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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.

The pH-dependent soil-water partitioning of six perfluoroalkyl substances (PFASs) of environmental concern (PFOA, PFDA, PFUnDA, PFHxS, PFOS and FOSA), was investigated for 11 temperate mineral soils and related to soil properties such as organic carbon content (0.2-3%), concentrations of Fe and Al (hydr)oxides, and texture. PFAS sorption was positively related to the perfluorocarbon chain length of the molecule, and inversely related to solution pH for all substances. The negative slope between log Kd and pH became steeper with increasing perfluorocarbon chain length of the PFAS (r2 = 0.75, p Funding Agencies|Swedish Research Council VR (Vetenskapsr?det) [2015-03938]; Swedish Geotechnical Institute

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 ~ 1000 μm apart and present at 40–100 cm depth in Tärnsjö, the discrete grains of P-Ca were ~ 700–1200 μm apart and present at 90–100 cm depth in Tönnersjöheden. 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.

The outcome of local policies to satisfy residential demand by accelerating urban planning and development is studied here for an infill programme with about 30 plans and a target of 7,000 new suburban dwellings, launched by a mid-sized Swedish city, Gothenburg. Interviews with developers and officials, questionnaires, policy and planning documents including appeals have been analyzed. Three municipal strategies for acceleration were applied: interdepartmental coordination, collaboration with developers and parallel processing of plans and permits. Plans were produced more rapidly, but the goal of parallel work on building permits was seldom achieved. A complex pattern of delay causes has been found and is discussed in the light of coordination strategies. Strong initial focus on the physical design in the detailed development plan overshadowed the need for an early identification of coordination issues throughout the stages of implementation. This emerges as one reason why developers have been reluctant or unable to start detailed design early on, instead of embracing the principle of parallel planning and preparation for a building permit.

Cultivated organic soils make a significant contribution to phosphorus (P) leaching losses from agricultural land, despite occupying a small proportion of cultivated area. However, less is known about P mobilisation processes and the P forms present in peat soils compared with mineral soils. In this study, P forms and their distribution with depth were investigated in two cultivated Histosol profiles, using a combination of wet chemical extraction and P K‐edge X‐ray absorption near‐edge structure (XANES) spectroscopy. Both profiles had elevated P content in the topsoil, amounting to around 40 mmol kg⁻¹, and P speciation in both profiles was strongly dominated by organic P. Topsoils were particularly rich in organic P (P‐org), with relative proportions of up to 80%. Inorganic P in the profiles was almost exclusively adsorbed to surface reactive aluminium (Al) and iron (Fe) minerals. In one of the pro‐files, small contributions of Ca‐phosphates were detected. A commonly used P saturation index (PSI) based on ammonium‐oxalate extraction indicated a low to moderate risk of P leaching from both profiles. However, the capacity of soil Al and Fe to retain P in organic soils could be reduced by high competition from organic compounds for sorption sites. This is not directly accounted for in PSI and similar indices. Accumulation of P‐org in the topsoil may be attributable by microbial peat decomposition and transformation of mineral fertiliser P by both microbiota and crops. Moreover, high carbon–phosphorus ratio in the surface peat material in both profiles suggests reduced net mineralisation of P‐org in the two soils. However, advancing microbial peat decomposition will eventually lead to complete loss of peat horizons and to mineralisation of P‐org. Hence, P‐org in both profiles represents a huge potentially mobilised P pool.

To improve phosphorus (P) fertilization and environmental assessments, a better understanding of release kinetics of solid‐phase P to soil solution is needed. In this study, Fe (hydr)oxide‐coated filter papers (Fh papers), isotopic exchange kinetics (IEK) and chemical extractions were used to assess the sizes of fast and slowly desorbing P pools in the soils of six long‐term Swedish field experiments. The P desorption data from the Fh‐paper extraction of soil (20 days of continual P removal) were fitted with the Lookman two‐compartment desorption model, which estimates the pools of fast (Q1) and slowly (Q2) desorbing P, and their desorption rates k1 and k2. The amounts of isotope‐exchangeable P (E) were calculated (E1min to E>3 months) and compared with Q1 and Q2. The strongest relationship was found between E1 min and Q1 (r2 = .87, p < .01). There was also an inverse relationship between the IEK parameter n (the rate of exchange) and k1 (r2 = .52, p < .01) and k2 (r2 = .52, p < .01), suggesting that a soil with a high value of n desorbs less P per time unit. The relationships between these results show that they deliver similar information, but both methods are hard to implement in routine analysis. However, Olsen‐extractable P was similar in magnitude to Q1 (P‐Olsen = 1.1 × Q1 + 2.3, r2 = .96), n and k1 were related to P‐Olsen/P‐CaCl2, while k2 was related to P‐oxalate/P‐Olsen. Therefore, these extractions can be used to estimate the sizes and desorption rates of the different P pools, which could be important for assessments of plant availability and leaching., Soil Use and Management, 38 (1), ISSN:0266-0032, ISSN:1475-2743

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. ispartof: ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY vol:41 issue:6 pages:1540-1554 ispartof: location:United States status: published

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 PO4

The charge-and concentration-dependent sorption behavior of a range of per-and polyfluoroalkyl substances (PFASs) was studied for three organic soil samples with different organic matter quality, one Spodosol Oe horizon (Mor Oe) and two Sphagnum peats with different degrees of decomposition (Peat Oi and Peat Oe). Sorption to the two peat materials was, on average, four times stronger compared to that onto the Mor Oe material. In particular, longer-chained PFASs were more strongly bound by the two peats as compared to the Mor Oe sample. The combined results of batch sorption experiments and 13C NMR spectroscopy suggested sorption to be positively related to the content of carbohydrates (i.e., O-alkyl carbon). Sorption of all PFAS subclasses was inversely related to the pH value in all soils, with the largest pH effects being observed for perfluoroalkyl carboxylates (PFCAs) with C-10 and C-11 perfluorocarbon chain lengths. Experimentally determined sorption isotherms onto the poorly humified Peat Oi did not deviate significantly from linearity for most substances, while for the Mor Oe horizon, sorption nonlinearity was generally more pronounced. This work should prove useful in assessing PFAS sorption and leaching in organic soil horizons within environmental risk assessment.

Arsenic (As) is reported to be effectively sorbed onto natural organic matter (NOM) via thiol coordination and polyvalent metal cation-bridged ternary complexation. However, the extent of sorption via complexation with oxygen-containing functional groups of NOM is poorly understood. By equilibrating arsenite, arsenate, and monothioarsenate with purified model-peat, followed by As K-edge X-ray absorption spectroscopic analysis, this study shows that complexation with oxygen-containing functional groups can be an additional or alternative mode of As sorption to NOM. The extent of complexation was highest for arsenite, followed by monothioarsenate and arsenate. Complexation was higher at pH 7.0 compared to 4.5 for arsenite and arsenate and vice versa for monothioarsenate because of partial transformation to arsenite at pH 4.5. Modeling of the As K-edge extended X-ray absorption fine structure data revealed that As···C interatomic distances were relatively longer in arsenate- (2.83 ± 0.01 Å) and monothioarsenate-treated peat (2.80 ± 0.02 Å) compared to arsenite treatments (2.73 ± 0.01 Å). This study suggests that arsenite was predominantly complexed with carboxylic groups, whereas arsenate and monothioarsenate were complexed with alcoholic groups of the peat. This study further implies that in systems, where NOM is the major sorbent, arsenate and monothioarsenate can have higher mobility than arsenite.

© 2019 Elsevier Ltd The role of organic matter (OM) in antimonate (further denoted as Sb(OH) 6 ) mobility in soil is unclear. The objective of this study was to evaluate Sb(OH) 6 –OM interaction. Antimonate solid:liquid distribution coefficients (K D ) were measured at low Sb concentrations in soil samples with a natural gradient in soil organic carbon (OC) that were collected from different depths of up to 3 m in two excavated soil profiles and in a subset of four soil samples with experimentally increased OM concentration from addition of Suwannee River OM. The K D values were related to soil properties by multiple linear regression and described with the CD–MUSIC model of ferrihydrite. The K D values ranged from 12 to 2800 L kg −1 and decreased strongly with increasing OC concentrations, when normalized to the amount of iron (Fe) and aluminium (Al) in acid oxalate extracts (r = −0.69; p < 0.0001). Experimentally increasing OC by ∼1.5 g kg −1 increased soluble Sb and decreased Sb(OH) 6 K D values by up to a factor of 8. The multiple regression model reveals that sorption of Sb(OH) 6 to Fe and Al hydroxides decreases with increasing pH and increasing dissolved organic carbon concentration. This effect could be explained with geochemical modelling by the competitive and electrostatic effects of adsorbed humic substances on Sb(OH) 6 surface complexation to the reactive surface sites of the Fe and Al hydroxides. Finally, both models could predict the in situ pore water Sb concentrations of unspiked samples, with a RMSE of 0.35 for the regression model and 0.43 for the geochemical model on the log 10 Sb concentrations. For these predictions, the 0.1 M Na 2 HPO 4 –extractable Sb concentration was measured and used to estimate the reversibly sorbed Sb pool. This study shows that increasing soil OM increases Sb(OH) 6 mobility at low soil Sb concentration, likely due to competitive sorption on Fe and Al hydroxides and a process based, geochemical model was calibrated to describe Sb(OH) 6 mobility in soil. ispartof: APPLIED GEOCHEMISTRY vol:104 pages:1-45 status: Published online

Application of wood ash to forests can restore pools of phosphorus (P) and other nutrients, which are removed following whole tree harvesting. Yet, the mechanisms that affect the fate of ash-P in the organic layer are less well known. Previous research into the extent to which ash application leads to increased P solubility in the soil is contradictory. We combined synchrotron P K-edge XANES spectroscopy, µ-XRF microscopy, and chemical extractions to examine the speciation and solubility of P. We studied organic horizons of two long-term field experiments, Riddarhyttan (central Sweden), which had received 3, 6, and 9 Mg ash ha−1, and Rödålund (northern Sweden), where 3 Mg ash ha−1 had been applied alone or combined with N every-three years since 2003. At the latter site, we also determined P in aboveground tree biomass. Overall, the ash application increased P in the organic layer by between 6 and 28 kg P ha−1, equivalent to 17–39 % of the initial P content in the applied ash. At Rödålund, there was 4.6 kg Ca-bound P ha−1 (9.5 %) in the ash treatment compared to 1.6 kg ha−1 in the ash + N treatment and < 0.4 kg ha−1 in the N treatment and the control. At Riddarhyttan, only the treatment with the highest ash dose had residual Ca-bound P (3.8 kg ha−1). In contrast, the ash application increased Al-bound P (p < 0.001) with up to 15.6 kg P ha−1. Moreover, the ash increased Olsen-P by up to two times. There was a strong relationship between the concentrations of Olsen-P and Al-bound P (R2 = 0.83, p < 0.001) as well as Fe-bound P (R2 = 0.74, p = 0.003), suggesting that the ash application resulted in an increased amount of relatively soluble P associated with hydroxy-Al and hydroxy-Fe compounds. Further, there was an 18 % increase in P uptake by trees in the ash treatment. By contrast, repeated N fertilization, with or without ash, reduced Olsen-P. The lower P extractability was concomitant with a 39 % increase in plant P uptake in the N treatment, which indicates elevated P uptake in response to higher N availability. Hence, the application of wood ash increased Al-bound P, easily available P, and P uptake. N fertilization, while also increasing tree P uptake, instead decreased easily available P and did not cause a shift in soil P speciation.

Colloids and nanoparticles leached from agricultural land are major carriers of potentially bioavailable nutrients with high mobility in the environment. Despite significant research efforts, accurate knowledge of macronutrients in colloids and nanoparticles is limited. We used multi-elemental synchrotron X-ray fluorescence (XRF) microscopy with multivariate spatial analysis and X-ray atomic absorption near-edge structure (XANES) spectroscopy at the P and S K-edges, to study the speciation of P and S in two fractions of leached particles, >0.45 and

Anaerobic conditions mobilize phosphorus (P) in soils and sediments. The role of anaerobic microsites in well-drained soil on P migration is unknown. This study aimed to identify mechanisms that control field-scale vertical P mobility as affected by organic fertilizers that may trigger variable redox conditions. Soils were sampled at different depths in a well-drained Luvisol after 19 years of application of organic fertilizers. The concentrations of P and manganese (Mn) in 0.45-μm-filtered extracts (10-3 M CaCl2) of field-moist soil samples were strongly correlated (r = + 0.95), and both peaked in and below the compacted plough pan, suggesting that reductive processes mobilize P. Waterlogged soil incubations confirmed that anaerobic respiration comobilizes Mn and P and that this leads to the release of colloidal P and iron (Fe). The long-term applications of farmyard manure and immature compost enhanced the concentrations of Mn, Fe, and aluminum (Al) in the soil solution of subsurface samples, whereas less such effect was found under the application of more stable organic fertilizers. Farmyard manure application significantly enhanced soil P stocks below the plough layer despite a small P input. Overall, multiple lines of evidence confirm that anaerobic respiration, sparked by labile organic matter, mobilizes P in this seemingly well-drained soil. ispartof: ENVIRONMENTAL SCIENCE & TECHNOLOGY vol:54 issue:8 pages:4922-4931 ispartof: location:United States status: published

Electric arc furnace slag (EAF) and argon oxygen decarburization slag (AOD) were investigated in column experiments to determine the effect of mineralogical composition on their P removal performance and lifespan. Polyethylene glycol (PEG) and NaOH solutions were used for pretreatment of the slags to adjust their dissolution properties. The modified slags exhibited better P removal performance at the beginning of the experiment, but had shorter lifespan than the unmodified slags. AOD and EAF modified with PEG and NaOH achieved 100% P removal during the first 84 and 60 pore volumes, respectively, which were ≥20 pore volumes longer than virgin AOD and EAF. However, virgin EAF and AOD both had a P removal efficiency above 90% during the first 280 pore volumes. Possibly, soluble minerals such as free lime are lost during the modification step, causing a decreased long-term P removal capacity. The XRD results showed that the high P removal ability of AOD and EAF was attributed to the dissolution of beta dicalcium silicate (β-C2) and gamma dicalcium silicate (γ-C2S), which were dominant mineral phases in the slags. Results from SEM-EDS analysis revealed significant P accumulation on the slag surface. Cracks on the EAF slag surface contributed to its longer lifespan. Analysis with P K-edge XANES spectroscopy showed that the P retained on the slag surface was dominated by amorphous calcium phosphate, with a substantial amount of carbonate apatite (around 30%). Amorphous calcium phosphate was transformed to crystalline apatite as the slag aged with column operating time.

Long-term application of manure can lead to an enrichment of phosphorus (P) in agricultural soils. To which extent this P leaches into drainage systems and thereby potentially contributing to eutrophication of surface waters, depends on the distribution and speciation of P present in the soil. In this study the P speciation and related soil characteristics were investigated for a sandy loam soil that had been receiving manure for >40 years. A combination of solution-state 31P-NMR, P K-edge XANES and wet chemical extractions was applied. Topsoil P contents were with 42 mmol kg−1 more than twice as high as in the sub soil (14–18 mmol kg−1). Linear combination fitting (LCF) of P K-edge XANES spectra indicated that P accumulation in the topsoil occurred predominantly via adsorption of inorganic P to Fe/Al hydroxide surfaces, resulting in substantial P saturation of these mineral phases. Up to 76% of the topsoil P was associated with Al or Fe. The organic P content was low (5–10%), but an additional important topsoil P pool identified with XANES-LCF was amorphous calcium phosphate (30%), which may have been added with manure or formed in situ. Towards the deeper subsoil the relative portion of primary apatite increased progressively and reached 80% of total P at a depth of 70 to 80 cm. These results highlight the importance of Fe and Al mineral phases for P retention in long-term manure-amended soils also under non-acidic conditions.

The molecular speciation of phosphorus (P) in forest soils is of strategic importance for sustainable forest management. However, only limited information exists about soil P speciation in boreal forests. We combined P K-edge XANES spectroscopy, wet chemical P extractions, and X-ray diffraction analysis of soil minerals to investigate the vertical distribution of P species in seven podzolised forest soils differing in soil properties and climatic conditions. The results showed that the total P stock was on average, 4.0 g m(-2) in the Oe horizon, 9.5 g m(-2) in the A and E horizons, and substantially higher (117.5 g m(-2), and 109.3 g m(-2)) in the B and C horizons down to 80 cm depth, respectively. Although the Oe horizons contain a minor total P stock, 87% of it was stored as organic P. The composition of P species in the P-depleted A/E horizons was highly variable depending on the site. However, of the P stored in B and C horizons down to 80 cm, 58% was adsorbed P, mostly to Al, while apatite accounted for 25% of P, most of which was found in the C horizons. The apatite stocks in the A/E, B, and C horizons (down to 80 cm) accounted for 2.5%, 20%, and 77.2%, respectively, of the total apatite for all the mineral soils studied. These figures can be explained, first, by the dissolution of primary mineral apatite caused mainly by acidification. Second, P uptake by plants and microorganisms, and the associated formation of the Oe horizons, led to the formation of soil organic P. Further, the formation of organo-metal complexes and podzolization led to the translocation of P to the B horizons, where P accumulated mostly as P adsorbed to imogolite-type materials (e.g. allophane) and ferrihydrite, as shown by P K-edge XANES spectroscopy. In conclusion, this study shows that despite the young age of these soils (

The complex chemistry of copper (Cu) in freshwater sediments at low concentrations is not well understood. We evaluated the transformation processes of Cu added to freshwater sediments under suboxic and anoxic conditions. Freshwater sediments from three sources in Michigan with different characteristics (Spring Creek, River Raisin, and Maple Lake) were spiked with 30 or 60 mg kg−1 Cu and incubated under a nitrogen atmosphere. After 28-d, each treatment subset was amended with organic matter (OM) to promote anoxic conditions and evaluate its effects on Cu speciation. OM addition triggered a shift from suboxic to anoxic conditions, and sequential extractions showed that Cu accordingly shifted from acid-soluble to oxidizable fractions. Extended X-ray absorption fine-structure (EXAFS) spectroscopy revealed that Cu sulfides dominated all anoxic samples except for Spring Creek 30 mg kg−1, where Cu(I) was predominantly complexed to thiol groups of OM. Covellite and chalcopyrite (CuFeS2) were the predominant Cu species in nearly all anoxic samples, as determined by Raman spectroscopy, scanning electron microscopy, and X-ray absorption near-edge structure (XANES) spectroscopy. Copper reduction also occurred under suboxic conditions: for two of three sediments, around 80% had been reduced to Cu(I), while the remaining 20% persisted as Cu(II) complexed to OM. However, in the third coarsest (i.e., Spring Creek), around 50% of the Cu had been reduced, forming Cu(I)-OM complexes, while the remainder was Cu(II)-OM complexes. Toxicity tests showed that survival of H. azteca and D. magna were significantly lower in suboxic treatments. Anoxic sediments triggered a near-complete transformation of Cu to sulfide minerals, reducing its toxicity.

We present a likelihood-based test for clustering among sub-population mean directions for circular data. The test is based on a two-level hierarchical model with von Mises distributed variation on each level. The properties of the tests are investigated and compared to the commonly applied techniques of second-order analysis and pseudo-pooling of directions for the situation at hand. Finally we apply the technique to some previously published data sets, to determine the presence of directional clustering among the sub-populations. The Canadian Journal of Statistics xx: 1–18; 2017 © 2017 Statistical Society of Canada

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.

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

Soil and water acidification was internationally recognised as a severe environmental problem in the late 1960s. The interest in establishing “critical loads” led to a peak in weathering research in the 1980s and 1990s, since base cation weathering is the long-term counterbalance to acidification pressure. Assessments of weathering rates and associated uncertainties have recently become an area of renewed research interest, this time due to demand for forest residues to provide renewable bioenergy. Increased demand for forest fuels increases the risk of depleting the soils of base cations produced in situ by weathering. This is the background to the research programme Quantifying Weathering Rates for Sustainable Forestry (QWARTS), which ran from 2012 to 2019. The programme involved research groups working at different scales, from laboratory experiments to modelling. The aims of this study were to (1) investigate the variation in published weathering rates of base cations from different approaches in Sweden, with consideration of the key uncertainties for each method; (2) assess the robustness of the results in relation to sustainable forestry; and (3) discuss the results in relation to new insights from the QWARTS programme and propose ways to further reduce uncertainties. In the study we found that the variation in estimated weathering rates at single-site level was large, but still most sites could be placed reliably in broader classes of weathering rates. At the regional level, the results from the different approaches were in general agreement. Comparisons with base cation losses after stem-only and whole-tree harvesting showed sites where whole-tree harvesting was clearly not sustainable and other sites where variation in weathering rates from different approaches obscured the overall balance. Clear imbalances appeared mainly after whole-tree harvesting in spruce forests in southern and central Sweden. Based on the research findings in the QWARTS programme, it was concluded that the PROFILE/ForSAFE family of models provides the most important fundamental understanding of the contribution of weathering to long-term availability of base cations to support forest growth. However, these approaches should be continually assessed against other approaches. Uncertainties in the model approaches can be further reduced, mainly by finding ways to reduce uncertainties in input data on soil texture and associated hydrological parameters but also by developing the models, e.g. to better represent biological feedbacks under the influence of climate change.

Elevated Arsenic (As) and Fluoride (F) concentrations in groundwater have been studied in the shallow aquifers of northeastern of La Pampa province, in the Chaco-Pampean plain, Argentina. The source of As and co-contaminants is mainly geogenic, from the weathering of volcanic ash and loess (rhyolitic glass) that erupted from the Andean volcanic range. In this study we have assessed the groundwater quality in two semi-arid areas of La Pampa. We have also identified the spatial distribution of As and co-contaminants in groundwater and determined the major factors controlling the mobilization of As in the shallow aquifers. The groundwater samples were circum-neutral to alkaline (7.4 to 9.2), oxidizing (Eh ~0.24 V) and characterized by high salinity (EC = 456–11,400 μS/cm) and Na+–HCO3– water types in recharge areas. Carbonate concretions (“tosca”) were abundant in the upper layers of the shallow aquifer. The concentration of total As (5.6 to 535 μg/L) and F (0.5 to 14.2 mg/L) were heterogeneous and exceeded the recommended WHO Guidelines and the Argentine Standards for drinking water. The predominant As species were arsenate As(V) oxyanions, determined by thermodynamic calculations. Arsenic was positively correlated with bicarbonate (HCO3−), fluoride (F), boron (B) and vanadium (V), but negatively correlated with iron (Fe), aluminium (Al), and manganese (Mn), which were present in low concentrations. The highest amount of As in sediments was from the surface of the dry lake. The mechanisms for As mobilization are associated with multiple factors: geochemical reactions, hydrogeological characteristics of the local aquifer and climatic factors. Desorption of As(V) at high pH, and ion competition for adsorption sites are considered the principal mechanisms for As mobilization in the shallow aquifers. In addition, the long-term consumption of the groundwater could pose a threat for the health of the local community and low cost remediation techniques are required to improve the drinking water quality.

The toxicity of vanadium in soils depends on its sorption to soil components. Here we studied the vanadate(V) sorption properties of 26 mineral soils. The data were used to optimise parameters for a Freundlich equation with a pH term. Vanadium K-edge XANES spectroscopy for three selected soils confirmed that the added vanadate(V) had accumulated mostly as adsorbed vanadate(V) on Fe and Al hydrous oxides, with only minor contributions from organically complexed vanadium(IV). Data on pH-dependent V solubility for seven soils showed that on average 0.36 H+ accompanied each V during adsorption and desorption. The resulting model provided reasonable fits to the V sorption data, with r2 > 0.99 for 20 of 26 soils. The observed KdS value, i.e. the ratio of total to dissolved V, was strongly dependent on V addition and soil; it varied between 3 and 4 orders of magnitude. The model was used to calculate the Freundlich sorption strength (FSS), i.e. the amount of V sorbed at [V] = 2.5 mg L−1, in the concentration range of observed plant toxicities. A close relationship between FSS and oxalate-extractable Fe and Al was found (r2 = 0.85) when one acidic soil was removed from the regression. The FSS varied between 27 and 8718 mg V kg−1, showing that the current environmental guidelines can be both under- and overprotective for vanadium. QC 20170609

The shift in major drivers of acidification from sulfur deposition to biological acidification has put the focus on the impact of biomass harvest for bioenergy on the acid base status of forests soils and surface waters. This paper presents a model-based assessment in which the impact of whole-tree harvest (WTH) is compared with that of no harvest at two different sulfur deposition levels by use of the HD-MINTEQ model. Additionally, the pH-sensitivity of 179 randomly selected boreal headwater streams was assessed. The results indicate that the exchangeable Ca2+ pool in humus and mineral soils (⩽B-horizon) is most affected by harvest. Concerning the pH, the WTH impact is restricted to shallow soils and for a much shorter period of time. The impact of WTH on the soil solution was primarily restricted to the recharge area and much less pronounced in the discharge area. Due to high buffering capacity of riparian soils and low pH-sensitivity of many headwater streams, the pH effects of WTH on surface waters will most probably be small, at least over a rotation period of several decades. Over time perspectives of multiple rotations, the pH effects are more uncertain due to a possible slow successive protonation of organic matter in the riparian zone. Another important aspect is the currently restricted availability of mobile anion charge balancing the acidity produced by tree growth. Therefore, the acidity is to a large extent arrested in the soil. At the current low S deposition levels, southwestern Sweden seems to be the least vulnerable region to further acid input due to high buffer capacity at low pH. The streams in central and northern Sweden are much more pH-sensitive, but restricted availability of mobile strong acid anions and large buffer capacity in the soils make them less vulnerable to WTH. The partly diverging results between experimental and model studies indicate that one or more processes (hydrological, chemical or biological) are not fully understood or that available data are lacking for a proper parameterization. Thus, the results from long-term WTH experiments are very important for understanding the processes involved as well as for improving and validating model predictions. We therefore encourage societal support of maintaining monitoring and research coupled to such experiments. For the future and for improving our current understanding of biogeochemical dynamics in forest ecosystems subjected to active forestry as well as for policy and management purposes, a mixture of experiments and models ought to be used.

With time, different soil-forming processes such as weathering, plant growth, accumulation of organic matter, and cultivation are likely to affect phosphorus (P) speciation. In this study, the depth distribution of P species was investigated for an agricultural clay soil, Lanna, Sweden. Small amounts of apatite-P was demonstrated in the topsoil whereas the speciation of Pat 70-100 cm depth consisted of approximately 86% apatite according to P K-edge XANES (X-ray absorption near-edge structure) spectroscopy. Because there were only minor differences in bulk mineralogy and texture, these variations in P speciation were interpreted as the result of apatite weathering of the topsoil. Speciation modeling on soil extracts supported this idea: hydroxyapatite was not thermodynamically stable in the top 50 cm of the soil. Apatite was enriched in the bulk soil relative to the clay fraction, as expected during apatite dissolution. Combined results from batch experiments, XANES spectroscopy and X-ray diffraction suggested chemical transformations of the topsoil as a result from accumulation of organic matter and airing from tillage followed by enhanced weathering of apatite, amphiboles, clay minerals, and iron oxides. This caused the formation of poorly crystalline secondary iron and aluminum (hydr)oxides in the topsoil, which retained part of the released P from apatite. Other P was incorporated into organic forms. Furthermore, the results also showed that short-term acidification below the current pH value (below 5.5 in the topsoil and 7.2 in the deeper subsoil) caused significant solubilization of P. This is attributed to two different mechanisms: the instability of Al-containing sorbents (e.g. Al hydroxides) at low pH (in the topsoil), and the acid-mediated dissolution of apatite (the subsoil). (C) 2016 Elsevier B.V. All rights reserved.

The global phosphorus crisis provided impetus to develop fertilizers with better P use efficiency. We tested layered double hydroxides (LDHs) as slow release fertilizers with superior performance to fertilize strongly P-fixing soils. Mg–Al LDHs with varying M2+/M3+ ratios were synthesized as NO3– forms and were exchanged with HPO42–. XRD and XANES spectroscopy confirmed the identity of the phosphate-exchanged LDH. Decreasing the M2+/M3+ ratio, i.e., increasing the anion exchange capacity, increased the selectivity of P adsorption due to the increasing charge density of the LDH layers. The fertilization efficiency of the phosphate-exchanged LDH (Mg/Al ratio of 2) was compared to that of a soluble P fertilizer in two P-deficient soils, an acid weathered soil and a calcareous soil. The P use efficiency of the P-LDH in the acid soil was up to 4.5 times higher than that of soluble P. This was likely related to a liming effect of the LDH. In the calcareous soil, the P use efficiency at low doses was only 20% ab...

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. QC 20160524

The cycling and long-term supply of phosphorus (P) in soils are of global environmental and agricultural concern. To advance the knowledge, a detailed understanding of both the vertical and lateral variation of P chemical speciation and retention mechanism(s) is required, a knowledge that is limited in postglacial forest soils. We combined the use of synchrotron X-ray fluorescence microscopy with multi-elemental co-localisation analysis and P K-edge XANES spectroscopy to reveal critical chemical and structural soil properties. We established a two-dimensional (2D) imagery of P retention and speciation at a microscale spatial resolution in two forest soil profiles formed in glaciofluvial and wave-washed sand. The abundance and speciation of P in the upper 40 cm was found to be influenced by soil weathering and podzolization, leading to spatial variability in P speciation on the microscale ( 600 μm) hot spots of inclusions in aluminosilicates or as discrete micro-sized apatite grains. The subsoil apatite represents a pool of P that trees can potentially acquire and thus add to the biogeochemically active P pool in temperate forest soils.

Vanadium (V), although serving as an important component of industrial activities, has bioinorganic implications to pose highly toxic hazards to humans and animals. Soils and sediments throughout the world exhibit wide ranges of vanadium concentrations. Although vanadium toxicity varies between different species, it is mainly controlled by soil redox potential (EH). Nonetheless, knowledge of the redox geochemistry of vanadium lags in comparison to what is known about other potentially toxic elements (PTEs). In particular, the redox-induced speciation and mobilization of vanadium in soils and sediments and the associated risks to the environment have not been reviewed to date. Therefore, this review aims to address 1) the content and geochemical fate of vanadium in soils and sediments, 2) its redox-induced release dynamics, 3) redox-mediated chemical reactions between vanadium and soil organic and inorganic colloidal materials in soil solution, 4) its speciation in soil solution and soil-sediments, and 5) the use of advanced geochemical and spectroscopic techniques to investigate these complex systems. Vanadium (+5) is the most mobile and toxic form of its species while being the thermodynamically stable valence state in oxic environments, while vanadium (+3) might be expected to be predominant under euxinic (anoxic and sulfidic) conditions. Vanadium can react variably in response to changing soil EH: under anoxic conditions, the mobilization of vanadium can decrease because vanadium (+5) can be reduced to relatively less soluble vanadium (+4) via inorganic reactions such as with H2S and organic matter and by metal-reducing microorganisms. On the other hand, dissolved concentrations of vanadium can increase at low EH in many soils to reveal a similar pattern to that of Fe, which may be due to the reductive dissolution of Fe(hydr)oxides and the release of the associated vanadium. Those differences in vanadium release dynamics might occur as a result of the direct impact of EH on vanadium speciation in soil solution and soil sediments, and/or because of the EH-dependent changes in soil pH, chemistry of (Fe)(hydr)oxides, and complexation with soil organic carbon. Release dynamics of vanadium in soils may also be affected positively by soil pH and the release of aromatic organic compounds. X-ray absorption spectroscopy (XAS) is a powerful tool to investigate the speciation of vanadium present in soil. X-ray absorption near edge structure (XANES) is often used to constrain the average valence state of vanadium in soils and sediments, and in limited cases extended X-ray absorption fine structure (EXAFS) analysis has been used to determine the average molecular coordination environment of vanadium in soil components. In conclusion, this review presents the state of the art about the redox geochemistry of vanadium and thus contributes to a better understanding of the speciation, potential mobilization, and environmental hazards of vanadium in the near-surface environment of uplands, wetlands, and agricultural ecosystems as affected by various colloidal particles. Further research is needed to elucidate the geochemistry and speciation of vanadium in the dissolved, colloidal, and soil sediments phases, including the determination of factors that control the redox geochemistry of vanadium.

Mofettes (natural geogenic CO2 exhalations) represent excellent sites to study the behavior of Cu in soils and the co-occurrence of different mobilization and immobilization processes since they exhibit both a gradient in redox conditions (oxic to permanently anoxic) and in soil organic matter (SOM; low to high contents). Soil and pore water samples from an 18 m-transect over a mofette showed a complex behavior of Cu, with highest mobility in the transition between oxic and anoxic conditions. Cu(II) sorption experiments on SOM-rich topsoil revealed that Cu mobility under oxic conditions was confined by adsorption to SOM while in the oxygen-free mofette center reduction and precipitation of sulfides was the dominating Cu-sequestering process. In transition areas with low amounts of oxygen (

Laboratory-based leaching tests are frequently used for in situ risk assessments of contaminant leaching to groundwater and surface waters. This study evaluated the ability of three standardised leaching tests to assess leaching of lead (Pb), zinc (Zn), arsenic (As) and antimony (Sb) from four intact soil profiles, by considering particulate (0.45-8 μm; percolation test), colloidal (10 kDa-0.45 μm) and truly dissolved (10 kDa) fractions of these elements. Deionised water was used as the percolation test leachant, while either deionised water or 1 mM CaCl

In peatlands, arsenite was reported to be effectively sequestered by sulfhydryl groups of natural organic matter. To which extent porewater arsenite can react with reduced sulfur to form thioarsenates and how this affects arsenic sequestration in peatlands is unknown. Here, we show that, in the naturally arsenic-enriched peatland Gola di Lago, Switzerland, up to 93% of all arsenic species in surface and porewaters were thioarsenates. The dominant species, monothioarsenate, likely formed from arsenite and zerovalent sulfur-containing species. Laboratory incubations with sulfide-reacted, purified model peat showed increasing total arsenic sorption with decreasing pH from 8.5 to 4.5 for both, monothioarsenate and arsenite. However, X-ray absorption spectroscopy revealed no binding of monothioarsenate via sulfhydryl groups. The sorption observed at pH 4.5 was acid-catalyzed dissociation of monothioarsenate, forming arsenite. The lower the pH and the more sulfhydryl sites, the more arsenite sorbed which in turn shifted equilibrium toward further dissociation of monothioarsenate. At pH 8.5, monothioarsenate was stable over 41 days. In conclusion, arsenic can be effectively sequestered by sulfhydryl groups in anoxic, slightly acidic environments where arsenite is the only arsenic species. At neutral to slightly alkaline pH, monothioarsenate can form and its slow transformation into arsenite and low affinity to sulfhydryl groups suggest that this species is mobile in such environments.

Argon oxygen decarburisation (ADD) slag may be used for phosphorus (P) removal, as its high pH and weatherable calcium (Ca) minerals provide sufficient Ca2+ and OH- for calcium phosphate (Ca-PO4) precipitation. This study examined the P removal performance of AOD slag for use as wastewater treatment material. Batch experiments were carried out using both synthetic P solution and real wastewater, followed by chemical modelling and X-ray absorption near edge structure (XANES) spectroscopy. The influences of initial P concentration, slag dose and modification by polyethylene glycol (PEG), an effective agent for generation of porous materials, were investigated to determine the optimal conditions for P removal by AOD slag. It was found that virgin AOD slag removed 94.8% of P from a synthetic P solution in 4 h and 97.8% in 10 h. This high P removal was accompanied by a rapid increase in pH from 7.0 to 10.74. The maximum P removal capacity (PRC) from synthetic P solution ranged from 1.3 to 27.5 mg P g(-1). The optimal AOD dose for P removal from wastewater, determined in 8-h batch experiments, was 25 g L-1. PEG modification increased the reaction rate and resulted in higher final pH, increasing PRC by 47.9%. Combined Visual MINTEQ and XANES analysis for detailed examination of P removal mechanisms revealed that the main P removal mechanism was precipitation of calcium phosphate. According to the XANES analysis, the main Ca-PO4 precipitate formed on virgin AOD slag under low initial P concentration and high pH was apatite, while brushite was the dominant product at high initial P concentration and low pH. (C) 2015 Elsevier Ltd. All rights reserved.

It is well known that chemical parameters, such as natural organic matter (NOM), cation content and pH may influence speciation and toxicity of metals in freshwaters. Advanced bioavailability models, e.g. Biotic Ligand Models (BLMs), can use these and other chemical parameters to calculate site specific recommendations for metals in the aquatic environment. However, since Al is not an input parameter in the BLM v.2.2.3, used in this study, there could be a discrepancy between calculated and measured results in Al rich waters. The aim of this study was to evaluate if the presence of Al in a circumneutral (pH ∼6) soft humic freshwater, Lake St. Envättern, will affect the Cu speciation and thereby the toxicity to the cladoceran Daphnia magna. The results show a statistically significant increase in the free Cu(2+) concentration with Al additions and that measured levels of Cu(2+) significantly differed from BLM calculated levels of Cu(2+). Furthermore, there was also a statistically significant elevated acute toxic response to D. magna at low additions of Al (10 μg/L). However, since the large difference between calculated and measured Cu(2+) resulted in a significant but minor (factor of 2.3) difference between calculated and measured toxicity, further studies should be conducted in Al rich soft waters to evaluate the importance of adding Al as an input parameter into the BLM software.