Ecotoxicity assessment of natural attenuation effects at a historical dumping site in the western Baltic Sea.

During the late 1950s and early 1960s of the past century, industrial waste material highly enriched in various contaminants (heavy metals, PAHs) was dumped in the inner Mecklenburg Bay, western Baltic Sea. Large-scale shifts in the spatial distribution of heavy metals in surface sediments were mapped by geochemical monitoring in the mid-1980s and 12 years later in 1997. A further study in 2001 was designed to investigate the small-scale spatial distribution of contaminants inside, on top of, and around the historical dumping ground and to examine possible effects to benthic organisms (Arctica islandica, microbiological toxicity tests). The site is located within an area characterized by a …

Identification of markers for the selection of patients undergoing renal cell carcinoma-specific immunotherapy

Renal cell carcinoma (RCC) represents the most common malignant tumor in the kidney and is resistant to conventional therapies. The diagnosis of RCC is often delayed leading to progression and metastatic spread of the disease. Thus, validated markers for the early detection of the disease as well as selection of patients undergoing specific therapy is urgently needed. Using treatment with the monoclonal antibody (mAb) G250 as a model, proteome-based strategies were implemented for the identification of markers which may allow the discrimination between responders and nonresponders prior to application of G250-mediated immunotherapy. Flow cytometry revealed G250 surface expression in approxi…

Comment on "Enthalpy of Uranium Adsorption onto Hematite".

Polycyclic aromatic hydrocarbons (PAHs) and their oxygen-containing derivatives (OPAHs) in soils from the Angren industrial area, Uzbekistan.

We measured the concentrations and depth distribution (0-10, 10-20 cm) of 31 PAHs and 12 OPAHs in soils at eleven equidistant sampling points along a 20-km transect in the Angren industrial region (coal mine, power plant, rubber factory, gold mine), Uzbekistan to gain an insight into their concentrations, sources, and fate. Concentrations of all compounds were mostly much higher in the 0-10 cm than in the 10-20 cm layer except in disturbed soil close to the coal mine. Proximity to one of the industrial emitters was the main determinant of PAH and OPAH concentrations. The Sigma31PAHs concentrations correlated positively with the Sigma7 carbonyl-OPAH (r=0.98, p<0.01), Sigma5 hydroxyl-OPAH (r=…

Natural gas hydrate investigations by synchrotron radiation X-ray cryo-tomographic microscopy (SRXCTM)

[1] We report the 3D microstructure analyses of natural gas hydrates sampled from Gulf of Mexico. The samples were characterized by synchrotron radiation X-ray cryo-tomographic microscopy (SRXCTM) using the ‘TOMCAT’ beam line at the Swiss Light Source (SLS). The SRXCTM demonstrates its applicability to unlock some microscopic features of the marine hydrates, in particular of crystallite size and grain boundary network. The gas hydrate domains are surrounded by a network of pores of typically a few micrometers, which are largely due to decomposition. Out of the SRXCTM data, the porosity, total volume of the voids, the void surface area and number of the total gas-filled voids have been calcu…

Polycyclic aromatic hydrocarbons and trace metal contamination of coastal sediment and biota from Togo

The state of contamination of tropical environments, particularly in Africa, remains a relatively under explored subject. Here, we determined polycyclic aromatic hydrocarbon (PAH) and trace metal concentrations in coastal sediment and biota samples (fish and mussels) from Togo (West Africa). In the sediments, the ∑21 PAH concentrations ranged from4 ng g(-1) to 257 ng g(-1), averaging 92 ng g(-1). Concentration ratios of low molecular weight PAHs (2-3 rings) versus high molecular weight PAHs (≥4 rings) were always lower than 1 (ranging from 0.08 to 0.46) indicating that high molecular weight PAHs were dominant in all sediment samples, and that PAHs originated mainly from anthropogenic combus…

Pore scale modelling of calcite cement dissolution in a reservoir sandstone matrix

E3S Web of Conferences 98, 05010 (1-5) (2019). doi:10.1051/e3sconf/20199805010

Modeling of Elemental Species

Aqueous Solubility Diagrams for Cementitious Waste Stabilization Systems: II, End-Member Stoichiometries of Ideal Calcium Silicate Hydrate Solid Solutions

Solubility in the fully hydrated CaO–SiO2–H2O system can be best described using two ideal C-S-H-(I) and C-S-H-(II) binary solid solution phases. The most recent structural ideas about the C-S-H gel permit one to write stoichiometries of polymerized C-S-H-(II) end-members as hydrated precursors of the stable tobermorite and jennite minerals in the form of 5Ca(OH)2·6SiO2·5H2O and 10Ca(OH)2·6SiO2·6H2O, respectively. For thermodynamic modeling purposes, it is more convenient to express the number of basic silica and portlandite units in these stoichiometries using the coefficients nSi and nCa. Thermodynamic solid-solution aqueous-solution equilibrium modeling by applying the Gibbs energy minim…

Processing of rock core microtomography images: Using seven different machine learning algorithms

The abilities of machine learning algorithms to process X-ray microtomographic rock images were determined. The study focused on the use of unsupervised, supervised, and ensemble clustering techniques, to segment X-ray computer microtomography rock images and to estimate the pore spaces and pore size diameters in the rocks. The unsupervised k-means technique gave the fastest processing time and the supervised least squares support vector machine technique gave the slowest processing time. Multiphase assemblages of solid phases (minerals and finely grained minerals) and the pore phase were found on visual inspection of the images. In general, the accuracy in terms of porosity values and pore…

Predicting the Breakthrough of Ternary Ca–Uranyl–Carbonate Species in Mineral Water Treated by a Fixed-Bed Granular Ferric Hydroxide Adsorbent

A CD-MUSIC surface complexation model was set up on the basis of batch equilibrium experiments with uranyl ions and akaganeite-based granular ferric hydroxide (GFH), which is often used in water pu...

Adsorption mechanism of arsenate by zirconyl-functionalized activated carbon

Arsenate [As(V)] and arsenite [As(III)] sorption at the solid-water interface of activated carbon impregnated with zirconyl nitrate (Zr-AC) was investigated using X-ray absorption spectroscopy (XAS) and surface complexation modeling. The XAS data at the Zr K-edge suggest that the structure of the zirconyl nitrate coating is built from chains of edge-sharing ZrO8 trigonal dodecahedra bound to each other through two double hydroxyl bridges. The 8-fold coordination of each Zr atom is completed by four O atoms, which share a bit less than the two theoretically possible bidentate nitrate groups. On impregnation, two of the O atoms may lose their nitrate group and be transformed to hydroxyl group…

Change of arsenite adsorption mechanism during aging of 2-line ferrihydrite in the absence of oxygen

Abstract Arsenite was effectively immobilized by 2-line ferrihydrite at different pH values (4.0, 5.5 and 7.4) and adsorbent dosages (0.4, 1, and 2 g/L) in the absence of oxygen, showing an initial surface diffusion-controlled period (Stage I, 2 h). Dissolved δ 56 Fe increased during Stage I and decreased during Stage II, resulting from aging of ferrihydrite and equilibrium isotopic exchange, respectively. The ferrihydrite aging was hampered by both high As concentrations and high pH values close to the pH zpc , due to inhibition of mineral dissolution as a prerequisite for mineral transformation. During Stage I, As was adsorbed by both bidentate binuclear corner-sharing ( 2 C ) and monoden…

Simultaneous segmentation and beam-hardening correction in computed microtomography of rock cores

We propose a post-reconstruction correction procedure for the beam-hardening artifact that neither requires knowledge of the X-ray spectrum nor of the attenuation coefficients in multi-mineral geologic samples. The beam-hardening artifact in polychromatic X-ray computer tomography (CT) hampers segmentation of the phase assemblage in geologic samples. We show that in cylindrically shaped samples like rock cores, the X-ray attenuation value for a single phase depends mainly on the distance from the center of the cylinder. This relationship could be easily extracted from the CT data for every phase and used to infer the presence of these phases at all positions in the sample. Our new approach …

Arsenite adsorption on goethite at elevated temperatures

Abstract Experimental closed-system ΔT acid–base titrations between 10 °C and 75 °C were used to constrain a temperature-dependent 1-pK basic Stern model of the goethite surface complexation reactions. Experimental data for the temperature dependence of pHPZC determined by the one-term Van’t Hoff extrapolation yield a value for goethite surface protonation enthalpy of −49.6 kJ mol−1 in good agreement with literature data. Batch titration data between 10 °C and 75 °C with arsenite concentrations between 10 μM and 100 μM yield adsorption curves, which increases with pH, peak at a pH of 9, and decrease at higher pH values. The slope of this bend becomes steeper with increasing temperature. A 1…

Squirt flow due to interfacial water films in hydrate bearing sediments

Sediments containing gas hydrate dispersed in the pore space are known to show a characteristic seismic anomaly which is a high attenuation along with increasing seismic velocities. Currently, this observation cannot be fully explained albeit squirt-flow type mechanisms on the microscale have been speculated to be the cause. Recent major findings from in situ experiments, using the gas in excess and water in excess formation method, and coupled with high-resolution synchrotron-based X-ray micro-tomography, have revealed the systematic presence of thin water films between the quartz grains and the encrusting hydrate. The data obtained from these experiments underwent an image processing proc…

Predicting breakthrough of vanadium in fixed-bed absorbent columns with complex groundwater chemistries: A multi-component granular ferric hydroxide−vanadate−arsenate−phosphate−silicic acid system

Granular ferric hydroxide (GFH) is often used for fixed bed adsorbent (FBA) columns in groundwater purification units around the world to remove arsenate contaminations. Groundwater can contain also other toxic (e.g., antimonite and vanadate) and non-toxic oxo-anions (phosphate and silicic acid) that are known to affect FBA lifetimes. Therefore, understanding the breakthrough of toxic compounds intended for removal by FBA is essential to their design, and is important to predict accurately breakthrough curves (BTCs) for FBAs in waterworks to plan future operating costs. Rapid small-scale column tests (RSCCT) and pilot-scale FBA were used to simulate vanadate BTCs for complex groundwater che…

Speciation of Copper in Enriched Agricultural Lime

Agricultural liming materials are used to lower soil acidity and to improve microbial functionality and plant growth. A brownish colored agricultural lime was found to contain up to 180 mg kg ―1 Cu, an amount well above any fertilizing materials code threshold. The dark color of the milled material was due to ample black and brown dendrites consisting of the tectomanganate mineral romanechite (ideally (Ba,H 2 O) 2 (Mn 4+ ,Mn 3+ ) 5 O 10 ) and a mixture of the two nanocrystalline Fe oxides ferrihydrite and goethite. A four-step sequential extraction analysis of the lime powder was not sufficient to argue whether the Cu load was contained in the carbonate matrix or in the oxide dendrites, or,…

Digital rock physics, chemistry, and biology: challenges and prospects of pore-scale modelling approach

Abstract Conventional and unconventional hydrocarbon rocks have complicated pore structures with heterogeneities distributed over various length scales (from nanometre to centimetre or even larger scales). Effective characterization of the properties of such rocks based on their digital twins is a challenging task. Digital rock physics (DRP) can be used to quantify the structural and morphological parameters of rocks directly and predict flow transport properties at the pore scale. Digital rock chemistry (DRC) or biology (DRB) applies when the changes in pore structures are due to interaction with solutes or microbial activities. Fluid–rock interactions or microbial activities complicate fl…

Tracing anthropogenic thallium in soil using stable isotope compositions.

Thallium stable isotope data are used in this study, for the first time, to apportion Tl contamination in soils. In the late 1970s, a cement plant near Lengerich, Germany, emitted cement kiln dust (CKD) with high Tl contents, due to cocombustion of Tl-enriched pyrite roasting waste. Locally contaminated soil profiles were obtained down to 1 m depth and the samples are in accord with a binary mixing relationship in a diagram of Tl isotope compositions (expressed as e(205)Tl, the deviation of the (205)Tl/(203)Tl ratio of a sample from the NIST SRM 997 Tl isotope standard in parts per 10(4)) versus 1/[Tl]. The inferred mixing endmembers are the geogenic background, as defined by isotopically l…

Speciation and Mobility of Arsenic in Agricultural Lime

Agricultural liming materials are used to correct soil acidity and to improve plant growth and microbial functionality. A relatively low-grade agricultural lime was found to contain up to 125 mg kg(-1) arsenic (As), which is above any fertilizing materials code threshold. The color of the milled material is brown due to ample oxide dendrites. Microprobe elemental maps confirmed that these accessory oxide mineral phases are responsible for the elevated As concentrations in the limestone. The black Mn-bearing dendrites contain minor amounts of As, whereas the brown Fe-bearing dendrites contain the major part of the As inventory, with an Fe/As molar ratio around 100. Because the elemental maps…

Trace metal(loid) mobility in waste deposits and soils around Chadak mining area, Uzbekistan

Abstract The assessment of potential trace metal(loid) contamination in tailing dumps and soils was characterized in the Chadak mining area (Uzbekistan). Concentrations of trace elements (V, Cr, Co, Ni, Cu, Zn, As, Cd, Sb, Pb) were determined by X-ray fluorescence analysis and compared with background and intervention values (IV). The concentrations of As, Zn, Sb, and Pb were higher in the abandoned than in the active tailing dump, ranging from 42–1689 mg/kg for As, 73–332 mg/kg for Zn, 14–1507 mg/kg for Sb, and 27–386 mg/kg for Pb. Selective extractions were applied in order to assess the mobility and availability of trace metal(loid)s in samples. Oxyanion-forming elements such as As and S…

From connected pathway flow to ganglion dynamics

During imbibition, initially connected oil is displaced until it is trapped as immobile clusters. While initial and final states have been well described before, here we image the dynamic transient process in a sandstone rock using fast synchrotron-based X-ray computed microtomography. Wetting film swelling and subsequent snap off, at unusually high saturation, decreases nonwetting phase connectivity, which leads to nonwetting phase fragmentation into mobile ganglia, i.e., ganglion dynamics regime. We find that in addition to pressure-driven connected pathway flow, mass transfer in the oil phase also occurs by a sequence of correlated breakup and coalescence processes. For example, meniscus…

Early diagenetic processes during Mn-carbonate formation: evidence from the isotopic composition of authigenic Ca-rhodochrosites of the Baltic Sea

The formation of authigenic Ca-rich rhodochrosite (ACR) in sapropelic sediments of the Gotland Basin, Baltic Sea, is governed by deepwater renewal processes whereby saline water from the North Atlantic flushes the brackish anoxic Baltic Deeps. The carbon and oxygen isotopic compositions of these Mn- carbonates suggest that ACR formation takes place just below the sediment surface and that dissolved compounds from the deepwater column, such as water and bicarbonate molecules, were incorporated in ACR during authigenesis. Porewaters near the sediment surface display 18 O values of 5.4‰ (VSMOW) and are generally depleted in 18 O, compared to the oxygen isotopic composition of water in equilibr…

Systematic Comparative Protein Expression Profiling of Clear Cell Renal Cell Carcinoma

Proteome-based technologies represent powerful tools for the analysis of protein expression profiles, including the identification of potential cancer candidate biomarkers. Thus, here we provide a comprehensive protein expression map for clear cell renal cell carcinoma established by systematic comparative two-dimensional gel electrophoresis-based protein expression profiling of 16 paired tissue systems comprising clear cell renal cell carcinoma lesions and corresponding tumor-adjacent renal epithelium using overlapping narrow pH gradients. This approach led to the mapping of 348 distinct spots corresponding to 248 different protein identities. By implementing restriction criteria concernin…

Cr(VI)/Cr(III) and As(V)/As(III) Ratio Assessments in Jordanian Spent Oil Shale Produced by Aerobic Combustion and Anaerobic Pyrolysis

With the increase in the awareness of the public in the environmental impact of oil shale utilization, it is of interest to reveal the mobility of potentially toxic trace elements in spent oil shale. Therefore, the Cr and As oxidation state in a representative Jordanian oil shale sample from the El-Lajjoun area were investigated upon different lab-scale furnace treatments. The anaerobic pyrolysis was performed in a retort flushed by nitrogen gas at temperatures in between 600 and 800 °C (pyrolytic oil shale, POS). The aerobic combustion was simply performed in porcelain cups heated in a muffle furnace for 4 h at temperatures in between 700 and 1000 °C (burned oil shale, BOS). The high loss-…

3-D imaging and quantification of graupel porosity by synchrotron-based micro-tomography

The air bubble structure is an important parameter to determine the radiation properties of graupel and hailstones. For 3-D imaging of this structure at micron resolution, a cryo-stage was developed. This stage was used at the tomography beamline of the Swiss Light Source (SLS) synchrotron facility. The cryo-stage setup provides for the first time 3-D-data on the individual pore morphology of ice particles down to infrared wavelength resolution. In the present study, both sub-mm size natural and artificial ice particles rimed in a wind tunnel were investigated. In the natural rimed ice particles, Y-shaped air-filled closed pores were found. When kept for half an hour at −8 °C, this morpholo…

Speciation and oxidation kinetics of arsenic in the thermal springs of Wiesbaden spa, Germany.

Since 1886 arsenic has been known to be present as a trace component in the Wiesbaden thermal waters at concentrations of over 100 microg L(-1). In this study for the first time molecular level speciation of arsenic was measured both in the water (by HG-AAS) and in wellstone scale deposits (by XANES). Most of the arsenic in the anoxic NaCl-type waters is in the reduced arsenite form. Hydrous ferric oxide (HFO) precipitates in the scale deposits scavenge only the minor dissolved arsenate portion which is, however, accumulated up to 3% w/w. Isothermal precipitation experiments at in-situ temperatures showed a difference between the progress of both arsenic and iron oxidation and precipitation…

Ba and Ni speciation in a nodule of binary Mn oxide phase composition from Lake Baikal

The partitioning and incorporation mechanism of Ni and Ba in a ferromanganese nodule from Lake Baikal were characterized by X-ray microfluorescence, microdiffraction, and absorption spectroscopy. Fe is speciated as goethite, and Mn as romanechite (psilomelane) and 10 A ˚ -vernadite (turbostratic buserite) with minor 7 A ˚ -vernadite (turbostratic birnessite). Barium is associated with romanechite and Ni with vernadite in distinct and irregularly distributed layers, and each type of Mn oxide is separated from the other type by goethite. The binary Mn oxide banding pattern is interpreted by a two-mode accretionary model, in which the variation in Ba flux induced by hydrothermal water pulses d…

Silicic acid competes for dimethylarsinic acid (DMA) immobilization by the iron hydroxide plaque mineral goethite.

Abstract A surface complexation modeling approach was used to extend the knowledge about processes that affect the availability of dimethylarsinic acid (DMA) in the soil rhizosphere in presence of a strong sorbent, e.g., Fe plaques on rice roots. Published spectroscopic and molecular modeling information suggest for the organoarsenical agent to form bidentate-binuclear inner-sphere surface complexes with Fe hydroxides similar to the inorganic As oxyanions. However, since also the ubiquitous silicic acid oxyanion form the same bidentate binuclear surface complexes, our hypothesis was that it may have an effect on the adsorption of DMA by Fe hydroxides in soil. Our experimental batch equilibr…

Connected pathway relative permeability from pore-scale imaging of imbibition

Abstract Pore-scale images obtained from a synchrotron-based X-ray computed micro-tomography (µCT) imbibition experiment in sandstone rock were used to conduct Navier–Stokes flow simulations on the connected pathways of water and oil phases. The resulting relative permeability was compared with steady-state Darcy-scale imbibition experiments on 5 cm large twin samples from the same outcrop sandstone material. While the relative permeability curves display a large degree of similarity, the endpoint saturations for the µCT data are 10% in saturation units higher than the experimental data. However, the two datasets match well when normalizing to the mobile saturation range. The agreement is p…

Mn, Fe, Zn and As speciation in a fast-growing ferromanganese marine nodule

The speciation of Mn, Fe, As and Zn in a fast-growing (0.02mm/yr), shallow-marine ferromanganese nodule has been examined by micro X-ray fluorescence, micro X-ray diffraction, and micro X-ray absorption spectroscopy. This nodule exhibits alternating Fe-rich and Mn-rich layers reflecting redox variations in water chemistry. Fe occurs as two-line ferrihydrite. The As is strictly associated with Fe and is mostly pentavalent, with an environment similar to that of As sorbed on or coprecipitated with synthetic ferrihydrite. The Mn is in the form of turbostratic birnessite with ~;10 percent trivalent manganese in the layers and probably ~;8 percent corner-sharing metal octahedra in the interlayer…

Microstructural evolution of gas hydrates in sedimentary matrices observed with synchrotron X-ray computed tomographic microscopy

The formation process of gas hydrates in sedimentary matrices is of crucial importance for the physical and transport properties of the resulting aggregates. This process has never been observed in situ at submicron resolution. Here we report on synchrotron-based microtomographic studies by which the nucleation and growth processes of gas hydrate were observed at 276 K in various sedimentary matrices such as natural quartz (with and without admixtures of montmorillonite type clay) or glass beads with different surface properties, at varying water saturation. Both juvenile water and metastably gas-enriched water obtained from gas hydrate decomposition was used. Xenon gas was employed to enha…

The Origin of Non-thermal Fluctuations in Multiphase Flow in Porous Media

Core flooding experiments to determine multiphase flow in properties of rock such as relative permeability can show significant fluctuations in terms of pressure, saturation, and electrical conductivity. That is typically not considered in the Darcy scale interpretation but treated as noise. However, in recent years, flow regimes that exhibit spatio-temporal variations in pore scale occupancy related to fluid phase pressure changes have been identified. They are associated with topological changes in the fluid configurations caused by pore-scale instabilities such as snap-off. The common understanding of Darcy-scale flow regimes is that pore-scale phenomena and their signature should have a…

Multi-phase classification by a least-squares support vector machine approach in tomography images of geological samples

Abstract. Image processing of X-ray-computed polychromatic cone-beam micro-tomography (μXCT) data of geological samples mainly involves artefact reduction and phase segmentation. For the former, the main beam-hardening (BH) artefact is removed by applying a best-fit quadratic surface algorithm to a given image data set (reconstructed slice), which minimizes the BH offsets of the attenuation data points from that surface. A Matlab code for this approach is provided in the Appendix. The final BH-corrected image is extracted from the residual data or from the difference between the surface elevation values and the original grey-scale values. For the segmentation, we propose a novel least-squar…

Identification of fatty acid binding proteins as markers associated with the initiation and/or progression of renal cell carcinoma

Renal cell carcinoma (RCC) representing the most common neoplasia of the kidney in Western countries is a histologic diverse disease with an often unpredictable course. The prognosis of RCC is worsened with the onset of metastasis, and the therapies currently available are of limited success for the treatment of metastatic RCC. Although gene expression analyses and other methods are promising tools clarifying and standardizing the pathological classification of RCC, novel innovative molecular markers for the diagnosis, prognosis, and for the monitoring of this disease during therapy as well as potential therapeutic targets are urgently needed. Using proteome-based strategies, a number of RC…

Coupling geochemical, mineralogical and microbiological approaches to assess the health of contaminated soil around the Almalyk mining and smelter complex, Uzbekistan

This study describes the impact of airborne pollution resulting from mining and smelting activities on the soils of the Almalyk mining and industrial area (NE Uzbekistan). Samples were collected along a transect downwind of the industrial area. Enriched contents of some metals were found in the upper soil layers near the metallurgical complex (Zn≤3010 mg kg(-1), Pb≤630 mg kg(-1), Cd≤30 mg kg(-1)) which suggests that these metals were derived from local stack emissions. The morphology and internal microstructure of metal-bearing spherical particles found in the heavy mineral fraction suggest that these particles were probably a result of inefficient flue gas cleaning technique of the smelter…

Isotopes Trace Biogeochemistry and Sources of Cu and Zn in an intertidal soil

River floodplain soils are sinks and potential sources for toxic trace metals like Cu and Zn. We hypothesize that stable Cu and Zn isotope ratios reflect both the mobilization and the sources of metals. We determined the soil properties, the concentrations and partitioning of Cu and Zn, and variations in δ65Cu and δ66Zn values in a core obtained from an Aquic Udifluvent developed on a freshwater intertidal mudflat of the River Elbe, Germany. The core was sampled at 2 cm intervals to a depth of 34 cm, which corresponds to approximately 9 yr of sedimentation. Elevated concentrations of Cu (up to 320 μg g−1) and Zn (up to 2080 μg g−1) indicated anthropogenic pollution. At the time of sampling …

Speciation of Cr in Leachates of a MSWI Bottom Ash Landfill

Cr concentrations and speciation were determined in leachate from a municipal solid waste incinerator bottom ash landfill both experimentally and by thermodynamic model calculations. Total dissolved Cr concentrations of 0.2 mmol L-1 were determined by GFAAS. Two orders of magnitude lower values were determined upon preconcentration by an in-situ solid-phase extraction technique based on the 8-HQ cation exchanger that is specific for Cr(III) but unspecific for Cr(VI). This suggests that chromate dominates the dissolved Cr concentrations in the leachates but was up to 5 orders of magnitude undersaturated with respect to the solubility of CaCrO4 or BaCrO4. Chromate adsorption by oxyhydroxides …

Surface complexation modeling of arsenate adsorption by akagenéite (β-FeOOH)-dominant granular ferric hydroxide

Abstract A surface complexation model has been set up for the first time with akaganeite (β-FeOOH), a major compound of granular ferric hydroxide (GFH) used in groundwater purification units worldwide for arsenic and other toxic pollutant removal. Unlike the situation for the α-FeOOH polymorph goethite, there is yet no published surface complexation model to predict competing oxyanion effects. This is due to a linked bulk-surface reactivity by which excess protons released in an unknown amount from tunnel sites hamper quantification of surface protonation by acid titration. The measured proton uptake thus exceeds what can be expected from OH groups active in surface protonation. However, ch…

Solubility of Zn(II) in Association with Calcium Silicate Hydrates in Alkaline Solutions

The binding of Zn(II) to the cement mineral calcium silicate hydrate (CSH) was investigated in a well-defined laboratory system. CSH (Ca:Si = 1:1) was synthesized by coprecipitation with varying contents of Zn(II). Zn(II) was added in the proportions 0, 0.1, 1.0, 5.0, and 10% in exchange for Ca. The resulting CSH was characterized by X-ray diffraction. The solid phases were then equilibrated in aqueous suspensions, and the solubilities of Ca, Si, and of Zn(II) were determined as a function of pH and Zn(II) content in the solid phase. The solubility of Ca and Si in equilibrium with the CSH phases was in agreement with that predicted by thermodynamic calculations. Dissolved Zn(II) concentrati…

Real-time 3D imaging of Haines jumps in porous media flow.

Newly developed high-speed, synchrotron-based X-ray computed microtomography enabled us to directly image pore-scale displacement events in porous rock in real time. Common approaches to modeling macroscopic fluid behavior are phenomenological, have many shortcomings, and lack consistent links to elementary pore-scale displacement processes, such as Haines jumps and snap-off. Unlike the common singular pore jump paradigm based on observations of restricted artificial capillaries, we found that Haines jumps typically cascade through 10–20 geometrically defined pores per event, accounting for 64% of the energy dissipation. Real-time imaging provided a more detailed fundamental understanding o…

Detection of a Ca-rich lithology in the Earth's deep (&gt;300 km) convecting mantle

Earth's deep convecting upper mantle is believed to represent a rather homogenous geochemical reservoir of spinel or garnet lherzolite with primitive major element and moderately depleted trace element composition. Only where subduction occurs is this homogeneity disrupted by a suite of rocks ranging from eclogites/garnet pyroxenites (former oceanic crust) to residual harzburgites. In addition to these well documented peridotitic and metabasaltic rocks we have now discovered the presence of a chemically distinct reservoir in the deep convecting upper mantle. In situ structural analyses (micro X-ray diffraction and micro Raman spectroscopy) and three-dimensional trace element mapping (confoc…

Simulating permeability reduction by clay mineral nanopores in a tight sandstone by combining computer X-ray microtomography and focussed ion beam scanning electron microscopy imaging

Solid earth 12(1), 1 - 14 (2021). doi:10.5194/se-12-1-2021

Microtomographic Quantification of Hydraulic Clay Mineral Displacement Effects During a CO2 Sequestration Experiment with Saline Aquifer Sandstone

We combined a noninvasive tomographic imaging technique with an invasive open-system core-flooding experiment and compared the results of the pre- and postflooded states of an experimental sandstone core sample from an ongoing field trial for carbon dioxide geosequestration. For the experiment, a rock core sample of 80 mL volume was taken from the 629 m Stuttgart Formation storage domain of a saline sandstone aquifer at the CCS research pilot plant Ketzin, Germany. Supercritical carbon dioxide and synthetical brine were injected under in situ reservoir p/T-conditions at an average flow rate of 0.1 mL/min for 256 h. X-ray computed microtomographic imaging was carried out before and after the…

Aqueous Solubility Diagrams for Cementitious Waste Stabilization Systems. 4. A Carbonation Model for Zn-Doped Calcium Silicate Hydrate by Gibbs Energy Minimization

A thermodynamic Gibbs energy minimization (GEM) solid solution-aqueous solution (SSAS) equilibrium model was used to determine the solubility of Zn from calcium silicate hydrate (CSH) phases doped with 0, 0.1, 1, 5, and 10% Zn at a unity (Ca+Zn)/Si molar ratio. Both the stoichiometry and standard molar Gibbs energy (G(o)298) of the Zn-bearing end-member in the ideal ternary Zn-bearing calcium silicate hydrate (CZSH) solid solution were determined by a "dual-thermodynamic" (GEM-DT) estimation technique. The SSAS model reproduces a complex sequence of reactions suggested to occur in a long-term weathering scenario of cementitious waste forms at subsurface repository conditions. The GEM model …

Comparison of Micro X-ray Computer Tomography Image Segmentation Methods: Artificial Neural Networks Versus Least Square Support Vector Machine

Micro X-ray computer tomography (XCT) is a powerful non-destructive method for obtaining information about rock structures and mineralogy. A new methodology to obtain porosity from 2D XCT digital images using artificial neural network and least square support vector machine is demonstrated following these steps: the XCT image was first preprocessed, thereafter clustering algorithms such as K-means, Fuzzy c-means and self-organized maps was used for image segmentation. Then artificial neural network was applied for image classification. For comparison, least square support vector machine approach was used for classification labeling of the scan images. The methodology shows how artificial ne…

Mobility of Cr and V in Spent Oil Shale: Impact of Thermal Treatment

Abstract Spent oil shale samples were evaluated for potential chromium and vanadium release upon aerobic combustion used in power generation, or anaerobic retorting used in shale oil recovery. Combusted samples released more Cr than retorted or raw samples due to chromate formation. The behavior of vanadium was just opposite in that more V was released from retorted than from aerobically combusted samples, probably due to reduced vanadyl cation formation.

Adsorption of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) by goethite.

Interaction between the goethite surface and 4-chloro-2-methylphenoxyacetic acid (MCPA) herbicide was studied using density functional theory (DFT) calculations combined with molecular dynamics (MD). The important step made here lies in the use of a periodic DFT method enabling the study of a mineral surface of different protonation states, in strong contrast with previous molecular modeling studies limited to single protonation state corresponding to the point of zero charge. Different surface OH groups and MCPA proton states were used to mimic the strong effects of pH on the outer- and inner-sphere surface complexes that are theoretically possible, together with their binding energies, an…

Exothermic adsorption of chromate by goethite

Abstract Goethite is a common Fe oxyhydroxide coating soil particle surfaces, which has a high Cr(VI) adsorption capacity under acidic pH conditions. Batch equilibrium adsorption experiments with chromate concentrations of 0.1, 0.2, and 0.3 mM were performed using solutions with ionic strengths of 0.1, 0.05, and 0.01 M and pH values of 3–11 and at four temperatures between 10 and 75 °C. The results of these experiments show that the amount of chromate adsorbed decreases as the pH increases towards the zero-point-of-surface-charge of goethite (pHPZC 9.1), which is typical for anions. The chromate adsorption efficiency also depends on the ionic strength of the solution. The amount of chromate…

Incorporation of trace metals Cu, Zn, and Cd into gypsum: Implication on their mobility and fate in natural and anthropogenic environments

Abstract The coexistence of calcium (Ca2+), sulfate (SO42−) with trace metal cations (M(II)) can possibly lead to M(II)-gypsum coprecipitation and solid solution formation. However, gypsum's role in the fixation of M(II) is still largely unknown. This study investigated the precipitation of Ca2+ and SO42− in the presence of M(II) (i.e., Cu2+, Zn2+, or Cd2+) and the incorporation of the metal cations into the gypsum structure at different environmental conditions. Trace metals in two natural gypsum samples (Yunnan and Neimeng, China) and one hydrometallurgical byproduct gypsum sample from a Cu refinery were also assessed. X-ray diffraction, scanning electron microscopy-energy dispersive X-ra…

Competitive arsenate and phosphate adsorption on α-FeOOH, LaOOH, and nano-TiO2: Two-dimensional correlation spectroscopy study

Abstract Competitive adsorption of arsenate (AsO43−) and phosphate (PO43−) on α-FeOOH, LaOOH, and nano-TiO2 was studied using batch adsorption experiments and in-situ flow cell ATR-FTIR coupled with two-dimensional correlation spectroscopy (2D-COS) for the first time. With a higher temporal resolution, our results found a highly dynamic adsorption sequence for AsO43− and PO43−. When AsO43− and PO43− were simultaneously exposed to the adsorbents at the same concentrations, AsO43− was preferentially adsorbed by α-FeOOH and TiO2, but PO43− adsorption was dominant on LaOOH. The results implied that the PO43− adsorbed on LaOOH had to be remobilized to allow for AsO43− adsorption, but that PO43− …

Low-Molecular-Weight Organic Acid Complexation Affects Antimony(III) Adsorption by Granular Ferric Hydroxide.

Antimony(III) mobility in natural aquatic environments is generally enhanced by dissolved organic matter. Tartaric acid is often used to form complexes with and stabilize dissolved Sb(III) in adsorption studies. However, competition between such low-molecular-weight organic acid complexation and adsorption of Sb(III) has received little attention, which prompted us to measure Sb(III) adsorption by iron oxyhydroxide adsorbents commonly used in water treatment plants. Sb K-edge X-ray absorption fine structure (EXAFS) spectra gave Sb–O and Sb–Fe distances and coordinations compatible with a bidentate binuclear inner-sphere complex with trigonal Sb(O,OH)3 polyhedra sharing corners with Fe(O,OH)…

Presence of polycyclic aromatic hydrocarbons in sediments and surface water from Shadegan wetland – Iran: A focus on source apportionment, human and ecological risk assessment and Sediment-Water Exchange

Abstract Polycyclic aromatic hydrocarbons (PAHs) contamination in aquatic system is of concern since it may constitute a sink of these contaminants for wetland ecosystem. We investigated pollution characteristics and ecological risks of PAHs by sampling contaminated sediments and water from the Shadegan wetland in Khuzestan province, south-west Iran. Concentrations of total PAHs in water and sediment samples varied from 42 ± 2.3–136 ± 7.5 ng/L and 10 ± 0.5–317 ± 14.3 µg/kg, respectively. Source apportionment of PAHs by both approaches (Principal component analysis-multiple linear regression (PCA-MLR) and molecular isomeric ratios of specific PAHs), indicated impact of potential anthropogeni…

Thorium-234 derived information on particle residence times and sediment deposition in shallow waters of the south-western Baltic Sea

Abstract Activities of the naturally occurring, short-lived and highly particle-reactive radionuclide tracer 234 Th in the dissolved and particulate phase were measured at three shallow-water stations (maximum water depths: 15.6, 22.7 and 30.1 m) in Mecklenburg Bay (south-western Baltic Sea) to constrain the time scales of the dynamics and the depositional fate of particulate matter. Activities of particle-associated (> 0.4 μm) and total (particulate + dissolved) 234 Th were in the range of 0.08–0.11 dpm L − 1 and 0.11–0.20 dpm L − 1 , respectively. The activity ratio of total 234 Th and its long-lived and conservative parent nuclide 238 U was well below unity (range: 0.09–0.19) indicating …

Silicate adsorption by goethite at elevated temperatures

Abstract Batch adsorption experiments with relatively low silica concentrations between 10 µM and 100 µM were conducted at three different ionic strength (0.01  − 0.1 M), and four different temperatures between 10 °C and 75 °C, yielding in a total of 550 experimental data points. The residual concentration of monosilicic acid is controlled by an adsorption equilibrium which is dependent on pH. The % Si adsorbed vs. − log[H + ] curves reveal an upward bend with a maximum at about a pH of 9. With acidification below pH 9 the residual Si concentration in the suspensions steadily increases, as well as in the increasingly alkaline pH range. The slope of the latter is becoming steeper with increa…

Aqueous solubility diagrams for cementitious waste stabilization systems. 3. Mechanism of zinc immobilizaton by calcium silicate hydrate.

Zinc oxide was added during hydration of alite (C3S) as an analogue for solidification/stabilization by cement of metal-bearing hazardous waste. Curing of samples was stopped at various intervals between 8 h and 100 d, and the reaction products were analyzed by both X-ray diffraction (XRD) and X-ray absorption spectroscopy (EXAFS at Zn, Ca, and Si K-edges). Calcium zincate hydrate (CaZn2(OH)6 x 2H2O) initially formed together with calcium silicate hydrate (CSH) vanishes from X-ray diffractograms after 14 d, and no other crystalline Zn-bearing phase could be detected thereafter. EXAFS Zn K-edge data analysis reveals that Zn(O,OH)4 tetrahedra continue to determine the first shell coordination…

LFER and the Effect of Temperature on Oxyanion Adsorption by Goethite

A linear relationship between the Gibbs free energy, ΔGr,H+, of the aqueous complex deprotonation reaction, and the Gibbs free energy, ΔGr,ads, of bidentate surface complexation reaction of oxyanions was derived from modelling of temperature dependent batch equilibrium adsorption experiments. As exemplified in this study, this relationship may be exploited to predict temperature-dependent adsorption behavior of oxyanions not yet known such as pertechnetate.

Microfungal Alkylation and Volatilization of Selenium Adsorbed by Goethite

Selenium adsorbed in the oxyanionic form by Fe-oxides like goethite is considered of benefit for long-term stabilization of (79)Se under near field conditions of radionuclide waste disposal sites. However, microbe-mediated volatilization of the uranium fission product (79)Se has not yet been considered for risk assessment based on the use of the water-solid distribution coefficient K(D). We have performed incubation experiments in a ternary system selenium-microbe-goethite and show that mycobiota including the common black microfungi genera Alternaria alternata are capable of volatilizing the Se even if immobilized by goethite. The microfungi were incubated in a standardized nutrient broth …