A new groundwater radiocarbon correction approach accounting for palaeoclimate conditions during recharge and hydrochemical evolution: The Ledo-Paniselian Aquifer,Belgium

The particular objective of the present work is the development of a new radiocarbon correction approach accounting for palaeoclimate conditions at recharge and hydrochemical evolution. Relevant climate conditions at recharge are atmospheric pCO₂ and infiltration temperatures, influencing C isotope concentrations in recharge waters. The new method is applied to the Ledo-Paniselian Aquifer in Belgium. This is a typical freshening aquifer where recharge takes place through the semi-confining cover of the Bartonian Clay. Besides cation exchange which is the major influencing process for the evolution of groundwater chemistry (particularly in the Bartonian Clay), also mixing with the original porewater solution (fossil seawater) occurs in the aquifer. Recharge temperatures were based on noble gas measurements. Potential infiltration water compositions, for a range of possible pCO₂, temperature and calcite dissolution system conditions, were calculated by means of PHREEQC. Then the sampled groundwaters were modelled starting from these infiltration waters, using the computer code NETPATH and considering a wide range of geochemical processes. Fitting models were selected on the basis of correspondence of calculated δ¹³C with measured δ¹³C. The ¹⁴C modelling resulted in residence times ranging from Holocene to Pleistocene (few hundred years to over 40 ka) and yielded consistent results within the uncertainty estimation. Comparison was made with the δ¹³C and Fontes and Garnier correction models, that do not take climate conditions at recharge into account. To date these are considered as the most representative process-oriented existing models, yet differences in calculated residence times of mostly several thousands of years (up to 19 ka) are revealed with the newly calculated ages being mostly (though not always) younger. Not accounting for climate conditions at recharge (pCO₂ and temperature) is thus producing substantial error on deduced residence times. The derived ¹⁴C model ages are correlated with He concentrations measured in the groundwater of the aquifer. The obtained residence times show a gap between about 14 and 21 ka indicating possible permafrost conditions which inhibited any groundwater recharge.     

Shallow-marine carbonate cementation in Holocene segments of the calcifying green alga Halimeda

Early-diagenetic cementation of tropical carbonates results from the combination of numerous physico-chemical and biological processes. In the marine phreatic environment it represents an essential mechanism for the development and stabilization of carbonate platforms. However, diagenetic cements that developed early in the marine phreatic environment are likely to become obliterated during later stages of meteoric or burial diagenesis. When lithified sediment samples are studied, this complicates the recognition of processes involved in early cementation, and their geological implications. In this contribution, a petrographic microfacies analysis of Holocene Halimeda segments collected on a coral island in the Spermonde Archipelago, Indonesia, is presented. Through electron microscopical analyses of polished samples, this study shows that segments are characterized by intragranular cementation of fibrous aragonite, equant High-Mg calcite (3.9 to 7.2 Mol% Mg), bladed Low-Mg calcite (0.4 to 1.0 Mol% Mg) and mini-micritic Low-Mg calcite (3.2 to 3.3 Mol% Mg). The co-existence and consecutive development of fibrous aragonite and equant High-Mg calcite results initially from the flow of oversaturated seawater along the aragonite template of the Halimeda skeleton, followed by an adjustment of cement mineralogy towards High-Mg calcite as a result of reduced permeability and fluid flow rates in the pores. Growth of bladed Low-Mg calcite cements on top of etched substrates of equant High-Mg calcite is explained by shifts in pore water pH and alkalinity through microbial sulphate reduction. Microbial activity appears to be the main trigger for the precipitation of mini-micritic Low-Mg calcite as well, based on the presumable detection of an extracellular polymeric matrix during an early stage of mini-micrite Low-Mg calcite cement precipitation. Radiocarbon analyses of five Halimeda segments furthermore indicate that virtually complete intragranular cementation in the marine phreatic environment with thermodynamically/kinetically controlled aragonite and High-Mg calcite takes place in about 100 years. Collectively, this study shows that early-diagenetic cements are highly diverse and provides new quantitative constraints on the rate of diagenetic cementation in tropical carbonate factories.     

Assessing Metal-Induced Changes in the Visible and Near-Infrared Spectral Reflectance of Leaves: A Pot Study with Sunflower (<Emphasis Type="Italic">Helianthus annuus</Emphasis> L.)

The aim of this study was to monitor changes in leaf spectral reflectance due to phytoaccumulation of trace elements (Cd, Pb, and As) in sunflower mutant (M5 mutant line 38/R4-R6/15-35-190-04-M5) grown in spiked and in situ metal-contaminated potted soils. Reflectance spectra (350–2500 nm) of leaves were collected using portable ASD spectroradiometer, and respective leaves sample were analyzed for total metal contents. The spectral changes were quite noticeable and showed increased visible and decreased NIR reflectance for sunflower grown in soil spiked with 900 mg As kg^?1, and in in situ metal-contaminated soils. These changes also involved a blue-shift feature of red-edge position in the first derivatives spectra, studied vegetation indices and continuum removed absorption features at 495, 680, 970, 1165, 1435, 1780, and 1925 nm wavelength. Correlograms of leaf-metal concentration and reflectance values show highest degrees of overall correlation for visible, near-infrared, and water-sensitive wavelengths. Partial least square and multiple linear regression statistical models (cross-validated), respectively, based on Savitzky–Golay filter first-order derivative spectra and combination of spectral feature such as vegetation indices and band depths yielded good prediction of leaf-metal concentrations.