Geochemistry of Triassic Carbonates: Exploration Guide to Pb–Zn Mineralization in North Tunisia

The Triassic carbonate rocks in Northern Tunisia (Nappes, Domes, Jurassic Mountains zones), consist of massive carbonates, clays and gypsum with authigenic minerals. These are associated with several Pb–Zn deposits and occurrences. At Jebel Ichkeul, Bechateur and Oum Edeboua, these Triassic carbonates exhibit enrichment in Pb (0.32 to 228 ppm), Zn (17 to 261 ppm), Cd (5 to 6 ppm) and Co (0.3 to 89.5 ppm), with respect to their average contents in crustal carbonates. The enrichment is more pronounced at Oum Edeboua (near the ore zone). Permeability is one of the most effective factors of dispersion of metallic trace elements, causing the development of geochemical halos. The genetic relationship of the Triassic carbonate rocks with the ore deposits was controlled by diapirism and tectonic movements, which favored mineralization along the Triassic‐cover contact as well as the remobilization of metals from the mineralized rocks. Analysis of metallic trace elements in Triassic rocks provides clues to the presence of possible mineral deposits. These could be effectively used for both geochemical interpretation and mineral exploration. Carbon and O‐isotope data (– 9.3‰ < δ¹³C < +3‰; +21.9 < δ¹⁸O < +31‰) suggest that the Triassic carbonates of all study areas have marine carbonates as their origin; some of them show significantly lower δ¹⁸O values indicating some exchange with hydrothermal fluids. Calcites associated with mineralization at Oum Edeboua have δ¹³C of –6.2‰ to –8.22‰ and δ¹⁸O of +24.88‰ to +25‰. The C‐isotope compositions of these calcites are ¹³C depleted, indicating an organic origin.     

A study on the dissolution rates of K-Cr(VI)-jarosites: kinetic analysis and implications

Background

The presence of natural and industrial jarosite type-compounds in the environment could have important implications in the mobility of potentially toxic elements such as lead, mercury, arsenic, chromium, among others. Understanding the dissolution reactions of jarosite-type compounds is notably important for an environmental assessment (for water and soil), since some of these elements could either return to the environment or work as temporary deposits of these species, thus would reduce their immediate environmental impact.

Results

This work reports the effects of temperature, pH, particle diameter and Cr(VI) content on the initial dissolution rates of K-Cr(VI)-jarosites (KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆). Temperature (T) was the variable with the strongest effect, followed by pH in acid/alkaline medium (H₃O⁺/OH^?). It was found that the substitution of CrO₄ ^2?in Y-site and the substitution of H₃O⁺ in M-site do not modify the dissolution rates. The model that describes the dissolution process is the unreacted core kinetic model, with the chemical reaction on the unreacted core surface. The dissolution in acid medium was congruent, while in alkaline media was incongruent. In both reaction media, there is a release of K⁺, SO₄ ^2? and CrO₄ ^2? from the KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆ structure, although the latter is rapidly absorbed by the solid residues of Fe(OH)₃ in alkaline medium dissolutions. The dissolution of KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆ exhibited good stability in a wide range of pH and T conditions corresponding to the calculated parameters of reaction order n, activation energy E _A and dissolution rate constants for each kinetic stages of induction and progressive conversion.

Conclusions

The kinetic analysis related to the reaction orders and calculated activation energies confirmed that extreme pH and T conditions are necessary to obtain considerably high dissolution rates. Extreme pH conditions (acidic or alkaline) cause the preferential release of K⁺, SO₄ ^2? and CrO₄ ^2? from the KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆ structure, although CrO₄ ^2? is quickly adsorbed by Fe(OH)₃ solid residues. The precipitation of phases such as KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆, and the absorption of Cr(VI) after dissolution can play an important role as retention mechanisms of Cr(VI) in nature.

     

Geochemical analysis of evaporite sedimentation in the Gachsaran Formation,Zeloi oil field,southwest Iran

In this study, the paleo-sedimentary depositional environment of the Gachsaran Formation and the Asmari reservoir cap rock (i.e., the stratigraphically lowest member of the Gachsaran Formation) was investigated from elemental geochemical data and mineralogical data obtained XRF and SEM analyses, respectively, of anhydrite samples collected from two oil wells in the Zeloi oil field in southwestern Iran. The present data reveal that arid conditions and cycles of transgression–regression of the sea contributed to the formation of evaporite sequences of the Gachsaran Formation in a coastal sabkha-lagoon basin that was partly closed to the sea. This interpretation was based on synthesis of statistical correlation analysis the geochemical data, chemostratigraphic correlation of geochemical ratios, and textural analysis of salts observed in SEM images.     

Using response surfaces to estimate impacts of climate change on flood peaks: assessment of uncertainty

The potential impacts of climate change are an increasing focus of research, and ever‐larger climate projection ensembles are available, making standard impact assessments more onerous. An alternative way of estimating impacts involves response surfaces, which present the change in a given indicator for a large number of plausible climatic changes defined on a regular sensitivity domain. Sets of climate change projections can then be overlaid on the response surface and impacts estimated from the nearest corresponding points of the sensitivity domain, providing a powerful method for fast impact estimation for multiple projections and locations. However, the effect of assumptions necessary for initial response surface development must be assessed. This paper assesses the uncertainty introduced by use of a sensitivity framework for estimating changes in 20‐year return period flood peaks in Britain. This sensitivity domain involves mean annual and seasonal precipitation changes, and a number of simplifications were necessary for consistency and to reduce dimensionality. The effect of these is investigated for nine catchments across Britain, representing nine typical response surfaces (response types), using three sets of climate projections. The results show that catchments can have different causes of uncertainty and some catchments have an overall higher level of uncertainty than others. These differences are compatible with the underlying climatological and hydrological differences between the response types, giving confidence in generalization of the results. This enables the development of uncertainty allowances by response type, to be used alongside the response surfaces to provide more robust impact estimates. Copyright © 2013 John Wiley & Sons, Ltd.     

Improvement of the solute transfer in a conceptual unsaturated zone scheme: a case study of the Seine River basin

For predicting the evolution of solute concentrations in groundwater and testing the impact of remediation policies, a coupling between the agronomical model STICS and the hydrogeological model MODCOU was implemented. When applied to the Seine River basin, this model accurately represents the temporal evolution of average nitrate concentrations in the aquifer, but with large local errors. We propose an improvement to the simple unsaturated zone (UZ) scheme NonsatSW used in STICS–MODCOU. The modifications are based on a comparison with the mechanistic model Metis considered as a reference as it solves Richards' equation. A more realistic saturation profile and a varying percolation rate are integrated in NonsatSW. This new model, named NonsatVG, is assessed by comparing it with NonsatSW and Metis. In an ideal case, NonsatVG generates a solute transfer and a dispersion closer to that of Metis than of NonsatSW. In real cases, without additional calibration, NonsatVG and Metis simulate better the average transfer velocities of the observed nitrate profiles. Furthermore, modifications in NonsatVG give a direct relationship between the depth of the water table and the saturation profile. We obtain, therefore, as in Metis, an evolution of the solute transfer velocity depending on the piezometric level. These dynamics are not simulated in NonsatSW. Despite a modified water transfer through the UZ, NonsatVG is also as valid as NonsatSW in the modelling of water transfer to the saturated zone. Finally, an application to the Seine basin shows that solute transfer velocities are lower with NonsatVG than with NonsatSW, but are in better agreement with literature. Copyright © 2010 John Wiley & Sons, Ltd.     

Early to mid‐Holocene climate change at Lago dell'Accesa (central Italy): climate signal or anthropogenic bias?

Despite the high potential of pollen records for climate reconstruction, pollen–climate relationships may be biased due to past and present human activities on the landscape. We use (i) transfer functions based on modern pollen–climate relationships to infer seasonal temperature and summer precipitation for the period 11 500–4500 cal. a BP and (ii) lake‐level change records based on different sedimentary proxies in multiple cores that are mainly indicative for summer hydrology at Lago dell'Accesa (central Italy). Quantitative reconstructions indicate lowest summer precipitation during two phases (8500–7700 cal. a BP and after 6000 cal. a BP) and a gradual winter temperature increase from 11 500 to ca. 8000 cal. a BP. Lowest summer precipitation was reconstructed during these phases characterised by vegetation shifts from open forests dominated by summergreen oaks (Quercus) to forests dominated by evergreen oaks (Quercus ilex), which are at present most abundant where summer drought is stronger. Similarly, the lake‐level record indicates two long‐lasting low summer precipitation phases (8800–7700 and 6400–4400 cal. a BP) that were interrupted by short‐term high summer precipitation events. Based on the broad agreement between the pollen‐inferred summer precipitation and the low‐frequency lake‐level changes, we suggest that the duration of the high summer precipitation events may have been too short to maintain drought‐sensitive trees, which may have been affected by high mortality rates when summer dry conditions returned. Although past and modern pollen–climate relationships may very likely have been affected by human activities since the Neolithic (i.e. when exploitation of the landscape started), we reject the hypothesis of a significant anthropogenic bias in the pollen‐based climate reconstruction. In addition, we suggest that pollen‐based and lake‐level reconstructions may have different inherent abilities of capturing high‐ and low‐frequency precipitation signals. Copyright © 2010 John Wiley & Sons, Ltd.     

Mercury Dynamics in a San Francisco Estuary Tidal Wetland: Assessing Dynamics Using In Situ Measurements

We used high-resolution in situ measurements of turbidity and fluorescent dissolved organic matter (FDOM) to quantitatively estimate the tidally driven exchange of mercury (Hg) between the waters of the San Francisco estuary and Browns Island, a tidal wetland. Turbidity and FDOM??representative of particle-associated and filter-passing Hg, respectively??together predicted 94?% of the observed variability in measured total mercury concentration in unfiltered water samples (UTHg) collected during a single tidal cycle in spring, fall, and winter, 2005?C2006. Continuous in situ turbidity and FDOM data spanning at least a full spring-neap period were used to generate UTHg concentration time series using this relationship, and then combined with water discharge measurements to calculate Hg fluxes in each season. Wetlands are generally considered to be sinks for sediment and associated mercury. However, during the three periods of monitoring, Browns Island wetland did not appreciably accumulate Hg. Instead, gradual tidally driven export of UTHg from the wetland offset the large episodic on-island fluxes associated with high wind events. Exports were highest during large spring tides, when ebbing waters relatively enriched in FDOM, dissolved organic carbon (DOC), and filter-passing mercury drained from the marsh into the open waters of the estuary. On-island flux of UTHg, which was largely particle-associated, was highest during strong winds coincident with flood tides. Our results demonstrate that processes driving UTHg fluxes in tidal wetlands encompass both the dissolved and particulate phases and multiple timescales, necessitating longer term monitoring to adequately quantify fluxes.     

Integrating spatial, temporal, and magnitude probabilities for medium-scale landslide risk analysis in Darjeeling Himalayas, India

Landslide risk assessment is based on spatially integrating landslide hazard with exposed elements-at-risk to determine their vulnerability and to express the expected direct and indirect losses. There are three components that are relevant for expressing landslide hazard: spatial, temporal, and magnitude probabilities. At a medium-scale analysis, this is often done by first deriving a landslide susceptibility map, and to determine the three types of probabilities on the basis of landslide inventories linked to particular triggering events. The determination of spatial, temporal, and magnitude probabilities depend mainly on the availability of sufficiently complete historical records of past landslides, which in general are rare in most countries (e.g., India, etc.). In this paper, we presented an approach to use available historical information on landslide inventories for landslide hazard and risk analysis on a medium scale (1:25,000) in a perennially typical data-scarce environment in Darjeeling Himalayas (India). We demonstrate how the incompleteness in the resulting landslide database influences the various components in the calculation of specific risk of elements-at-risk (e.g., buildings, population, roads, etc.). We incorporate the uncertainties involved in the risk estimation and illustrate the range of expected losses in the form of maximum and minimum loss curves. The study demonstrates that even in data-scarce environments, quantitative landslide risk assessment is a viable option, as long as the uncertainties involved are expressed.     

Soil porosity resulting from the assemblage of silt grains with a clay phase: New perspectives related to utilization of X-ray synchrotron computed microtomography

Understanding the assemblage of basic grains is essential for predicting many soil properties. X-ray synchrotron microtomography with a high resolution was used for visualisation and quantification of the assemblage of silt grains with a clay phase containing 20% of clays. The 3D computed image was analysed after appropriate segmentation by using: (i) autocorrelation functions which enables anisotropy discussion of the assemblage; (ii) chord distribution which gives information on the size distribution of the void and solid phases; and (iii) the Hoshen-Kopelman algorithm (6-connectivity) in order to label each void with a unique number and thus enabling discussion of the connectivity. Our results show that X-ray synchrotron microtomography enables a more accurate analysis of the assemblage of silt grains with a clay phase than with conventional methods. Thus, it showed the isotropy of the silt-clay assemblage in the studied soil material. The void and solid phase volumes were smaller than 80 and 120 μm in all directions, respectively. The mean distance between two interfaces was 6.9 and 13.4 μm for the void and solid phase, respectively. X-ray synchrotron microtomography of the soil material studied also showed that the voids resulting from the assemblage of the silt grains with the clay phase can be considered as fully connected in the studied dried materials.     

An Intercomparison Study of the Germanium Isotope Composition of Geological Reference Materials

Recent analytical developments in germanium stable isotope determination by multicollector ICP‐MS have provided new perspectives for the use of Ge isotopes as geochemical tracers. Here, we report the germanium isotope composition of the NIST SRM 3120a elemental reference solution that has been calibrated relative to internal isotopic standard solutions used in the previous studies. We also intercalibrate several geological reference materials as well as geological and meteoritic samples using different techniques, including online hydride generation and a spray chamber for sample introduction to MC‐ICP‐MS, and different approaches for mass bias corrections such as sample–calibrator bracketing, external mass bias correction using Ga isotopes and double‐spike normalisation. All methods yielded relatively similar precisions at around 0.1‰ (2s) for δ^74/70Ge values. Using igneous and mantle‐derived rocks, the bulk silicate Earth (BSE) δ^74/70Ge value was re‐evaluated to be 0.59 ± 0.18‰ (2s) relative to NIST SRM 3120a. Several sulfide samples were also analysed and yielded very negative values, down to ?4.3‰, consistent with recent theoretical study of Ge isotope fractionation. The strong heavy isotope depletion in ore deposits also contrasts with the generally positive Ge isotope values found in many modern and ancient marine sediments.