Challenges in geochemical modelling of metal(loid) solubility and binding mechanisms along a soil profile at a multi-contaminated site

Recognising the need for robust models in predicting groundwater contamination risks from metal(loid)s in contaminated topsoil, this study focuses on the geochemical behaviour of As, Cd, Cu, Pb, Sb and Zn in one of Sweden's most heavily contaminated areas. Samples were collected from the waste zone and underlying subsoil down to 5 m and batch experiments were carried out to assess pH-dependent solubility. The results indicate that Cd, Cu, Pb and Zn are efficiently immobilized in the waste zone, while As(V) and Sb(V) are more easily leached. With the exception of Pb and Cu at high pH, the mobilized metals appear to be predominantly in a truly dissolved state, as confirmed by ultrafiltration at 10 kDa. Speciation modelling using Visual MINTEQ did not suggest a significant role of precipitates such as Zn or Pb arsenates and phosphates, although their involvement could not be ruled out. To better understand sorption/ desorption patterns, a multi-surface geochemical model was established, drawing on the Stockholm Humic and CD-MUSIC models for organic matter and Fe/Al (hydr)oxide sorption. However, when default parameters were used, the model consistently overestimated the solubility of Cd, Cu, Pb and Zn in both the waste zone and the uncontaminated subsoil. In contrast, As(V) solubility was generally underestimated, also when the reactive surface area of the Fe- and Al (hydr)oxides was decreased in the model. The model's performance was better for Sb(V), though not without imperfections. When the parameters for organic matter were adjusted such that 100% of the solid-phase organic matter was active with respect to ion binding, but only 25% of the dissolved organic matter, the model description improved considerably for Pb and Cu in the upper soil layers. The model revealed distinct differences in the adsorption behaviour of the metal cations, with Pb being sorbed mostly to Fe/Al (hydroxides), whereas a considerable part of Cu was sorbed to organic matter, particularly in the waste zone. Possibly, the dissolution of easily weatherable metal-containing mineral phases may have contributed to the poor model performance for Cd, Zn and for Cu in the deeper soil layers, although other factors, such as a contribution of hydrous SiO2 or Mn oxides to metal binding, could not be ruled out. Metal sorption to carbonate phases may also have been a contributing factor in the waste zone. Lastly, the reactivity of Fe- and Al (hydr) oxides may have been overestimated by oxalate extraction when default parameters for high-surface-area ferrihydrite were applied. These findings provide valuable insights for environmental management and underscore the need for a more detailed characterization of metal(loid) sorption in contaminated soils, as well as the development of improved modelling strategies to enhance solubility predictions

Mineralogical characterization and speciation of sulfur, zinc and lead in pyrite cinder from Bergvik, Sweden

Roasting of sulfide ores to produce sulfuric acid began on an industrial scale in the middle 1800 ' s and is still used extensively worldwide. The residual, pyrite cinders, have commonly been disposed in the environment where they pose a potential and serious threat to aquatic life. In this project, two profiles in a pyrite cinder deposit in Bergvik, Sweden, have been sampled and a comprehensive mineralogical characterization have been carried out. The objectives were to investigate the composition and morphology of pyrite cinder grains and the speciation of sulfur, Pb and Zn in the solid phase. Scanning electron microscopy showed pyrite cinder grains with a core of the ore minerals pyrite and sphalerite enclosed in layers of iron oxides/hydroxides (mainly hematite). XANES analysis, supported by X-ray diffraction analysis, SEM-EDS and bulk element analysis, showed that content of the residual sulfur in the cinder is mainly sulfides, 55-80%, predominately sphalerite. The remaining mass of sulfur is assumed to be adsorbed or precipitated as secondary sulfate minerals, predominantly associated with the grain surfaces. Calculated saturation indexes indicated barite, anglesite and perhaps aluminite. EXAFS spectroscopy indicated that about half of the Zn was bound to O and half was bound to S. LCF analysis of EXAFS spectra indicated that the main Zn species were sphalerite (40-50%) and franklinite (10-20%). The remaining Zn was associated with iron oxides/hydroxides and Zn minerals like hydrozincite or possibly zinc oxides. SEM-EDS analysis showed Pb precipitate located on both the surface of the grains and in the interior as inclusions. The analytical interpretation indicated anglesite

Large-scale arsenic mobilization from legacy sources in anoxic aquifers: Multiple methods and multi-decadal perspectives

While geogenic arsenic (As) contamination of aquifers have been intensively investigated across the world, the mobilization and transport of As from anthropogenic sources have received less scientific attention, despite emerging evidence of poor performance of widely used risk assessment models. In this study we hypothesize that such poor model performance is largely due to insufficient attention to heterogeneous subsurface properties, including the hydraulic conductivity K and the solid-liquid partition (Kd), as well as neglect of laboratory-to-field scaling effects. Our multi-method investigation includes i) inverse transport modelling, ii) in-situ measurements of As concentrations in paired samples of soil and groundwater, and iii) batch equilibrium experiments combined with (iv) geochemical modelling. As case study we use a unique 20-year series of spatially distributed monitoring data, capturing an expanding As plume in a Chromated Copper Arsenate (CCA)-contaminated anoxic aquifer in southern Sweden. The in-situ results showed a high variability in local Kd values of As (1 to 107 L kg-1), implying that over-reliance of data from only one or few locations can lead to interpretations that are inconsistent with field-scale As transport. However, the geometric mean of the local Kd values (14.4 L kg-1) showed high consistency with the independently estimated field-scale "effective Kd" derived from inverse transport modelling (13.6 L kg-1). This provides empirical evidence for the relevance of using geometric averaging when estimating large-scale "effective Kd" values from local measurements within highly heterogenous, isotropic aquifers. Overall, the considered As plume is prolonged by about 0.7 m year-1, now starting to extend beyond the borders of the industrial source area, a problem likely shared with many of the world's As-polluted sites. In this context, geochemical modelling assessments, as presented here, provided a unique understanding of the processes governing As retention, including local variability in, e.g., Fe/Al-(hydr) oxides contents, redox potential and pH

Per- and polyfluoroalkyl substance (PFAS) retention by colloidal activated carbon (CAC) using dynamic column experiments

Developing effective remediation methods for per- and polyfluoroalkyl substance (PFAS)-contaminated soils is a substantial step towards counteracting their widespread occurrence and protecting our ecosystems and drinking water sources. Stabilisation of PFAS in the subsurface using colloidal activated carbon (CAC) is an innovative, yet promising technique, requiring better understanding. In this study, dynamic soil column tests were used to assess the retardation of 10 classical perfluoroalkyl acids (PFAAs) (C-5-C-11 perfluoroalkyl carboxylic acids (PFCAs) and C-4, C-6, C-8 perfluoroalkane sulfonates (PFSAs)) as well as two alternative PFAS (6:2 and 8:2 fluorotelomer sulfonates) using CAC at 0.03% w/w, to investigate the fate and transport of PFAS under CAC treatment applications. Results showed high retardation rates for long-chain PFAS and eight times higher retardation for the CAC-treated soil compared to the non-treated reference soil for the Sigma PFAS. Replacement of shorter chain perfluorocarboxylic acids (PFCAs), such as perfluoropentanoic acid (PFPeA), by longer chained PFAS was observed, indicating competition effects. Partitioning coefficients (K-d values) were calculated for the CAC fraction at similar to 10(3)-10(5) L kg(-1) for individual PFAS, while there was a significant positive correlation (p < 0.05) between perfluorocarbon chain length and K-d. Mass balance calculations showed 37% retention of Sigma PFAS in treated soil columns after completion of the experiments and 99.7% higher retention rates than the reference soil. Redistribution and elution of CAC were noticed and quantified through organic carbon analysis, which showed a 23% loss of carbon during the experiments. These findings are a step towards better understanding the extent of CAC's potential for remediation of PFAS-contaminated soil and groundwater and the limitations of its applications

Fly ash-based waste for ex-situ landfill stabilization of per- and polyfluoroalkyl substance (PFAS)-contaminated soil

In response to world-wide soil and groundwater contamination per- and polyfluoroalkyl substances (PFAS), stakeholders require immediate mitigation. Soil deposition in landfill is a common mitigation scheme, but PFAS losses occur via landfill leachate. These leaching losses can be reduced by strategically utilizing other deposited waste materials for ex-situ contaminant stabilization. This screening study tested activated carbon (AC) and eight types of wastes (compost, rubber granulate, bentonite clay, industrial sludge, incineration slag, incineration bottom ash (n=4), incineration fly ash-based air pollution control residue (FA-APC) (n=16)) in amending (adding 4%, 5%, 10% or 25% sorbent) field-contaminated (n=19) and PFAS-fortified (n=11) soils. A subset of FA-based residue types, all originating from grate-fire incineration (G-F-I) plants, achieved extraordinarily high removal of PFAS. The removal was up to 98% (25% addition) of the sum of six dominant PFAS for field-contaminated soil and >99% of the sum of 11 PFAS for fortified soil (10/25% addition) (>99.9% for PFOS). Calculated partitioning coefficient revealed significant trends between sorption strength and perfluorocarbon chain length (0.21-0.47 log units per CF2-moiety), indicating high importance of hydrophobic sorption (R2>0.98). However, with incremental G-F-I FA-APC addition this relationship disappeared, indicating an alternative sorption mechanism. The exceptional PFAS sorption by G-F-I FA-APC was not explained by G-F-I surface area, surface charge, soil mineral- and metal composition, or solution DOC, metal, or ion composition (H+, Ca2+, Mg2+, Al3+ and Ba2+). Although the mechanism remains unknown, this study showed that landfill sites can utilize G-F-I FA-APC for ex-situ stabilization at negative cost, thus preventing PFAS-containing leachate

Laboratory-scale and pilot-scale stabilization and solidification (S/S) remediation of soil contaminated with per- and polyfluoroalkyl substances (PFASs)

Remediation of soil contaminated with per-and polyfluoroalkyl substances (PFAS) is critical due to the high per-sistence and mobility of these compounds. In this study, stabilization and solidification (S/S) treatment was evaluated at pilot-scale using 6 tons of soil contaminated with PFAS-containing aqueous film-forming foam. At pilot scale, long-term PFAS removal over 6 years of precipitation (simulated using irrigation) in leachate from non-treated contaminated reference soil and S/S-treated soil with 15 % binder and 0.2 % GAC was compared. PFAS removal rate from leachate, corresponding to reduction in leaching potential after 6 years, was 97 % for four dominant PFASs (perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorohexanesulfonic acid (PFHxS) and per-fluorooctanesulfonic acid (PFOS)), but low (3%) for short-chain perfluoropentanoic acid (PFPeA). During the pilot scale experiment, PFAS sorption strength (i.e., soil-water partitioning coefficient (Kd)) increased 2to 40-fold for both reference and S/S-treated soil, to much higher levels than in laboratory-scale tests. However, PFAS behavior in pilot scale and laboratory-scale tests was generally well-correlated (p &lt; 0.001), which will help in future S/S recipe optimization. In addition, seven PFASs were tentatively identified using an automated suspect screening approach. Among these, perfluorohexanesulfonamide and 3:2 fluorotelomer alcohol were tentatively identified and the latter had low removal rates from leachate (&lt; 12 %) in S/S treatment

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

Immobilizing arsenic in contaminated anoxic aquifer sediment using sulfidated and uncoated zero-valent iron (ZVI)

Arsenic (As) is carcinogenic and of major concern in groundwater. We collected sediment material from a contaminated anoxic aquifer in Sweden and investigated the immobilization of As by four commercial zero-valent iron (ZVI) particles. Solid-phase As and Fe speciation was assessed using X-ray absorption spectroscopy (XAS) and solution-phase As speciation using chromatographic separation. Without ZVI addition, arsenite dominated in solution and As(V) species in the solid phase. Adding ZVI caused a sharp increase in solution pH (9.3-9.8), favoring As oxidation despite a lowered redox potential. ZVI greatly improved As retention by complex binding of arsenate to the Fe(III) (hydr)oxides formed by ZVI corrosion. Uncoated ZVI, both in nano-and microscale, performed better than their sulfidated counterparts, partly due to occlusion of As by the Fe(III) (hydr) oxides formed. The effect of particle size (micro vs. nano ZVI) on As immobilization was small, likely because immobilization was related to the corrosion products formed, rather than the initial size of the particles. Our results provide a strong geochemical background for the application of ZVI particles to remove As in contaminated aquifers under anoxic conditions and illustrate that immobilization mechanisms can differ between ZVI in As spiked solutions and sediment suspensions.Environmental implication: Arsenic ranks first on the list by the US ATSDR of substances posing a threat to human health and the WHO considers groundwater the riskiest source for human intake of As. However, dealing with As contamination remains a scientific challenge. We studied the immobilization of groundwater As by commercially available ZVI particles at field-realistic conditions. Arsenic immobilization was highly efficient in most cases, and the results suggest this is a promising in situ strategy with long-term performance. Our results provide a strong geochemical background for using ZVI to remove As in contaminated anoxic aquifers

Biochar and peat amendments affect nitrogen retention, microbial capacity and nitrogen cycling microbial communities in a metal and polycyclic aromatic hydrocarbon contaminated urban soil

Soil contaminants may restrict soil functions. A promising soil remediation method is amendment with biochar, which has the potential to both adsorb contaminants and improve soil health. However, effects of biochar amendment on soil -plant nitrogen (N) dynamics and N cycling microbial guilds in contaminated soils are still poorly understood. Here, a metal- and polycyclic aromatic hydrocarbon (PAH) contaminated soil was amended with either biochar (0, 3, 6 % w/w) and/or peat (0, 1.5, 3 % w/w) in a full -factorial design and sown with perennial ryegrass in an outdoor field trial. After three months, N and the stable isotopic ratio 8 15 N was measured in soil, roots and leaves, along with microbial responses. Aboveground grass biomass decreased by 30 % and leaf N content by 20 % with biochar, while peat alone had no effect. Peat in particular, but also biochar, stimulated the abundance of microorganisms (measured as 16S rRNA gene copy number) and basal respiration. Microbial substrate utilization (MicroResp TM) was altered differentially, as peat increased respiration of all carbon sources, while for biochar, respiration of carboxylic acids increased, sugars decreased, and was unaffected for amino acids. Biochar increased the abundance of ammonia oxidizing archaea, while peat stimulated ammonia oxidizing bacteria, Nitrobacter -type nitrite oxidizers and comB-type complete ammonia oxidizers. Biochar and peat also increased nitrous oxide reducing communities ( nosZI and nosZII ), while peat alone or combined with biochar also increased abundance of nirK -type denitrifiers. However, biochar and peat lowered leaf delta 15 N by 2 -4 %o, indicating that processes causing gaseous N losses, like denitrification and ammonia volatilization, were reduced compared to the untreated contaminated soil, probably an effect of biotic N immobilization. Overall, this study shows that in addition to contaminant stabilization, amendment with biochar and peat can increase N retention while improving microbial capacity to perform important soil functions

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