Remediation of Cr(VI) from chromium slag by biocementation

Here we demonstrate a calcifying ureolytic bacterium Bacillus sp. CS8 for the bioremediation of chromate (Cr(VI)) from chromium slag based on microbially induced calcite precipitation (MICP). A consolidated structure like bricks was prepared from chromium slags using bacterial cells, and five stage Cr(VI) sequential extraction was carried out to know their distribution pattern. Cr(VI) mobility was found to significantly be decreased in the exchangeable fraction of Cr slag and subsequently, the Cr(VI) concentration was markedly increased in carbonated fraction after bioremediation. It was found that such Cr slag bricks developed high compressive strength with low permeability. Further, leaching behavior of Cr(VI) in the Cr slag was studied by column tests and remarkable decrease in Cr(VI) concentration was noticed after bioremediation. Cr slags from columns were characterized by SEM–EDS confirming MICP process in bioremediation. The incorporation of Cr(VI) into the calcite surface forms a strong complex that leads to obstruction in Cr(VI) release into the environment. As China is facing chromium slag accidents at the regular time intervals, the technology discussed in the present study promises to provide effective and economical treatment of such sites across the country, however, it can be used globally.     

Isotopes as tracers of sources of lead and strontium in aerosols (TSP & PM2.5) in Beijing

Even after its being phased out in gasoline in the late 90s, lead (Pb) is still present at relatively high levels in the atmosphere of Beijing, China (0.10–0.18 μg m^?3). Its origin is subject to debate as several distinct sources may contribute to the observed pollution levels. This study proposes to constrain the origin(s) of Pb and strontium (Sr) in aerosols, by coupling both Pb and Sr isotope systematics. The characterisation of the main pollution sources (road traffic, smelters, metal refining plants, coal combustion, cement factories, and soil erosion) shows that they can unambiguously be discriminated by the multi-isotope approach (²⁰⁶Pb/²⁰⁴Pb and ⁸⁷Sr/⁸⁶Sr). The study of total suspended particulates (TSP) and fine particles (PM_2.5) from Beijing and its vicinity indicates that both size fractions are controlled by the same sources. Lead isotopes indicate that metal refining plants are the major source of atmospheric lead, followed by thermal power stations and other coal combustion processes. The role of this latter source is confirmed by the study of strontium isotopes. Occasionally, emissions from cement plants and/or input from soil alteration are isotopically detectable.     

Significance of autochthonous Bacillus sp. KK1 on biomineralization of lead in mine tailings

The aim of the study was to isolate and characterize potential autochthonous bacteria for biomineralization of Pb in mine tailings. A total of four bacteria were isolated from the soil samples and assayed for tolerance to Pb and other heavy metals. Isolate KK1 exhibited maximum Pb resistance and was subsequently identified as Bacillus sp. based on the partial 16S rRNA gene sequences. The isolate KK1 reduced the Pb ions and did not harbor pbrT gene. Selective sequential extraction of bioaugmented soil revealed that the isolate significantly reduced (26%) the exchangeable fraction and increased (38%) the carbonate fraction of Pb. X-ray diffraction studies confirmed the role of bacterially induced calcite precipitation in the bioremediation of mine tailings. A significant increase in the urease (334%), DHO (dehydrogenase) (14%), and phosphatase (37%) activity was observed in the bioaugmented mine soil.     

Exploration of heterogeneous chemistry in model atmospheric particles using extended X-ray absorption fine structure analysis

As models of the composition and heterogeneous chemical reactions of the troposphere undergo refinement, novel application of state-of-the-art analytical techniques will be necessary to propound realistic characterizations of mineral dust chemistry. In this study, strontium carbonate particles treated with gaseous nitric acid and nitrogen dioxide were examined with X-ray absorption fine structure analysis (EXAFS). The X-ray spectra of carbonate and nitrate standards were fitted to ab initio calculations, which were used to determine the structure and consistency of strontium nitrate formed on strontium carbonate. By examining differences in mean square radial displacement and lattice spacing values obtained for bulk Sr(NO₃)₂ as compared to Sr(NO₃)₂ formed on SrCO₃, EXAFS proves effective as a tool for investigating the local structure and composition of heterogeneous aerosol particles. The implications of findings on reacted strontium carbonate for atmospheric models of calcium carbonate aerosol are discussed.     

Herbicide movement and dissipation at four midwestern sites

Abstract

This study was conducted to evaluate atrazine (2‐chloro‐4‐ethylamino‐6‐isopropyl‐1, 3, 5‐triazine) and alachlor (2‐chIoro‐N‐(methoxymethyl)acetamide) dissipation and movement to shallow aquifers across the Northern Sand Plains region of the United States. Sites were located at Minnesota on a Zimmerman fine sand, North Dakota on Hecla sandy loam, South Dakota on a Brandt silty clay loam, and Wisconsin on a Sparta sand. Herbicide concentrations were determined in soil samples taken to 90 cm four times during the growing season and water samples taken from the top one m of aquifer at least once every three months. Herbicides were detected to a depth of 30 cm in Sparta sand and 90 cm in all other soils. Some aquifer samples from each site contained atrazine with the highest concentration in the aquifer beneath the Sparta sand (1.28 μg L^‐1). Alachlor was detected only once in the aquifer at the SD site. The time to 50% atrazine dissipation (DT₅₀) in the top 15 cm of soil averaged about 21 d in Sparta and Zimmerman sands and more than 45 d for Brandt and Hecla soils. Atrazine DT₅₀ was correlated positively with % clay and organic carbon (OC), and negatively with % fine sand. Alachlor DT₅₀ ranged from 12 to 32 d for Zimmerman and Brandt soils, respectively, and was correlated negatively with % clay and OC and positively with % sand.     

基质结构对水平潜流人工湿地净化效果影响

为研究基质填充结构变化对人工湿地净化效果的影响,构建2个不同基质结构的对比水平潜流人工湿地实验系统,对城市污水处理厂出水进行深度处理。实验结果表明,1～7 mm石英砂均混填充结构人工湿地系统对COD、NH4+-N和TP的平均去除率分别为49.5%,40.1%和56.1%;比较而言,1～7 mm石英砂分层填充结构湿地系统对3种污染物的平均去除率分别为53.7%,60.4%和68.6%。方差分析表明,不同石英砂结构的人工湿地对COD、NH4+-N及TP的净化效果差异显著(p<0.05)。此外,不同水力停留时间条件下,基质填充结构不同的湿地系统对以上3种污染物的净化效果也存在显著差异(p<0.05),去除率随着水力停留时间的增加而升高,当HRT为36 h时,各系统均能取得较好的净化效果。     

Engineered in situ bioremediation of a petroleum hydrocarbon-contaminated aquifer: assessment of mineralization based on alkalinity, inorganic carbon and stable carbon isotope balances

A concept is proposed to assess in situ petroleum hydrocarbon mineralization by combining data on oxidant consumption, production of reduced species, CH₄, alkalinity and dissolved inorganic carbon (DIC) with measurements of stable isotope ratios. The concept was applied to a diesel fuel contaminated aquifer in Menziken, Switzerland, which was treated by engineered in situ bioremediation. In the contaminated aquifer, added oxidants (O₂ and NO₃⁻) were consumed, elevated concentrations of Fe(II), Mn(II), CH₄, alkalinity and DIC were detected and the DIC was generally depleted in ¹³C compared to the background. The DIC production was larger than expected based on the consumption of dissolved oxidants and the production of reduced species. Stable carbon isotope balances revealed that the DIC production in the aquifer originated mainly from microbial petroleum hydrocarbon mineralization, and that geochemical reactions such as carbonate dissolution produced little DIC. This suggests that petroleum hydrocarbon mineralization can be underestimated if it is determined based on concentrations of dissolved oxidants and reduced species.     

Carbon dioxide adsorption on amine-impregnated mesoporous materials prepared from spent quartz sand

Mesoporous MCM-41 was synthesized using cetyltrimethyl ammonium bromide (CTAB) as a cationic surfactant and spent quartz sand as the silica source. Modification of the mesoporous structure to create an absorbent was then completed using 3-aminopropyltrimethoxysilane. Amine-Quartz-MCM (The A-Q-MCM) adsorbents were then characterized by N₂ adsorption/desorption, elemental analysis (EA), X-ray fluorescence (XRF), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), as well as the carbon dioxide (CO₂) adsorption/desorption performance. In this study, spent quartz sand was utilized to synthesize Quartz-MCM (Q-MCM) and the amine functionalized material, A-Q-MCM, which exhibited a higher uptake of CO₂ at room temperature compared with the nongrafted material. The results showed that Q-MCM is similar to MCM-41 synthesized using commercial methods. The surface area, pore volume, and pore diameter were found to be as high as 1028 m²/g, 0.907 cm³/g, and 3.04 nm, respectively. Under the condition of CO₂ concentration of 5000 ppm, retention time of 50 cc/min, and the dosage of 1 g/cm³, the mean adsorption capacity of CO₂ onto A-Q-MCM was about 89 mg/g, and the nitrogen content of A-Q-MCM was 2.74%. The adsorption equilibrium was modeled well using a Freundlich isotherm.

Implications:In this study, spent quartz sand was utilized to synthesize Q-MCM. The amine functionalized material exhibited a higher uptake of CO₂ at room temperature compared with the nongrafted material. The results showed that Q-MCM is similar to MCM-41 synthesized using commercial methods. The adsorption equilibrium was modeled well using a Freundlich isotherm.     

Seasonal variation in long-range transported dust to a subtropical islet offshore northern Taiwan: Chemical composition and Sr isotopic evidence in rainwater

We investigated chemical and Sr isotopic composition of monthly rainwater collected on Peng-Chia-Yu (PCY) in northern Taiwan. Rainwater ⁸⁷Sr/⁸⁶Sr ratios, Na/Cl, Ca/Cl, Sr/Cl, Sr/Ca, NH₄/Cl, NO₃/Cl, SO₄/Cl and Na/Sr, showed clear seasonal cycles, reflecting mixture of loess carbonates (high Ca/Sr and more radiogenic ⁸⁷Sr/⁸⁶Sr) and seawater (low Ca/Sr and intermediate ⁸⁷Sr/⁸⁶Sr). Model results showed that the former source contributes up to 45% during the winter monsoon period, but seawater is the dominant Sr source in rainwater (>50%) at other times. Two anomalously low ⁸⁷Sr/⁸⁶Sr values occurred in July and August 1998, coinciding with the Merapi eruption in Indonesia. Air-mass backward trajectories and the geochemical and isotopic compositions in rainwater and Merapi lava (i.e. Ca/Sr = 100 and ⁸⁷Sr/⁸⁶Sr = 0.705400) suggested that the Merapi eruption delivered ash across the western equatorial Pacific to PCY. Aerosols leaching experiments were conducted to examine the impact of the 1998 eruption, demonstrating that only a minor terrestrial signature can be extracted by distilled water, implying rapid dispatch of volcanic gases or high-efficiency dissolution of ash related substance in acidic rains.     

Reactive transport of 85Sr in a chernobyl sand column: static and dynamic experiments and modeling

The effects of nonlinear sorption and competition with major cations present in the soil solution on radioactive strontium transport in an eolian sand were examined. Three laboratory techniques were used to identify and quantify the chemical and hydrodynamic processes involved in strontium transport: batch experiments, stirred flow-through reactor experiments and saturated laboratory columns. The major goal was to compare the results obtained under static and dynamic conditions and to describe in a deterministic manner the predominant processes involved in radioactive strontium transport in such systems. Experiments under dynamic conditions, namely flow-through reactor and column experiments, were in very good agreement even though the solid/liquid ratio was very different. The experimental data obtained from the flow-through reactor study pointed to a nonlinear, instantaneous and reversible sorption process. Miscible displacement experiments were conducted to demonstrate the competition between stable and radioactive strontium and to quantify its effect on the 85Sr retardation factor. The results were modeled using the PHREEQC computer code. A suitable cation-exchange model was used to describe the solute/soil reaction. The model successfully described the results of the entire set of miscible displacement experiments using the same set of parameter values for the reaction calculations. The column study revealed that the stable Sr aqueous concentration was the most sensitive variable of the model, and that the initial state of the sand/solution system had also to be controlled to explain and describe the measured retardation factor of radioactive strontium. From these observations, propositions can be made to explain the discrepancies observed between some data obtained from static (batches) and dynamic (reactor and column) experiments. Desorbed antecedent species (stable Sr) are removed from the column or reactor in the flow system but continue to compete for sorption sites in the batch system. Batch experiments are simple and fast, and provide a very useful means of multiplying data. However, interpretation becomes difficult when different species compete for sorption sites in the soil/solution system. A combination of batches, flow-through reactor and column experiments, coupled with hydrogeochemical modeling, would seem to offer a very powerful tool for identifying and quantifying the predominant processes on a cubic decimeter scale (dm3) and for providing a range of radioactive strontium retardation factor as a function of the geochemistry of the soil/solution system.     

Calcite precipitates in Slovenian bottled waters

Storage of bottled waters in varying ambient conditions affects its characteristics. Different storage conditions cause changes in the initial chemical composition of bottled water which lead to the occurrence of precipitates with various morphologies. In order to assess the relationship between water composition, storage conditions and precipitate morphology, a study of four brands of Slovenian bottled water stored in PET bottles was carried out. Chemical analyses of the main ions and measurements of the physical properties of water samples were performed before and after storage of water samples at different ambient conditions. SEM/EDS analysis of precipitates was performed after elapsed storage time. The results show that the presence of Mg²⁺, SO₄ ²⁻, SiO₂, Al, Mn and other impurities such as K⁺, Na⁺, Ba and Sr in the water controlled precipitate morphology by inhibiting crystal growth and leading to elongated rhombohedral calcite crystal forms which exhibit furrowed surfaces and calcite rosettes. Different storage conditions, however, affected the number of crystallization nuclei and size of calcite crystals. Hollow calcite spheres composed of cleavage rhombohedrons formed in the water with variable storage conditions by a combination of evaporation and precipitation of water droplets during high temperatures or by the bubble templating method.

     

Bioremediation of a diesel fuel contaminated aquifer: simulation studies in laboratory aquifer columns

The in situ bioremediation of aquifers contaminated with petroleum hydrocarbons is commonly based on the infiltration of groundwater supplemented with oxidants (e.g., O₂, NO₃⁻) and nutrients (e.g., NH₄⁺, PO₄³⁻). These additions stimulate the microbial activity in the aquifer and several field studies describing the resulting processes have been published. However, due to the heterogeneity of the subsurface and due to the limited number of observation wells usually available, these field data do not offer a sufficient spatial and temporal resolution. In this study, flow-through columns of 47-cm length equipped with 17 sampling ports were filled with homogeneously contaminated aquifer material from a diesel fuel contaminated in situ bioremediation site. The columns were operated over 96 days at 12°C with artificial groundwater supplemented with O₂, NO₃⁻ and PO₄³⁻. Concentration profiles of O₂, NO₃⁻, NO₂⁻, dissolved inorganic and organic carbon (DIC and DOC, respectively), protein, microbial cells and total residual hydrocarbons were measured. Within the first 12 cm, corresponding to a mean groundwater residence time of < 3.6 h, a steep O₂ decrease from 4.6 to < 0.3 mg l⁻¹, denitrification, a production of DIC and DOC, high microbial cell numbers and a high removal of hydrocarbons were observed. Within a distance of 24 to 40.5 cm from the infiltration, O₂ was below 0.1 mg l⁻¹ and a denitrifying activity was found. In the presence and in the absence of O₂, n-alkanes were preferentially degraded compared to branched alkanes. The results demonstrate that: (1) infiltration of aerobic groundwater into columns filled with aquifer material contaminated with hydrocarbons leads to a rapid depletion of O₂; (2) O₂ and NO₃⁻ can serve as oxidants for the mineralization of hydrocarbons; and (3) the modelling of redox processes in aquifers has to consider denitrifying activity in presence of O₂.     

The Fate of Hydrogen Peroxide as an Oxygen Source for Bioremediation Activities within Saturated Aquifer Systems

ABSTRACT

In situ bioremediation is an innovative technique for the remediation of contaminated aquifers that involves the use of microorganisms to remediate soils and groundwaters polluted by hazardous substances. During its application, this process may require the addition of nutrients and/or electron acceptors to stimulate appropriate biological activity. Hydrogen peroxide has been commonly used as an oxygen source because of the limited concentrations of oxygen that can be transferred into the groundwater using above-ground aeration followed by reinjection of the oxygenated groundwater into the aquifer or subsurface air sparging of the aquifer. Because of several potential interactions of H₂O₂ with various aquifer material constituents, its decomposition may be too rapid, making effective introduction of the H₂O₂ into targeted treatment zones extremely difficult and costly. Therefore, a bench-scale study was conducted to determine the fate of H₂O₂ within subsurface aquifer environments. The purpose of this investigation was to identify those aquifer constituents, both biotic and abiotic, that are most active in controlling the fate of H₂O₂. The decomposition rates of H₂O₂ were determined using both equilibrated water samples and soil slurries. Results showed H₂O₂ decomposition to be effected by several commonly found inorganic soil components; however, biologically mediated catalytic reactions were determined to be the most substantial.     

The exposition of a calcareous Mediterranean soil to toxic concentrations of Cr, Cd and Pb produces changes in the microbiota mainly related to differential metal bioavailability

The involvement of the bacterial community of an agricultural Mediterranean calcareous soil in relation to several heavy metals has been studied in microcosms under controlled laboratory conditions. Soil samples were artificially polluted with Cr(VI), Cd(II) and Pb(II) at concentrations ranging from 0.1 to 5000 mg kg⁻¹ and incubated along 28 d. The lowest concentrations with significant effects in soil respirometry were 10 mg kg⁻¹ Cr and 1000 mg kg⁻¹ Cd and Pb. However, only treatments showing more than 40% inhibition of respirometric activity led to significant changes in bacterial composition, as indicated by PCR-DGGE analyses. Presumable Cr- and Cd-resistant bacteria were detected in polluted microcosms, but development of the microbiota was severely impaired at the highest amendments of both metals. Results also showed that bioavailability is an important factor determining the impact of the heavy metals assayed, and even an inverted potential toxicity ranking could be achieved if their soluble fraction is considered instead of the total concentration. Moreover, multiresistant bacteria were isolated from Cr-polluted soil microcosms, some of them showing the capacity to reduce Cr(VI) concentrations between 26% and 84% of the initial value. Potentially useful strains for bioremediation were related to Arthrobacter crystallopoietes, Stenotrophomonas maltophilia and several species of Bacillus.     

Geochemistry of a septic-system plume in a coastal barrier bar, Point Pelee, Ontario, Canada

The major ion and trace metal geochemistry of a septic system plume in a shallow sand aquifer was characterized to assess geochemical processes controlling the transport of nutrients and their release to a nearby wetland. The plume was generated from a 16-year-old tile bed, and is more than 60 m long, 40 m wide and 7 m thick. The groundwater pH at the site is near neutral, but up to 0.4 units lower in the plume core as a result of H⁺ generated from NH₃ and DOC oxidation in the unsaturated zone. The plume can be divided into distinct redox zones, which show differences in nutrient mobility. Proximal to the tile bed, there is a shallow suboxic zone, with intermediate Eh values (>400 mV), low concentrations of dissolved oxygen (<1.0 mg/l), and elevated concentrations of Mn (1–3 mg/l) and nutrients (10–80 mg/l NO₃–N, 1–15 mg/l NH₃–N, 0.1–1.5 mg/l PO₄–P, 6–13 mg/l dissolved organic carbon). At the base of the aquifer, there is a reduced zone (Eh<200 mV) with elevated concentrations of Fe (1–14 mg/l), PO₄ and NH₃, but negligible concentrations of NO₃ (<0.01 mg/l N). Distal from the tile bed, the shallow groundwater is suboxic to oxic, and has elevated concentrations of NO₃ and NH_3, but negligible PO₄. In the lower reduced zone, elevated concentrations of PO₄ occur up to 60 m away. The release of groundwater containing even very low concentrations of PO₄ (<0.02 mg/l P) can lead to the development of eutrophic conditions in surface water bodies. Geochemical calculations indicate that, in the Mn-rich zone, the groundwater is close to saturation or supersaturated with respect to hydroxyapatite, rhodochrosite, calcite and ferrihydrite. In the reduced zone, the groundwater is close to saturation or supersaturated with respect to hydroxyapatite, vivianite, calcite and siderite. Formation of these phases, or related phases, are likely limiting the concentrations of dissolved PO₄, Fe and Mn and controlling the geochemical evolution of the plume.     

Effects of endosulfan exposure and Taura Syndrome Virus infection on the survival and molting of the marine penaeid shrimp, Litopenaeus vannamei

Molting in crustaceans is an important endocrine-controlled biological process that plays a critical role in growth and reproduction. Many factors can affect this physiological cycle in crustaceans including environmental stressors and disease agents. For example the pathology of Taura Syndrome Virus (TSV) of shrimp is closely related to molting cycle. Similarly, endosulfan, a commonly used pesticide is a potential endocrine disruptor. This study explores interrelationships between pesticide exposure, virus infection and their interactions with physiology and susceptibility of the shrimp. Litopenaeus vannamei (Pacific white shrimp) were challenged with increasing doses of endosulfan and TSV (TSV-C, a Belize reference strain) to determine the respective median lethal concentrations (LC₅₀s). The 96-h endosulfan LC₅₀ was 5.32 μg L⁻¹, while the 7-d TSV LC₅₀ was 54.74 mg L⁻¹. Subsequently, based on their respective LC₅₀ values, a 20-d interaction experiment with sublethal concentrations of endosulfan (2 μg L⁻¹) and TSV (30 mg L⁻¹) confirmed a significant interaction (p < 0.05, χ² = 5.29), and thereby the susceptibility of the shrimp. Concurrently, molt-stage of animals, both at the time of exposure and death, was compared with mortality. For animals challenged with TSV, no strong correlation between molt-stage and mortality was observed (p > 0.05). For animals exposed to endosulfan, animals in the postmolt stage were shown to be more susceptible to acute toxicity (p < 0.05). For animals exposed to both TSV and endosulfan, interference of endosulfan-associated stress lead to increasingly higher susceptibility at postmolt (p < 0.05) during the acute phase of the TSV disease cycle.     

改性锰砂滤料处理高铁锰煤矿矿井水

采用KMnO4溶液浸渍法制备了新型改性锰砂滤料,研究了滤料表面性能和过滤处理高铁锰矿井水的效果。结果表明,锰砂滤料除铁锰性能优于石英砂、陶粒以及瓷砂,采用KMnO4溶液浸渍能够提高锰砂滤料的过滤性能,最优的浸渍浓度为5%。5%KMnO4改性锰砂滤料过滤处理高铁锰矿井水的最佳工艺参数为：过滤周期24 h,反冲洗强度3.2 L/（s.m2）,反冲洗时间5 min;通过比表面积测试分析和SEM表征分析发现,KMnO4溶液浸渍能够提高锰砂滤料比表面积,并在锰砂滤料表面形成了氧化膜,从而提高除铁除锰效果,而且浸渍液浓度越高,这种作用越明显。     

Effect of metals on a siderophore producing bacterial isolate and its implications on microbial assisted bioremediation of metal contaminated soils

A bacterial isolate producing siderophore under iron limiting conditions, was isolated from mangroves of Goa. Based on morphological, biochemical, chemotaxonomical and 16S rDNA studies, the isolate was identified as Bacillus amyloliquefaciens NAR38.1. Preliminary characterization of the siderophore indicated it to be catecholate type with dihydroxy benzoate as the core component. Optimum siderophore production was observed at pH 7 in mineral salts medium (MSM) without any added iron with glucose as the carbon source. Addition of NaCl in the growth medium showed considerable decrease in siderophore production above 2% NaCl. Fe⁺² and Fe⁺³ below 2 μM and 40 μM concentrations respectively, induced siderophore production, above which the production was repressed. Binding studies of the siderophore with Fe⁺² and Fe⁺³ indicated its high affinity towards Fe⁺³. The siderophore concentration in the extracellular medium was enhanced when MSM was amended with essential metals Zn, Co, Mo and Mn, however, decreased with Cu, while the concentration was reduced with abiotic metals As, Pb, Al and Cd. Significant increase in extracellular siderophore production was observed with Pb and Al at concentrations of 50 μM and above. The effect of metals on siderophore production was completely mitigated in presence of Fe. The results implicate effect of metals on the efficiency of siderophore production by bacteria for potential application in bioremediation of metal contaminated iron deficient soils especially in the microbial assisted phytoremediation processes.     

Eu uptake by calcite: Preliminary results from coprecipitation experiments and observations with surface-sensitive techniques

A lack of information in databases for contamination risk assessment about the transport behaviour of the trivalent f-orbital elements in groundwater systems where calcite is at equilibrium motivated this study of Eu³⁺ uptake. The free drift technique was used to examine the effects of Eu³⁺ concentration, presence of Na⁺ or K⁺ and temperature, as well as calcite nucleation and precipitation kinetics, on the partitioning of calcite. Changes in surface composition and morphology resulting from exposure of single crystals of Iceland spar to Eu³⁺-bearing solutions were observed with X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). First results confirm that calcite has high affinity for Eu³⁺. Rates of nucleation and precipitation strongly affect the extent of uptake but the presence of Na⁺ and K⁺ has no effect, suggesting formation of solid solution as CaCO₃–EuOHCO₃. Surface-sensitive techniques prove that Eu³⁺ is adsorbed to calcite even when the surface is dissolving and adsorption is not accompanied by precipitation of a separate Eu³⁺-solid phase. Adsorbed Eu modifies calcite's dissolution behaviour, roughening terraces and rounding step edges, and producing surface morphology where some surface sites appear blocked. Results imply that Eu³⁺ concentrations in natural calcites are limited by Eu³⁺ availability rather than by a lack of ability to fit into calcite's atomic structure. This behaviour can probably be expected for other trivalent rare Earth elements (REE), actinides and fission products whose behaviour is similar to that of Eu³⁺. These elements are likely to be incorporated within the calcite bulk in systems where it is precipitating and the demonstrated strong partitioning ensures some uptake even where calcite is at or under saturation.     

Metal and metalloid accumulation in shrews (Soricomorpha, Mammalia) from two protected Mediterranean coastal sites

Although ecotoxicological data on heavy metals are abundant, information on other potentially toxic elements with attributed deficiency and/or toxic disturbances is scarce. Here we quantify zinc, copper, iron, manganese, chromium, molybdenum, strontium, barium, and boron in bones of greater white-toothed shrews, Crocidura russula, inhabiting two protected Mediterranean coastal sites: the Ebro Delta, a wetland impacted by human activities, and the Medas Islands, a reference site. Natural and anthropogenic inputs significantly increase Fe, Mn, Mo, Sr, Ba, and B in specimens from the Ebro Delta, whereas Cu and Cr were higher in Medas' shrews. Principal component analysis allowed complete separation between sites along the first two axes in particular due to B, Sr, and Cu. This study provides metal reference values in bones of insectivores, explores their variability and bioaccumulation patterns in depth, and assesses the potential environmental risk and toxicity for biota exposed to the above elements.