We present here an improved and reliable method for measuring the concentration of dissolved inorganic carbon (DIC) and its isotope composition (delta(13)C(DIC)) in natural water samples. Our apparatus, a gas chromatograph coupled to an isotope ratio mass spectrometer (GCIRMS), runs in a quasi-automated mode and is able to analyze about 50 water samples per day. The whole procedure (sample preparation, CO(2(g))-CO(2(aq)) equilibration time and GCIRMS analysis) requires 2 days. It consists of injecting an aliquot of water into a H(3)PO(4)-loaded and He-flushed 12 mL glass tube. The H(3)PO(4) reacts with the water and converts the DIC into aqueous and gaseous CO(2). After a CO(2(g))-CO(2(aq)) equilibration time of between 15 and 24 h, a portion of the headspace gas (mainly CO(2)+He) is introduced into the GCIRMS, to measure the carbon isotope ratio of the released CO(2(g)), from which the delta(13)C(DIC) is determined via a calibration procedure. For standard solutions with DIC concentrations ranging from 1 to 25 mmol . L(-1) and solution volume of 1 mL (high DIC concentration samples) or 5 mL (low DIC concentration samples), delta(13)C(DIC) values are determined with a precision (1sigma) better than 0.1 per thousand. Compared with previously published headspace equilibration methods, the major improvement presented here is the development of a calibration procedure which takes the carbon isotope fractionation associated with the CO(2(g))-CO(2(aq)) partition into account: the set of standard solutions and samples has to be prepared and analyzed with the same 'gas/liquid' and 'H(3)PO(4)/water' volume ratios. A set of natural water samples (lake, river and hydrothermal springs) was analyzed to demonstrate the utility of this new method.

In this paper we present chemical composition data for major elements in rivers from three islands of the Lesser Antilles. The Lesser Antilles are a tropical volcanic subduction arc and are characterized by steep gradients of relief, bedrock age and precipitation. They constitute a natural laboratory where the response of the weathering engine to large variations of runoff can be understood. Data indicate that the Lesser Antilles are characterized by extremely variable chemical weathering (40-430 t/km 2 /a) and CO 2 consumption (300-3500.10 3 mol/km 2 /a) rates, amongst the highest found on Earth and consistent with the previous studies on the weathering of volcanic rock. A noteworthy observation is that, along the runoff gradient, concentrations of rock-derived solutes do not follow a pure dilution law and that a buffering mechanism exists stabilizing solute concentrations. As a result concentrations vary much less than runoff and chemical weathering rates are mainly controlled by runoff. Precipitation patterns in the Lesser Antilles are essentially orographic and controlled by the adiabatic decompression of the water-saturated Atlantic air masses. The production of acidity by volcanic degassing is an additional factor that modulates the runoff effect. Two main conclusions can be drawn from this study. First, chemical weathering fluxes of oceanic islands are strongly dependent upon relief repartition, which cautions the use of regional mean values to compare volcanic islands. Second, volcanic activity in the Lesser Antilles subduction arc, by creating relief, promotes high orographic precipitation and/or infiltration regimes, that in turn results in elevated chemical weathering and atmospheric CO 2 consumption fluxes. This feedback mechanism, implying mainly precipitation and relief, is proposed to act in complement to the temperature-related feedback proposed by previous authors for stabilizing the atmospheric CO 2 content of the atmosphere in response to volcanic CO 2 degassing. This study highlights the importance of the water cycle in controlling chemical weathering of volcanic arc islands and associated CO 2 consumption rates.

International audienceIn this paper, we use carbon isotopes in the dissolved load of rivers from the Lesser Antilles volcanic arc (Guadeloupe, Martinique and Dominica islands) to constrain the source of the carbon dioxide (CO2) involved in the neutralization reactions during water-rock interactions. The d13C data span a large range of variations, from -19% to -5 _ 2% for DIC (dissolved inorganic carbon) concentrations ranging from 11 mM to 2000 mM. Coupled with major element concentrations, carbon isotopic ratios are interpreted as reflecting a mixture of magmatic CO2 (enriched in heavy carbon (d13C_-3 _ 5%) and biogenic CO2 produced in soils (enriched in light carbon (d13C<-17%)). Carbon isotopes show that, at the regional scale, 23 to 40% of CO2 consumed by weathering reactions is of magmatic origin and is transferred to the river system through aquifers under various thermal regimes. These numbers remain first-order estimates as the major uncertainty in using carbon isotopes as a source tracer is that carbon isotopes can be fractionated by a number of processes, including soil and river degassing. Chemical weathering is clearly, at least, partly controlled by the input of magmatic CO2, either under hydrothermal (hot) or surficial (cold) weathering regimes. This study shows that the contribution of magmatic CO2 to chemical weathering is an additional parameter that could explain the high weathering rates of volcanic rocks. The study also shows that a significant part of the carbon degassed from the Earth's interior is not released as CO2 to the atmosphere, but as DIC to the ocean because it interacts with the groundwater system. This study calls for a better understanding of the contributions of deep carbon to the hydrosphere and its influence on the development of the Critical Zone