Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.     

Modelling shallow landslide susceptibility: a new approach in logistic regression by using favourability assessment

A new method for estimating shallow landslide susceptibility by combining Geographical Information System (GIS), nonparametric kernel density estimation and logistic regression is described. Specifically, a logistic regression is applied to predict the spatial distribution by estimating the probability of occurrence of a landslide in a 16 km² area. For this purpose, a GIS is employed to gather the relevant sample information connected with the landslides. The advantages of pre-processing the explanatory variables by nonparametric density estimation (for continuous variables) and a reclassification (for categorical/discrete ones) are discussed. The pre-processing leads to new explanatory variables, namely, some functions which measure the favourability of occurrence of a landslide. The resulting model correctly classifies 98.55% of the inventaried landslides and 89.80% of the landscape surface without instabilities. New data about recent shallow landslides were collected in order to validate the model, and 92.20% of them are also correctly classified. The results support the methodology and the extrapolation of the model to the whole study area (278 km²) in order to obtain susceptibility maps.     

Long-term groundwater resource observatory for Southwestern Madagascar

Madagascar has one of the highest poverty rates in the world and consequently the long-term monitoring of groundwater resources is not a priority for the authorities. However, groundwater is often the only sustainable resource that has a satisfactory quality to supply the population. This is especially true in the south-west of the country, which is a semi-arid region and a global change hot spot (intense land use and climate changes). In response to the lack of data, the Groundwater Resource Observatory for Southwestern Madagascar (GROSoM) was established to monitor piezometry and meteorology over the longer term as part of a humanitarian response. The first site was setup in 2014 in a catchment located over a carbonate plateau; in 2018, a second site was installed in an alluvial setting within a crystalline basement catchment and a third site will be installed in 2020 to monitor groundwater dynamics in a coastal setting. The three sites, located between Toliara and Taolagnaro cities, are complementary and representative of various hydrogeological systems in Southwestern Madagascar. Each site includes a weather station and between 3 and 6 piezometric probes. The monitoring data indicate a strong inter-annual variability in precipitation, which induces a strong variability in aquifers recharge. One of the driest years in 2016 seems to be consistent with strong El Niño – Southern Oscillation (ENSO) effects observed at the global scale, while years with higher recharge appear to be related to cyclones such as Fundi in 2015 and Eketsang in 2019. Preliminary results of cross-disciplinary studies demonstrated a link between groundwater and health issues (i.e., admissions to basic health centres). This observatory aims to produce long-term data and has two objectives: (i) strengthening the early warning system for humanitarian crises in Madagascar; (ii) contributing to a better understanding of the effects of climate change on groundwater resources in this semi-arid region.     

Biomarkers of exposure and effect in the Brazilian flounder Paralichthys orbignyanus (Teleostei: Paralichthyidae) from the Patos Lagoon estuary (Southern Brazil)

Biomarkers of exposure (liver metallothionein-like proteins content and catalase and glutathione S-transferase activities) and effect (liver lipoperoxidation and blood cell DNA damage) of contaminants were analyzed in the Brazilian flounder Paralichthys orbignyanus from the Patos Lagoon estuary (Southern Brazil). Flounders were collected for a year in two sites: "Coroa do Boi" (polluted site) and "Saco do Justino" (non-polluted site). Results indicated that micronucleated cells frequency was the best biomarker to distinguish flounders from the two sites. Taken together, data from DNA damage analyses (micronucleus test and comet assay) indicated that flounders from the non-polluted site efficiently repaired the DNA breaks, contrary to those from the polluted site, which probably had their DNA repair system inhibited or exhausted. Furthermore, data from enzyme activities (catalase and GST) and lipid peroxidation indicated that flounders from the polluted site were under oxidative stress in summer and autumn.     

Effects of the 'Prestige' oil spill on macroalgal assemblages: large-scale comparison

An assessment of the effects of the 'Prestige' oil spill on intertidal, macroalgal assemblages was carried out comparing abundance data obtained before and after the spill. Four zones in the North and Northwest coast of Spain were sampled, one of them located at the immediate vicinity of the spill, the zone most heavily oiled. Macroalgal assemblages had similar structure between years. Neither critical decrease in abundance of the dominant macroalgae, nor increase in opportunistic species were found. Some differences in abundance were observed, but they did not show any pattern, being more likely the result of the natural variability of the assemblage. Extensive, but not intense fuel deposition on the shores and a limited use of aggressive cleanup methods are suggested as possible causes for the lack of the effects in these assemblages after the 'Prestige' oil spill.     

Multivariate discriminant analysis distinguishes metal- from non metal-related biomarker responses in the clam Chamaelea gallina

Molecular biomarkers are among the most sensitive and earliest responses to pollutants. However, lack of detailed knowledge on variability of responses and their possible seasonal variation limit their use. In addition, the seasonality of biological processes modulates the response of organisms to pollutant stressors. Using multivariate statistics, we have studied the influence of environmental and biological factors on the response of a battery of molecular biomarkers in the clam Chamaelea gallina collected along the South-Spanish littoral. Multivariate discriminant analysis clearly distinguished biomarker response between clean and polluted areas, using heavy metals as indicator of pollution. Such differences disappeared when the dataset was normalised for metal content, thus indicating that pollution was the main significant cause of the changes observed between clean and polluted sites. In conclusion, this work shows that, when applying a complete biomarker panel, multivariate statistical tools can be used to discern pollutant- from non pollutant-related responses.     

Least-squares prediction of horizontal coordinate distortions in Canada

A least-squares prediction method is described to estimate horizontal coordinate distortions at lower order points of a network using known coordinate differences (NAD27 coordinate distortions Δϕ′s and Δλ′s) at higher order points between NAD27 coordinates and coordinates derived from a recent (MAY 76), relatively distortion free, adjustment of these points. Empirical autocovariance functions of Δϕ and Δλ and crosscovariance function between Δϕ and Δλ are derived from some 5,250 data points and modelled using series of exponential functions. Empirical mean square values of Δϕ and Δλ, which are a measure of the distortions in NAD27 ϕ and λ, are 0.051 and 0.645 arcsecs² respectively. The corresponding mean value of the product ΔϕΔλ, which is a measure of the correlation between Δϕ and Δλ, is 0.056 arcsecs². The accuracy obtainable for predicted Δϕ and Δλ at an arbitrary point (e.g., lower order station) is a function of the accuracy and configuration of known Δϕ′s and Δλ′s in the surrounding area. Accuracies obtainable for various types of data configuration are given. Under favorable conditions taking place in about 60% of cases, accuracies in terms of ms agreement with known values of 0″.02 (0.6 m) and 0″.01 (0.2 m along parallel at latitude 50°) for the predicted latitude and longitude distortions are obtainable. Finally, a comparison with a method based on the use of complex polynomials is made. Presented at International Symposium on Geodetic Networks and Computations, Munich, August–September 1981.     

Field characterization and data integration to define the hydraulic heterogeneity of a shallow granular aquifer at a sub-watershed scale

Providing a sound basis for aquifer management or remediation requires that hydrogeological investigations carried out to understand groundwater flow and contaminant transport be based on representative data that capture the heterogeneous spatial distribution of aquifer hydraulic properties. This paper describes a general workflow allowing the characterization of the heterogeneity of the hydraulic properties of granular aquifers at an intermediate scale of a few km². The workflow involves characterization and data integration steps that were applied on a 12-km² study area encompassing a decommissioned landfill emitting a leachate plume and its main surface water receptors. The sediments composing the aquifer were deposited in a littoral–sublittoral environment and show evidence of small-scale transitional heterogeneities. Cone penetrometer tests (CPT) combined with soil moisture and electrical resistivity (SMR) measurements were thus used to identify and characterize spatial heterogeneities in hydraulic properties over the study area. Site-specific statistical relationships were needed to infer hydrofacies units and to estimate hydraulic properties from high-resolution CPT/SMR soundings distributed all over the study area. A learning machine approach was used due to the complex statistical relationships between colocated hydraulic and CPT/SMR data covering the full range of aquifer materials. Application of this workflow allowed the identification of hydrofacies units and the estimation of horizontal hydraulic conductivity, vertical hydraulic conductivity and porosity over the study area. The paper describes and discusses data acquisition and integration methodologies that can be adapted to different field situations, while making the aquifer characterization process more time-efficient and less labor-intensive.