Bank-derived carbonate sediment transport and dissolution in the Hawaiian Archipelago

This investigation used two approaches to examine the flux of bank-derived carbonate particles and determine the potential influence of benthic carbonate particle dissolution on the carbon chemistry of the waters around the Hawaiian Archipelago. First, the particle flux near several representative carbonate banks in the Hawaiian Archipelago was measured and compared with the flux at a distal site (ALOHA) approximately 100 km north of Oahu, Hawaii. The results of four sediment trap deployments on three carbonate banks in the Hawaiian Archipelago demonstrate that the flux of bank-derived carbonate particles are consistently one to two orders of magnitude higher than the fluxes at the distal station. Furthermore, the mineralogy of the carbonate flux near the banks, which includes very soluble bank-derived aragonite and magnesian calcite particles, is distinctly different from that of the distal fluxes. Second, the chemistry of the waters at each bank station along the archipelago was characterized and compared with the chemistry of the distal waters to determine if differences in the particle flux were reflected in the carbon chemistry. Higher alkalinity and carbonate ion concentrations were observed around all of the banks studied. The saturation state of these waters suggests that the dissolution of some magnesian calcite and aragonite phases could explain the higher alkalinity values. Calculations suggest that the dissolution of benthically-derived aragonite and magnesian calcite may be an important component of the North Pacific alkalinity budget and a potential sink for anthropogenic CO₂.     

贵州万山汞矿尾矿堆及地表水的环境地球化学特征

对贵州万山汞矿区尾渣堆(主要为炉渣组成)、地表水及河流沉淀物的汞迁移进行了研究。由于赋矿岩石为白云岩，高温煅烧的炉渣中含CaO等碱性物质，炉渣的风化作用释放出汞以及碱性水．流经尾渣堆的地表水碱性强(pH10．6-11．8)、电导率高，且具有明显不同的主要离子组成．万山汞矿矿石单一，主要为辰砂，其他矿石极少，因此炉渣及其渗滤水中除汞外的重金属含量很低．尾渣堆中的汞及碱性物质是对周围环境的主要威胁．在尾渣堆下游汞含量很快降低，约300n，范围内水中的溶解汞从300—1900，ng/L降至72ng／L，而且水的碱性也被中和．但是，由于尾渣堆中的汞及碱性物质含量高，尾渣堆的长时间风化及水流的溶解会将大量汞搬运到周围的土壤及水体并对生物产生不利影响．     

墨西哥湾东北部海区常压与超压沉积盆地 孔隙水的地球化学特征对比研究*

Brazos-Trinity IV盆地和Ursa盆地均位于墨西哥湾东北部海域,两者相隔300km,经历了截然不同的更新世沉积历史。Brazos-Trinity IV盆地属于更新世晚期浊流沉积体系,沉积速率低,几乎不产生超压,而Ursa盆地受密西西比河流域的影响,具有极高的沉积速率,是一个典型的超高压沉积盆地。国际大洋综合钻探计划IODP308航次分别在两个盆地取得了钻孔样品,分析获得了沉积物孔隙水的各项地球化学数据。文章以这些分析结果为基础,讨论超压Ursa盆地U1322钻孔和常压Brazos-Trinity IV盆地U1319钻孔沉积物孔隙水中阴阳离子随深度的变化情况,并对孔隙水中保守性组分进行了相关性分析。对比研究发现U1322钻孔的碱度,Cl^-,PO^3-₄和pH值明显低于U1319钻孔; 碱度与PO^3-₄,Ca²⁺,B³⁺之间以及K⁺与Li⁺在U1319钻孔呈现很好的相关性,而在U1322钻孔则无明显的相关关系; U1322钻孔孔隙水Cl^-随深度逐渐降低,孔隙水被淡化。超压Ursa盆地沉积物孔隙水阴离子异常的主要原因可能是因为盆地底层的Blue Unit砂体将高和低超压区连接,流体在超压作用下由高压区流向低压区,阴离子含量较低的流体与沉积物孔隙水混合,造成U1322钻孔中阴离子浓度的异常,这可能也是U1322钻孔孔隙水保守性组分之间相关性较差的主要原因。     

Determination of the Concentration of Carbonic Species in Natural Waters: Results from a World‐Wide Proficiency Test

The results of an international interlaboratory proficiency test for the determination of carbonic species are presented. Eight laboratories analysed twelve water samples (four synthetic waters, one lake water, four geothermal waters, one seawater and two petroleum waters) by two methods: (a) individual laboratory analytical procedure and (b) acid–base titration curves in tabular form following a standardised protocol. In case (b), the concentrations of carbonic species were calculated by the organiser using the (1) Hydrologists' method, (2) Geochemists' method and/or (3) initial pH and total alkalinity method. For synthetic waters, the averaged % trueness and precision of measurement of the two methods were (trueness = 7.6, precision = 9.4) and (9.0, 3.4) for total alkalinity, and (6.6, 31.0) and (7.8, 6.1) for carbonic alkalinity, respectively. This indicates that the total alkalinity calculation procedure is in general correct in the individual laboratory method, but the carbonic alkalinity calculation procedure has serious problems. The measurements of total alkalinity for lake and seawaters were in agreement in both the methods; however, the individual laboratory measurement method for geothermal and petroleum waters was conceptually incorrect. Thus, the analytical procedures for the determination of carbonic species were reviewed. To apply the Hydrologists' and/or Geochemists' methods, the location of NaHCO₃EP and H₂CO₃EP is necessary, even for samples with pH lower than that of NaHCO₃EP, and a backward titration curve after complete removal of CO₂ must be performed. The initial pH and total alkalinity method is appropriate where a complete analysis of species that contribute to the alkalinity is known.     

Geochemistry of iron ochres and mine waters from Levant Mine,Cornwall

The geochemistry of metal-rich mine waters and mineral precipitates from the Levant mine, Cornwall, has been examined. Sulphide oxidation at Levant mine has produced a wide range of secondary sulphides, oxides, chlorides, sulphates and carbonates in a gossan environment. The mine waters display a wide variation in alkalinity, pH, chloride, sulphate, sodium, potassium and heavy metal content which can be explained by variable degrees of mixing between acidic, metal-rich, rock drainage waters and neutral to alkaline sea waters. Transition metals are soluble in the acidic mine waters with concentrations up to 665 mg/l Cu, 41 mg/l Zn, 76 mg/l Mn, 6 mg/l Co and >2500 mg/l total Fe. The production of acid rock drainage and leaching of metals can be related to sulphide oxidation. Where these metal-rich acidic waters mix with infiltrated sea water, neutralization occurs and some metals are precipitated (principally Cu). Where pools of mine drainage are stagnant native copper and cuprite are precipitated, frequently observed replacing iron pipes and rail tracks and wooden shaft supports, due to electrode potential differences. In these solutions, dissolved copper species are also reduced by interaction with wood-derived organic species. Precipitation of iron oxyhydroxides, caused by a pH increase, also occurs and leads. to coprecipitation of other metals, including Cd, Co, Ph, Mn, Ag and Zn, thus limiting the release of dissolved metals in solution from the mine. However, the release of suspended metal-rich ochres in mine discharge waters (with high Ph, Zn, Cd, Mn, Ni, Sn, Sb, As, Bi, Cu, Co and Ag) will still present a potential environmental hazard.     

Pore water evolution in sandstones of the Groundhog Coalfield,northern Bowser Basin,British Columbia

The succession of sandstone cements in chert and volcanic lithic arenites and wackes from the northern Bowser Basin of British Columbia comprises a record of diagenesis in shallow marine, deltaic, and coastal plain siliciclastic sediments that pass through the oil window and reach temperatures near the onset of metamorphism. The succession of cements is consistent with seawater in the sandstones mixing with acid waters derived from dewatering of interbedded organic rich muds. Sandstone cement paragenesis includes seven discrete cement stages. From earliest to latest the cement stages are: (1) pore-lining chlorite; (2) pore-lining to pore-filling illite; (3) pore-filling kaolinite; (4) oil migration through some of the remaining connected pores; (5) chlorite dissolution; (6) quartz cement; and (7) calcite cement. These seven cement stages are interpreted as a record of the evolution of pore waters circulating through the sandstones after burial. The earliest cement stages, as well as the depositional environments, are compatible with seawater as the initial pore fluid. Seawater composition changed during transport through the sandstones, first by loss of Mg²⁺ and Fe²⁺ during chlorite precipitation (stage 1). Dewatering of interbedded organic-rich mudstones probably added Mg²⁺ and Fe²⁺ to partially buffer the loss of these cations to chlorite. Acids produced during breakdown of organic matter are presumed to have mixed into sandstone pore fluids due to further compaction of the muds, leading to reduction of initial alkalinity. Reduction in alkalinity, in turn, favours change from chlorite to illite precipitation (stage 2), and finally to kaolinite (stage 3). Pore waters likely reached their peak acidity at the time of oil migration (stage 4). Chlorite dissolution (stage 5) and quartz precipitation (stage 6) occurred when pores were filled by these hydrocarbon-bearing and presumably acidic fluids. Fluid inclusions in fracture-filling quartz cements contain petroleum, high-pressure methane, and methane-rich aqueous solutions. Homogenization temperatures from primary two-phase inclusions are consistent with quartz cementation during progressive heating between approximately 100 and 200°C. Following quartz precipitation, alkaline pore waters were re-established, as evidenced by late-stage calcite cement (stage 7).     

Predictive modelling of dump water impact on the surroundings of the lignite dump site Jänschwalde (Eastern Germany)

Open cast mining of lignite leads to dumps containing highly mineralised pore waters. To predict the impact of the dump waters on the undisturbed aquifers two steps are necessary. (1) The prediction of dump water quality at times when steady state flow conditions will be established. (2) The simulation of the dump ground water migration with a model that is able to handle the complexity of the homogeneous and heterogeneous interactions of the migration process.For the investigated site Jänschwalde, which is still dewatered, a chemical mass balance was performed. The predicted alkalinity potentials exceed acidity potentials for the dump as a whole. The distribution of these parameters show high alkalinity potentials for the northern part.In order to model the migration process the transport code PCGEOFIM^® [Anwenderdokumentaion, IBGW Leipzig, (in German)] was coupled with the geochemical equilibrium code PHREEQC [USGS, Water-Resources Investigations Report]. This was done to simulate redox reactions, mineral dissolution and precipitation, and cation exchange in the ground water zone. The model is verified by a column flow test. The results of the simulations show a small effect of the migrating dump waters on the quartenary aquifer with respect to acidity changes. This results from calcite buffering and cation exchange. The impact on the quartenary aquifer by sulphate is much higher.     

Seasonal Influence of the Needle Rush <Emphasis Type="Italic">Juncus roemarianus</Emphasis> on Saltmarsh Pore Water Geochemistry

Previous studies have shown that saltmarsh macrophytes have a significant influence on sediment biogeochemistry, both through radial release of oxygen from roots and also via primary production and release of labile organic exudates from roots. To assess the seasonal influence of the needle rush, Juncus roemarianus, on saltmarsh sediment geochemistry, pore waters and sediments were collected from the upper 50 cm of two adjacent sites, one unvegetated and the other vegetated by Juncus roemarianus, in a Georgia saltmarsh during winter and summer. Pore waters collected at 1- to 2-cm intervals were analyzed for pH, alkalinity, dissolved phosphate, ammonium, Fe(II), Fe(III), Mn(II), sulfide, sulfate, and organic carbon. Sediments were collected at 5-cm intervals and analyzed for iron distribution in the solid phase using a two-step sequential extraction. The upper 50 cm of the sediment pore waters are mostly sulfidic during both winter and summer. The pore water and sediment geochemistry suggest organic matter degradation is coupled mostly to Fe(III) and sulfate reduction. In summer, there is greater accumulation of alkalinity, sulfide, ammonium, and phosphate in the pore waters and lower levels of ascorbate extractable Fe, which is presumed to be comprised primarily of readily reducible Fe(III) oxides, in the sediments, consistent with higher organic matter degradation rates in summer compared to winter. Lower pH, alkalinity, ammonium, and sulfide concentrations in sediments with Juncus, compared to nearby unvegetated sediments, is consistent with release of oxygen into the Juncus rhizosphere, especially during summer.     

Oilfield waters and sandstone diagenesis

The evolution of the organic geochemistry and carbonate alkalinity of oilfield waters is apparently regular and predictable; this evolution can be typified by five generalizations (1) at or near 80°C there appears to be an exponential rise in the concentration of organic acid anions; (2) the maximum concentration of organic acid anions occurs over approximately the 80–100°C temperature interval; (3) the highest concentrations of difunctional acid anions are associated with the other organic species maxima; (4) difunctional acid anions are the first to be decarboxylated, typically at temperatures of 100–110°C; (5) with increasing temperature (110–130°C) monofunctional acid anions begin to become decarboxylated, resulting in a fluid alkalinity dominated by bicarbonate. Dissolution experiments using artificial and natural oilfield waters demonstrate that mono- and difunctional carboxylic acid anions and hydroxybenzoic acid anions (present in both oilfield waters and the aqueous phase of hydrous pyrolysates) are capable of greatly enhancing Al, Si, Fe and Ca concentrations in solutions from dissolution of minerals by organometallic complexation. This enhancement of mineral solubility has been called upon to explain aluminosilicate dissolution porosity which is quantitatively important in many subsurface reservoirs; certainly, no other viable mechanism has been proposed to explain aluminum transport in the subsurface. When integrated into basin models, the regular evolution of organic and carbonate alkalinity in oilfield waters and the changing mineral stabilities that accompany that evolution help explain commonly observed diagenetic sequences in clastic systems.     

Major ion composition and carbonate equilibrium in the sediment pore water of the Razdol’naya River estuary of Amur Bay,the Sea of Japan

The complex study of the river water and pore solutions from the bottom sediments in the lower reaches of the Razdol’naya River was conducted in February 2010. The major ion composition of the waters indicates the submarine origin of the near-bottom and pore waters in the lower reaches of the Razdol’naya River in the winter. The river estuary extends upstream for more than 20 km. It was established that the studied sediments are reduced oozes containing pyrite, hydrotroilite, and iron monosulfide, which is direct evidence for sulfate-reduction in the sediments. The diagenesis of organic matter is the main reason for the considerable decrease in the amount of sulfates and the increase in the alkalinity of the sediment pore water. The sedimentary pore water sampled from the deep river pits is characterized by excess alkalinity that cannot be explained by sulfate-reduction and methane genesis. It was suggested that the chemical weathering of silicate minerals and the bacterial mineralization of salts of organic acids could result in the excess alkalinity of the sediment pore water.     

Transformation of the chemical composition of the waters of small lakes on Kola Peninsula owing to a decrease in technogenic air pollution and to climate warming

The emission of sulfur dioxide and metals from copper-nickel melting plants on Kola Peninsula (Russia) decreased pronouncedly over the last two decades. The decrease in the sulfate content and increase in the acid-neutralizing capability of waters were proven on the basis of the data of surveys on 75 small lakes repeated once every five years from 1990 to 2010. The variations of other parameters of the chemical composition of the waters of small lakes depend on the geological and landscape conditions of the formation of waters. The alkalinity and pH values increased in 46% of the lakes; 24% of them showed a further decrease of these parameters; and no reliable changes were traced in 31% of the lakes. The concentrations of Cu and Ni in the lacustrine water decreased 5-to 10-fold over the last two decades.     

Hydrogeochemical characteristics of mine water in the Harz Mountains,Germany

Water samples (springs, creeks, mine adits) from different former mining districts of the Harz Mountains and the nearby Kupferschiefer (copper shale) basin of Sangerhausen were analysed for major ions and trace metals. Due to more intensive water rock interactions including the ore minerals, the mine water concentrations of main components and trace metals are generally higher compared to non mining affected surface waters of the mountain range. Furthermore, the content of major ions in mine water is enriched by mixing processes with saline waters from Permian layers in the Kupferschiefer district and at the deeper levels of the mines in the Upper Harz Mountains. The waters of the different mining districts can be distinguished by trace metal occurrences and concentrations derived from the different ore bodies. Water from the Kupferschiefer mines shows the highest Na, Cl, Cu, Mo and U concentrations, whereas a combination of elevated As and Se concentrations is typical for most of the samples from the mines around St. Andreasberg. However, there are exceptions, and some water samples of all the investigated mining districts do not follow these general trends. Despite the influence of mining activities and ore mineralisation, hydrochemical effects due to rain water dilution can be seen in most of the waters. According to the elevation of the mountain range, higher precipitation rates decrease the ion concentrations in the waters of springs, creeks and mine adits.     

Mg,Ca and O18O16 exchange in the sediment-pore water system,hole 149, DSDP

The diagenesis and geochemical evolution of deep-sea sediments are controlled by the interaction between sediments and their associated pore waters. With increasing depth, the pore water of Hole 149 (DSDP) exhibits a strong depletion in Mg and a corresponding enrichment in Ca, while the alkalinity remains relatively constant. Dissolved SiO₂ is nearly constant in the upper 100 m of sediment, but is highly enriched in the deepest pore waters. The pore waters exhibit a depletion in K with increasing depth, and $\text{O}{}^{18}\text{O}{}^{16}$ pore water ratios also decrease.The sediment section has three zones of sedimentary regimes with increasing depth in the drill hole: an upper 100 m section of detrital clays, a middle section enriched in calc-akalic volcanics which have undergone submarine weathering to a smectite phase, and a lower section of siliceous ooze which still has a diagenetic smectite phase. The quartz-feldspar ratios and $\text{O}{}^{18}\text{O}{}^{16}$ composition of the silicate phases are in agreement with these interpretations.The submarine weathering of volcanics to a smectite can account for the observed pore water gradients. Volcanics release Ca and Mg to the pore waters causing the alkalinity values to increase. Smectite is formed, depletes the pore waters in Mg and O¹⁸ and causes the alkalinity to decrease. The net reaction allows for the observed relationship between pore water Ca and Mg gradients with little net change in alkalinity. Given the abundance of volcanics in many deep-sea sediments, especially in lower sections which often form near ridge crests, the submarine formation of smectite may be an additional oceanic Mg sink which has not yet been fully considered.     

Comparative major ion geochemistry of Piedmont streams in the Atlanta,Georgia region: possible effects of urbanization

. The major ion stream chemistry for an urbanized basin (Peachtree Creek) in the Atlanta (Georgia, USA) metropolitan region was analyzed and compared upon a time-series basis with the stream chemistry of a nearby, but far less developed basin (Sweetwater Creek). The major ion chemistry from both streams indicated that all parameters fell below safe drinking water standards as would be expected in watersheds underlain by low-solubility aluminosilicate bedrock. Base flow TDS concentrations for the urbanized basin (Peachtree Creek) were ~30% greater than Sweetwater Creek and were characterized by elevated concentrations of base cations (Ca, Mg, Na), alkalinity, sulfate, and chloride. The less-urbanized Sweetwater Creek basin is underlain by a higher percentage of more soluble amphibolite and, therefore, the higher concentration of solutes within the urban base flow can not readily be explained by differential mineral weathering. The increased inorganic solute loads might have resulted from pollution input (leaky underground sewer lines?) and/or evaporative concentration; however, these explanations are presently speculative. Major ion concentrations within the urban Peachtree Creek basin were diluted by an average of ~50% compared with only ~25% in the Sweetwater Creek basin as a result of the increased contribution of direct surface runoff. The regression correlation coefficients for the ions that evolve through mineral weathering (Ca, Mg, Na, and HCO3) are much higher in urban stream flow than in Sweetwater Creek waters. This might indicate that storm waters in the urban basin are more closely derived from a two end member mixture (groundwater and street runoff) than waters from Sweetwater Creek, which represent a more complex mixture.     

西昌市尔乌泉域泉水水文地球化学特征及成因

泉和泉群是川西南乡村居民首要的生活水源,对本区泉水水文地球化学特征及成因的研究具有重要的科学价值和指导意义。以尔乌泉域泉水和地表水为研究对象,通过分析泉水和地表水常规水化学组分、氢氧同位素和氚同位素,探讨了该泉域泉水水文地球化学特征及成因。结果显示:尔乌泉域泉水为中偏碱性低矿化水,其水化学类型为HCO3—Ca·Mg和HCO3·SO4—Ca·Mg型水。地表水因受泉水补给影响具有与泉水相似的组分特征。氢氧同位素分析显示尔乌泉水和地表水补给来源为大气降水,且未发生氧同位素漂移。氚同位素进一步确定泉水为非现代水,地下水经历较长的径流时间。受断裂带和褶皱构造的影响,入渗补给的大气降水与碎屑岩中碳酸盐岩、石膏等矿物发生水岩相互作用,后与第四系黏土物质发生阳离子交换反应,致使泉水水化学组分以Ca2+、Mg2+、HCO-3和SO2-4为主。此外,居民生活污水的排放和化学肥料的施用也对泉水中Na+和SO2-4组分产生影响。     

Radium-based pore water fluxes of silica, alkalinity, manganese, DOC, and uranium: A decade of studies in the German Wadden Sea

A decade of studies of metal and nutrient inputs to the back-barrier area of Spiekeroog Island, NW German Wadden Sea, have concluded that pore water discharge provides a significant source of the enrichments of many components measured in the tidal channels during low tide. In this paper we add studies of radium isotopes to help quantify fluxes into and out of this system. Activities of radium isotopes in surface water from tidal channels in the back-barrier area exhibit pronounced changes in concert with the tide, with highest activities occurring near low tide. Other dissolved components: silica, total alkalinity (TA), manganese, and dissolved organic carbon (DOC) exhibit similar changes, with patterns matching the Ra isotopes. Uranium follows a reverse pattern with highest concentrations at high tide. Here we use radium isotope measurements in water column and pore water samples to estimate the fluxes of pore waters that enter the tidal channels during low tide. Using a flushing time of 4 days and the average activities of ²²⁴Ra, ²²³Ra, and ²²⁸Ra measured in the back-barrier surface and pore waters, we construct a balance of these isotopes, which is sustained by a deep pore water flux of (2-4) × 10⁸ L per tidal cycle. This flux transports Ra and the other enriched components to the tidal channels and causes the observed low tide enrichments. An independent estimate of pore water recharge is based on the depletion of U in the tidal channels. The U-based recharge is about two times greater than the Ra-based discharge; however, other sinks of U could reduce the recharge estimate. The pore waters have wide ranges of enrichment in silica, alkalinity, manganese, DOC, and depletion of U with depth. We estimate concentrations of these components in pore water from the depth expected to contribute the majority of the pore water flux, 3.5 m, to determine fluxes of these components to the tidal channels. Samples from this depth have minimum concentrations of silica, alkalinity, manganese, and DOC. We also estimate the exports of these components (and import of U) due to mixing based on average measured concentrations in the tidal creeks and the 4-day flushing time. A comparison of these estimates reveals that the exports (negative in the case of U) equal or exceed the pore water fluxes. By using values slightly higher than the minimum concentrations at 3.5 m to calculate inputs, the two estimates could be forced to match. We conclude that pore water drainage is the major factor regulating fluxes of Ra isotopes, silica, alkalinity, manganese, DOC, and uranium in this system.     

Origin of fluorine in mineral waters of Bujanovac valley (Serbia, Europe)

This paper deals with mineral and thermomineral water occurrences of the Bujanovac valley in south eastern part of Serbia related to granitoides of the Bujanovac massif along both the margin and the floor of the valley. In past decades (1966–2010) numerous hydrogeological, hydrogeochemical and geophysical explorations were carried out. One of results of these explorations is the completion of test holes and exploratory—production wells. They provide groundwater for three water bottling factories: “Heba”, “Bivoda”, “Prohor” as well as the “Vrelo Bujanovac Banja Spa Centre” for rehabilitation, treatment, and prevention. All stated consumers use the same mineral water aquifer. The content of fluoride in the majority of examined mineral waters is higher than 4 mg/1, whereby they are singled out as typical fluoride waters. The content of calcium ions in them amounts 80 mg/1, and the values of the saturation index in relation to calcium fluoride (SI) range from 0.4 to 0.7 mg/1, which points to mineral waters saturated in relation to fluorite. However, in the study area, there are mineral water occurrences with the content of fluoride significantly lower than in the majority of analysed waters representing hydrochemical anomalies. These waters occur as hydrochemical anomalies in marl and sandstone wherein Secondary mineral water aquifers, originating from cracked granite of the Bujanovac massif, are formed. When mineral waters from granite (with the increased content of fluoride) reach these secondary aquifers, the content of fluoride ions lowers to about 1 mg/1, which is of great significance from the point of view of mineral water utilisation as table bottled water. In this paper, it is proved that, in addition to the presence of some minerals as basic fluorine bearers, the role of the lithological environment where the natural process of defluoridation occurs is significant, which is confirmed by the revitalization of the A-4 well. The paper deals with mineral water deposits of the Bujanovac valley, and the natural way of lowering of fluorine content in the given waters.     

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).     

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).     

Geochemical response of acid groundwater to neutralization by alkaline recharge

Solute transport and chemical neutralization (pH 3 to 7) within a shallow heterogeneous aquifer producing acid mine drainage (AMD) are examined at an abandoned surface coal mine in West Virginia. The aquifer is undergoing partial neutralization by mixing with alkalinity from a leaking sludge disposal pond, extending in preferential zones controlled by aquifer heterogeneity. Hydraulic heads interpolated from wells indicate leakage from a central alkaline (pH 7.1, 0.72 meq/L alkalinity) sludge pond is a principal source of recharge. Chemically-conservative sodium, added to AMD during treatment and leaked into the aquifer with the sludge, develops a dispersion plume over a restricted portion of the aquifer that correlates with pH, hydraulic head, and dissolved metals distributions. Concentrations of aluminum, iron, sulfate and acidity display higher concentrations downgradient from the pond as sludge alkalinity is consumed along flow paths. Before reaching springs, most dissolved iron is oxidized and hydrolyzed, likely precipitating in the aquifer as a ferric hydroxide or hydroxysulfate phase. The spatial pattern of iron and aluminum concentrations suggests accelerated oxidation caused by gas transport along the outer slopes of the spoil. Dissolved aluminum concentrations increase with total acidity, suggesting that dissolution of silicate minerals results from acidity released by iron hydrolysis. Neutralization reactions and higher pH are favored in more highly permeable portions of the spoil, where ferrihydrite and aluminum hydroxysulfate minerals (such as basaluminite) are supersaturated. In acid-producing zones at pH < 4.5, jurbanite is near equilibrium and an aluminum-sulfate phase with similar properties may limit aluminum concentrations, but become undersaturated in zones of advancing neutralization. At this particular site, ferrous iron produced by pyrite oxidation is almost completely oxidized over short transport distances, allowing hydrolysis of iron and aluminum should sufficient alkalinity be added to these acid waters.