Solid-liquid Partition Coefficient Research Articles

Unraveling Drug Delivery from Cyclodextrin Polymer-Coated Breast Implants: Integrating a Unidirectional Diffusion Mathematical Model with COMSOL Simulations.

Breast cancer ranks among the most commonly diagnosed cancers worldwide and bears the highest mortality rate. As an integral component of cancer treatment, mastectomy entails the complete removal of the affected breast. Typically, breast reconstruction, involving the use of silicone implants (augmentation mammaplasty), is employed to address the aftermath of mastectomy. To mitigate postoperative risks associated with mammaplasty, such as capsular contracture or bacterial infections, the functionalization of breast implants with coatings of cyclodextrin polymers as drug delivery systems represents an excellent alternative. In this context, our work focuses on the application of a mathematical model for simulating drug release from breast implants coated with cyclodextrin polymers. The proposed model considers a unidirectional diffusion process following Fick's second law, which was solved using the orthogonal collocation method, a numerical technique employed to approximate solutions for ordinary and partial differential equations. We conducted simulations to obtain release profiles for three therapeutic molecules: pirfenidone, used for preventing capsular contracture; rose Bengal, an anticancer agent; and the antimicrobial peptide KR-12. Furthermore, we calculated the diffusion profiles of these drugs through the cyclodextrin polymers, determining parameters related to diffusivity, solute solid-liquid partition coefficients, and the Sherwood number. Finally, integrating these parameters in COMSOL multiphysics simulations, the unidirectional diffusion mathematical model was validated.

Using the quantitative ion character-activity relationships (QICAR) model to predict the solid-liquid release of metals in soil

Dissolved metals in the soil’s liquid phase are more easily absorbed by biological tissues, thus posing potential risks to living organisms. Therefore, studying the solid-liquid partition coefficient (Kd) of metals in the soil helps understand their environmental risks. We collected 102 Kd data of metals in soil from the literature to build a quantitative ion character-activity relationship model (s-QICAR) based on the metals’ physicochemical properties. Correlation analysis showed ten elemental physicochemical properties related to Kd, including covalent bond index, atomic mass, and first hydrolysis constant, with R2 = 0.502–0.989. Through comparative screening, 39s-QICAR models were finally established, including covalent bond index and first hydrolysis constant. The established s-QICAR model predicted the Kd values of Mo, Sb, and La in the 39 soil samples, ranging from 21 to 19978. Finally, a coupling analysis was conducted between Kd-metal and soil physicochemical properties. The s-QICAR model with covalent bond index as the independent variable was mainly affected by soil pH and cation exchange capacity, while the s-QICAR model with first hydrolysis constant was influenced primarily by clay content. Therefore, this study established a predictive model for soil Kd, providing a basis for soil environmental risk assessment and management. Environmental ImplicationDissolved metals present in the soil liquid phase are more easily absorbed by biological tissues, thus posing potential risks to living organisms. Therefore, studying the solid-liquid partition coefficient (Kd) of metals in the soil helps understand their environmental risks. Common Kd values are obtained by measuring the content of soil solid and liquid phase metals. However, this method is time-material consuming. We study the relationship between element properties and their Kd, then establish a model that does not rely on measured data to predict Kd of soil elements, providing a basis for soil environmental risk assessment and management.

A methodological framework to study the behavior and kinetic influence of V, Mn, Co, Ni, Cu, Zn, As, Se and Mo during pyrite formation via the polysulfide pathway at ambient temperature

Pyritization links the biogeochemical cycles of Fe, S and C to those of trace elements (TE) such as As, Ni, Cu, Co, Mn, Zn, Se and Mo in reducing environments. The scavenging modes of such impurities in pyrite are parameters of importance for evaluating to which extent pyrite can immobilize TE under diverse (sub)surface conditions. Furthermore, determining the fate of TE during pyritization is a prerequisite to evaluate the ability of pyrite to record the chemical signature of surrounding waters at the time of precipitation. Here, we provide a methodological framework to study the incorporation of TE during a reaction sequence leading to pyrite formation via the polysulfide pathway. Laboratory syntheses were conducted by reacting a FeS precursor with elemental sulfur – both readily obtained by reducing FeCl3 with Na2S in solution under strict anoxia – at ambient temperature and in the presence of aqueous V, Mn, Co, Ni, Cu, Zn, As, Se and Mo in a TE/Fe molar ratio of 0.5 mol%. Within this simplified framework, our experiments aimed at reproducing the early formation of pyrite in water column aggregates/bottom sediments before the late diagenetic aging phases. Solids and liquids were sampled over time during the reaction sequence leading to pyrite formation, up to 3100 h, and further analyzed by ICP-OES, XRD, XRF and STEM-EDXS to obtain information on (1) the kinetics of pyrite formation and (2) the extent of TE incorporation in the solid phase, during and after the complete conversion of FeS to FeS2. Pyrite formation kinetic is observed to be strongly influenced by the identity of the added TE, with the delay before nucleation decreasing in the order Ni >> Mn, Co > Cu, Zn, Se > Control, V >> As, Mo. During the full reaction sequence, i.e. FeS plus S(0) conversion to FeS2, Mn remains in the liquid phase, Ni, Co, V, Cu, and Se quickly precipitate and remain sequestered overtime, Zn and Mo precipitate and are further released into solution, and As is partially incorporated in the solid. Elemental mapping at the microscale using STEM-EDXS show that, except for Mn, the TE are associated with pyrite. Moreover, while TE are homogeneously distributed at the particle scale for Co, Cu, Zn, As, and Se, Ni-pyrite exhibited an enriched core. The solid-liquid partition coefficients of each TE during our pyritization experiments in our simplified model system are calculated and ranks as follows: Cu ≥ Ni ≥ Co > Se > V > Mo >> As > Zn >> Mn. These partitions are discussed in the light of values reported in the literature from natural settings. The important differences observed exemplify the complexity to predict TE pyrite-water partition in sedimentary environments, in particular when considering additional multifactorial processes such as the local biogeochemistry of micro-environments, as well as the partial sequestration of TE by non-sulfide minerals such as authigenic clays and carbonates.

Modeling and simulation of trifluralin herbicide movement due to its application on soils by chemigation

The Trifluralin (TFN) is a pre-emergent herbicide which is widely used in agriculture. Usually, this pesticide is directly applied to the soil, where it can remain for long periods or can be transported. In this sense, knowing the dynamics of an herbicide soil transport is essential to avoid environmental contamination problems and risks to human health. Thus, this study aims to model and simulate TFN movement on soils with two different textures, a sandy loam and clay loam soil. It was considered that the herbicide was applied via chemigation trough a subsurface drip irrigation system, under a non-steady regime. Therefore, the transport parameters of TFN in these soils and physical-hydric characteristics of these were used, while the physical environment modeling were conducted using the Hydrus 2D software. The results showed that both in sandy and clayey soils, the TFN tends to be retained by the soil, close to where it was applied, not exceeding a layer greater than 2.5 mm outside the dripper radius, even in more favorable conditions such as the presence of irrigation. Finally, it could be concluded that this herbicide movement in the soil is of low potential, due to this product high solid-liquid partition coefficient (Kd), even in sandy soil, which has low cation exchange capacity (CEC).

ZnO Nanomaterials and Ionic Zn Partition within Wastewater Sludge Investigated by Isotopic Labeling

The increasing commercial use of engineered zinc oxide nanomaterials necessitates a thorough understanding of their behavior following their release into wastewater. Herein, the fates of zinc oxide nanoparticles (ZnO NPs) and ionic Zn in a real primary sludge collected from a municipal wastewater system are studied via stable isotope tracing at an environmentally relevant spiking concentration of 15.2 µg g−1. Due to rapid dissolution, nanoparticulate ZnO does not impart particle‐specific effects, and the Zn ions from NP dissolution and ionic Zn display indistinguishable behavior as they partition equally between the solid, liquid, and ultrafiltrate phases of the sludge over a 4‐h incubation period. This work provides important constraints on the behavior of engineered ZnO nanomaterials in primary sludge—the first barrier in a wastewater treatment plant—at low, realistic concentrations. As the calculated solid–liquid partition coefficients are significantly lower than those reported in prior studies that employ unreasonably high spiking concentrations, this work highlights the importance of using low, environmentally relevant doses of engineered nanomaterials in experiments to obtain accurate risk assessments.

Evaluation of semi-mechanistic models to predict soil to grass transfer factor of 137Cs based on long term observations in French pastures

The aim of this study was to evaluate and improve the accuracy of the semi-mechanistic models used in regulatory exposure assessment tools, to describe the transfer factors of 137Cs from pasture soils to grass observed in different grazing areas of France between 2004 and 2017. This involved a preliminary parameterization step of the dynamic factor describing the ageing of radiocesium in the root zone using a Bayesian approach. A data set with mid-term (10 years about) and long term (more than 20 years) field and literature data from 4 European countries was used. A double kinetics of the bioavailability decay was evidenced with two half-life periods equal to 0.46 ± 0.11 yr and 9.57 ± 1.12 yr for the fast and slow declining rates respectively. We, then, tested a few existing alternative models proposed in literature. The comparison with field data showed that these models always underestimated the observations by one to two orders of magnitude, suggesting that the solid-liquid partition coefficient (Kd) was overestimated by models. The results suggest that semi mechanistic models might fail in the long-term prediction of the radionuclide transfer from soil-to-plant in the food chain. They highlight the need to calculate Kd using easily exchangeable 137Cs (i.e. labile fraction) rather than total soil 137Cs.

Anaerobic digestibility of resin acids in primary sludge: Effect of ozone pretreatment

Resin acids in pulp and paper mills wastewater are potentially partitioned in the solids in post–primary clarification due to higher hydrophobicity with log Kow ∼1.74–5.80. They are known to adversely affect anaerobic digestion (AD) process, although the effect has not been quantified deterministically in control studies. The objective of the present work was to determine the effect of untreated and ozonated spiked resin acids on AD of primary sludge. Batch adsorption tests were conducted to determine the solid-liquid partition coefficient (Kd) of resin acids on the primary sludge. Higher Kd was obtained at pH 4; however, it was decreased by 78–98% at pH 8. Thereafter, batch AD of model resin acids in primary sludge using food to microorganism ratio (S0/X) of 0.5gtCOD/gVSSindicated only 15–20% removal of resin acids in the liquid phase anaerobically. While, ozonation in pure water using 0.74–1.48 mg O3/mg tCOD showed >90% reduction of the test resin acids, an ozone dose of 0.52 mg O3/mg tCOD reduced 50–70% spiked resin acids’ load to the digester. However, no further removal of resin acids occurred during AD over 30 days. About 42% reduction in methane production compared to the control digestor occurred in the presence of 150 mg/L of resin acids. When treated with 0.52 mg O3/mg tCOD, methane production improved and was comparable to the control digestor, indicating that resin acids may not be detrimental to AD at a concentration range of 45–75 mg/L.

Physicochemical and time factors affecting 137Cs transfer through a paddy soil–rice system

ABSTRACT To clarify the factors affecting 137Cs transfer from soil to brown rice in comparison with 133Cs transfer and also to determine the key parameters of the solid-liquid partition coefficient (K d), concentration factor from soil solution to brown rice (CF), and transfer factor from soil to brown rice (TF), we analyzed the results of our previous paper in which a rice pot-culture experiment under different fertilization treatments using three paddy soils in Fukushima 3 years after the Fukushima Daiichi Nuclear Power Station accident was conducted. The TF values for 137Cs were the same as or smaller than the literature values obtained within 2 years of the accident, 2–17 times higher than those for global fallout 137Cs from atmospheric nuclear tests, and 2–20 times higher than those for natural 133Cs. The CF values for 137Cs were negatively correlated with the soil solution K+ concentration. A theoretical approach, under the assumption that 137Cs in soil is mainly adsorbed at the frayed edge site (FES) and ion exchange of 137Cs with K+ and NH4 + ions is in equilibrium, partly explained the variability in the soil solution 137Cs concentrations under different soil and fertilization conditions and suggested that the major portion of 137Cs in soil would be adsorbed in FES under lower K+ and NH4 + concentrations but fixed in the collapsed interlayer sites under higher K+ and NH4 + concentrations, the ranges of which are typically observed in agricultural soils. Our results indicate that the major factors affecting 137Cs transfer from soil to brown rice would be the 137Cs, K+, and NH4 + concentrations in the soil solution and the time elapsed from the deposition of 137Cs, and emphasize the necessity of including the dynamic 137Cs adsorption and fixation process in soil into the TF prediction models applicable to agricultural soils received with periodical fertilizations.

On the Effect of Filling Rate on Positive Macrosegregation Patterns in Large Size Cast Steel Ingots

The effect of filling velocity on positive macrosegregation in large size steel ingots was studied. Macrosegregation and macro/microstructures were characterized on the hot-tops and a portion of the upper section of two ingots. The measurements revealed that segregation features in the two ingots varied as a function of the alloying elements, and that the severity of positive macrosegregation in the casting body was reduced when the filling rate was increased. It was also found that at the higher filling rate, grain morphologies in the first solidified zones of the ingot changed from columnar to equiaxe, and secondary dendrite arm spacing (SDAS) became slightly smaller in the intermediate and final solidified zones. The experimental findings were analyzed in the framework of diffusion and convection-controlled solidification, as well as liquid metal flow theories. The solute dependence of segregation features was related to the difference in the solid-liquid partition coefficient and diffusion capability of each element in the liquid iron. Calculation of Reynolds numbers (Re) during the filling process, for both ingots, showed that higher filling velocity caused more instable movement of the liquid metal in the initial solidification stage, resulting in the modification of grain morphology, as well as accelerated solidification rate.

Characteristics of Copper Sorption by Various Agricultural Soils in China and the Effect of Exogenic Dissolved Organic Matter on the Sorption

ABSTRACTTo explore the effect of exogenic dissolved organic matter (DOM) on Cu(II) sorption in agricultural soils, 26 agricultural soils were collected across China. Exogenic dissolved organic matter, extracting from wheat straw (DOMW) and swine manure (DOMS), respectively, were added to the soils to conduct a series of batch sorption and characterization experiments. The solid-liquid partition coefficient (Kd) ranged from 0.02 to 76.46 L g−1, suggesting different Cu(II) sorption on various soils. PCA analysis indicated that pH, free Fe/Al oxides, carbon, and total Cu content had a significant positive relationship with the Cu(II) sorption, respectively. And the contribution rate of pH was the highest (38.15%). Moreover, DOM markedly inhibited the Cu(II) sorption in alkaline soils while promoted the Cu(II) sorption in acidic soils, which were interacted by the soil properties and DOM characteristics. The effect of DOMS on Cu(II) sorption were more obvious than DOMW, which were further confirmed by Fourier transform infrared (FTIR) spectroscopy. FTIR also showed Cu(II) was primarily adsorbed on the specific functional groups, such as CO, OH, and CO, providing direct evidences for the binding of Cu(II) with DOM. This study can guide the rational use of organic fertilizers, and also provide baseline knowledge for the prevention and control of soil pollution.

Adsorption Characteristics and the Effect of Dissolved Organic Matter on Mercury(II) Adsorption of Various Soils in China

ABSTRACTTo evaluate the adsorption characteristics and effects of dissolved organic matter (DOM) from wheat straw (DOMW) and swine manure (DOMS) on mercury [Hg(II)] adsorption by soils, a series of experiments was conducted on 26 soils with different soil properties.Results showed that the values of Kd (a solid–liquid partition coefficient) of soils varied within a range of 0.768–14.386 L g−1. Kd values were mainly controlled by soil organic matter (SOM), cation exchange capacity (CEC), soil nitrogen (N), and soil sulfur (S). When DOMW and DOMS were added to the soil samples, the amount of Hg(II) adsorbed by the soils decreased significantly. Furthermore, based on the decreased percentage of adsorption of Hg(II) by soil upon adding DOMW (PDOMW) or DOMS (PDOMS), about 73.08% soils, the values of PDOMS were smaller than those of PDOMW. The PDOMW values were related to SOM, pH, free Fe oxide content, and CEC, whereas PDOMS values were related to soil free Fe/Al oxide contents. Therefore, we should pay more attention about mercury risk caused by the addition of exogenous organic matter in soils, especially for the soils with low or high pH, less SOM, low CEC, and less free Fe/Al oxide.

Determination of solid–liquid partition coefficient of volatile compounds by solid phase ratio variation based headspace analysis

A novel method has been developed for the determination of the solid–liquid partition coefficient of volatile analytes using headspace gas chromatography (HS–GC). The method is based on the headspace measurement for the three-phase equilibrium in sample vials containing different amounts of solid sample. Theory is presented that allows calculation of partition coefficient of the analyte from the HS–GC data obtained at the condition of solid phase ratio variation (SPRV). Analysis of errors demonstrates that this solid phase ratio variation method generates results with reasonable precision for all volatile compounds, much better than the liquid-focused (i.e., liquid phase ratio variation) method reported early.The solid phase ratio variation method was used to determine the solid–liquid partition coefficient of toluene in a water–polystyrene system, using polymer particles with average size ranging from 0.4 to 2.1μm. The results show that the partition coefficient of toluene in the given system is proportional to the specific surface area of the polymer particles, as expected.In summary, the method is a simple and practical tool for determining the solid–liquid partition coefficient of volatile analytes.

A cement degradation model for evaluating the evolution of retardation factors in radionuclide leaching models

Near-surface cement-based disposal systems for hazardous materials such as radioactive waste will undergo chemical alterations due to interaction with the surrounding environment. One of the most relevant long-term geochemical alteration processes is decalcification or leaching of the cement phases by percolating water. Consequently, the cementitious components of the disposal system will evolve through different chemical degradation states, also altering physical material parameters such as porosity and bulk density and chemical parameter relevant to solute migration such as the solid–liquid partition coefficient or distribution ratio. This paper presents a novel approach in which geochemical modelling serves as a fundamental basis for assessing the evolution of geochemical conditions within a cement-based near-surface disposal facility. On one hand, geochemical modelling is used to quantify uncertainties related to the infiltrating water composition and C–S–H degradation model, both of which allow for various conceptualisations of the evolution of retardation factor. On the other hand, the concept of mixed tank reactor is used to represent cement degradation within the entire disposal system. This paves the way to establish a link between the evolution of the geochemical conditions and the evolution of the retardation factor via the knowledge of amount of percolated water through the system. The usefulness of the approach is demonstrated via a number of case studies concerning leaching of radionuclides (14C and 94Nb) from a cementitious near-surface disposal facility. The studies reveal that there is a large effect of the conceptualisation on calculated fluxes from the disposal facility, depending on the type of radionuclide. A crucial factor is the amount of radionuclide mass present in the disposal system when large changes in the retardation factor occur, for instance, when different retardation factors exist in different chemical degradation states.

Influence of trace elements on the textural properties of synthetic chrysotile: Complementary insights from macroscopic and nanoscopic measurements

The present study shows that the presence of Li, Sb, As and B as trace elements significantly influences textural properties such as particle size distribution, morphology and specific surface area of chrysotile synthesized under hydrothermal conditions (P=8.2MPa, T=300°C and high-alkaline pH (13.5)). Conversely, traces of Cs did not have any textural effect under these conditions. Furthermore, chrysotile nanotubes size and morphology depend strongly on the element considered. Indeed, large chrysotile with cylinder in cylinder morphology (outer diameter up to 50nm) precipitated in the presence of Li, Sb and As. This implies lower specific surface area (124–160m2g−1) compared to undoped chrysotile (184m2g−1 with about 14nm in width). The presence of boron favors the precipitation of thin fibrous nanotubes similar to undoped chrysotile in width, but significantly longer, with tubes length that can reach three microns in length. In this case, the specific surface area increase slightly from 184 to 196m2/g. The solid–liquid partition coefficient for each investigated trace element was determined using Langmuir equation. This well-tubular geo-material can be used as a model to better understand the effects of trace elements on the precipitation of minerals that are relevant in Earth systems (e.g., serpentinization processes) and societal applications (e.g., asbestos toxicity and CO2 sequestration).

Biodegradation kinetic constants and sorption coefficients of micropollutants in membrane bioreactors

In order to elucidate the capability of biomass developed in membrane bioreactors (MBR) to degrade and sorb emerging micropollutants, biodegradation (kbiol) and sorption (ksor) kinetic constants as well as solid-liquid partition coefficients (Kd) of 13 selected pharmaceutical and personal care products (PPCPs) were determined with MBR heterotrophic biomass adding a pulse (100ppb of each compound) and following the liquid and solid phase concentrations over time. The results obtained were compared to literature data referring to conventional activated sludge (CAS) systems. Two experiments were performed: one in the MBR itself and the second one in a batch reactor with the same type and concentration of biomass as in the MBR. Overall, both biodegradation and sorption coefficients were in the same range as previously reported by other studies in CAS systems, indicating that MBR biomass does not show better capabilities for the biological degradation and/or sorption of PPCPs compared to the biomass developed in CAS reactors. Therefore, the higher PPCPs removal efficiencies found in MBRs are explained by the high biomass concentrations obtained at the long sludge retention times at which this type of reactors are usually operated.

Sorption of 17β-Estradiol to Pig Slurry Separates and Soil in the Soil-Slurry Environment

Contamination of freshwater by estrogens from manure applied to agricultural land is of grave concern because of the potentially harmful effects on aquatic life and human health. Recent developments in liquid manure (slurry) management include partial removal of particulate slurry dry matter (PSDM) by separation technologies, which may also remove parts of the estrogens and enhance infiltration of the slurry on field application and hence the interaction between estrogens and the soil matrix. This study investigated how 17β-estradiol (E2), a natural estrogen commonly found in pig manure, sorbs to agricultural soils, to different size fractions of pig slurry separates, and to soils amended with each size fraction to simulate conditions in the soil-slurry environment. A crude fiber fraction (SS1) was prepared by sieving (<500 μm) the solids removed by an on-farm separation process. Three other size fractions (SS2 > SS3 > SS4) were prepared from the liquid fraction of the separated slurry by sedimentation and centrifugation. Sorption experiments were conducted in 0.01 mol L(-1) CaCl(2) and in natural pig urine matrix. Sorption in 0.01 mol L(-1) CaCl(2) was higher than that in pig urine for all solids used. Sorption of E2 to soil increased with its organic carbon content for both liquid phases. The solid-liquid partition coefficients of slurry separates were 10 to 30 times higher than those of soils, but the organoic carbon normalized partition coefficient values, reflecting sorption per unit organic carbon, were lower for slurry separates. Mixing slurry separates with soil increased the sorption of E2 to the solid phase significantly in the order: SS1 < SS3 < SS2 for both liquid phases. In contrast, SS4 reduced the sorption of E2 to the solid phase by increasing the sorption to suspended or dissolved organic matter. The study suggested that potentially 50 to 75% of E2 in slurry can be removed from the liquid fraction of slurry by physical separation.

Rare earth element geochemistry of groundwaters from coal bearing aquifer in Renlou coal mine, northern Anhui Province, China

Rare earth element (REE) concentrations of two different types of groundwaters (high SO 4 2− water-SW and high alkaline water-CW) from coal bearing aquifer (−400∼−280 m) in Renlou coal mine, northern Anhui Province, China were measured. The results indicated that they had different REE characteristics: the total concentrations of REEs (∑REE) of SW were lower than those of CW in general although they all had heavy REEs enriched relative to light REEs. The dissolved REE inorganic species of SW included Ln 3+, LnCO 3 +, LnSO 4 +, Ln(CO 3) 2 − and Ln(SO 4) 2 −, whereas the CW are Ln(CO 3) 2 − and LnCO 3 + dominant, and the proportions of Ln(CO 3) 2 − increased while other species decreased with pH increasing. Combined with correlation analysis, the enrichment and fractionation of SW (low alkaline water) were considered to be affected by alkaline concentrations via affecting the types and proportions of REE inorganic species. However, the effect of alkaline concentrations to the enrichment and fractionation of REEs of CW (high alkaline water) was less important than total dissolved solids and pH, which reflected the contribution from different rocks they flowed over, different degrees of water-rock interactions and/or REE solid-liquid partition coefficients.

Evaluation of the Affinity of Some Toxic Elements to Schwertmannite in Natural Streams Contaminated with Acid Mine Drainage

In order to evaluate fixation potential of schwertmannite for fluvial transport of various toxic elements, we examined bottom precipitates and stream waters collected from the rivers contaminated with acid mine drainage (AMD), which arose from the abandoned Nishinomaki mine (Shimonita, Gunma, Japan). Mineralogical and morphological observations revealed that schwertmannite was the main mineral of the precipitates. The affinity of various toxic ions to schwertmannite was evaluated on the basis of (1) apparent solid–liquid partition coefficients (Kd’s) between precipitates and stream waters, (2) coprecipitation behaviors during schwertmannite formation in a laboratory test, and (3) consideration on coprecipitation processes using partial charge model (PCM). As a result, oxyanions of V, As, Mo and Sb, Kd’s of which were relatively large (>104 (ml g−1)), were considered to be immobilized by schwertmannite precipitates. A laboratory test also demonstrated that these ions except Mo coprecipitated with schwertmannite. In addition, partial charges and average electronegativities predicted on the basis of PCM suggested that the oxyanions of V, As, Mo, and Sb could create stable inner sphere complexes with schwertmannite embryos, which results in their high affinity to schwertmannite. On the other hand, cationic ions of Mn, Cu, Zn, Sr, Cs, and U, Kd’s of which were relatively small (<104 (ml g−1)), were thought to have a tendency to flow downstream without uptake by schwertmannite precipitates. All these results suggested that schwertmannite has high fixation potential for fluvial transport of various toxic oxyanions in AMD-contaminated rivers.

Chemical imaging with NanoSIMS: A window into deep-Earth geochemistry

We use a combination of nanometer-resolution secondary ion mass spectrometry (NanoSIMS) and analytical transmission electron microscopy (ATEM) for chemical imaging of material transformed in a laser-heated diamond anvil cell (LH-DAC), in the pressure and temperature range of Earth's lower mantle. MORB (mid-ocean ridge basalt), one of the components of subducted oceanic lithosphere, was transformed to an assemblage of Mg-perovskite, Ca-perovskite, stishovite and a calcium ferrite-structure phase at 55 GPa and 2100 °C in an LH-DAC. Elemental imaging spanning the entire range of concentrations, from major elements such as silicon (49.5 wt.% SiO 2) to trace elements such as strontium (118 ppm), scandium, and yttrium (both at 40 ppm) was obtained with a Cameca NanoSIMS 50. We observe a preferential partitioning of scandium, yttrium and strontium in the calcium silicate perovskite phase, and we compare this to recently measured solid–liquid partition coefficients and fractionation at lower pressures. This type of measurement demonstrates that even the most complex mineral assemblages can be probed using this combination of techniques and opens new pathways towards the characterization and quantification of geochemical interactions and processes occurring in the deep Earth.

A castability model based on elemental solid-liquid partitioning in advanced nickel-base single-crystal superalloys

A castability model that accounts for the characteristic segregation behavior of constituent elements in Ni-base superalloys has been developed and experimentally verified in production scale casting trials. The model ranks alloy compositions with respect to their susceptibility to freckle formation during directional solidification. Thirty-nine distinct Ni-base single-crystal superalloys encompassing a broad range of compositions were investigated to assess the influence of the constituent elements on their solidification characteristics. Linear regression was applied to the fitted solid-liquid partition coefficients of the major constituent elements to develop formulas capable of describing elemental interactions. The high-density refractory elements Ta, W, and Re were found to segregate most severely during solidification. Increasing the amount of Cr and Mo in high-refractory single-crystal alloys reduced the extent of W and Re microsegregation during solidification. This effect was found to minimize the occurrence of freckle defects due to the corresponding decrease in the density inversion term, which is effectively the driving force for thermosolutal convective instabilities known to cause macroscopic grain defects during single-crystal solidification. Model predictions were validated using production scale casting trials where additions of 1.5 wt pct (1.9 at. pct) Cr and 3.0 wt pct (2.0 at. pct) Mo to a high-refractory superalloy more than halved the number of solidification-related grain defects formed. These findings suggest that elemental interactions between Cr, Mo, W, and Re need to be considered when optimizing alloys for high-temperature creep properties.