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).     

Carbon dioxide dynamics in rivers and coastal waters of the “big island” of Hawaii,USA, during baseline and heavy rain conditions

The distributions of the partial pressure of carbon dioxide (pCO₂) and total alkalinity (TA) were examined for a 6-month period in the Wailuku and Wailoa rivers and coastal waters of Hilo Bay on the west coast of the Island of Hawaii, USA. Main results for the largest and turbulent Wailuku River show in the watershed an oversaturation in CO₂ with respect to atmospheric equilibrium and a CO₂ undersaturation in the estuary. In the Wailoa river-estuary system, extremely high pCO₂ values ranging from 1500 to 10500 ppm were measured with significant shifts in pCO₂ from drought to flood period. In the two rivers, water residence time, groundwater inputs and occasional flood events are the predominant drivers of the spatial and temporal patterns in the distribution of pCO₂. In Hilo Bay, CO₂ oversaturation dominates and the bay was a source of CO₂ to the atmosphere during the study period. TA is conservative along the salinity gradient, indicating calcification in the bay is not a significant source of CO₂ to the atmosphere.     

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).     

CO<Subscript>2</Subscript> absorption by alkaline soils and its implication to the global carbon cycle

Motivated by the rapid increase in atmospheric CO₂ due to human activities since the Industrial Revolution, and the climate changes it produced, the world’s concerned scientific community has made a huge effort to investigate the global carbon cycle. However, the results reveal that the global CO₂ budget cannot be balanced, unless a “missing sink” is invoked. Although numerous studies claimed to find the “missing sink”, none of those claims has been widely accepted. This current study showed that alkaline soil on land are absorbing CO₂ at a rate of 0.3–3.0 μmol m⁻² s⁻¹ with an inorganic, non-biological process. The intensity of this CO₂ absorption is determined by the salinity, alkalinity, temperature and water content of the saline/alkaline soils, which are widely distributed on land. Further studies revealed that high salinity or alkalinity positively affected the CO₂ absorbing intensity, while high temperature and water content had a negative effect on the CO₂ absorbing intensity of these soils. This inorganic, non-biological process of CO₂ absorption by alkaline soils might have significant implications to the global carbon budget accounting.     

Geochemical evidence of seawater intrusion into a coastal geothermal field of central Greece: example of the Thermopylae system

Thermal water of Thermopylae and from other geothermal fields located in the southern part of the Sperchios basin (central Greece) are characterized by high salinity (total dissolved salts, or TDS, range from 1.2 to 30.3 g L⁻¹) associated with a degassing of CO₂. To determine the mineralization processes, geochemical and isotopic investigations (major elements, ¹⁸O, ²H and ¹³C) have been carried out upon 17 thermal waters from springs and boreholes. This study emphasizes that all the thermal waters result from the mixing of a seawater end-member, several fresh water components depending on the field location, and a mantle-derived CO₂ rising upward through an E–W fault system. The seawater identified in the thermal mixture is likely to be evolved Aegean seawater (ASW). Once intruded into the basin sediments, the trapped seawater has its chemical content modified by both water–rock interactions and massive dissolution of the deep CO₂ (pCO₂ of 10^0.5 atm). The modelling performed with PHREEQC indicates that the anomalous major ion ratios measured in the so-called evolved ASW are explained by the dissolution of calcite and dolomitization process associated to precipitation of gypsum within the thermal aquifer.     

An organic carbon budget for the Mississippi River turbidity plume and plume contributions to air-sea CO2 fluxes and bottom water hypoxia

We investigated seasonal variability in organic carbon (OC) budgets using a physical-biological model for the Mississippi River turbidity plume. Plume volume was calculated from mixed layer depth and area in each of four salinity subregions based on an extensive set of cruise data and satellite-derived suspended sediment distributions. These physical measurements were coupled with an existing food web model to determine seasonally dependent budgets for labile (reactive on time scales of days to weeks) OC in each salinity subregion. Autochthonous gross primary production (GPP) equaled 1.3×10¹² g C yr⁻¹ and dominated labile OC inputs (88% of the budget) because riverine OC was assumed mostly refractory (nonreactive). For perspective, riverine OC inputs amounted to 3.9×10¹² g C yr⁻¹, such that physical inputs were 3 times greater than biological inputs to the plume. Annually, microbial respiration (R) accounted for 65% of labile OC losses and net metabolism (GPP—R) for the entire plume was, autotrophic, equaling 5.1×10¹¹ g C yr⁻¹. Smaller losses of labile OC occurred via sedimentation (20%), advection (10%), and export to higher trophic levels (5%). In our present model, annual losses of labile OC are 10% higher than inputs, indicating future improvements are required. Application of our model to estimate air-sea carbon dioxide (CO₂) fluxes indicated the plume was a net sink of 2.0×10⁹ mol CO₂ yr⁻¹, of which 90% of the total drawdown was from biotic factors. In all seasons, low salinity waters were a source of CO₂ (pCO₂=560–890 μatm), and intermediate to high salinity waters were a sink of CO₂ (pCO₂=200–370 μatm). Our model was also used to calculate O₂ demand for the development, of regional hypoxia, and our spring and early summer budgets indicated that sedimentation of autochthonous OC from the immediate plume contributed 23% of the O₂ demand necessary for establishment of hypoxia in the region.     

Salinity reflux and dolomitization of southern Australian slope sediments: the importance of low carbonate saturation levels

Anomalously saline waters in Ocean Drilling Program Holes 1127, 1129, 1130, 1131 and 1132, which penetrate southern Australian slope sediments, and isotopic analyses of large benthic foraminifera from southern Australian continental shelf sediments, indicate that Pleistocene–Holocene meso‐haline salinity reflux is occurring along the southern Australian margin. Ongoing dolomite formation is observed in slope sediments associated with marine waters commonly exceeding 50‰ salinity. A well‐flushed zone at the top of all holes contains pore waters with normal marine trace element contents, alkalinities and pH values. Dolomite precipitation occurs directly below the well‐flushed zone in two phases. Phase 1 is a nucleation stage associated with waters of relatively low pH (ca 7) caused by oxidation of H₂S diffusing upward from below. This dolomite precipitates in sediments < 80 m below the sea floor and has δ¹³C values consistent with having formed from normal sea water (? 1‰ to + 1‰ Vienna Pee Dee Belemnite). The Sr content of Phase 1 dolomite indicates that precipitation can occur prior to substantial metastable carbonate dissolution (< 300 ppm in Holes 1129 and 1127). Dolomite nucleation is interpreted to occur because the system is undersaturated with respect to the less stable minerals aragonite and Mg‐calcite, which form more readily in normal ocean water. Phase 2 is a growth stage associated with the dissolution of metastable carbonate in the acidified sea water. Analysis of large dolomite rhombs demonstrates that at depths > 80 m below the sea floor, Phase 2 dolomite grows on dolomite cores precipitated during Phase 1. Phase 2 dolomite has δ¹³C values similar to those of the surrounding bulk carbonate and high Sr values relative to Phase 1 dolomite, consistent with having formed in waters affected by aragonite and calcite dissolution. The nucleation stage in this model (Phase 1) challenges the more commonly accepted paradigm that inhibition of dolomitization by sea water is overcome by effectively increasing the saturation state of dolomite in sea water.     

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.     

Nature and role of CO2 in some hot and cold HCO3/Na/CO2-rich Portuguese mineral waters: a review and reinterpretation

 At the northern part of the Portuguese mainland, the upflow zone of several hot and cold HCO₃/Na/CO₂-rich mineral waters is mainly associated with important NNE–SSW faults. Several geochemical studies have been carried out on thermal and non-thermal hydromineral manifestations that occur along or near these long tectonic alignments. The slight chemical differences that exist between these meteoric hot and cold HCO₃/Na/CO₂-rich mineral waters seem to be mainly caused by CO₂. δ¹³C_(TIDC) values observed in these groundwaters range between –6.00 and –1.00‰ versus V-PDB (V denotes Vienna, the site of the International Atomic Energy Agency; PDB originates from the CaCO₃ of the rostrum of a Cretaceous belemnite, Belemnitella americana, collected in the Peedee formation of South Carolina, USA) indicating a deep-seated (mantle) origin for most of the CO₂. Nevertheless, in the case of the heavier δ¹³C_(TIDC) values, the contribution of metamorphic CO₂ or the dissolution of carbonate rock levels at depth cannot be excluded. Concerning the hot waters, the lack of a positive ¹⁸O-shift should be attributed to water-rock interaction in a low temperature environment, rather than to the isotopic influence of CO₂ on the δ¹⁸O-value of the waters. Received: 9 August 1999 · Accepted: 8 March 2000     

Biocalcification in the Eastern Oyster (<Emphasis Type="Italic">Crassostrea virginica)</Emphasis> in Relation to Long-term Trends in Chesapeake Bay pH

Anthropogenic carbon dioxide (CO₂) emissions reduce pH of marine waters due to the absorption of atmospheric CO₂ and formation of carbonic acid. Estuarine waters are more susceptible to acidification because they are subject to multiple acid sources and are less buffered than marine waters. Consequently, estuarine shell forming species may experience acidification sooner than marine species although the tolerance of estuarine calcifiers to pH changes is poorly understood. We analyzed 23 years of Chesapeake Bay water quality monitoring data and found that daytime average pH significantly decreased across polyhaline waters although pH has not significantly changed across mesohaline waters. In some tributaries that once supported large oyster populations, pH is increasing. Current average conditions within some tributaries however correspond to values that we found in laboratory studies to reduce oyster biocalcification rates or resulted in net shell dissolution. Calcification rates of juvenile eastern oysters, Crassostrea virginica, were measured in laboratory studies in a three-way factorial design with 3 pH levels, two salinities, and two temperatures. Biocalcification declined significantly with a reduction of ∼0.5 pH units and higher temperature and salinity mitigated the decrease in biocalcification.     

Tufa and travertines of southern Italy: deep‐seated,fault‐related CO2 as the key control in precipitation

Continental carbonates of Quaternary age in southern Italy commonly exhibit the facies of calcareous tufa, often reported as related to shallow aquifers fed by meteoric waters and to organic processes. A close spatial relationship exists between the mappable tufa deposits and major Quaternary extensional faults. With respect to the Ca‐Mg‐HCO₃ composition of limestone aquifers’ springs, tufa‐depositing springs exhibit higher salinity and alkalinity, are slightly warmer, have lower pH and are enriched in SO₄ and CO₂. Their δ¹³C values are systematically positive and compatible with a deep‐seated carbon source. A clear input of soil‐derived organic carbon is indicated only for small, non‐mappable tufas deposited by perched springs. The dataset indicates that the large tufa deposits owe their origin to a supplementary source of CO₂ advected by degassing through active faults, as a necessary prerequisite for inducing a rise of total dissolved salts and alkalinity. Meteoric waters that have come from a shallow aquifer are able to precipitate only limited amount of carbonates.     

Oceannographic Chemistry of Calcium Carbonate in the Sea Area at the Pearl River Mouth

Based on the analytical results for 101 samples from 50 survey spots,this paper describes the changes in rations of various components in calcium carbonate from the sea area at the Pearl River mouth with pH.Relations of ∑CO2 with salinity,and Ca concentration with salinity in different parts of the river mouth have been established.The annual throughput of Ca from the Pearl River and the saturation degrees of calcite and aragonite have been calculated.     

A case-study of complex gas–water–rock–pollutants interactions in shallow groundwater: Šalek Valley (Slovenia)

The complex geochemical interactions in the groundwater of the industrial area of Šalek Valley (Slovenia) between natural and anthropogenic fluids were studied by means of major (Ca, Mg, Na, K, HCO₃ ⁻, Cl⁻ and SO₄ ²⁻) and trace elements’ (As , Cd, Cu, Pb, Zn, Hg, Se and V) abundances, geochemical classification and statistical analysis of data. Cation abundances indicate mixing between a dolomitic end-member and an evaporitic or geothermal end-member. Anion abundances indicate mixing between bicarbonate waters and either sulphate-enriched waters (suggesting hydrothermalism) or chlorine-rich waters. Principal component analysis (PCA) allowed the extraction of seven factors, which describe, respectively: water–rock interaction mainly on dolomitic rocks; redox conditions of water; Cd–Zn enrichment in chlorine-rich waters (probably from industrial wastes); hydrothermal conditions in waters close to major faults; Pb and Cu pollution; V and K enrichments, indicating their common organic source; the role of partial pressure of CO₂ dissolved in water, which is highest in three wells with bubbling gases. Average underground discharge rates of solutes from the Valley range between 0.09 t/a (V) and 1.8 × 104 t/a (HCO₃ ⁻) and indicate how natural fluids can significantly contribute to the levels of elements in the environment, in addition to the amount of elements released by human activities.     

Diel Aquatic CO<Subscript>2</Subscript> System Dynamics of a Bermudian Mangrove Environment

Mangrove ecosystems play an important, but understudied, role in the cycling of carbon in tropical and subtropical coastal ocean environments. In the present study, we examined the diel dynamics of seawater carbon dioxide (CO₂) and dissolved oxygen (DO) for a mangrove-dominated marine ecosystem (Mangrove Bay) and an adjacent intracoastal waterway (Ferry Reach) on the island of Bermuda. Spatial and temporal trends in seawater carbonate chemistry and associated variables were assessed from direct measurements of dissolved inorganic carbon, total alkalinity, dissolved oxygen (DO), temperature, and salinity. Diel pCO₂ variability was interpolated across hourly wind speed measurements to determine variability in daily CO₂ fluxes for the month of October 2007 in Bermuda. From these observations, we estimated rates of net sea to air CO₂ exchange for these two coastal ecosystems at 59.8 ± 17.3 in Mangrove Bay and 5.5 ± 1.3 mmol m⁻² d⁻¹ in Ferry Reach. These results highlight the potential for large differences in carbonate system functioning and sea-air CO₂ flux in adjacent coastal environments. In addition, observation of large diel variability in CO₂ system parameters (e.g., mean pCO₂: 390–2,841 μatm; mean pH_T: 8.05–7.34) underscores the need for careful consideration of diel cycles in long-term sampling regimes and flux estimates.     

Stable carbon and oxygen isotope fractionation in bivalve (Placopecten magellanicus) larval aragonite

The relationship between stable isotope composition (δ¹³C and δ¹⁸O) in seawater and in larval shell aragonite of the sea scallop, Placopecten magellanicus, was investigated in a controlled experiment to determine whether isotopes in larval shell aragonite can be used as a reliable proxy for environmental conditions. The linear relationship between δ¹³C_DIC and δ¹³C_aragonite (r² = 0.97, p < 0.0001, RMSE = 0.18) was:

δ¹³C_DIC=1.15(±0.05)∗δ¹³C_aragonite-0.85(±0.04)     

Carbon Cycling and the Coupling Between Proton and Electron Transfer Reactions in Aquatic Sediments in Lake Champlain

We used fine-scale porewater profiles and rate measurements together with a multiple component transport–reaction model to investigate carbon degradation pathways and the coupling between electron and proton transfer reactions in Lake Champlain sediments. We measured porewater profiles of O₂, Mn²⁺, Fe²⁺, HS⁻, pH and pCO₂ at mm resolution by microelectrodes, and profiles of NO₃ ⁻, SO₄ ²⁻, NH₄ ⁺, total inorganic carbon (DIC) and total alkalinity (TA) at cm resolution using standard wet chemical techniques. In addition, sediment–water fluxes of oxygen, DIC, nitrate, ammonium and N₂ were measured. Rates of gross and net sulfate reduction were also measured in the sediments. It is shown that organic matter (OM) decomposes via six pathways: oxic respiration (35.2%), denitrification (10.4%), MnO₂ reduction (3.6%), FeOOH reduction (9.6%), sulfate reduction (14.9%), and methanogenesis (26.4%). In the lake sediments, about half of the benthic O₂ flux is used for aerobic respiration, and the rest is used for the regeneration of other electron acceptors produced during the above diagenetic reactions. There is a strong coupling between O₂ usage and Mn²⁺ oxidation. MnO₂ is also an important player in Fe and S cycles and in pH and TA balance. Although nitrate concentrations in the overlying water were low, denitrification becomes a quantitatively important pathway for OM decomposition due to the oxidation of NH₄ ⁺ to NO₃ ⁻. Finally, despite its low concentration in freshwater, sulfate is an important electron acceptor due to its high efficiency of internal cycling. This paper also discusses quantitatively the relationship between redox reactions and the porewater pH values. It is demonstrated here that pH and pCO₂ are sensitive variables that reflect various oxidation and precipitation reactions in porewater, while DIC and TA profiles provide effective constraints on the rates of various diagenetic reactions.     

Carbonate characteristics of waters of the Arctic Ocean continental slope

Carbonate characteristics of the water mass of the deepwater part of the Arctic Ocean (AO) in the continental slope area were determined, and the range and reasons of their variability during summer-fall season were revealed. The AO water area is a meaningful sink for atmospheric carbon dioxide. The warm intermediate Atlantic waters (AW) are also undersaturated with carbon dioxide relative to its content in the atmosphere. While these waters move along AO continental slope, the value pCO₂ in the AW core decreases to 8–10 μatm (mainly, due to drop in the water temperature). The potential absorption capacity of the AO deepwater basin is estimated at approximately 48 Tg of carbon (without sea ice taken into account). Joint analysis of carbonate and hydrological parameters showed that near-bottom waters formed on the shallow shelf of the Laptev Sea, which is rich in inorganic and organic carbon of terrestrial and marine genesis, take part in formation of halocline waters of the AO. They are modified due to interaction with AW penetrating to the shelf and are transferred to the deepwater AO segment, where they occur in the halocline according to their density. Transformed near-bottom waters of the Laptev Sea shelf, similar to waters of the halocline of Pacific origin in the eastern sector of the AO, are traced above the continental slope in Amundsen Basin on the basis of higher CO₂ concentrations.     

Transmission of <Emphasis Type="Italic">δ</Emphasis><Superscript>13</Superscript>C signals and its paleoclimatic implications in Liangfeng Cave system of Guizhou Province,SW China

A series of samples, including vegetation, soil organic matter, soil waters, spring, bedrock, pool water, drip waters (upper-drip waters and ground-drip waters) and their corresponding speleothems were collected at Liangfeng Cave (LFC) system of Guizhou Province, southwest of China, respectively, from 2003 to 2004 year, then their stable carbon isotopes were measured and analyzed. Results reveal that vegetation is C₃ type in LFC system; cave overlying δ ¹³C signals, including values and variations, could be transmitted to drip water (speleothem); speleothem δ ¹³C mainly shows a biogenic δ ¹³C value character (soil CO₂ from plant respiration and decay); and there are remarkable seasonal variations of δ ¹³C values for drip water TDIC (speleothem), which are lighter at least 2.0‰ in the rainy seasons than in the dry ones. So, it could be feasible to reconstruct high-resolution changes of paleoecology and paleoclimate by using speleothem δ ¹³C values.     

Fluid inclusion and stable isotope evidence for the genesis of quartz-scheelite veins, Metaggitsi area, central Chalkidiki Peninsula, N. Greece

Scheelite mineralization accompanied by muscovite and albite, and traces of Mo-stolzite and stolzite occurs in epigenetic quartz vein systems hosted by two-mica gneissic schists, and locally amphibolites, of the Paleozoic or older Vertiskos Formation, in the Metaggitsi area, central Chalkidiki, N Greece. Three types of primary fluid inclusions coexist in quartz and scheelite: type 1, the most abundant, consists of mixed H₂O-CO₂ inclusions with highly variable (20–90 vol.%) CO₂ contents and salinities between 0.2 and 8.3 equivalent weight % NaCl. Densities range from 0.79 to 0.99 g/cc; type 1 inclusions contain also traces (<2 mol%) of CH₄. Type 2 inclusions are nearly 100 vol.% liquid CO_2, with traces of CH₄, and densities between 0.75 and 0.88 g/cc. Type 3 inclusions, the least abundant, contain an aqueous liquid of low salinity (0.5 to 8.5 equivalent weight% NaCl) with 10–30 vol.% H₂O gas infrequently containing also small amounts of CO₂ (<2 mol%); densities range from 0.72 to 0.99 g/cc. The wide range of coexisting fluid inclusion compositions is interpreted as a result of fluid immiscibility during entrapment. Immiscibility is documented by the partitioning of CH₄ and CO₂, into gas-rich (CO₂-rich) type 1 inclusions, and the conformity of end-member compositions trapped in type 1 inclusions to chemical equilibrium fractionation at the minimum measured homogenization temperatures, and calculated homogenization pressures. Minimum measured homogenization temperatures of aqueous and gas-rich type 1 inclusions of 220°–250 °C, either to the H₂O, or to the CO₂ phase, is considered the best estimate of temperature of formation of the veins, and temperature of scheelite deposition. Corresponding fluid pressures were between 1.2 and 2.6 kbar. Oxygen fugacities during mineralization varied from 10⁻³⁵ to 10⁻³¹ bar and were slightly above the synthetic Ni-NiO buffer values. The fluid inclusion data combined with δ¹⁸O water values of 3 to 6 per mil (SMOW) and δ¹³C CO₂₋ fluid of −1.2 to +4.3 per mil (PDB), together with geologic data, indicate generation of mineralizing fluids primarily by late- to post-metamorphic devolatilization reactions. Received: 8 April 1997 / Accepted: 8 July 1997     

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.