| 1. |
- Yu, Changxun, et al.
(författare)
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Iron behavior in a northern estuary: Large pools of non-sulfidized Fe(II) associated with organic matter
- 2015
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Ingår i: Chemical Geology. - : Elsevier BV. - 0009-2541 .- 1872-6836. ; 413, s. 73-85
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Tidskriftsartikel (refereegranskat)abstract
- The estuaries of the Northern Baltic Sea (Gulf of Bothnia) receive an abundance of diagenetically reactive catchment-derived Fe, which is to a large degree complexed with organicmatter or present as Fe (hydr-) oxides. However, our understanding of sedimentary Fe diagenesis in these estuaries is limited. To address this limitation, the present study examines Fe geochemistry in a 3.5-m-thick estuarine benthic mud layer and three samples of suspended particulate matter of a catchment on the eastern Gulf of Bothnia. The age-depth model of the mud, constructed on the basis of sedimentary features as well as Cs-137 and aquatic plant C-14 determinations, revealed a high average rate of sedimentation (5 cm . yr(-1)) for the upper mud unit (0-182.5 cm, corresponding to 1973-2011), in response to intensive land-use (ditching) in the catchment since the 1960s and 1970s. The intensive land-use has resulted in a strong increase in the Fe accumulation rates, but has not caused a recognizable impact on the diagenetic processes of Fe including features such as degree of sulfidization and solid-phase partitioning. Iron X-ray absorption spectroscopy (XAS) indicated that in the suspended particulate matter, large proportions (47-58%) of Fe occur as Fe(III)-organic complexes and 2-line ferrihydrite. In the mud, the former is completely reduced, and reactive Fe (defined via extraction with 1 MHCl) was high throughout (52-68%, median = 61%) and strongly dominated by Fe(II). This reactive Fe(II) pool was sulfidized to only a limited extent (degree of reactive sulfidization = 11-26%, median = 17%). This phenomenon is attributed to the brackish-water conditions (i.e. low in sulfate) and the abundant input of reactive Fe(III) from the catchment, leading to a surplus of dissolved Fe2+ over dissolved sulfide in the sediment. The low availability of dissolved sulfide, in combination with the high average sedimentation rate, limits the formation of intermediate reduced sulfur compounds at the water-sediment interface, thereby retarding the conversion of FeS into pyrite (ratios of pyrite-S to AVS = 0.17-1.73, median = 0.37; degree of pyritization = 1-17%, median = 3%). Iron XAS, in combination with wavelet transform analysis, of representative sediment segments from the upper and lower mud units suggests that the non-sulfidized Fe(II) pool is dominantly complexed by organic matter, with the remaining Fe(II) occurring as mackinawite. This has implications for the understanding of early Fe diagenesis in settings with a high input of organic matter and relatively low supply of sulfate. (C) 2015 Elsevier B.V. All rights reserved.
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| 2. |
- Yu, Changxun, et al.
(författare)
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Manganese accumulation and solid-phase speciation in a 3.5 m thick mud sequence from the estuary of an acidic and Mn-rich creek, northern Baltic Sea
- 2016
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Ingår i: Chemical Geology. - : Elsevier BV. - 0009-2541 .- 1872-6836. ; 437, s. 56-66
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Tidskriftsartikel (refereegranskat)abstract
- In sediments, manganese (Mn) is typically enriched in the form of authigenic Mn hydroxides at the water-sediment interface where intensive redox cycling of Mn occurs. Here we show, based on existing hydrochemical and geochemical (sediment core) data and new detailed chemical and mineralogical characterization of a 3.5 m long sediment core from a Boreal estuary, that the behavior of Mn can be profoundly different and more complex in estuarine settings receiving an abundance of terrestrial Mn. The most notable feature in the 3.5 m long sediment core is two depth intervals (60-155 cm and 181-230 cm) where there are strong fine-scale variations in Mn concentrations with peaks episodically reaching up to 10-25 g kg(-1) and 6.7-12 g kg(-1), respectively. X-ray absorption spectroscopy and sequential chemical extraction show that Mn occurs mainly as authigenic rhodochrosite at these two depth intervals and is mainly surface-sorbed in other sections with relatively low and stable Mn concentrations. The data suggests that the strong fine-scale variations in Mn concentrations are a reflection of the extent of formation and settling of Mn hydroxides, the precursors of the authigenic rhodochrosite (and also of the surface-sorbed Mn), rather than Mn input to the estuary or redox-related Mn translocation within the sediment. There was agreement between the results of linear combination fitting of extended X-ray absorption fine structure data and a 7-step sequential chemical extraction (SCE) in terms of quantification of surface-sorbed Mn species, whereas the SCE experiment failed to fractionate a majority of rhodochrosite into SCE step-2 (1M NH4-acetate at pH 6), which is frequently employed to dissolve carbonate. We ascribe this discrepancy to only partial dissolution of rhodochrosite in the weakly acidic (pH = 6) NH4-acetate leach.
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| 3. |
- Åström, Mats E., 1963-, et al.
(författare)
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Extensive accumulation of rare earth elements in estuarine sediments affected by leaching of acid sulfate soils
- 2020
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Ingår i: Boreal Environment Research. - : Finnish Environmental Inst. - 1239-6095 .- 1797-2469. ; 25, s. 105-120
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Tidskriftsartikel (refereegranskat)abstract
- The concentrations, loads and speciation of rare earth elements (REEs) were studied in a 3.5 m thick mud depositional succession from an estuary in the Gulf of Bothnia. The uppermost 182.5 cm of the mud, estimated to have deposited from the early 1970s to 2011 (sampling year), had very high REE concentrations (596-1456 ppm) and accumulation rates (5.2-28 g m(-2) year(-1)). This was explained by large REE export from acid sulfate soils after they became efficiently drained with modern drainage techniques. Geochemical and synchrotron-based spectroscopic (XANES) analyses showed that the REEs in the mud are relatively firmly bound in non-clastic phases, likely adsorbed by clay minerals and also to some extent by iron oxyhydroxides. Below 182.5 cm, the REE concentrations successively decreased down to background values at the base at 3.5 m, reflecting less efficient drainage and leaching of the acid sulfate soils in previous decades and centuries.
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| 4. |
- Augustsson, Anna, et al.
(författare)
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Failure of generic risk assessment model framework to predict groundwater pollution risk at hundreds of metal contaminated sites : Implications for research needs
- 2020
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Ingår i: Environmental Research. - : Elsevier. - 0013-9351 .- 1096-0953. ; 185, s. 1-9
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Tidskriftsartikel (refereegranskat)abstract
- Soil pollution constitutes one of the major threats to public health, where spreading to groundwater is one of several critical aspects. In most internationally adopted frameworks for routine risk assessments of contaminated land, generic models and soil guideline values are cornerstones. In order to protect the groundwater at contaminated sites, a common practice worldwide today is to depart from health risk-based limit concentrations for groundwater, and use generic soil-to-groundwater spreading models to back-calculate corresponding equilibrium levels (concentration limits) in soil, which must not be exceeded at the site. This study presents an extensive survey of how actual soil and groundwater concentrations, compiled for all high-priority contaminated sites in Sweden, relate to the national model for risk management of contaminated sites, with focus on As, Cu, Pb and Zn. Results show that soil metal concentrations, as well as total amounts, constitute a poor basis for assessing groundwater contamination status. The evaluated model was essentially incapable of predicting groundwater contamination (i.e. concentrations above limit values) based on soil data, and erred on the "unsafe side" in a significant number of cases, with modelled correlations not being conservative enough. Further, the risk of groundwater contamination was almost entirely independent of industry type. In essence, since neither soil contaminant loads nor industry type is conclusive, there is a need for a supportive framework for assessing metal spreading to groundwater accounting for site-specific, geochemical conditions.
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| 5. |
- Drake, Henrik, et al.
(författare)
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Variability of sulphur isotope ratios in pyrite and dissolved sulphate in granitoid fractures down to 1km depth - Evidence for widespread activity of sulphur reducing bacteria
- 2013
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Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 1872-9533. ; 102, s. 143-161
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Tidskriftsartikel (refereegranskat)abstract
- Euhedral pyrite crystals in 46 open bedrock (granitoid) fractures at depths down to nearly 1 km were analysed for sulphur isotope ratios (delta S-34) by the in situ secondary ion mass spectrometry (SIMS) technique and by conventional bulk-grain analysis, and were compared with groundwater data. Twenty nine of the fractures sampled for pyrite had corresponding data for groundwater, including chemistry and isotopic ratios of sulphate, which provided a unique opportunity to compare the sulphur-isotopic ratios of pyrite and dissolved sulphate both at site and fracture-specific scales. Assessment of pyrite age and formation conditions were based on the geological evolution of the area (Laxemar, SE Sweden), and on data on co-genetic calcite as follows: (1) the isotopic ratios of the calcite crystals (delta O-18, delta C-13, Sr-87/Sr-86) were compared with previously defined isotopic features of fracture mineral assemblages precipitated during various geological periods, and (2) the delta O-18 of the calcites were compared with the delta O-18 of groundwater in fractures corresponding to those where the calcite/pyrite assemblages were sampled. Taken together, the data show that all the sampled fractures carried pyrite/calcite that are low-temperature and precipitated from the current groundwater or similar pre-existing groundwater, except at depths of -300 to -600 m where water with a glacial component dominates and the crystals are from pre-modern fluids. An age of <10 Ma are anticipated for the pre-modern fluids. The delta S-34(pyr) showed huge variations across individual crystals (such as -32 to +73 parts per thousand) and extreme minimum (-50 parts per thousand) and maximum (+91 parts per thousand) values. For this kind of extreme S-isotopic variation at earth-surface conditions there is no other explanation than activity of sulphur reducing bacteria coupled with sulphate-limited conditions. Indeed, the most common subgrain feature was an increase in delta S-34(pyr) values from interior to rim of the crystal, which we interpret are related to successively higher delta S-34 values of the dissolved source SO42- caused by ongoing bacterial sulphate reduction in fractures with low-flow or stagnant waters. The measured groundwater had delta S-34(SO4) values of +9 parts per thousand to +37 parts per thousand, with the highest values associated with low sulphate concentrations. These values are overall, and especially in the sulphate-poor waters down to -400 m, somewhat higher than the anticipated initial values, and can thus, like for the S-34-enriched pyrites, be explained by a Rayleigh distillation process driven by microbial sulphate reduction. An intriguing feature was that the delta S-34(SO4) values of the groundwater were in no case reaching up to the values required to produce biogenic pyrite with delta S-34 values of +40 parts per thousand to +91 parts per thousand. To explain this feature, we suggest that groundwater in low-flow fractures with near-stagnant water (carrying sulphate and pyrite with high delta S-34) is masked by high-flow parts of the fracture system carrying groundwater that often contains sulphate in abundance and considerably less fractionated with respect to S-34 and S-32. In order to gain detailed knowledge of chemical processes and patterns in groundwater in fractured rock, fracture-mineral investigations are a powerful tool, as we have shown here for the sulphur system. (C) 2012 Elsevier Ltd. All rights reserved.
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| 6. |
- Mathurin, Frédéric A., et al.
(författare)
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Effect of tunnel excavation on source and mixing of groundwater in a coastal granitoidic fracture network.
- 2012
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 46:23, s. 12779-12786
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Tidskriftsartikel (refereegranskat)abstract
- The aim of this study was to assess how the excavation of the Äspö Hard Rock Laboratory tunnel has impacted on sources and mixing of groundwater in fractured crystalline (granitoidic) bedrock. The tunnel is 3600 m long and extends to a depth of 460 m at a coastal site in Boreal Europe. The study builds on a unique data set consisting of 1117 observations on chloride and δ(18)O of groundwater collected from a total of 356 packed-off fractures between 1987 and 2011. On the basis of the values of these two variables in selected source waters, a classification system was developed to relate the groundwater observations to source and postinfiltration mixing phenomena. The results show that the groundwater has multiple sources and a complex history of transport and mixing, and is composed of at least glacial water, marine water, recent meteoric water, and an old saline water. The tunnel excavation has had a large impact on flow, sources, and mixing of the groundwater. Important phenomena include upflow of deep-lying saline water, extensive intrusion of current Baltic Sea water, and substantial temporal variability of chloride and δ(18)O in many fractures.
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| 7. |
- Mathurin, Frédéric A., et al.
(författare)
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High cesium concentrations in groundwater in the upper 1.2km of fractured crystalline rock - Influence of groundwater origin and secondary minerals
- 2014
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Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier Ltd. - 0016-7037 .- 1872-9533. ; 132, s. 187-213
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Tidskriftsartikel (refereegranskat)abstract
- Dissolved and solid phase cesium (Cs) was studied in the upper 1.2km of a coastal granitoid fracture network on the Baltic Shield (Äspö Hard Rock Laboratory and Laxemar area, SE Sweden). There unusually high Cs concentrations (up to 5-6μgL-1) occur in the low-temperature (<20°C) groundwater. The material includes water collected in earlier hydrochemical monitoring programs and secondary precipitates (fracture coatings) collected on the fracture walls, as follows: (a) hydraulically pristine fracture groundwater sampled through 23 surface boreholes equipped for the retrieval of representative groundwater at controlled depths (Laxemar area), (b) fracture groundwater affected by artificial drainage collected through 80 boreholes drilled mostly along the Äspö Hard Rock Laboratory (underground research facility), (c) surface water collected in local streams, a lake and sea bay, and shallow groundwater collected in 8 regolith boreholes, and (d) 84 new specimens of fracture coatings sampled in cores from the Äspö HRL and Laxemar areas. The groundwater in each area is different, which affects Cs concentrations. The highest Cs concentrations occurred in deep-seated saline groundwater (median Äspö HRL: 4.1μgL-1; median Laxemar: 3.7μgL-1) and groundwater with marine origin (Äspö HRL: 4.2μgL-1). Overall lower, but variable, Cs concentrations were found in other types of groundwater. The similar concentrations of Cs in the saline groundwater, which had a residence time in the order of millions of years, and in the marine groundwater, which had residence times in the order of years, shows that duration of water-rock interactions is not the single and primary control of dissolved Cs in these systems. The high Cs concentrations in the saline groundwater is ascribed to long-term weathering of minerals, primarily Cs-enriched fracture coatings dominated by illite and mixed-layer clays and possibly wall rock micaceous minerals. The high Cs concentrations in the groundwater of marine origin are, in contrast, explained by relatively fast cation exchange reactions. As indicated by the field data and predicted by 1D solute transport modeling, alkali cations with low-energy hydration carried by intruding marine water are capable of (NH4 + in particular and K+ to some extent) replacing Cs+ on frayed edge (FES) sites on illite in the fracture coatings. The result is a rapid and persistent (at least in the order of decades) buildup of dissolved Cs concentrations in fractures where marine water flows downward. The identification of high Cs concentrations in young groundwater of marine origin and the predicted capacity of NH4 + to displace Cs from fracture solids are of particular relevance in the disposal of radioactive nuclear waste deep underground in crystalline rock. © 2014 Elsevier Ltd.
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| 8. |
- Mathurin, Frédéric A., et al.
(författare)
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REE and Y in groundwater in the upper 1.2 km of Proterozoic granitoids (Eastern Sweden) - Assessing the role of composition and origin of groundwaters, geochemistry of fractures, and organic/inorganic aqueous complexation
- 2014
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Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 1872-9533. ; 144, s. 342-378
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Tidskriftsartikel (refereegranskat)abstract
- Yttrium and rare earth elements (YREEs) are studied in groundwater in the shallow regolith aquifer and the fracture networks of the upper 1.2 km of Paleoproterozoic granitoids in boreal Europe (Laxemar and Forsmark areas, Sweden). The study includes groundwater sampled via a total of 34 shallow boreholes reaching the bottom of the regolith aquifer, and 72 deep boreholes with equipment designed for retrieval of representative groundwater at controlled depths in the fractured bedrock. The groundwater composition differs substantially between regolith and fracture groundwater and between areas, which affects the dissolved YREE features, including concentrations and NASC normalized patterns. In the fresh groundwater in the regolith aquifers, highest YREE concentrations occur (10th and 90th percentile; Laxemar: 4.4-82 mu g L-1; Forsmark: 1.9-19 mu g L-1), especially in the slightly acidic groundwater (pH: 6.3-7.2 - Laxemar), where the normalized YREE patterns are slightly enriched in light REEs (La-NASC/Y-NASC: 1.1-2.4). In the recharge areas, where redox potentials of the regolith groundwater is more moderate, negative Ce anomaly (Laxemar: 0.37-0.45; Forsmark: 0.15-0.92) and positive Y anomaly (mainly in Forsmark: 1.0-1.7) are systematically more pronounced than in discharge areas. The significant correlations between the YREE features and dissolved organic carbon, minor elements, and somewhat pH suggest a strong control of humic substances (HSs) together with Al rich colloids and redox sensitive Fe-Mn hydrous precipitates on the dissolved YREE pools. In the bedrock fractures, the groundwater is circumneutral to slightly basic and displays YREE concentrations that are at least one order of magnitude lower than the regolith groundwater, and commonly below detection limit in the deep brackish and saline groundwater, with some exceptions such as La and Y. At intermediate depth (>50 m), where groundwater of meteoric origin percolates, the La-NASC/Y-NASC values moderately to substantially decrease (Laxemar: 0.24-2.65; Forsmark: 0.02-0.06) and Y and Ce anomalies are negligible as compared to the regolith groundwater. Aqueous speciation modeling predicts substantial binding of dissolved Y and La, respectively, to HSs. This, in turn, suggests that the features of the YREE pool in the meteoric fracture groundwater are dominantly controlled by the capacity of fracture minerals to sorb HS ligands inherited from the overlying terrestrial regolith. In the deep bedrock fractures (>100/200 m), the YREE features vary substantially with the groundwater paleo-origin. In Laxemar, where groundwater with pronounced glacial origin percolates, the YREE concentrations decrease with increasing mixing fraction of glacial melt water. There, the dissolved YREEs are mostly bound to HSs, and inherited their fractionation features (La-NASC/Y-NASC: 0.15-2.1) from water-rock interaction in the intermediate bedrock fractures. In Forsmark, the YREE and heavy REE enrichment (La-NASC/Y-NASC: 0.007-0.23) are more systematic in the groundwater with pronounced marine origin, due to water-mineral interactions in the sea sediment and in the fractures while infiltrating and percolating. YREE features significantly change in the deep saline groundwater with a long residence time, which displays La-NASC/Y-NASC similar to those of the local bedrock. The findings of this study are relevant in terms of safety assessment for nuclear waste disposal in crystalline rock carrying groundwater influenced by various paleo-climatic recharges. (C) 2014 Elsevier Ltd. All rights reserved.
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| 9. |
- Tillberg, Mikael, et al.
(författare)
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Fractionation of Rare Earth Elements in Greisen and Hydrothermal Veins Related to A-Type Magmatism
- 2019
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Ingår i: Geofluids. - : Hindawi Limited. - 1468-8115 .- 1468-8123. ; 2019
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Tidskriftsartikel (refereegranskat)abstract
- This study focuses on concentrations and fractionation of rare earth elements (REE) in a variety of minerals and bulk materials of hydrothermal greisen and vein mineralization in Paleoproterozoic monzodiorite to granodiorite related to the intrusion of Mesoproterozoic alkali- and fluorine-rich granite. The greisen consists of coarse-grained quartz, muscovite, and fluorite, whereas the veins mainly contain quartz, calcite, epidote, chlorite, and fluorite in order of abundance. A temporal and thus genetic link between the granite and the greisen/veins is established via high spatial resolution in situ Rb-Sr dating, supported by several other isotopic signatures (delta S-34, Sr-87/Sr-86, delta O-18, and delta C-13). Fluid-inclusion microthermometry reveals that multiple pulses of moderately to highly saline aqueous to carbonic solutions caused greisenization and vein formation at temperatures above 200-250 degrees C and up to 430 degrees C at the early hydrothermal stage in the veins. Low calculated Sigma REE concentration for bulk vein (15ppm) compared to greisen (75ppm), country rocks (173-224ppm), and the intruding granite (320ppm) points to overall low REE levels in the hydrothermal fluids emanating from the granite. This is explained by efficient REE retention in the granite via incorporation in accessory phosphates, zircon, and fluorite and unfavorable conditions for REE partitioning in fluids at the magmatic and early hydrothermal stages. A noteworthy feature is substantial heavy REE (HREE) enrichment of calcite in the vein system, in contrast to the relatively flat patterns of greisen calcite. The REE fractionation of the vein calcite is explained mainly by fractional crystallization, where the initially precipitated epidote in the veins preferentially incorporates most of the light REE (LREE) pool, leaving a residual fluid enriched in the HREE from which calcite precipitated. Fluorite occurs throughout the system and displays decreasing REE concentrations from granite towards greisen and veins and different fractionation patterns among all these three materials. Taken together, these features confirm efficient REE retention in the early stages of the system and minor control of the REE uptake by mineral-specific partitioning. REE-fractionation patterns and fluid-inclusion data suggest that chloride complexation dominated REE transport during greisenization, whereas carbonate complexation contributed to the HREE enrichment in vein calcite.
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| 10. |
- Uddh Söderberg, Terese, 1976-, et al.
(författare)
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Challenges in geochemical modelling of metal(loid) solubility and binding mechanisms along a soil profile at a multi-contaminated site
- 2024
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Ingår i: Applied Geochemistry. - : Elsevier. - 0883-2927 .- 1872-9134. ; 170
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Tidskriftsartikel (refereegranskat)abstract
- 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 meters 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.
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