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Aquatic Geochemistry (v.19, #3)

Messinian Ca–Cl Brines from Mediterranean Basins: Tracing Diagenetic Effects by Ca/Mg Versus Ca/Sr Diagram by Tiziano Boschetti; Vinicio Manzi; Lorenzo Toscani (pp. 195-208).

In natural resource exploration, Ca–Cl basinal brines are important for understanding the origin and spatial and temporal distribution of hydrocarbons and sedimentary ore deposits. Little attention has been paid to the possible connection between fossil basinal brines and paleo-seawaters and to the implications for reconstructing paleo-seawater compositions. Secular variations of Ca/Mg and Ca/Sr ratios in seawater have been documented mainly using fluid inclusions in halite, calcareous fossils and mineral analyses. However, brines and other sedimentary records connected to paleo-seawater or its evaporated residues may be chemically affected by burial diagenesis or the effects of continental waters of meteoric origin, thus complicating interpretations of the analytical results. To investigate these effects on fluids and minerals related to the Messinian salinity crisis of the Mediterranean basin, we re-evaluate published data from: (1) brackish-to-brine waters from onshore (Northern Apennine foredeep; Levantine basin) and offshore (porewaters from the Deep Sea Drilling Project); (2) Messinian parental seawater deduced from calcareous fossils, fluid inclusions and sulfate minerals; (3) meteoric waters dissolving evaporites. The compositional trends related to seawater evaporation, diagenesis and mixing that affect the Ca/Mg and Ca/Sr molar ratios of the basinal brines are effectively discriminated on a binary plot depicting the proper fields for seawater and meteoric-derived fluids. Brines showing stronger dolomitization start from Ca/Mg and Ca/Sr molar ratios of Messinian seawater deduced from the published analysis of fluid inclusions and open ocean fossils, that are therefore here validated ex post.

Keywords: Ca/Mg and Ca/Sr ratios; Ca–Cl brines; Diagenetics effects; Messinian seawater

Isotopic and Chemical Constraints on the Biogeochemistry of Dissolved Inorganic Carbon and Chemical Weathering in the Karst Watershed of Krka River (Slovenia) by Saša Zavadlav; Tjaša Kanduč; Jennifer McIntosh; Sonja Lojen (pp. 209-230).

The hydrogeochemical and carbon isotope characteristics of the Krka River, Slovenia, were investigated to estimate the carbon transfer from the land ecosystem in the watershed. During the 3-year sampling period (2008–2010), temperature, pH, electrical conductivity, major ion content, dissolved inorganic carbon (DIC) and dissolved organic carbon content, and the isotopic composition of DIC (δ¹³C_DIC) were monitored in the main stream of the Krka River and its tributaries. The major solute composition of analysed waters is dominated by an input of HCO₃ ⁻, Ca²⁺ and Mg²⁺ originating from carbonate dissolution. The Mg²⁺/Ca²⁺ and Mg²⁺/HCO₃ ⁻ molar ratio values ranging from 0.24 to 0.71 and 0.05 to 0.30, respectively, indicate a high degree of dolomite dissolution relative to calcite. Dissolved CO₂ concentrations in the river were up to tenfold supersaturated relative to the atmosphere, resulting in supersaturation with respect to calcite and degassing of CO₂ downstream. The δ¹³C values in river water range from −15.6 to −9.4 ‰ and are controlled by the input of tributaries, exchange with atmospheric CO₂, degradation of organic matter, and dissolution of carbonates. The mass balance calculations for riverine DIC suggest that the contribution from carbonate dissolution and degradation of organic matter have major influence, whereas the exchange with atmospheric CO₂ has minor influence on the inorganic carbon pool in the Krka River.

Keywords: River; Carbonate weathering; Biogeochemical processes; Dissolved inorganic carbon; Stable carbon isotopes

Strontium Isotopic Signatures of Streams from Taylor Valley, Antarctica, Revisited: The Role of Carbonate Mineral Dissolution by Carolyn B. Dowling; W. B. Lyons; Kathleen A. Welch (pp. 231-240).

We have collected and analyzed a larger set of stream waters for major ions and strontium isotopes in Taylor Valley, McMurdo Dry Valleys, Antarctica. These new data substantiate the concept that the dissolution of carbonate minerals is a significant source of strontium, even in polar desert environments where liquid water is primarily limited to stream channels. In Taylor Valley, most of the carbonate minerals present are the result of secondary processes, such as mineral precipitation and/or eolian deposition, and not through primary geologic sources, such as bedrock or till sources. In Von Guerard Stream (Lake Fryxell basin) and Andersen Creek (Lake Hoare basin), water samples were collected during the austral summer to determine short-term ⁸⁷Sr/⁸⁶Sr patterns. The observed variability in both time and space may be dependent on the relative amounts of primary and secondary carbonates present in the streambeds and hyporheic zone as well as contingent on the relative proportions of carbonate and aluminosilicate weathering.

Keywords: Strontium isotopes; Carbonate weathering; Aluminosilicate weathering; Taylor Valley, Antarctica

Changes in Nutrient Biogeochemistry in Response to the Regression of Zostera noltii Meadows in the Arcachon Bay (France) by Marie-Lise Delgard; Bruno Deflandre; Jonathan Deborde; Marion Richard; Céline Charbonnier; Pierre Anschutz (pp. 241-259).

From 1989 to 2007, a severe decline in Zostera noltii meadows was reported in the Arcachon Bay, with an accelerated regression after 2005. We investigated the inter-annual variability of the biogeochemistry of the sediment in an area affected by seagrass decline. In late summer and in winter of the years 2006, 2010, and 2011, sediment cores were collected at low tide on vegetated and adjacent non-vegetated sediments located in the eastern part of the Arcachon Bay. The geochemical analyses of sediment solid-phase organic carbon, reactive P and Fe, and the pore water concentrations of Fe²⁺, DIP, and NH₄ ⁺ are presented. The changes in the chemistry of sediment and pore water between 2006 and 2010 are interpreted as a consequence of the decrease in the Z. noltii biomass between 2006 and 2010. The absence of significant seasonal variations in biomass throughout the growth period (March–September) in 2011 is most likely related to the regression of Z. noltii meadow that strongly affects the study area. In contrast to the healthy meadow in 2006, the declining meadow favored the dissolution of sedimentary particulate phosphorus in winter. In late summer, the low biomass of seagrass resulted in a net release of ammonium in the pore water of the upper 20 cm of sediment. This study clearly shows that seagrass decay may enhance nutrient release in sediments, resulting in a significant supply of phosphorus to the water column of a magnitude comparable to annual inputs to the lagoon from the rivers and the tidal pump.

Keywords: Zostera noltii ; Regression; Geochemistry; Nutrients; Sediments; Arcachon

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Aquatic Geochemistry (v.19, #3)

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Aquatic Geochemistry (v.19, #3)