Competitive Arsenate and Phosphate Adsorption on Ferrihydrite as Described by the CD-MUSIC Model

The solubility and bioavailability of arsenic in the environment are to a large extent governed by adsorption reactionswith iron (hydr)oxides, the extent of which is affected by competitive interactions with other ions, for example, phosphate. Here,batch experiments were performed with ferrihydrite suspensions to determine the adsorption of arsenate [As(V)] and phosphate(PO4)atdifferent As(V)-PO4ratios. A surface complexation model based on the Charge Distribution MUltisite Ion Complexation(CD-MUSIC) concept (the"Ferrihydrite CD-MUSIC model") was developed to describe these interactions in a way consistent withresults from spectroscopic studies. For this purpose, several previously published data sets on As(V) and PO4adsorption inferrihydrite suspensions were reviewed, including a number of systems containing other major ions (CO32-and Ca2+), and newsurface complexation constants were derived. During model development, it was found that the inclusion of ternary complexes wasnot needed to describe the observed Ca2+-PO4interactions. For both As(V) and PO4, the resulting model predicts the presence ofcorner-sharing bidentate complexes as well as monodentate complexes, with the latter being important particularly at low pH. Theexperimental results showed that As(V) and PO4displayed similar adsorption patterns in the single-ion systems studied, which wereconducted using a constant anion-to-Fe ratio of 0.2. Even so, As(V) was preferentially adsorbed over PO4in competitive systems,particularly at low As(V)-to-PO4ratios when theKdvalues for As(V) were up to 2.1 times as high as those for PO4. The model,which described these patterns very well, suggests that adsorbed As(V) consists of a larger fraction of bidentate complexes than inthe case of PO4. This causes aflatter adsorption isotherm for As(V), which leads to a stronger As(V) adsorption as the As(V)-to-Feratio decreases, compared to that for PO

Bismuth(III) Forms Exceptionally Strong Complexes with Natural Organic Matter

The use of bismuth in the society has steadily increased during the last decades, both as a substitute for lead in hunting ammunition and various metallurgical applications, as well as in a range of consumer products. At the same time, the environmental behavior of bismuth is largely unknown. Here, the binding of bismuth(III) to organic soil material was investigated using extended X-ray absorption spectroscopy (EXAFS) and batch experiments. Moreover, the capacity of suwannee river fulvic acid (SRFA) to enhance the solubility of metallic bismuth was studied in a long-term (2 years) equilibration experiment. Bismuth(III) formed exceptionally strong complexes with the organic soil material, where >99% of the added bismuth(III) was bound by the solid phase, even at pH 1.2. EXAFS data suggest that bismuth(III) was bound to soil organic matter as a dimeric Bi3+ complex where one carboxylate bridges two Bi3+ ions, resulting in a unique structural stability. The strong binding to natural organic matter was verified for SRFA, dissolving 16.5 mmol Bi per gram carbon, which largely exceeds the carboxylic acid group density of this compound. Our study shows that bismuth(III) will most likely be associated with natural organic matter in soils, sediments, and waters

Combining a Standardized Batch Test with the Biotic Ligand Model to Predict Copper and Zinc Ecotoxicity in Soils

Extraction of soil samples with dilute CaCl2 solution in a routinely performed batch test has potential to be used in site-specific assessment of ecotoxicological risks at metal-contaminated sites. Soil extracts could potentially give a measure of the concentration of bioavailable metals in the soil solution, thereby including effects of soil properties and contaminant "aging." We explored the possibility of using a 0.001 M CaCl2 batch test combined with biotic ligand models (BLMs) for assessment of ecotoxicity in soils. Concentrations of Cu2+ and Zn2+ in soil extracts were linked to responses in ecotoxicity tests (microbial processes, plants, and invertebrates) previously performed on metal-spiked soils. The batch test data for soils were obtained by spiking archived soil materials using the same protocol as in the original studies. Effective concentration values based on free metal concentrations in soil extracts were related to pH by linear regressions. Finally, field-contaminated soils were used to validate model performance. Our results indicate a strong pH-dependent toxicity of the free metal ions in the soil extracts, with R-2 values ranging from 0.54 to 0.93 (median 0.84), among tests and metals. Using pH-adjusted Cu2+ and Zn2+ concentrations in soil extracts, the toxic responses in spiked soils and field-contaminated soils were similar, indicating a potential for the calibrated models to assess toxic effects in field-contaminated soils, accounting for differences in soil properties and effects of contaminant "aging." Consequently, evaluation of a standardized 0.001 M CaCl2 batch test with a simplified BLM can provide the basis for an easy-to-use tool for site-specific risk assessment of metal toxicity to soil organisms. Environ Toxicol Chem 2022;00:1-14. (c) 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC

Significance of phosphorus inclusions and discrete micron-sized grains of apatite in postglacial forest soils

Recent advances in soil phosphorus (P) studies have revealed unique P hot spots and discrete micron-sized grains at soil microsites, but the significance of these so-called 'hot spots' and grains in P cycling and long-term supply is yet to be determined. We examined soil particles and pore space distribution at a micro-scale in two postglacial forest soils by laser ablation ICP-MS imaging. This allowed us to semi-quantitatively reveal both axial and lateral abundance, distribution, and co-localization of P with elements known to influence its chemical speciation (e.g., Si, Al, Mn, Ca, and Fe). The results show topsoil P to be co-localised predominantly with Si, Al, and Fe. However, in the subsoils, P was co-localised mainly with Ca, Si, Al, and Mg in spots within Si and Al-bearing minerals and with only Ca in discrete micron-sized grains. While the spots of P-Ca inclusions were similar to 1000 mu m apart and present at 40-100 cm depth in Tarnsjo, the discrete grains of P-Ca were similar to 700-1200 mu m apart and present at 90-100 cm depth in Tonnersjoheden. The P concentrations in these 'hot spots' and grains were 7 to 600 times greater than the average soil P concentrations, with the highest values (3434-8716 mmol P kg(-1)) occurring in the C horizons of the two soils. When combined with previous P speciation results obtained by synchrotron P K-edge XANES in the same soils, our work confirms geogenic apatite to have been dissolved in the topsoil and its P transformed to P adsorbed by Al-Si and Fe phases, and to organic P. Most importantly, our work shows subsoil spots of P-Ca inclusions and micron-sized grains to be a long-term source of P and Ca. Highlights The significance of high-P spots and discrete grains to long-term P supply is largely unknown. For the first time, P concentration and speciation was resolved by LA-ICP-MS multi-elemental analysis. The P spots exist as dispersed apatite inclusions and micron-sized grains in the subsoil. P in these spots and grains were up to 600 times greater than the bulk soil P concentrations

Влияние рыбьего жира на активность АТФ-чувствительных калиевых каналов коронарных сосудов крыс, перенесших пренатальный стресс

РЫБИЙ ЖИРКАЛИЕВЫЕ КАНАЛЫКОРОНАРНЫЕ СОСУДЫКРЫСЫКАЛИЕВЫЕ КАНАЛЫАТФ-ЧУВСТВИТЕЛЬНЫЕ КАЛИЕВЫЕ КАНАЛЫБЕРЕМЕННОСТЬ ЖИВОТНЫХСТРЕС

Evidence of the mineral ZnHAsO4 center dot H2O, koritnigite, controlling As(V) and Zn(II) solubility in a multi-contaminated soil

Assessing element speciation and solubility control mechanisms in multi-contaminated soils poses great challenges. In this study, we examined the speciation and mechanisms controlling the solubility of As and Zn in a soil historically contaminated with As, Cu, Cr, and Zn salts used for wood preservation. The leaching behavior of dissolved species, particles, and colloids was studied in an irrigation experiment with intact soil columns. Batch experiments were used to study the solubility of dissolved species as a function of pH (2-8). The speciation of As and Zn in bulk soil and leached particles was studied with microscale X-ray fluorescence (mu-XRF) and extended Xray absorption fine structure (EXAFS) spectroscopy. Chemical speciation and solubility were evaluated by geochemical modelling. mu-XRF of bulk soil and particles showed that As and Zn were correlated in space. Bulkand mu-EXAFS of As and Zn, in combination with calculated ion activity products of possible As-Zn minerals, suggested a koritnigite (ZnHAsO4 center dot H2O) phase controlling the dissolved fraction of As(V) and Zn with an apparent log K-sp of 21.9 +/- 0.46. This phase lowered the solubility of As by almost two orders of magnitude in soil at pH > 5, and could therefore be of great importance at other multi-contaminated sites

The Adsorption of Per- and Polyfluoroalkyl Substances (PFASs) onto Ferrihydrite Is Governed by Surface Charge

An improved quantitative and qualitative understanding of the interaction of per- and polyfluoroalkyl substances (PFASs) and short-range ordered Fe (hydr)oxides is crucial for environmental risk assessment in environments low in natural organic matter. Here, we present data on the pH-dependent sorption behavior of 12 PFASs onto ferrihydrite. The nature of the binding mechanisms was investigated by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and by phosphate competition experiments. Sulfur K-edge XANES spectroscopy showed that the sulfur atom of the head group of the sulfonated PFASs retained an oxidation state of +V after adsorption. Furthermore, the XANES spectra did not indicate any involvement of inner-sphere surface complexes in the sorption process. Adsorption was inversely related to pH (p < 0.05) for all PFASs (i.e., C-3-C-5 and C-7-C-9 perfluorocarboxylates, C-4, C-6, and C-8 perfluorosulfonates, perfluorooctane sulfonamide, and 6:2 and 8:2 fluorotelomer sulfonates). This was attributed to the pH-dependent charge of the ferrihydrite surface, as reflected in the decrease of surface zeta-potential with increasing pH. The importance of surface charge for PFAS adsorption was further corroborated by the observation that the adsorption of PFASs decreased upon phosphate adsorption in a way that was consistent with the decrease in ferrihydrite zeta-potential. The results show that ferrihydrite can be an important sorbent for PFASs with six or more perfluorinated carbons in acid environments (pH <= 5), particularly when phosphate and other competitors are present in relatively low concentrations