggests that the REE are associated with very fine particles (>0.015 and <0.4 μm); the abundance of these particles in the river controls the partitioning of REE between solution and solid phases.Twenty percent of the water samples had dissolved Pb and total Hg concentrations that exceeded the Italian guidelines for drinking water (>10 μg/L Pb and >1 μg/L Hg). The highest concentrations of these heavy metals were observed at high-flow conditions and they were likely due to the weathering of mine wastes and to uncontrolled urban wastes discharged into the rivers.     

Dispersion and cycling of organic matter from the Sepik River outflow to the Papua New Guinea coast as determined from biomarkers

The Sepik River is a major contributor of water, sediment and associated organic loads to the coastal waters of northern New Guinea. With a narrow continental shelf and strong coastal currents, much of this exported material is available for long distance transport into the Bismarck Sea and beyond. CTD casts and associated instrument data showed that the river signature was visible in optical measurements of deep profiles from the Sepik Canyon. Discrete water samples were collected in clean Niskin bottles for organic analysis. Additional high volume samples for lipid classes were collected with Infiltrex samplers deployed on a floating mooring, along with two sediment trap arrays set at 100 and 260 m depth. The Infiltrex samplers were set at 55, 180, 200 and 220 m depth in an effort to target the surface layers and those of westward flowing water in the New Guinea Coastal Undercurrent (NGCUC). The samplers allowed analysis of lipid classes in both dissolved and particulate phases.Analyses of lignin phenols, hydrocarbons, fatty acids, sterols, and n-alcohols in the samples were used to estimate the cycling of the organic input from the river system to the coastal waters and possible entrainment in the NGCUC. The molecular biomarkers confirmed the Sepik River as a significant source of reduced carbon in the near coastal zone influenced by the plume. They indicated that ca. 90% of the organic carbon delivered to the coastal zone is dispersed or degraded, with only about 10% of terrestrial carbon being deposited on to the narrow shelf of coastal sediments. The dissolved lignin phenols provided evidence for desorption of organics from particles with increasing depth. However, this desorption process did not change the C/N ratio of the dissolved organic carbon (DOC) in the deep water of the Sepik Canyon. The hydrocarbons, sterols and fatty acids showed the change from lipid content dominated by phytoplankton in surface layers to zooplankton and bacterial biomarkers in deeper waters. The organic biomarkers provided evidence that some of the dissolved organic input from the Sepik River was injected into fast moving undercurrents. However, concentrations of terrestrial biomarkers were diluted and/or degraded to non-detectable levels within 100 km of the source.     

海南岛南部一地全新世生物屑灰岩的成岩作用

引言研究标本由我所碳酸岩组采自海南岛南部的一个地点。在那里,沿岸覆于原生礁之上有一套由生物骨屑(主要是珊瑚)砂、砾所组成的、已被碳酸盐胶结的岩层,其厚约3米左右(图1)。此岩层一般称为“次生礁”。它是由当时原生礁盘上的生物被海浪击碎并冲带到礁盘上沉积下来的,这里属连岛砂堤沉积,它现已完全暴露地表。次生礁在它抬升过程中,下部被海蚀形成海蚀龛。     

The contrasting biogeochemistry of iron and manganese in the Pacific Ocean

Vertical and horizontal distributions of dissolved and suspended particulate Fe and Mn, and vertical fluxes of these metals (obtained with sediment traps) were determined throughout the Pacific Ocean. In general, dissolved Fe is low in surface and deep waters (0.1 to 0.7 nmol/kg), with maxima associated with the intermediate depth oxygen minimum zone (2.0 to 6.6 nmol/kg). Vertical distributions of dissolved Mn are similar to previous reports, exhibiting a surface maximum, a subsurface minimum, a Mn maximum layer coincident with the oxygen minimum zone, and lowest values in deep waters.Near-shore removal processes are more intense for dissolved Fe than for dissolved Mn. Dissolved Mn in the surface mixed layer remains elevated much farther offshore than dissolved Fe. Elevated near-surface dissolved Mn concentrations occur in the North Pacific Equatorial Current, suggesting transport from the eastern boundary. Near-surface mixed-layer dissolved Mn concentrations are higher in the North Pacific gyre reflecting enhanced northern hemisphere aeolian sources.Residence time estimates for the settling of refractory paniculate Fe and Mn from the upper water column are 62–220 days (Fe), and 105–235 days (Mn). In contrast, residence times for the scavenging of dissolved Fe and Mn are 2–13 years (Fe) and 3–74 years (Mn). Scavenging residence times for dissolved Mn based on horizontal mixing in the surface mixed layer of the northeast Pacific are 0.4 years (nearshore) to 19 years (1000 km offshore).There is no evidence for in situ Fe redox dissolution within sub-oxic waters in the eastern tropical North Pacific. Dissolved Fe appeared to be controlled by dissolution from sub-oxic sediments, with oxidative scavenging in the water column or upper sediment layers. However, in situ Mn dissolution within the oxygen minimum zone was evident.     

塔里木盆地塔中上奥陶统碳酸盐台地高频层序控制的早期成岩作用及其对储层分布的影响

上奥陶统良里塔格组碳酸盐岩是塔里木盆地塔中地区重要的油气储层。在碳酸盐岩岩石学、微相和测井曲线分析基础上,将塔中良里塔格组划分为5个四级层序、15个五级层序,建立了高频层序地层格架。显著的选择性溶蚀,悬垂型、新月型等大气水胶结物的发育,溶蚀孔壁较弱的阴极发光特征,粒内与粒间胶结物较低的Fe、Mn含量,亮晶颗粒灰岩的δ13C、δ18O与泥晶灰岩接近等特征表明,塔中地区Ⅰ号断裂带附近准同生期大气水溶蚀作用以及早期海水胶结作用普遍发育。对比分析显示大气淡水透镜体均发育于高频层序向上变浅旋回的顶部,即高频层序格架制约了早期成岩作用的形成分布。现在保存的早期成岩溶蚀孔面孔率可达到4%~5%,因此早期溶蚀孔的发育为晚期溶蚀改造提供了流体活动空间和条件,对碳酸盐岩有效储层的产出具有重要控制。综合分析提出,塔中Ⅰ号断裂坡折带TZ54-TZ826和TZ72-TZ62-TZ24井区等高陡型台缘是同生-准同生溶蚀孔发育的有利储层区。     

车西洼陷陡坡带沙三下亚段近岸水下扇储层成岩演化及其对储层物性影响

利用岩芯观察、铸体薄片、扫描电镜、阴极发光及岩石物性测试等多种资料,本文对济阳坳陷车西洼陷陡坡带沙三下亚段近岸水下扇储层进行了探讨。结果表明,车西洼陷沙三下段近岸水下扇储层岩石类型宏观上主要表现为泥质杂基支撑砾岩、碎屑支撑砾岩、砾质砂岩等沉积,微观上以岩屑砂岩和长石质岩屑砂岩为主,灰泥质杂基含量最高可达40%。车西洼陷沙三下段近岸水下扇储层为典型的特低孔、特低渗储层类型,其平均孔隙度和渗透率分别为3.42%、2.02×10-3μm2;但在3 500~4 000 m深度段发育异常高孔带,孔隙度可达10.2%,储集空间多为溶蚀孔和微裂缝。研究区储层经历了复杂的成岩演化过程,目前处于中成岩B期,其成岩演化序列为:压实作用/碳酸盐胶结→长石溶蚀/碳酸盐胶结物溶蚀→石英溶蚀/碳酸盐胶结/灰泥重结晶→石英加大/碳酸盐胶结溶蚀→碳酸盐胶结。不同亚相所经历的成岩演化有所差异,其中中扇辫状水道中远端及中扇前缘经历了多期溶蚀作用,储层物性相对较好,平均孔隙度分别可达4.5%,7.25%,为研究区近岸水下扇砂砾岩储层的“甜点区”。     

资阳地区震旦系古岩溶作用及其特征讨论

在资阳地区震旦系灯影组的白云岩地层中发现了四川盆地又一含气区块,通过对地层资料、露头特征及构造史的分析研究,证实该储层为古岩溶作用的产物,在此基础上对古岩溶的分带性、旋回性及岩溶地貌特征进行了讨论,从而为储层特征研究及勘探预测奠定了基础。     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^–1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^–1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

The application of cathodoluminescence to interpreting the diagenesis of an ancient calcrete profile

A laterally extensive calcrete profile has been identified in the Late Asbian (Lower Carboniferous) shallow marine shelf limestones of the Llangollen area, North Wales. The upper surface of the profile is defined by a laterally discontinuous palaeokarstic surface and by laminated calcareous crusts which developed within the underlying limestone. The profile contains a unique series of early pore-filling vadose cements which only occur down to 1 m below the palaeokarstic surface. Cathodoluminescence reveals that these cements pre-date the late pore-filling meteoric phreatic cements which occur throughout local Asbian lithologies. A spar cement stratigraphy has been established for the calcrete profile. Subaerial vadose cements comprise two generations of non-luminescent cement, followed by a brightly luminescent generation which occasionally shows an acicular habit. This needle-fibre calcite represents the final stage of vadose cementation. Precipitation of vadose cements was contemporary with subaerial alteration and micritization of the limestone. Textures, visible only with cathodoluminescence, provide evidence of recurrent periods of fabric dissolution. The most extensive phase of dissolution occurred immediately after the precipitation of the non-luminescent subaerial vadose cements. Several different textures have been recorded, each reflecting the morphology of a partially dissolved substrate. Dissolution textures are generally confined to the walls of the larger pores and to early brecciation fractures. These probably acted as fluid pathways in the calcrete during early subaerial diagenesis. Much of the non-marine micrite in the calcrete profile appears as needle-fibre calcite under cathodoluminescence. This acicular calcite was probably formed in response to localized supersaturation of meteoric pore fluids caused by periods of near-surface evaporation. Since needle-fibre luminescence is strongly variable, these ambient conditions are not believed to have directly controlled the activator ion concentrations of cementing pore waters. Needle-fibre calcite is considered to be a cement precipitate which has almost completely recrystallized to micrite, probably during the late stages of subaerial diagenesis. Two generations of subaerial micrite which define a ‘micrite stratigraphy’, have been distinguished under cathodoluminescence. Reconstructing the diagenetic history of this ancient calcrete profile has revealed that subaerial alteration was multistaged, with many diagenetic processes acting simultaneously during a single phase of emergence.     

Climatic and lithologic controls on the temporal and spatial variability of CO2 consumption via chemical weathering: An example from the Australian Victorian Alps

A detailed geochemical study on river waters of the Australian Victorian Alps was carried out to determine: (i) the relative significance of silicate, carbonate, evaporite and sulfide weathering in controlling the major ion composition and; (ii) the factors regulating seasonal and spatial variations of CO₂ consumption via silicate weathering in the catchments. Major ion chemistry implies that solutes are largely derived from evaporation of precipitation and chemical weathering of carbonate and silicate lithologies. The input of solutes from rock weathering was determined by calculating the contribution of halite dissolution and atmospheric inputs using local rain and snow samples. Despite the lack of carbonate outcrops in the study area and waters being undersaturated with respect to calcite, the dissolution of vein calcite accounts for up to 67% of the total dissolved cations, generating up to 90% of dissolved Ca and 97% of Mg. Dissolved sulfate has δ³⁴S values of 16 to 20‰_CDT, indicating that it is derived predominantly from atmospheric deposition and minor gypsum weathering and not from bacterial reduction of FeS₂. This militates against sulphuric acid weathering in Victorian rivers. Ratios of Si vs. the atmospheric corrected Na and K concentrations range from ~ 1.1 to ~ 4.3, suggesting incongruent weathering from plagioclase to smectite, kaolinite and gibbsite.Estimated long-term average CO₂ fluxes from silicate weathering range from ~ 0.012 × 10⁶ to 0.039 × 10⁶ mol/km²/yr with the highest values in rivers draining the basement outcrops rather than sedimentary rocks. This is about one order of magnitude below the global average which is due to low relief, and the arid climate in that region. Time series measurements show that exposure to lithology, high physical erosion and long water–rock contact times dominate CO₂ consumption fluxes via silicate weathering, while variations in water temperature are not overriding parameters controlling chemical weathering. Because the atmospheric corrected concentrations of Na, K and Mg act non-conservative in Victorian rivers the parameterizations of weathering processes, and net CO₂ consumption rates in particular, based on major ion abundances, should be treated with skepticism.     

Anaerobic microbial activity affects earliest diagenetic pathways of bivalve shells

The earliest diagenetic post‐mortem exposure of biogenic carbonates at the sea floor and in the uppermost sediment column results in the colonization of hard‐part surfaces by bacterial communities. Some of the metabolic redox processes related to these communities have the potential to alter carbonate shell properties, and hence affect earliest diagenetic pathways with significant consequences for archive data. During a three‐month in vitro study, shell subsamples of the ocean quahog Arctica islandica (Linnaeus, 1767) were incubated in natural anoxic sediment slurries and bacterial culture medium of the heterotrophic Shewanella sediminis HAW ‐EB 3. Bulk analyses of the liquid media from the Shewanella sediminis incubation revealed an over ten‐fold increase in total alkalinity, dissolved inorganic carbon and Ω_Aragonite, and the alteration of the Mg/Ca, Mg/Sr and Sr/Ca ratios relative to control incubations without cultures. Ion ratios were most affected in the incubation with anoxic sediment, depicting a 25% decrease in Mg/Ca relative to the control. Shell sample surfaces that were exposed to both incubations displayed visible surface dissolution features, and an 8 wt% loss in calcium content. No such alteration features were detected in control shells. Apparently, alteration of shell carbonate properties was induced by microbially driven decomposition of shell intercrystalline organic constituents and subsequent opening of pathways for pore fluid–crystal exchange. This study illustrates the potential influence of benthic bacterial metabolism on biogenic carbonate archives during the initial stages of diagenetic alteration within a relatively short experimental duration of only three months. These results suggest that foremost the biological effect of bacterial cation adsorption on divalent cation ratios has the potential to complicate proxy interpretation. Results shown here highlight the necessity to consider bacterial metabolic activities in marine sediments for the interpretation of palaeo‐environmental proxies from shell carbonate archives.     

Natural spatial and temporal variations in groundwater chemistry in fractured,sedimentary rocks: scale and implications for solute transport

Natural tracers (major ions, δ¹⁸O, and O₂) were monitored to evaluate groundwater flow and transport to a depth of 20 m below the surface in fractured sedimentary (primarily shale and limestone) rocks. Large temporal variations in these tracers were noted in the soil zone and the saprolite, and are driven primarily by individual storm events. During nonstorm periods, an upward flow brings water with high TDS, constant δ¹⁸O, and low dissolved O₂ to the water table. During storm events, low TDS, variable δ¹⁸O, and high dissolved O₂ water recharges through the unsaturated zone. These oscillating signals are rapidly transmitted along fracture pathways in the saprolite, with changes occurring on spatial scales of several meters and on a time scale of hours. The variations decreased markedly below the boundary between the saprolite and less weathered bedrock. Variations in the bedrock units occurred on time scales of days and spatial scales of at least 20 m. The oscillations of chemical conditions in the shallow groundwater are hypothesized to have significant implications for solute transport. Solutes and colloids that adsorb onto aquifer solids can be released into solution by decreases in ionic strength and pH. The decreases in ionic strength also cause thermodynamic undersaturation of the groundwater with respect to some mineral species and may result in mineral dissolution. Redox conditions are also changing and may result in mineral dissolution/precipitation. The net result of these chemical variations is episodic transport of a wide range of dissolved solutes or suspended particles, a phenomenon rarely considered in contaminant transport studies.     

Geochemistry and stable isotopic composition of tufa waters and precipitates from the Interlake Region, Manitoba, Canada: Constraints on groundwater origin, calcitization, and tufa formation

New major, trace and isotopic geochemical results from a regional study of springs discharging from the major carbonate rock aquifer in the Interlake Region of Manitoba, Canada, are used to understand water–rock reactions, timing of recharge/discharge, tufa formation processes, and as baseline data. Spring waters are fresh with total dissolved solids (TDS) concentrations ranging from 150 to 880 mg/L. Waters discharging in the northern part of the study area have lower TDS, are dominantly Ca–Mg–HCO₃ waters with low SO₄ concentrations (<< 50 mg/L), and appear to have interacted primarily with Silurian carbonate lithologies. In contrast, waters in the southeastern part of the study area have higher TDS and have elevated SO₄ concentrations (up to 210 mg/L). Spring waters have elevated Mg/Ca_molar (1.23 ± 0.23), typically greater than congruent dissolution of dolomite. Ca and Mg concentrations and Mg/Ca_molar indicate that groundwater residence times were sufficient to allow equilibration with bedrock dolomite lithologies; elevated tritium in northern waters indicates a significant recharge component in the 1960's and 1970's. Tufa precipitates that have formed from many of the spring waters are low-Mg calcite (MgO = 1.70 to 5.80 wt.%). Sr concentrations are variable (57 to 657 ppm) and tufa Sr/Ca_molar ratios appear to be entirely controlled by spring water Sr/Ca_molar. Empirically determined Sr distribution coefficients (D_Sr = 0.389 ± 0.083) indicate rapid crystallization following CO₂ degassing, consistent with heavier δ¹³C_VPDB compared to spring waters. Sulfate concentrations are generally too low for calcitization (dedolomitization) reactions driven by anhydrite dissolution to be the dominant control on the elevated groundwater Mg/Ca_molar, implying either extensive sulfate reduction along the flow paths (however, δ¹³C_DIC suggests the elevated SO₄ is more consistent with Fe-sulfide oxidation), or that other processes are involved. Major ion ratios suggest that the waters in the southern part of the study area are more consistent with interaction with siliciclastic rocks than with anhydrite dissolution. We suggest that calcitization (dedolomitization) reactions driven by anhydrite dissolution may not dominate all carbonate aquifers and that mixing of waters in karst conduits combined with ion exchange reactions are important controls on water chemistry in these systems.     

Rare earth elements (REE) of dissolved and suspended loads in the Xijiang River, South China

The Xijiang River is the main channel of the Zhujiang (Pearl River), the second largest river in China in terms of water discharge, and flows through one of the largest carbonate provinces in the world. The rare earth element (REE) concentrations of the dissolved load and the suspended particulate matter (SPM) load were measured in the Xijiang River system during the high-flow season. The low dissolved REE concentration in the Xijiang River is attributed to the interaction of high pH and low DOC concentration. The PAAS-normalized REE patterns for the dissolved load show some common features: negative Ce anomaly, progressively heavy REE (HREE) enrichment relative to light REE (LREE). Similar to the world’s major rivers the absolute concentration of the dissolved REE in the Xijiang River are mainly pH controlled. The degree of REE partitioning between the dissolved load and SPM load is also strongly pH dependent. The negative Ce anomaly is progressively developed with increasing pH, being consistent with the oxidation of Ce (III) to Ce (IV) in the alkaline river waters, and the lack of Ce anomalies in several DOC-rich waters is presumably due to both Ce (III) and Ce (IV) being strongly bound by organic matter. The PAAS-normalized REE patterns for the dissolved load and the SPM load in rivers draining the carbonate rock area exhibit middle REE (MREE) enrichment and a distinct maximum at Eu, indicating the preferential dissolution of phosphatic minerals during weathering of host lithologies. Compared to the Xijiang River waters, the MREE enrichment with a maximum at Eu disappeared and light REE were more depleted in the South China Sea (SCS) waters, suggesting that the REE sourced from the Xijiang River must be further fractionated and modified on entering the SCS. The river fluxes of individual dissolved REE introduced by the Xijiang River into the SCS vary from 0.04 to 4.36 × 10⁴ mol a⁻¹.     

Solute generation and CO2 consumption during silicate weathering under subtropical,humid climate,northern Okinawa Island,Japan

The chemical characteristics of freshwaters draining the silicate rocks in the northern part of Okinawa Island were studied to understand solute generation processes, and to determine rates of chemical weathering and CO₂ consumption. It was observed that the water chemistry is highly influenced by marine aerosols, contributing more than 60% of total solute. Significant positive correlations observed for chloride versus dissolved silica and chloride versus bicarbonate suggest a strong influence of evapotranspiration on the seasonality of solute concentration. It was also found that chemical weathering has been highly advanced in which the dominant kaolinite minerals are being gibbsitized. Carbonic acid was found to be the major chemical weathering agent, releasing greater than 80% of weathering-derived dissolved cations and silica while the remaining portion was attributed to weathering by sulfuric acid generated via oxidation of pyrite contained in the rocks. The flux of basic cations, weathering-derived silica and CO₂ consumption were relatively high due to favourable climatic condition, topography and high rate of mechanical erosion. Silicate weathering rates for basic cations were estimated to be 6.7–9.7 ton km^− 2 y^− 1. Carbon dioxide consumed by silicate weathering was 334–471 kmol km^− 2 y^− 1 which was slightly higher than that consumed by carbonate weathering. In general, divalent cations (Mg and Ca) and bicarbonate alkalinity derived from carbonate dissolution were higher than those from silicate weathering. As a consequence, the evolution of chemical species in the freshwaters of northern area of Okinawa Island to a large extent could be explained by mixing of two components, characterized by waters with Na⁺ and Cl⁻ as predominant species and waters enriched with Ca²⁺ and HCO₃⁻.