Applied Geochemistry (v.25, #8)

Forest clearing through slash and burn to open up agricultural land is an ongoing process in large parts of the Amazon Basin. This activity severely affects the structure and balance of the natural ecosystem, and also has the potential to cause substantial changes in landscape geochemistry. The latter is the topic of this study, with special attention on translocation of potentially toxic trace elements from deforested areas to downstream aquatic and terrestrial systems. Sampling of floodplain sediments and mountain soils (Inceptisols on redbed lithologies) was carried out in two adjacent Subandean river basins, with deforestation extents of ca. 1/3 and 2/3 of the basin areas. Several toxic and potentially toxic metals (e.g., Hg, Cd, Pb, Cu and Ni) and other major and minor elements showed concentration peaks at certain depths in the alluvial deposits of both basins. These peaks were associated with organic matter, and occurred just below layers of combustion residues originating from burning of in situ biomass. Downward migration of particles originating in the combustion residues is suggested to be the direct mechanisms of the metal enrichments. Further evidence of an in situ origin of the metal peaks in the sediments was provided by the geochemical composition of soils located upstream of the floodplains. Disturbed soils (i.e. soils of pasture, coffee plantations, secondary forest and recently swidden fields) were found to be similar to soils under natural forest. Moreover, trace element concentrations in floodplain deposits were similar in the two drainage basins despite the large difference in exploitation degree. Thus, no evidence was found of large scale (basin-wide) increases in trace-metal leaching or translocation as a result of the extensive deforestation and agricultural land-use that has been practiced in the Amazonian highland jungle over more than 100 a.

Geochemistry of highly acidic mine water following disposal into a natural lake with carbonate bedrock by Christian Wisskirchen; Bernhard Dold; Kurt Friese; Jorge E. Spangenberg; Peter Morgenstern; Walter Glaesser (1107-1119).
► Mean lake water element composition did not differ greatly from discharged AMD. ► Most elements showed increasing concentrations from the surface to lake bottom. ► Jarosite formed in the upper part, settled, and dissolved in the deeper part of the lake. ► Elements migrated into the underlying carbonates in the sequence As< Pb ≈ Cu < Cd < Zn = Mn. ► Gypsum and hydroxide precipitation had not resulted in complete clogging of the lake bedrocks.Acid mine drainage (AMD) from the Zn–Pb(–Ag–Bi–Cu) deposit of Cerro de Pasco (Central Peru) and waste water from a Cu-extraction plant has been discharged since 1981 into Lake Yanamate, a natural lake with carbonate bedrock. The lake has developed a highly acidic pH of ∼1. Mean lake water chemistry was characterized by 16,775 mg/L acidity as CaCO3, 4330 mg/L Fe and 29,250 mg/L SO4. Mean trace element concentrations were 86.8 mg/L Cu, 493 mg/L Zn, 2.9 mg/L Pb and 48 mg/L As, which did not differ greatly from the discharged AMD. Most elements showed increasing concentrations from the surface to the lake bottom at a maximal depth of 41 m (e.g. from 3581 to 5433 mg/L Fe and 25,609 to 35,959 mg/L SO4). The variations in the H and O isotope compositions and the element concentrations within the upper 10 m of the water column suggest mixing with recently discharged AMD, shallow groundwater and precipitation waters. Below 15 m a stagnant zone had developed. Gypsum (saturation index, SI ∼ 0.25) and anglesite (SI ∼ 0.1) were in equilibrium with lake water. Jarosite was oversaturated (SI ∼ 1.7) in the upper part of the water column, resulting in downward settling and re-dissolution in the lower part of the water column (SI ∼ −0.7). Accordingly, jarosite was only found in sediments from less than 7 m water depth. At the lake bottom, a layer of gel-like material (∼90 wt.% water) of pH ∼1 with a total organic C content of up to 4.40 wet wt.% originated from the kerosene discharge of the Cu-extraction plant and had contaminant element concentrations similar to the lake water. Below the organic layer followed a layer of gypsum with pH 1.5, which overlaid the dissolving carbonate sediments of pH 5.3–7. In these two layers the contaminant elements were enriched compared to lake water in the sequence As < Pb ≈ Cu < Cd < Zn = Mn with increasing depth. This sequence of enrichment was explained by the following processes: (i) adsorption of As on Fe-hydroxides coating plant roots at low pH (up to 3326 mg/kg As), (ii) adsorption at increasing pH near the gypsum/calcite boundary (up to 1812 mg/kg Pb, 2531 mg/kg Cu, and 36 mg/kg Cd), and (iii) precipitation of carbonates (up to 5177 mg/kg Zn and 810 mg/kg Mn; all data corrected to a wet base). The infiltration rate was approximately equal to the discharge rate, thus gypsum and hydroxide precipitation had not resulted in complete clogging of the lake bedrocks.

Iron–bentonite interactions in the Kawasaki bentonite deposit, Zao area, Japan by Keisuke Fukushi; Tomonori Sugiura; Tomoaki Morishita; Yoshio Takahashi; Noriko Hasebe; Hiroshi Ito (1120-1132).
Greenish veins occurring in brecciated bentonite were found in the Kawasaki bentonite deposit of the Zao region in Miyagi Prefecture, Japan. Their occurrence possibly indicates the interaction of bentonite with Fe-rich hydrothermal solutions. In order to prove the hypothesis and understand the long-term mineralogical and petrographic evolution of bentonite during such interactions, the greenish veins and the surrounding altered bentonite were analyzed using X-ray fluorescence (XRF), scanning electron microscopy (SEM), X-ray diffraction (XRD), electron probe micro-analysis (EPMA), scanning transmission electron microscopy with energy dispersed spectroscopy (STEM-EDS) and micro X-ray absorption near-edge structure (XANES). The greenish veins resulting from hydrothermal solution are composed of mixed-layer minerals consisting of smectite and glauconite (glaucony), pyrite and opal. The occurrences indicate that glaucony and pyrite formed almost simultaneously from hydrothermal solution prior to opal precipitation. The mineral assemblages of the greenish veins and their surroundings indicate that the hydrothermal activity had most likely taken place at a temperature of less than 100 °C and that the pH and Eh conditions of the reacted solution were neutral to alkaline pH and reducing. The unaltered bentonite is composed mainly of Al smectite and opal. These minerals coexist as a mixture within the resolution level of the microprobe analyses. On the other hand, the bentonite in contact with the greenish veins consists of discrete opal grains and dioctahedral Al smectite containing Fe and was altered mineralogically and petrographically by the hydrothermal activity. Both the clay minerals and the opal were formed by dissolution and subsequent precipitation from the interaction of the original bentonite with the hydrothermal solution.Because of the similarity of the alteration conditions to those in the geological disposal environment, it was considered that the occurrence of Fe–bentonite interactions in the Kawasaki bentonite deposit could yield valuable input for predicting bentonite stability under disposal conditions.

Aquifer Storage Recovery (ASR) of chlorinated municipal drinking water in a confined aquifer by John A. Izbicki; Christen E. Petersen; Kenneth J. Glotzbach; Loren F. Metzger; Allen H. Christensen; Gregory A. Smith; David O’Leary; Miranda S. Fram; Trevor Joseph; Heather Shannon (1133-1152).
About 1.02 × 106  m3 of chlorinated municipal drinking water was injected into a confined aquifer, 94–137 m below Roseville, California, between December 2005 and April 2006. The water was stored in the aquifer for 438 days, and 2.64 × 106  m3 of water were extracted between July 2007 and February 2008. On the basis of Cl data, 35% of the injected water was recovered and 65% of the injected water and associated disinfection by-products (DBPs) remained in the aquifer at the end of extraction. About 46.3 kg of total trihalomethanes (TTHM) entered the aquifer with the injected water and 37.6 kg of TTHM were extracted. As much as 44 kg of TTHMs remained in the aquifer at the end of extraction because of incomplete recovery of injected water and formation of THMs within the aquifer by reactions with free-chlorine in the injected water. Well-bore velocity log data collected from the Aquifer Storage Recovery (ASR) well show as much as 60% of the injected water entered the aquifer through a 9 m thick, high-permeability layer within the confined aquifer near the top of the screened interval. Model simulations of ground-water flow near the ASR well indicate that (1) aquifer heterogeneity allowed injected water to move rapidly through the aquifer to nearby monitoring wells, (2) aquifer heterogeneity caused injected water to move further than expected assuming uniform aquifer properties, and (3) physical clogging of high-permeability layers is the probable cause for the observed change in the distribution of borehole flow. Aquifer heterogeneity also enhanced mixing of native anoxic ground water with oxic injected water, promoting removal of THMs primarily through sorption. A 3 to 4-fold reduction in TTHM concentrations was observed in the furthest monitoring well 427 m downgradient from the ASR well, and similar magnitude reductions were observed in depth-dependent water samples collected from the upper part of the screened interval in the ASR well near the end of the extraction phase. Haloacetic acids (HAAs) were completely sorbed or degraded within 10 months of injection.

Behavior of metals (Cu, Zn and Cd) in the initial stage of water system contamination: Effect of pH and suspended particles by B.S. Smolyakov; A.P. Ryzhikh; S.B. Bortnikova; O.P. Saeva; N.Yu. Chernova (1153-1161).
The fate of potentially harmful metals (PHM) after their entry into an unpolluted fresh water body depends on the physicochemical and biological parameters of the aquatic ecosystem. This paper considers the effect of pH and suspended particles (SP) on the behavior of Cu, Zn and Cd when they enter a fresh water reservoir. In a field experiment, four mesocosms were constructed in the Novosibirskoye Reservoir to allow systematic variation of SP concentration (15 or 250 mg/L) and pH (8.5 or 6.5). The initial concentrations of Cu, Zn and Cd in the mesocosms were 1000, 1000 and 200 μg/L, respectively. Natural bottom sediments were used to provide additional mineral SP, and water hyacinth was used as a floating plant species. Over 11 days, measurements were made of several indicators: residual metal concentration in solution ([PHM]w); metal concentration in SP ([PHM]s); primary productivity of the phytoplankton community; mass of settled SP; PHM concentration in settled SP; and PHM bioaccumulation by water hyacinth. The ratio [PHM]w/[PHM]s in the water varied in the order Cu < Zn < Cd and was higher at pH 6.5 than at pH 8.5. This observation reflects different PHM sorption (Cu > Zn > Cd) onto mineral SP and PHM biosorption by planktonic organisms. Phytoplankton acts as a renewable source of organic SP and plays an important role in metal removal from the water in the mesocosms. After 11 days the residual concentrations of Cu, Zn and Cd in the mesocosm without SP addition (initial SP concentration was 15 mg/L) were 272, 355 and 84 μg/L, respectively. The residual concentrations of Cu, Zn and Cd in mesocosms with SP addition were 57, 100 and 14 μg/L at pH 8.5 and 80, 172 and 20 μg/L at pH 6.5, respectively. Therefore, addition of SP resulted in faster and more complete removal of metals into the bottom sediments. Floating plants (water hyacinth) accumulated PHM (Cu > Zn > Cd) more effectively at pH 8.5 than at pH 6.5, and PHM concentrations in the roots were higher than in settling SP. The general trends of PHM removal from contaminated water via sedimentation and bioaccumulation are compared with changes of metal speciation in solution.

Increasing concentrations of arsenic and vanadium in (southern) Swedish streams by Teresia Wällstedt; Louise Björkvald; Jon Petter Gustafsson (1162-1175).
The aim of this study was to investigate temporal trends and controlling factors of As and V in running waters throughout Sweden. For this purpose, data on stream water chemistry from 62 streams of varying catchment size and characteristics, included in the Swedish environmental monitoring programmes were evaluated. The geochemical software Visual MINTEQ was used to model the speciation and trend analyses were performed on total concentrations of As and V as well as modelled fractions (dissolved species as well as arsenate and vanadate adsorbed to ferrihydrite). The trend analyses showed increasing total concentrations of As and V in southern Sweden. Concentrations of As and V correlated significantly to Fe concentrations in 59 and 60 of the 62 streams respectively, indicating that Fe is an important determining factor for As and V concentrations in Swedish streams. This was confirmed by the geochemical modelling that indicated that the adsorbed fraction is the dominant form of As and V and that the concentrations of As and V in Swedish streams are thus highly determined by concentrations of colloidal or particulate Fe. It is therefore suggested that the increasing trends of As and V are to a large extent due to increasing concentrations of colloidal Fe, which is stabilised by increasing concentrations of DOC. Further the geochemical modelling indicates that the dissolved fraction of As and V generally is small, with the exception of a few streams with high pH and/or phosphate concentrations.

Bulk organic matter characteristics in the Pichavaram mangrove – estuarine complex, south-eastern India by Rajesh Kumar Ranjan; Joyanto Routh; A.L. Ramanathan (1176-1186).
The Pichavaram mangrove ecosystem is located between the Vellar and Coleroon Estuaries in south-eastern India. To document the spatial-depth-based variabilities in organic matter (OM) input and cycling, five sediment cores were collected. A comparative study was carried out of grain-size composition, pore water salinity, dissolved organic C (DOC), loss-on-ignition (LOI), elemental ratios (C/N and H/C), pigments (Chl a, Chl b, and total carotenoids), and humification indices. Sand is the major fraction in these cores ranging from 60% to 99% followed by silt and clay; cores from the estuarine margin have high sand content. In mangrove forests, pore-water DOC concentrations are high (32 ± 14 mg L−1), whereas salinity levels are low (50 ± 5.5‰). Likewise, LOI, organic C and N, and pigment concentrations are high in mangroves. OM is mainly derived from upstream terrestrial matter and/or mangrove litter, and marine OM. The humification indices do not vary significantly with depth because of rapid OM turnover. The bulk parameters indicate that the Vellar and Coleroon Estuaries are more affected by anthropogenic processes than mangrove forests. Finally, greater variability and sometimes lack of specific trends in bulk parameters implies that the 2004 tsunami caused extensive mixing in sediments.

Leaching experiments on a Mn-rich slag from the recycling of alkaline batteries – Solid phase characterization and geochemical modeling by Priscilla Pareuil; François Bordas; Emmanuel Joussein; Philippe Vieillard; Jean-Claude Bollinger (1187-1197).
Square sections of a Mn-rich slag from an alkaline battery recycling plant were submitted to 6-month batch leaching procedures. High-Purity Water (HPW), acidic (pH 4) and alkaline (pH 12) conditions were used in order to observe the behavior of primary solid phases as well as the constituent elements (Mn, Mg, Al, Si, Ca). The experiments were coupled with both KINDIS(P) modeling and mineralogical study (SEM-EDS). Experimental results showed that the Mn-rich slag was sensitive to acidic conditions which induced the dissolution of primary phases. Moreover, pH 4 conditions did not result in the formation of newly formed solid products, leading to the greatest mobilization of metallic elements (especially Mn). Alkaline conditions favored the precipitation of secondary phases, especially rhodochrosite, calcite and Mg-saponite, inducing low mobilization of the contained elements. The KINDIS(P) modeling allowed the stability of primary phases and newly formed products to be predicted. Although the modeled results have to be considered with caution, they allow the assessment and understanding of future environmental behavior of the solid material in given conditions. In this case, the reuse of Mn-rich slag in acidic conditions has to be avoided because of the acidic dissolution of the primary phases.

Chemistry of ash-leachates to monitor volcanic activity: An application to Popocatépetl volcano, central Mexico by M.A. Armienta; S. De la Cruz-Reyna; A. Soler; O. Cruz; N. Ceniceros; A. Aguayo (1198-1205).
Monitoring volcanic activity and assessing volcanic risk in an on-going eruption is a problem that requires the maximum possible independent data to reduce uncertainty. A quick, relatively simple and inexpensive method to follow the development of an eruption and to complement other monitoring parameters is the chemical analysis of ash leachates, particularly in the case of eruptions related to dome emplacement. Here, the systematic analysis of SO 4 2 - , Cl and F concentrations in ash leachates is proposed as a valuable tool for volcanic activity monitoring. However, some results must be carefully assessed, as is the case for S/Cl ratios, since eruption of hydrothermally altered material may be confused with degassing of incoming magma. Sulfur isotopes help to identify SO4 produced by hydrothermal processes from magmatic SO2. Lower S isotopic values correlated with higher F percentages represent a better indicator of fresh magmatic influence that may lead to stronger eruptions and emplacement of new lava domes. Additionally, multivariate statistical analysis helps to identify different eruption characteristics, provided that the analyses are made over a long enough time to sample different stages of an eruption.

Two Italian areas, characterized by different seismological histories, were investigated to enhance the basic knowledge of gas migration mechanisms during earthquakes. Sharp variations occur in the movement and concentration of some gaseous species due to the evolution of the local stress regime. The first area (Colpasquale) is located in the central Italian region of Marche and provided a good location to study gas migration in a seismically active region. The area was devastated by a sequence of shallow earthquakes over a 3 month-long period (September–December, 1997). The occurrence of this catastrophic event, as well as the long duration of the “seismic sequence”, presented a unique opportunity to study gas migration in a zone undergoing active displacement. Soil gas surveys were performed 1 day, 1 week, 1 year and 2 years after the main shock (Ms 5.6) in the Colpasquale area. In particular, results highlight a change in the Rn distribution during the three monitoring years indicating a variation of gas migration that may be linked to the evolution of the stress regime.The second study area is located in the Campidano Graben (southern part of Sardinia Island). This area is characterized by seismic quiescence, displaying an almost complete lack of historical earthquakes and instrumentally recorded seismicity. The consistently low values observed for all analyzed gases suggest that the studied area is likely characterized by sealed, non-active faults that prevent significant gas migration. The comparison of data from both studied areas indicate that soil gas geochemistry is useful to locate tectonic discontinuities even when they intersect non-cohesive clastic rocks near the surface and thus are not visible (i.e., “blind faults”).

A high-resolution dataset of trace element concentrations is presented for the Murray–Darling Basin, Australia, Australia’s most important river system. The data were obtained by solution quadrupole ICP-MS resulting in concentrations for 44 elements. Of these, 21 were determined with a long-term external precision of better than 1% and a further 13 at a precision better than 2%. Trace element maps for the surface sediments constructed from such high precision data reveal small but coherent variations in the four major sub-catchments of the basin, even in ratios of elements with very similar geochemical behaviour, such as Y/Ho, Nb/Ta and Zr/Hf. The origin of these chemical fingerprints of drainage systems are discussed in terms of the geochemical character of the upper continental crust. The potential of trace element maps for palaeo-environmental and climatic reconstruction is then illustrated. First, a sample of dust collected in a trap located in the far southeastern corner of the study area is used to pinpoint the location of the dust source. Next the fine-scale change in down-stream alluvial sediment chemistry is analysed to estimate the importance of sediment contribution from tributaries with a view to reconstructing river flow dynamics. Finally, the chemistry of dune sediments is compared with surrounding floodplain alluvium to estimate relative age of deposition. These examples demonstrate that in low-elevation river systems, such as the Murray–Darling Basin, extended trace element maps of sediment offer substantially more applications than radiogenic isotope data alone.

► Oxidation state, pH and complexing ligands are dominating factors for Np sorption onto kaolinite. ► Carbonate and humic acid influence Np(V) sorption on kaolinite. ► Effect of humic acid is even more pronounced in the case of Np(IV).The sorption of Np(V) and Np(IV) onto kaolinite has been studied in the absence and presence of humic acid (HA) in a series of batch equilibrium experiments under different experimental conditions: [Np]0: 1.0 × 10-6 or 1.0 × 10-5  M, [HA]0: 0 or 50 mg/L, I: 0.01 or 0.1 M NaClO4, solid to liquid ratio: 4 g/L, pH: 6–11, anaerobic or aerobic conditions, without or with carbonate. The results showed that the Np(V) sorption onto kaolinite is affected by solution pH, ionic strength, Np concentration, presence of carbonate and HA. In the absence of carbonate, the Np(V) uptake increased with pH up to ∼96% at pH 11. HA further increased the Np(V) sorption between pH 6 and 9 but decreased the Np(V) sorption between pH 9 and 11. In the presence of carbonate, the Np(V) sorption increased with pH and reached a maximum of 54% between pH 8.5 and 9. At higher pH values, the Np(V) sorption decreased due to the presence of dissolved neptunyl carbonate species with a higher negative charge that were not sorbed onto the kaolinite surface which is negatively charged in this pH range. HA again decreased the Np(V) uptake in the near-neutral to alkaline pH range due to formation of aqueous neptunyl humate complexes. The decrease of the initial Np(V) concentration from 1.0 × 10−5  M to 1.0 × 10−6  M led to a shift of the Np(V) adsorption edge to lower pH values. A higher ionic strength increased the Np(V) uptake onto kaolinite in the presence of carbonate but had no effect on Np(V) uptake in the absence of carbonate.To the best of the authors’ knowledge, this is the first study on the sorption of Np(IV) onto kaolinite in the presence of HA. For this, a synthetic HA with pronounced reducing properties was applied. This HA effectively reduced Np(V) to Np(IV) and stabilized the tetravalent oxidation state during sorption experiments over a wide pH range. The Np(IV) uptake onto kaolinite is strongly affected by HA. Especially in the near-neutral pH range the Np(IV) uptake was found to be very low in the presence of HA which was attributed to the strong Np(IV) humate complexation in solution. Thus, depending on the prevailing geochemical conditions, HA has an immobilizing as well as a mobilizing effect on Np(V). In the case of Np(IV), the mobilizing effect predominates.

► Soil-gas technique is applied to study gas permeability of Orciatico clay units. ► Clay permeability depends on thermal and mechanical alteration degree. ► Soil-gas distributions are due to shallow fracturing of clays. ► Rn and CO2 soil-gas anomalies highlight secondary permeability in clay sequence. ► Soil-gas results are supported by detailed geoelectrical surveys.The physical properties of clay allow argillaceous formations to be considered geological barriers to radionuclide migration in high-level radioactive-waste isolation systems. As laboratory simulations are short term and numerical models always involve assumptions and simplifications of the natural system, natural analogues are extremely attractive surrogates for the study of long-term isolation. The clays of the Orciatico area (Tuscany, Central Italy), which were thermally altered via the intrusion of an alkali-trachyte laccolith, represent an interesting natural model of a heat source which acted on argillaceous materials. The study of this natural analogue was performed through detailed geoelectrical and soil–gas surveys to define both the geometry of the intrusive body and the gas permeability of a clay unit characterized by different degrees of thermal alteration. The results of this study show that gas permeability is increased in the clay sequences subjected to greater heat input from the emplacement of the Orciatico intrusion, despite the lack of apparent mineral and geotechnical variations. These results, which take into consideration long time periods in a natural, large-scale geological system, may have important implications for the long-term safety of underground storage of nuclear waste in clay formations.

► Dry soil over a petroleum field may give positive fluxes of CH4 due to microseepage from the underground hydrocarbon accumulations. ► Microseepage flux is influenced by subsurface geo-structural features and gas-oil setting. ► The 13C/12C ratios of CH4 in the flux chambers demonstrates that seeping methane is thermogenic.Methane microseepage is the result of natural gas migration from subsurface hydrocarbon accumulations to the Earth’s surface, and it is quite common in commercial petroleum fields. While the role of microseepage as a pathfinder in petroleum exploration has been known for about 80 a, its significance as an atmospheric CH4 source has only recently been studied, and flux data are currently available only in the USA and Europe. With the aim of increasing the global data-set and better understanding flux magnitudes and variabilities, microseepage is now being extensively studied in China. A static flux chamber method was recently applied to study microseepage emissions into the atmosphere in four different sectors of the Yakela condensed gas field in Tarim Basin, Xinjiang, China, and specifically in: (a) a faulted sector, across the Luntai fault systems; (b) an oil–water interface sector, at the northern margin of the field; (c) an oil–gas interface sector, in the middle of the field; (d) an external area, outside the northern gas field boundaries. The results show that positive CH4 fluxes are pervasive in all sectors and therefore, only part of the CH4 migrating from the deep oil–gas reservoirs is consumed in the soil by methanotrophic oxidation. The intensity of gas seepage seems to be controlled by subsurface geologic settings and lateral variabilities of natural gas pressure in the condensed gas field. The highest CH4 fluxes, up to ∼14 mg m−2  d−1 (mean of 7.55 mg m−2  d−1) with higher spatial variability (standard deviation, σ: 2.58 mg m−2  d−1), occur in the Luntai fault sector. Merhane flux was lower in the oil–water area (mean of 0.53 mg m−2  d−1) and the external area (mean of 1.55 mg m−2  d−1), and at the intermediate level in the gas–oil sector (mean of 2.89 mg m−2  d−1). These values are consistent with microseepage data reported for petroleum basins in the USA and Europe. The build-up of methane concentration in the flux chambers is always coupled with an enrichment of 13C, from δ13C1 of −46‰ to −42.5‰ (VPDB), which demonstrates that seeping methane is thermogenic, as that occurring in the deep Yakela reservoir. Daily variations of microseepage are very low, with minima in the afternoon, corresponding to higher soil temperature (and higher methanotrophic consumption), and maxima in the early morning (when soil temperatures are lowest). A preliminary and rough estimate of the total amount of CH4 exhaled from the Yakela field is in the order of 102  tonnes a−1.The present data can statistically improve the accuracy of the global microseepage flux data-set, but further surveys are needed in order to understand the frequency of occurrence and spatial variability of positive CH4 fluxes in soils over petroleum fields.

Carbon isotopes to constrain the origin and circulation pattern of groundwater in the north-western part of the Bohemian Cretaceous Basin (Czech Republic) by Hana Jiráková; Frédéric Huneau; Zbyněk Hrkal; Hélène Celle-Jeanton; Philippe Le Coustumer (1265-1279).
► Deep CO2 gas causes a depletion in groundwater 14C activity. ► Depleted δ13C indicate interactions with fossile organic matter. ► The Bohemian Cretaceous Basin groundwater ages are up to 11 ka BP.The Bohemian Cretaceous Basin represents a complex hydrogeological system composed of several aquifers with very favourable hydrogeological properties. These aquifers have been exploited for many years. The sustainability of such resources might be guaranteed by well organised water management, which requires a detailed knowledge about the functioning of the hydrogeological system. Although many efforts have previously been made to evaluate groundwater residence time, the many intricate geochemical processes complicate groundwater dating. The current study clarifies the functioning of this complex hydrogeological basin using hydrogeochemical and isotopic investigations. Chemical data and a combination of 13C and 14C isotopes within the Cenomanian and the Turonian layers indicate groundwater interactions with deep-seated CO2, rock matrix, surface waters and fossil organic matter. Very depleted δ13C values (average δ13C ∼ −13.4‰) suggest interactions with fossil organic matter, whereas enriched values account for the interaction with deep CO2 gas ascending from the upper mantle via the numerous faults and fractures, and also, to a lesser extent, from calcite dissolution. Geochemical processes that take place in the system cause a clear depletion in 14C that greatly complicates groundwater residence time evaluation. Different dilution correction models have been applied considering the different C origins. The stable isotope content, mainly 18O values, indicates both the contribution of modern precipitation and the partial infiltration of palaeowaters during colder climatic conditions from the end of the Pleistocene. The apparent 14C groundwater ages range from modern to 11.1 ka BP, which suggests some post glacial infiltration from melting ice sheets. Finally, all the acquired information was used to propose a conceptual model of C origin within the basin.

► Four factors (i.e., salinity factor, As-enrichment factor, reduction factor, and hardness factor) control groundwater geochemistry. ► Hydrochemical facies analysis showed that most of the water samples are dominated by Ca and HCO3 ions. ► Cluster 1 water types are highly enriched in As; an alternative water source is thus needed for domestic water supply. Possible solutions are to install tube wells in the deeper Pleistocene aquifers or use clean surface water sources such as reservoirs or rain water. ► Cluster 4 water types contain low concentration As, below the Bangladesh standard (<50 μg/L), and this type of water is generally suitable for extraction for domestic uses. ► Statistical analyses show that As, Fe and Mn are strongly correlated in sediments. By comparison, As is not correlated with Fe but is positively correlated with Mn in groundwater. ► Geochemical correlations along with results of sequential leaching experiments suggest that bacterial reductive dissolution of MnOOH and FeOOH is the primary mechanism for releasing As into the groundwater. ► Geochemical studies using sequential-extraction results and scanning electron microscopy on sediment samples demonstrate that Fe- and Mn-oxyhydroxides and Fe- and Mn-oxyhydroxide-coated quartz and feldspar, are the dominant carriers of As in the sediments.Core sediments from three boreholes (to a depth of 50 m) and groundwater from 20 As-enriched water wells were collected in the Chapai-Nawabganj area of northwestern Bangladesh for geochemical analyses. Multivariate statistical analyses including factor analysis, cluster analysis and multidimensional scaling were applied to the hydrogeochemical data. The results show that a few factors adequately represent the traits that define water chemistry. Sodium, Cl, SO4, total dissolved solids (TDS), and electrical conductivity (EC) are grouped under the first factor representing the salinity sources of waters. The second factor, represented by As and Mn, is related to As mobilization processes. The third factor of Fe and alkalinity is strongly influenced by bacterial Fe(III) reduction which would raise both Fe and HCO 3 - concentrations in water. The fourth factor of Ca and Mg reflects the hardness of the Ca–HCO3 type of groundwater, which is confirmed by the hydrochemical facies analysis. Cluster analysis leads to the formulation of four water types including highly, moderately, and slightly As-enriched groundwater as well as groundwater with elevated SO 4 2 - , from anthropogenic sources. Multivariate analyses of the geochemical parameters suggest that Fe- and Mn-oxyhydroxides and mineral phases of phyllosilicates (e.g., biotite) are the main hosts of As in the sediments. Statistical analysis also shows that As is closely associated with Fe and Mn in sediments while As is positively correlated with Mn in groundwater. These correlations along with results of sequential leaching experiments suggest that reductive dissolution of MnOOH and FeOOH mediated by anaerobic bacteria represents an important mechanism for releasing As into the groundwater.