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 δ15N 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™) 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 δ15N by 2-4 ‰, 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.

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.

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 R2 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;41:1540-1554. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Speciation of Cu and Zn in bottom ash from solid waste incineration studied by XAS, XRD, and geochemical modelling.

Millions of tons of bottom ash (BA) is generated from incineration of industrial and municipal solid waste each year within EU. The magnitude of leaching of metals like Cu and Zn is critical for hazard and risk assessment of these ashes. Although speciation of metals is a key factor to understand and predict metal leaching, speciation of Cu and Zn in BA is not well known. In this study six metal separated and carbonized BA were investigated by a combination of X-ray absorption spectroscopy, X-ray diffraction, leaching/extraction tests, and geochemical modelling. Five of the BA were from grate boilers and one from a fluidized bed incinerator. The aims were to identify similarities in Cu and Zn speciation and to identify main species. The combination of several techniques was necessary to draw conclusions about speciation and displayed coherent results. A similar speciation of Cu and Zn was indicated in the five studied grate boiler ashes although the proportions between species may vary. Copper(II) oxide and Cu metal were the main Cu species in all BA. Zinc(II) oxide and willemite (Zn2SiO4) were identified in grate boiler ashes. The fluidized bed ash contained Zn-Si-minerals and possibly franklinite or gahnite, while the Zn(II) oxide content was low, if any. The results have implications for classification and risk assessment of MIBA.

Phosphate competition with arsenate on poorly crystalline iron and aluminum (hydr)oxide mixtures.

Phosphate competes with arsenate for sorption sites on poorly crystalline iron and aluminum (hydr)oxides. The competition has implications e.g. for the management of arsenic-contaminated soil and water. Phosphate competition with arsenate on mixed phases containing both iron and aluminum (hydr)oxides has rarely been investigated. Here, the phosphate competition with arsenate on mixtures of poorly crystalline aluminum hydroxide (Alhox) and ferrihydrite (Fh), was investigated in batch experiments at pH 6.5. X-ray absorption spectroscopy (XAS) was performed on the phosphorus and arsenic K edges, which offered a unique insight in the partitioning of arsenate and phosphate on mixed Alhox-Fh sorbents. Under the studied conditions the sorption capacity of the mixed sorbents (per mol Al or Fe) increased at higher Alhox to Fh ratios. The XAS measurements provided direct evidence that phosphate competed more effectively with arsenate for sorption sites on Alhox than on Fh. For example, in a mixture with 50% of both sorbents and with similar additions of arsenate and phosphate, 71% of the oxyanions adsorbed on Fh and 46% on Alhox were arsenate. Consequently, phosphate may mobilize arsenate more easily from mixed iron-aluminum matrices that are rich in aluminum.

Assessing costs and benefits of improved soil quality management in remediation projects: A study of an urban site contaminated with PAH and metals.

Contaminants in the soil may threaten soil functions (SFs) and, in turn, hinder the delivery of ecosystem services (ES). A framework for ecological risk assessments (ERAs) within the APPLICERA - APPLICable site-specific Environmental Risk Assessment research project promotes assessments that consider other soil quality parameters than only contaminant concentrations. The developed framework is: (i) able to differentiate the effects of contamination on SFs from the effects of other soil qualities essential for soil biota; and (ii) provides a robust basis for improved soil quality management in remediation projects. This study evaluates the socio-economic consequences of remediation alternatives stemming from a Tier 1 ERA that focusses on total contaminant concentrations and soil quality standards and a detailed, site-specific Tier 3 Triad approach that is based on the APPLICERA framework. The present study demonstrates how Tier 1 and Tier 3 ERAs differ in terms of the socio-economic consequences of their remediation actions, as well as presents a novel method for the semi-quantitative assessment of on-site ES. Although the presented Tier 3 ERA is more expensive and time-consuming than the more traditional Tier 1 ERA approach, it has the potential to lower the costs of remediation actions, decrease greenhouse gas emissions, reduce other environmental impacts, and minimise socio-economic losses. Furthermore, the remediation actions stemming from the Tier 3 ERA were predicted to exert far less negative ES effects than the actions proposed based on the results of the Tier 1 ERA.

Metal sorption to Spodosol Bs horizons: Organic matter complexes predominate.

While metal sorption mechanisms have been studied extensively for soil surface horizons, little information exists for subsoils, for example Spodosol Bs horizons. Here the sorption of cadmium(II), copper(II) and lead(II) to seven Bs horizons from five sites was studied. Extended X-ray absorption fine structure (EXAFS) spectroscopy showed that cadmium(II) and lead(II) were bound as inner-sphere complexes to organic matter. Addition of o-phosphate (to 1 µmol l-1) did not result in any significant enhancement of metal sorption, nor did it influence EXAFS speciation. An assemblage model using the SHM and CD-MUSIC models overestimated metal sorption for six out of seven soil samples. To agree with experimental results, substantial decreases (up to 8-fold) had to be made for the fraction 'active organic matter', fHS, while the point-of-zero charge (PZC) of ferrihydrite had to be increased. The largest decreases of fHS were found for the soils with the lowest ratio of pyrophosphate-to oxalate-extractable Al (Alpyp/Alox), suggesting that in these soils, humic and fulvic acids were to a large extent inaccessible for metal sorption. The low reactivity of ferrihydrite towards lead(II) can be explained by potential spillover effects from co-existing allophane, but other factors such as ferrihydrite crystallisation could not be ruled out. In conclusion, organic matter was the predominant sorbent for cadmium(II), copper(II) and lead(II). However, for lead(II) the optimised model suggests additional, but minor, contributions from Fe (hydr)oxide surface complexes. These results will be important to correctly model metal sorption in spodic materials.

Phosphate effects on cadmium(II) sorption to ferrihydrite.

HYPOTHESIS: Phosphate influences the sorption of metals to iron (hydr)oxides. An enhanced formation of inner-sphere complexes on the (hydr)oxide surface can be attributed to electrostatic interactions and/or to changes in metal coordination on the iron (hydr)oxide surface. Phosphate was expected to increase cadmium(II) sorption on ferrihydrite. It should be possible to identify changes in cadmium(II) coordination upon phosphate addition by Extended X-ray absorption fine structure (EXAFS) spectroscopy and implement the identified complexes in a surface complexation model (SCM). EXPERIMENTS: The effect of phosphate addition on cadmium(II) sorption to ferrihydrite was studied by a series of batch experiments covering the pH range from 4 to 8. EXAFS spectroscopy was performed on ferrihydrite from the batch experiments at the cadmium K edge. The identified surface complexes were incorporated in the Charge distribution multisite complexation (CD-MUSIC) model, and new surface complexation constants were optimized. FINDINGS: Without phosphate addition cadmium(II) formed inner-sphere bidentate complexes on the ferrihydrite surface. With phosphate there was an increased cadmium(II) sorption that could not be explained by electrostatic interactions alone. The enhancement was best explained by the formation of a ternary complex including cadmium(II), phosphate and ferrihydrite surface groups.

Predicting sulphate adsorption/desorption in forest soils: evaluation of an extended Freundlich equation.

Sulphate adsorption and desorption can delay the response in soil acidity against changes in acid input. Here we evaluate the use of an extended Freundlich equation for predictions of pH-dependent SO4 adsorption and desorption in low-ionic strength soil systems. Five B horizons from Spodosols were subjected to batch equilibrations at low ionic strength at different pHs and dissolved SO4 concentrations. The proton coadsorption stoichiometry (η), i.e. the number of H(+) ions co-adsorbed for every adsorbed SO4(2)(-) ion, was close to 2 in four of five soils. This enabled the use of a Freundlich equation that involved only two adjustable parameters (the Freundlich coefficient KF and the non-ideality parameter m). With this model a satisfactory fit was obtained when only two data points were used for calibration. The root-mean square errors of log adsorbed SO4 ranged from 0.006 to 0.052. The model improves the possibility to consider SO4 adsorption/desorption processes correctly in dynamic soil chemistry models.