Seasonal variability in concentration, composition, age, and fluxes of particulate organic carbon exchanged between the floodplain and Amazon river

International audienceThe composition, sources, and age of particulate organic matter were determined in an Amazonian river-floodplain system during rising, high, falling, and low water periods over 7 yr (1999-2006), and a mass balance for total organic carbon (dissolved and particulate) was estimated. The Curuai floodplain, composed of several temporally interconnected lakes, is permanently connected to the Amazon River via channels. Organic matter (OM) is imported to the floodplain from the Amazon River mainly during the rising water period and produced in the floodplain and exported to the river during high and falling water periods. No significant exchanges occurred during low water periods. The OM produced in the floodplain is characterized by low C/N ratios and by high chlorophyll a concentrations (Chl-a). The δ13C signature has a seasonal trend, with more negative δ13C values during the high water period than other periods. Δ14C results indicate that the bulk OM present in floodplain lakes is predominantly post-bomb (i.e., post-1950). Particulate organic carbon (POC) and dissolved organic carbon (DOC) fluxes exported by the Curuai floodplain represent 1.3% and 0.1%, respectively, of the POC and DOC annual fluxes in the mainstem Amazon River at Óbidos but may reach up to 3.3% and 0.8% during falling water. Based on Δ14C, δ13C, Chl-a, and elemental analysis of the particulate organic matter, we demonstrate that floodplain lakes have intense phytoplankton and macrophyte primary production, which is partly exported to the main river channel. Floodplains are thus a significant source of modern and labile organic carbon to the river mainstem, where it can be rapidly degraded and recycled back to the atmosphere

Determinación de elementos mayores en sedimentos provenientes de zonas afectadas por actividades petroleras en Ecuador

Heavy metal pollution is one of the biggest problems of great concern at the global, regional and local levels due to mining and oil activities, because those elements constitute a threat to aquatic biota and human health. The major elements and heavy metals tend to accumulate in sediments, which act as secondary sources of contamination, and this process is closely related to the redox conditions, the particle size distribution of the sediments and the amount of sedimentary organic matter. Therefore, the aim of this work conducted in the frame of the MONOIL Research Program between France and Ecuador, is to determine the concentration of major elements (K, Mg, Na, Fe, Mn and Al) in the fine fraction of sediments, particles <4/μm, collected in the basins of the Aguarico, Napo and Esmeraldas Rivers, which are areas affected by the oil industry in Ecuador. Concentrations of major elements in the fine fraction are then compared to concentrations in the bulk, which was determined in the same sampling points in a previous work. Environmental parameters in surface waters such as temperature, dissolved oxygen (DO), pH, conductivity and oxide reduction potential (ORP) were determined in situ in each sampling point. The isolation of the fine fraction was carried out based on Stokes’ law after a homogenization, quartering and dissolution of the sediment in distilled water. Mineralization in sediments was performed by a triacid attack with HCl, HNO3 and HF. The major elements were determined by atomic absorption spectrophotometry (AAS). The ranges of major elements in the fine fraction of sediments were: Fe: 18-49, Al: 26-59, K: 3-15, Mg: 3-13, Na: 1-11 and Mn: 0.38-0.89 mg g-1; while concentrations in the bulk sediment concentrations were: Fe: 25-49, Al: 45-82, K: 5-20 Mg: 4-16, Na: 3-24 and Mn: 0.43-1.28 mg g-1. In the sediment samples of the Northern Ecuadorian Amazon rivers, 43% Na, 93% Fe, 70% Mg, 62% Mn and 94% K are associated with the fine fraction. The concentrations of Mg, Na and Mn in bottom sediments are influenced by oil activities, while Fe, K and Al concentrations depend on the natural origin of sediments. However, downstream up to the border with Peru, no significant increase in the concentrations of major elements in relation to the control points, upstream of the ZIL, the Local Area of influence of oil activities, was observed.La contaminación por metales pesados debido a la actividad petrolera es uno de los problemas de mayor preocupación a nivel mundial, regional y local, porque constituyen un peligro para la biota acuática y la salud humana. Los elementos mayores y metales pesados tienden a acumularse en los sedimentos, los cuales actúan como recursos secundarios de contaminación. Estos están íntimamente relacionados con las condiciones redox, la distribución del tamaño de las partículas en los sedimentos y la cantidad de materia orgánica sedimentaria. Por tanto, el objetivo de este proyecto realizado dentro del marco del programa de Investigación Franco-Ecuatoriano MONOIL, es determinar la concentración de los elementos mayores (K, Mg, Na, Fe, Mn y Al) en la fracción fina de sedimentos colectados en las cuencas de los ríos Aguarico, Napo y Esmeraldas, que constituyen áreas de influencia de la zona petrolera en el Ecuador, y compararlos con las concentraciones analizadas en el bulk de cada muestra en estudios anteriores. Los parámetros ambientales in situ que se determinaron en cada punto de muestreo fueron temperatura, oxígeno disuelto, pH, conductividad y potencial de óxido reducción. La separación de la fracción fina, partículas <4/μm, de los sedimentos se realizó en base a la ley de Stokes tras un proceso de homogenización, cuarteo y disolución en agua destilada. La mineralización de los sedimentos se realizó por un ataque triácido con HCl, HNO3 y HF. Los elementos mayores se determinaron por Espectrometría de Absorción Atómica (AAS). Los rangos de los elementos mayores encontrados en la fracción fina de sedimentos fueron Fe: 18-49, Al: 26-59, K: 3-15, Mg: 3-13, Na: 1-11 y Mn: 0.38-0.89 mg g-1. Mientras que las concentraciones en el bulk de los sedimentos fueron Fe: 25-49, Al: 45-82, K: 5-20, Mg: 4-16, Na: 3-24 y Mn: 0.43-1.28 mg g-1. En las muestras analizadas, el 43% del Na, el 93% del Fe, el 70% de Mg, el 62% de Mn y el 94% de K están asociados con la fracción fina de los sedimentos. Las concentraciones de Mg, Na y Mn están influenciadas por las actividades petroleras mientras que el contenido de Fe, K y Al está relacionado con el origen natural de los sedimentos. Sin embargo, aguas abajo, hasta la frontera con Perú, no se observa un incremento significativo en las concentraciones de elementos mayores en relación a los puntos de control, aguas arriba de la ZIL, Zona de Influencia Local de las actividades petroleras

Sensitive determination of methylmercury delta C-13 compound specific stable isotopic analysis by purge and trap gas chromatography combustion isotope ratio mass spectrometry

Despite several decades of mercury research, answering fundamental questions on where and how methylmercury (CH3Hg) toxin is naturally produced in aquatic ecosystems, is still highly challenging. Investigating complex and/or coupled processes in the context of global changes requires new high-resolution analytical tools. The purpose of the compound specific carbon stable isotopic analysis (delta C-13-CSIA) of the methyl group of methylmercury (CH3Hg), is to explore how the carbon cycle contributes to CH3Hg sources and formation pathways. The main problem associated with recent CH3Hg delta C-13-CSIA methods is the limited sensitivity when using Liquid Injection (LI)-GC-C-IRMS techniques, requiring several micrograms of CH3Hg (as Hg). In this work, we present the development and application of an original Purge-&-Trap system (PT) coupled to a GC-C-IRMS with the purpose of transferring and analyzing the total amount of CH3Hg available in a sample vial in the low nanogram range. The new PT-GC-C-IRMS system enhance the sensitivity by a factor better than 200, relative to LI-GC-C-IRMS, by minimizing the sample mass requirements. The delta C-13(CH3Hg) values obtained, following the same sample derivatization approach coupled to PT-GC-C-IRMS (-53.5 +/- 1.9 %), were in good agreement with the ones obtained in a previous study (-53.8 +/- 1.1 %). The standard solution was prepared from the same salt, requesting only 25-200 ng of CH3Hg (as Hg). This new methodology represents a milestone towards the analysis of large array of biological samples displaying CH3Hg concentrations in the low-mid ng g(-1) range, in order to explore the meaning of the carbon stable isotopic signature of CH3Hg in the environment

Inverse models to analyze the spatiotemporal variations of chemical weathering fluxes in a granito-gneissic watershed : Mule Hole, South India

Water-rock reactions are driven by the influx of water, which are out of equilibrium with the mineral assemblage in the rock. Here a mass balance approach is adopted to quantify these reactions. Based on field experiments carried out in a granito-gneissic small experimental watershed (SEW), Mule Hole SEW (similar to 4.5 km(2)), quartz, oligoclase, sericite, epidote and chlorite are identified as the basic primary minerals while kaolinite, goethite and smectite are identified as the secondary minerals. Observed groundwater chemistry is used to determine the weathering rates, in terms of 'Mass Transfer Coefficients' (MTCs), of both primary and secondary minerals. Weathering rates for primary and secondary minerals are quantified in two steps. In the first step, top red soil is analyzed considering precipitation chemistry as initial phase and water chemistry of seepage flow as final phase. In the second step, minerals present in the saprolite layer are analyzed considering groundwater chemistry as the output phase. Weathering rates thus obtained are converted into weathering fluxes (Q(weathering)) using the recharge quantity. Spatial variability in the mineralogy observed among the thirteen wells of Mule Hole SEW is observed to be reflected in the MTC results and thus in the weathering fluxes. Weathering rates of the minerals in this silicate system varied from few 10 mu mol/L (in case of biotite) to 1000 s of micromoles per liter (calcite). Similarly, fluxes of biotite are observed to be least (7 +/- 5 mol/ha/yr) while those of calcite are highest (1265 791 mol/ha/yr). Further, the fluxes determined annually for all the minerals are observed to be within the bandwidth of the standard deviation of these fluxes. Variations in these annual fluxes are indicating the variations in the precipitation. Hence, the standard deviation indicated the temporal variations in the fluxes, which might be due to the variations in the annual rainfall. Thus, the methodology adopted defines an inverse way of determining weathering fluxes, which mainly contribute to the groundwater concentration

Clay mineral composition of river sediments in the Amazon Basin

Clay minerals are important in evaluating the maturity of suspended sediments, weathering intensity and source area. However, there are processes that can change the mineral assemblage such as river transportation, deposition, remobilization and tributary inputs. In terms of water discharge and sediment yield, the Amazon is one of the largest rivers in the world. Most of the suspended sediments come from the Andes, crossing the lowlands before reaching the ocean. This study measures the spatial distribution of clay mineral assemblages over the entire Amazon basin. The results obtained show the main features of the Amazon River main stem and larger tributaries from their sources to their confluence. Clay mineral composition highlights the evolution of the Madeira and Maranon-Solimoes River, which start in the Andes with high illite+chlorite content. Downstream, smectite contents increase. Moreover, all shield tributaries show high kaolinite content. The lower Amazon River is characterized by relative high smectite content, different from the Andean sources. The clay mineral results show that suspended sediments of the Amazon River have three main sources: 1) the Andes mountains; 2) the Amazon shields and 3) the Piedmont basins, especially the Pastaza alluvial megafan and the Fitzcarrald Arch basin. Lateral bank erosion plays also a significant role, by the introduction of more mature sediments into the river, enriched in smectite

Volatile organic compounds identification and specific stable isotopic analysis (δ13C) in microplastics by purge and trap gas chromatography coupled to mass spectrometry and combustion isotope ratio mass spectrometry (PT-GC-MS-C-IRMS)

Microplastics (MPs) have become one of the major global environmental issues in recent decades due to their ubiquity in the environment. Understanding MPs source origin and reactivity is urgently needed to better constrain their fate and budget. Despite improvements in analytical methods to characterize MPs, new tools are needed to help understand their sources and reactivity in a complex environment. In this work, we developed and applied an original Purge-&-Trap system coupled to a GC–MS-C-IRMS to explore the δ13C compound-specific stable isotope analysis (CSIA) of volatile organic compounds (VOC) embedded in MPs. The method consists of heating and purging MP samples, with VOCs being cryo-trapped on a Tenax sorbent, followed by GC–MS-C-IRMS analysis. The method was developed using a polystyrene plastic material showing that sample mass and heating temperature increased the sensitivity while not influencing VOC δ13C values. This robust, precise, and accurate methodology allows VOC identification and δ13C CSIA in plastic materials in the low nanogram concentration range. Results show that the monomer styrene displays a different δ13C value (− 22.2 ± 0.2‰), compared to the δ13C value of the bulk polymer sample (− 27.8 ± 0.2‰). This difference could be related to the synthesis procedure and/or diffusion processes. The analysis of complementary plastic materials such as polyethylene terephthalate, and polylactic acid displayed unique VOC δ13C patterns, with toluene showing specific δ13C values for polystyrene (− 25.9 ± 0.1‰), polyethylene terephthalate (− 28.4 ± 0.5‰), and polylactic acid (− 38.7 ± 0.5‰). These results illustrate the potential of VOC δ13C CSIA in MP research to fingerprint plastic materials, and to improve our understanding of their source cycle. Further studies in the laboratory are needed to determine the main mechanisms responsible for MPs VOC stable isotopic fractionation

Seasonal effect on trace metal elements behaviour in a reservoir of northern Thailand

International audienc

A note on Be-10-derived mean erosion rates in catchments with heterogeneous lithology : examples from the western Central Andes

Millennial catchment-mean erosion rates derived from terrestrial cosmogenic nuclides are generally based on the assumption that the lithologies of the parent rock each contain the same proportion of quartz. This is not always true for large catchments, in particular at the edge of mountainous plateaus where quartz-rich basement rocks may adjoin sedimentary or volcano-sedimentary rocks with low quartz content. The western Central Andes is an example of this type of situation. Different quartz contents may be taken into account by weighting the TCN production rates in the catchment. We recall the underlying theory and show that weighting the TCN production rate may also lead to bias in the case of a spatial correlation between erosion rate and lithology. We illustrate the difference between weighted and unweighted erosion rates for seven catchments (16 samples) in southern Peru and northern Chile and show variations up to a factor of 2 between both approaches. In this dataset, calculated erosion rates considering only granitoid outcrops are better correlated with catchment mean slopes than those obtained without taking into account the geological heterogeneity of the drained watershed. This dataset analysis demonstrates that weighting erosion rates by relative proportions of quartz is necessary to evaluate the uncertainties for calculated catchment-mean erosion rates and may reveal the correlation with geomorphic parameters

Cl and Na fluxes in an Andean foreland basin of the Peruvian Amazon : an anthropogenic impact evidence

The dissolved load of the Amazon River is generally considered to be lowly impacted by anthropogenic activities. In this work, based on the chemical and hydrological database of the Environmental Research Observatory-HYBAM (http://www.ore-hybam.org), we explore the importance of the Peruvian Foreland petroleum activity on the dissolved Na and Cl fluxes of the Amazon River. The main result of this study allows us suggesting that oil extraction activity, concentrated in the El Tigre River basin, a small foreland watershed in the Peruvian Amazon, influenced drastically the Na and Cl exportation of the Amazon River during the 2006-2007 period. During these years, the dissolved exportations of this basin represented almost 20 % of the annual dissolved Cl Amazon flux and almost 12 % of the annual dissolved Na Amazon flux for a mean annual discharge\1 % of the Amazon River discharge. Since the last decades, the anthropogenic activities are increasing over the whole Amazon basin, especially in Andean countries. In this context, our results demonstrate that extractive activity cannot be considered as negligible on the hydro-chemistry of the Amazonian Rivers especially for the weathering budget estimation based on river-dissolved loads. Moreover, Cl and Na can be used to trace the formation waters derived from oil extraction at a large spatial scale. The environmental impacts of contaminants associated with deep water released to the hydrosystem (polycyclic aromatics hydrocarbons, metallic trace elements, etc.) at local and regional scales are still underestimated and should be monitored to map their local and regional influence and to prevent their risks on human health