Solid Phase Partitioning Research Articles

Persistent thallium enrichment and its high ecological risks developed from historical carbonaceous Hg-Tl mining waste

Thallium (Tl) is a priority pollutant with high biotoxicity and has been of great concern worldwide in recent years. The former Lanmuchang Hg-Tl mining site in southwest China is a hotspot of multiple metal(loid)s pollution that previously caused large-scale chronic Tl poisoning, mainly resulting from carbonaceous Tl-bearing mining waste. However, arable land destroyed by historical mining wastes persists at high ecological risks decades after reclamation, but little is known about the solid phase partitioning and species of Tl during soil formation of underlying mining wastes as potential Tl sources. In this study, a representative reclaimed soil profile (100 cm depth) was selected in the lowlands to explore the geochemical cycling and environmental fate of Tl in mining waste-derived subsoil. The Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) analysis revealed an unexpected enrichment of Mn (2920–7250 mg/kg) and Tl (205–769 mg/kg) in the mining waste-derived subsoil. Results from BCR sequential extraction, X-ray Photoelectron Spectroscopy (XPS), and Electron Probe Microanalyses (EPMA) indicate that high Tl loading Mn oxide particulates (up to 15,712 ppm Tl) dominate the sequestration of Tl in the subsoil via oxidation-complexation and have a high potential for migration to both topsoil and groundwater. In addition, insights from microbial fossils and Fe-metabolizing bacteria closely related to Tl indicated that Fe (hydr)oxide particulates showing high Tl levels (up to 3865 mg/kg) point to biomineralization. Detailed mineralogical investigations revealed that hematite-siderite syngenetic particulates could serve as a promising mineralogical proxy for redox oscillations under periodic flooding and recorded the frequent groundwater level fluctuations experienced in the probed profile. Despite the potential for long-term preservation of high Tl loading Fe/Mn (hydr)oxides under HCO3-rich groundwater conditions in karst areas, the reductive release of Tl will be inevitable during flooding, implying that underlying carbonaceous mining waste will pose persistent and severe hazards to the ecosystem.

Colloidal and solid phase partitioning between ferrihydrite, humic acid and copper coprecipitates

Our understanding of the interactions between Fe oxides, humic acids (C), and Cu precipitation products in the environment are limited by our ability to measure specific forms and chemical interactions. Here, we examine the effect of solution pH, Fe:C molar ratio from 1:0 to 1:3, and Cu concentration on dissolved and colloidal Cu concentrations after sorption (SOR) or coprecipitation (CPT) reactions. This included specifically measuring the colloidal phases formed using asymmetrical flow field flow fractionation coupled to a total organic carbon analyzer and an inductively coupled plasma mass spectrometer. In the case of 1:0 Fe:C reactions, more Cu was associated with bulk solids and colloidal solids in CPT reaction products, particularly at pH 5 and 6. As C content increased, precipitation reactions led to more Cu retained in the bulk solid phase at lower pH, but more in the dissolved and colloidal phase at higher pH. Of the colloids formed at pH 7, about 10% of the dissolved Cu is present as Fe–C–Cu ternary phases, with the remainder as Cu–C or inorganic Cu phases, yet at pH 6, only Fe–Cu colloids were observed. Applying an additivity approach while using a NICA-Donnan C complexation model combined with a ferrihydrite surface complexation model, the model often predicts higher than observed dissolved Cu in CPT reactions with no C present, but lower than observed dissolved Cu with C present. In applying the model specifically to colloidal phases, much lower concentrations of colloid bound Cu is predicted than observed in the 1:0 Fe:C scenario, but as C content increases, more colloidal Cu is predicted than observed. Given the availability and lability of Cu in environmental systems is assumed to correspond to dissolved Cu, this work notes some differences in the dissolved and colloidal phases formed in different contexts.

Solid-Phase Partitioning and Leaching Behavior of Pb and Zn from Playground Soils in Kabwe, Zambia.

Zambia’s Kabwe mine wastes (KMWs) are responsible for contaminating the surrounding soil and dust in the Kabwe district. Unfortunately, these wastes arise from the historical mining activities of lead (Pb) and Zinc (Zn), which lacked adequate waste management strategies. As a result, potentially toxic elements (PTEs) (Pb and Zn) spread across the Kabwe district. To assess the soil pollution derived from previous mining activities, we studied topsoil samples (n = 8) from the school playground soils (SPs). In this study, the degree of contamination, geochemical partitioning, and leachability, coupled with the release and retention of Pb and Zn, were studied. The SPs were classified as extremely enriched (EF > 40) and contaminated with Pb (Igeo > 5). On average, Pb (up to 89%) and Zn (up to 69%) were bound with exchangeable, weak acid-soluble, reducible and oxidizable phases, which are considered as ’geochemically mobile’ phases in the environment. The leachates from the soils (n = 5) exceeded the Zambian standard (ZS: 190:2010) for Pb in potable drinking water (Pb < 0.01 mg/L). Furthermore, the spatial distribution of Pb and Zn showed a significant reduction in contents of Pb and Zn with the distance from the mine area.

Effects of cement addition on arsenic leaching from soils excavated from projects employing shield-tunneling method

Tunnel construction in soft alluvial deposits is generally done using the shield-tunneling method, a technique that requires the mixing of cementitious materials with excavated soils to reinforce and stabilize the excavated tunnel walls. Although the mechanical properties of soft soils and sediments are improved after introduction of cementitious materials, this process could increase the pH of these geological materials and mobilize naturally occurring arsenic (As). In the present study, the effects of cement addition on As leaching from tunnel-excavated soils naturally contaminated with As were investigated. Sequential extraction experiments were also carried out to determine the chemical forms, solid-phase partitioning and leachability of As in the soils. The results of attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) showed slight changes in the chemical properties of soils due to cement addition but the chemical phases of As remained unchanged. In the absence of cement, sequential extraction showed higher As leaching from the soils when the exchangeable As fraction and total As content increased. In contrast, As leaching increased up to pH 10.3 and then decreased at higher pH values when cement was added. This trend was observed irrespective of the soil samples, which indicates that pH adjustment is an important countermeasure in restricting As leaching from excavated soils.

Rare-Earth Elements as Natural Tracers for In Situ Remediation of Groundwater.

The utility of rare-earth elements (REEs) as natural geochemical tracers for the analysis of groundwater remediation was examined in several example permeable reactive barriers (PRBs). The PRBs utilize zero-valent iron and organic carbon plus limestone mixtures for contaminant treatment. Zero-valent iron removed REEs from groundwater to below detection levels (2-4 ng/L) and subsequent rebound of REE concentrations in regions down-gradient of the treatment zones was not observed. In addition, REE concentrations within and down-gradient of an organic carbon/limestone PRB were significantly reduced to <1% of influent levels. Thus, REEs are sensitive tracers for evaluating the interaction of groundwater with materials placed in the subsurface for contaminant remediation. Analysis of geochemical tracers for understanding in situ remediation becomes important in situations where down-gradient contaminant concentrations fail to decrease within expected timeframes. The field data indicated that increased solid-phase partitioning of REEs occurred with increasing pH and heavy REEs were preferentially removed compared to light REEs in ZVI systems. In the organic carbon PRB, unexpected negative europium anomalies were observed, revealing new information about redox conditions within the treatment zone. REE concentrations and shale-normalized profiles can be used as natural tracers to better understand in situ technologies for groundwater remediation.

Respiratory bioaccessibility and solid phase partitioning of potentially harmful elements in urban environmental matrices

Studies regarding the role of geochemical processes in urban environmental matrices (UEM) and their influence on respiratory bioaccessibility in humans are scarce in humid tropical regions, especially in Brazil. Contaminated UEM are potentially hazardous to humans if particles <10 μm in diameter are inhaled and reach the tracheobronchial region. In this study, we evaluated samples collected in Brazilian UEMs with a large environmental liability left by former mining industries and in a city with strong industrial expansion. UEM samples were classified into soil, sediment and mine tailings according to the characteristics of the collection sites. The respiratory bioaccessibility of potentially harmful elements (PHE) was evaluated using artificial lysosomal fluid (ALF, pH 4.5), and the BCR-sequential extraction was performed to evaluate how the respiratory bioaccessibility of the PHE was related to the solid phase partitioning. The bioaccessible fraction (BAF) ranged from 54 to 98% for Cd; 21–89% for Cu; 46–140% for Pb, 35–88% for Mn and; 41–84% for Zn. The average BAF of the elements decreased in the following order: Soil: Cd > Pb > Mn > Zn > Cu; Tailing: Pb > Cd > Zn > Mn > Cu; and Sediments: Pb > Mn > Cd > Zn > Cu. BCR-fractions were useful to predict the PHE bioaccessibility (R2 = 0.79–0.98), thus suggesting that particle geochemistry and mineralogy can influence PHE behaviour in the pulmonary fluid. Therefore, this approach provides a combination of quantitative and qualitative data, which allows us to carry out a more realistic assessment of the current situation of the potentially contaminated site and possible alternatives for decision making by the stakeholders.

1,6-Dehydropinidine Is an Abundant Compound in Picea abies (Pinaceae) Sprouts and 1,6-Dehydropinidine Fraction Shows Antibacterial Activity against Streptococcus equi Subsp. equi.

Knowledge about the defensive chemistry of coniferous trees has increased in recent years regarding a number of alkaloid compounds; in addition to phenolics and terpenes. Here, we show that Norway spruce (Picea abies (L.) H. Karst.), an important boreal zone tree species; accumulates 1,6-dehydropinidine (2-methyl-6-(2-propenyl)-1,6-piperideine) in its needles and bark. We reanalyzed previously published GC-MS data to obtain a full picture of 1,6-dehydropinidine in P. abies. 1,6-dehydropinidine appeared to especially accumulate in developing spring shoots. We used solid-phase partitioning to collect the alkaloid fraction of the sprouts and thin-layer chromatography to purify 1,6-dehydropinidine. The antibacterial properties of the 1,6-dehydropinidine fraction were tested using a broth microdilution method; with Streptococcus equi subsp. equi as a model organism. Based on our results 1,6-dehydropinidine is common in alkaloid extractions from P. abies (0.4 ± 0.03 mg g−1 dw in mature needles) and it is especially abundant in young spruce shoots (2.7 ± 0.5 mg g−1 dw). Moreover; 1,6-dehydropinidine extracted from P. abies sprouts showed mild antibacterial potential against Streptococcus equi subsp. equi (MIC 55 µg mL−1). The antibacterial activity of a plant compound thought of as an intermediate rather than an end-product of biosynthesis calls for more detailed studies regarding the biological function of these coniferous alkaloids

Solid-phase partitioning and release-retention mechanisms of copper, lead, zinc and arsenic in soils impacted by artisanal and small-scale gold mining (ASGM) activities

Artisanal and small-scale gold mining (ASGM) operations are major contributors to the Philippines’ annual gold (Au) output (at least 60%). Unfortunately, these ASGM activities lacked adequate tailings management strategies, so contamination of the environment is prevalent. In this study, soil contamination with copper (Cu), lead (Pb), zinc (Zn) and arsenic (As) due to ASGM activities in Nabunturan, Davao de Oro, Philippines was investigated. The results showed that ASGM-impacted soils had Cu, Pb, Zn and As up to 3.6, 83, 73 and 68 times higher than background levels, respectively and were classified as ‘extremely’ polluted (CD = 30–228; PLI = 5.5–34.8). Minerals typically found in porphyry copper-gold ores like pyrite, chalcopyrite, malachite, galena, sphalerite and goethite were identified by XRD and SEM-EDS analyses. Furthermore, sequential extraction results indicate substantial Cu (up to 90%), Pb (up to 50%), Zn (up to 65%) and As (up to 48%) partitioned with strongly adsorbed, weak acid soluble, reducible and oxidisable fractions, which are considered as ‘geochemically mobile’ phases in the environment. Although very high Pb and Zn were found in ASGM-impacted soils, they were relatively immobile under oxidising conditions around pH 8.5 because of their retention via adsorption to hydrous ferric oxides (HFOs), montmorillonite and kaolinite. In contrast, Cu and As release from the historic ASGM site samples exceeded the environmental limits for Class A and Class C effluents, which could be attributed to the removal of calcite and dolomite by weathering. The enhanced desorption of As at around pH 8.5 also likely contributed to its release from these soils.

The solid-phase partitioning of arsenic in unconsolidated sediments of the Mekong Delta, Vietnam and its modes of release under various conditions

Arsenic (As) contamination of the groundwater in the Mekong Delta is a serious problem affecting millions of people who rely on this important resource for drinking and agriculture. In this study, borehole cores up to a depth of 40 m were collected in the Vietnamese-side of the delta, and the solid-phase partitioning of As with depth was investigated to understand the factors and processes controlling the release of this toxic element under oxic, acidic and reducing conditions. The results showed that in most of the sediments, substantial amounts of As are partitioned with exchangeable phases that are easily released into solution. Two borehole cores obtained between the Hau and Tien Rivers also had significantly high As partitioned with organic/sulfide phases and one of these cores had abundant As-bearing pyrite in 1-m thick peat layers. Leaching experiments in deionized (DI) water coupled with principal component analysis suggest that As release was controlled by sorption-desorption reactions with clays/phyllosilicates (i.e., kaolinite, muscovite and clinochlore), proton-promoted dissolution of iron-oxyhydroxides, and oxidation of pyrite/organic matter. The mobility of As was further promoted under acidic conditions in the presence of chloride (Cl−), which suggests that seasonal drying/flooding episodes generating acid sulfate soils, as well as salt water intrusion due to excessive groundwater abstraction may exacerbate this problem in the future.

Ideal-Filter Capillary Electrophoresis (IFCE) Facilitates the One-Step Selection of Aptamers.

Selection of aptamers from oligonucleotide libraries currently requires multiple rounds of alternating steps of partitioning of binders from nonbinders and enzymatic amplification of all collected oligonucleotides. Herein, we report a highly practical solution for reliable one-step selection of aptamers. We introduce partitioning by ideal-filter capillary electrophoresis (IFCE) in which binders and nonbinders move in the opposite directions. The efficiency of IFCE-based partitioning reaches 109 , which is ten million times higher than that of typical solid-phase partitioning methods. One step of IFCE-based partitioning is sufficient for the selection of a high-affinity aptamer pool for a protein target. Partitioning by IFCE promises to become an indispensable tool for fast and robust selection of binders from different types of oligonucleotide libraries.

Distribution of Zinc, Copper, and Iron in the Tailings Dam of an Abandoned Mine in Shimokawa, Hokkaido, Japan

This paper addresses the mechanism of acid mine drainage generation in tailings from an abandoned mine site and predicts the evolution of zinc (Zn), copper (Cu), and iron (Fe) concentrations. Batch leaching experiments and sequential extractions were conducted to investigate the leaching behavior of these contaminants from the tailings and to understand their solid-phase partitioning. Acid-base accounting and principal component analysis (PCA) were used to confirm factors affecting Zn, Cu, and Fe leaching and acid formation based on the leaching experiments. There were strong positive correlations between Zn, Fe, or EC and SO42−, indicating that pyrite and sphalerite are the major minerals releasing Zn and Fe. This aligns with the PCA results. In the upper part of the tailings, the water-soluble and sulfide fractions of Zn, Cu, and Fe were almost flushed out, whereas they remained high in the deeper tailings. This implies that the tailings will likely continue to release these contaminants (Zn > Cu > Fe) for a long time unless remedial measures are taken.

Quality and quantity of piperidine alkaloids in needles and bark of Scots pine (Pinus sylvestris) seedlings

The Northern boreal forest zone is dominated by two coniferous species that synthesize piperidine alkaloids: Scots pine (Pinus sylvestris) and Norway spruce (Picea abies). These compounds are known to have antifeedant properties. We have earlier shown that Norway spruce has a diverse alkaloid chemistry, but reports from P. sylvestris are few, and no quantitative analysis has been conducted so far. Here we have studied 2-year-old seedlings of P. sylvestris to reveal possible differences in alkaloid chemistry compared to P. abies. Alkaloids were extracted from bark and mature needles by solid-phase partitioning and analysed by GC–MS. We detected only four individual compounds from P. sylvestris samples, confirming earlier assumptions that the species lacks large parts of the biosynthesis pathway of coniferous alkaloids. Euphococcinine, also present in mature P. abies needles, is the sole end-product of alkaloid biosynthesis in P. sylvestris, although a compound tentatively identified as an isomer of euphococcinine was also detected. The two other alkaloid compounds detected are also encountered in P. abies, but only in juvenile plant parts, such as developing needles and stems. Concentrations of all alkaloids were extremely low, with totals amounting to about 25% of the amount found in P. abies. It is also notable that concentrations in three out of ten seedlings were under the detection limit, in bark or in both plant parts, whereas in P. abies individuals lacking alkaloids are virtually non-existent. The compound composition, concentrations and absence of alkaloids in some individuals emphasize the difference between these two major boreal zone species, and this calls for further studies on the ecological significance of these compounds.

Solid-phase partitioning of mercury in artisanal gold mine tailings from selected key areas in Mindanao, Philippines, and its implications for mercury detoxification.

The solid-phase partitioning of mercury could provide necessary data in the identification of remediation techniques in contaminated artisanal gold mine tailings. This study was conducted to determine the total mercury content of mine wastes and identify its solid-phase partitioning through selective sequential extraction coupled with cold vapour atomic absorption spectroscopy. Samples from mine tailings and the carbon-in-pulp (CIP) process were obtained from selected key areas in Mindanao, Philippines. The results showed that mercury use is still prevalent among small-scale gold miners in the Philippines. Tailings after ball mill-gravity concentration (W-BM and Li-BM samples) from Mt Diwata and Libona contained high levels of mercury amounting to 25.024 and 6.5 mg kg-1, respectively. The most prevalent form of mercury in the mine tailings was elemental/amalgamated mercury, followed by water soluble, exchangeable, organic and strongly bound phases, respectively. In contrast, mercury content of carbon-in-pulp residues were significantly lower at only 0.3 and 0.06 mg kg-1 for P-CIP (Del Pilar) and W-CIP (Mt Diwata), respectively. The bulk of mercury in P-CIP samples was partitioned in residual fraction while in W-CIP samples, water soluble mercury predominated. Overall, this study has several important implications with regards to mercury detoxification of contaminated mine tailings from Mindanao, Philippines.

Linkage between solid-phase apportionment and bioaccessible arsenic, chromium and lead in soil from Glasgow, Scotland, UK

ABSTRACTThe chemical composition of soil from the Glasgow (UK) urban area was used to identify the controls on the availability of potentially harmful elements (PHEs) in soil to humans. Total and bioaccessible concentrations of arsenic (As), chromium (Cr) and lead (Pb) in 27 soil samples, collected from different land uses, were coupled to information on their solid-phase partitioning derived from sequential extraction data. The total element concentrations in the soils were in the range &lt;0.1–135mgkg–1 for As; 65–3680mgkg–1 for Cr and 126–2160mgkg–1 for Pb, with bioaccessible concentrations averaging 27, 5 and 27% of the total values, respectively. Land use does not appear to be a predictor of contamination; however, the history of the contamination is critically important. The Chemometric Identification of Substrates and Element Distribution (CISED) sequential chemical extraction and associated self-modelling mixture resolution analysis identified three sample groupings and 16 geochemically distinct phases (substrates). These were related to iron (n=3), aluminium–silicon (Al–Si; n=2), calcium (n=3), phosphorus (n=1), magnesium (Mg; n=3), manganese (n=1) and easily extractable (n=3), which was predominantly made up of sodium and sulphur. As, Cr and Pb were respectively found in 9, 10 and 12 of the identified phases, with bioaccessible As predominantly associated with easily extractable phases, bioaccessible Cr with the Mg-dominated phases and bioaccessible Pb with both the Mg-dominated and Al–Si phases. Using a combination of the Unified Barge Method to measure the bioaccessibility of PHEs and CISED to identify the geochemical sources has allowed a much better understanding of the complexity of PHE mobility in the Glasgow urban environment. This approach can be applied to other urban environments and cases of soil contamination, and made part of land-use planning.

PCDD/F and dioxin-like PCB minimization: A 13-year experimental study along the flue gas cleaning system of a secondary aluminium refining plant

A 13-years study shows that a careful design of the flue gas cleaning system of a full scale secondary aluminium refining plant results in a minimized and very stable emission of Polychlorinated Dibenzo–p–Dioxins (PCDD), Polychlorinated Dibenzo Furans (PCDF) and dioxin-like Polychlorinated Biphenyls (PCB). The value of equivalent toxicity of PCDD/F in the emission was definitely of an order of magnitude less than the regulation limit.In the initial flue gas cleaning system, the PCB mean fingerprint after the slow cooling of the flue gas was typical of de novo synthesis. Instead, in the presence of quenching, there was evidence that the fast cooling of flue gas prevented the PCB de novo synthesis. In fact, the PCB profile was similar to that in the air collected from the aspiration hoods for the quenching. The gas-phase and solid-phase partitioning of PCBs, before and after the fabric filters, highlights the predominant role of the vapor phase with respect to the total removal efficiency. The polycyclic aromatic hydrocarbons breakdown could be an additional de novo formation pathway even in industrial plants.

Iron behavior in a northern estuary: Large pools of non-sulfidized Fe(II) associated with organic matter

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 organic matter 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 137Cs and aquatic plant 14C determinations, revealed a high average rate of sedimentation (5cm·yr−1) for the upper mud unit (0–182.5cm, 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 1M HCl) 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.

Distribution and partitioning of major and trace elements in pyrite-bearing sediments of a Mediterranean coastal lagoon

The formation of iron sulphide minerals exerts significant control on the behaviour of trace elements in sediments. In this study, three short sediment cores, retrieved from the remote Antinioti lagoon (N. Kerkyra Island, NW Greece), are investigated concerning the solid phase composition, distribution, and partitioning of major (Al, Fe) and trace elements (Cd, Cu, Mn, Pb, and Zn). According to 210Pb, the sediments sampled correspond to depositions of the last 120 years. The high amounts of organic carbon (4.1–27.5%) result in the formation of Fe sulphides, predominantly pyrite, already at the surface sediment layers. Pyrite morphologies include monocrystals, polyframboids, and complex FeS–FeS2 aggregates. According to synchrotron-generated micro X-ray fluorescence and X-ray absorption near-edge structure spectra, authigenically formed, Mn-containing, Fe(III) oxyhydroxides (goethite type) co-exist with pyrite in the sediments studied. Microscopic techniques evidence the formation of galena, sphalerite and CuS, whereas sequential extractions show that carbonates are important hosts for Mn, Cd, and Zn. However, significant percentages of non-lattice held elements are bound to Fe/Mn oxyhydroxides that resist reductive dissolution (on average 60% of Pb, 46% of Cd, 43% of Zn and 9% of Cu). The partitioning pattern changes drastically in the deeper part of the core that is influenced by freshwater inputs. In these sediments, the post-depositional pyritization mechanism, illustrated by overgrowths of Fe monosulphides on pre-existing pyrite grains, results in relatively high degree of pyritization that reaches 49% for Cd, 66% for Cu, 32% for Zn and 7% for Pb.

Temporal variations of accumulated cesium in natural soils after an uncharacteristic external exposure

The accumulation behaviors and solid phase partitioning patterns of stable cesium, which have been recognized as an indicator of the long-term movement of radioactive cesium (137Cs or 134Cs) in ecosystems, were studied in typical and natural soils of Japanese origin, namely, red clay, leaf-mold and andosol soils. The retention and migration of soil-phase cesium have been explained relative to various factors, such as soil organic matter contents, competitive cation concentrations and the adsorption ratio of Cs to the solid phase. Cesium was adsorbed nearly quantitatively in the leaf-mold type soil, and the rate of Cs absorption increased as the particle size decreased in the red clay and andosol soils. The distributions of Cs within the soil solid phases were defined using the selective sequential extraction scheme and were used to explain its relative incorporation in the soil fractions. Solid phase fractionation indicated that nearly half of the total cesium concentrations in the soils were in the ‘residual’ fraction (representing the metal that was incorporated within the crystalline lattice of the soil and was difficult to extract). These findings are expected to provide information regarding suitable conditions for remediation, immobilization or the recovery of cesium from contaminated soils with excess cesium concentrations.

Sulfate Availability Drives Divergent Evolution of Arsenic Speciation during Microbially Mediated Reductive Transformation of Schwertmannite

The effect of SO4(2-) availability on the microbially mediated reductive transformation of As(V)-coprecipitated schwertmannite (Fe8O8(OH)3.2(SO4)2.4(AsO4)0.004) was examined in long-term (up to 400 days) incubation experiments. Iron EXAFS spectroscopy showed siderite (FeCO3) and mackinawite (FeS) were the dominant secondary Fe(II) minerals produced via reductive schwertmannite transformation. In addition, ∼ 25% to ∼ 65% of the initial schwertmannite was also transformed relatively rapidly to goethite (αFeOOH), with the extent of this transformation being dependent on SO4(2-) concentrations. More specifically, the presence of high SO4(2-) concentrations acted to stabilize schwertmannite, retarding its transformation to goethite and allowing its partial persistence over the 400 day experiment duration. Elevated SO4(2-) also decreased the extent of dissimilatory reduction of Fe(III) and As(V), instead favoring dissimilatory SO4(2-) reduction. In contrast, where SO4(2-) was less available, there was near-complete reduction of schwertmannite- and goethite-derived Fe(III) as well as solid-phase As(V). As a result, under low SO4(2-) conditions, almost no Fe(III) or As(V) remained toward the end of the experiment and arsenic solid-phase partitioning was controlled mainly by sorptive interactions between As(III) and mackinawite. These As(III)-mackinawite interactions led to the formation of an orpiment (As2S3)-like species. Interestingly, this orpiment-like arsenic species did not form under SO4(2-)-rich conditions, despite the prevalence of dissimilatory SO4(2-) reduction. The absence of an arsenic sulfide species under SO4(2-)-rich conditions appears to have been a consequence of schwertmannite persistence, combined with the preferential retention of arsenic oxyanions by schwertmannite. The results highlight the critical role that SO4(2-) availability can play in controlling solid-phase arsenic speciation, particularly arsenic-sulfur interactions, under reducing conditions in soils, sediments, and shallow groundwater systems.

Metal contamination and solid phase partitioning of metals in the stream and bottom sediments in a reservoir receiving mine drainage

This study was conducted to assess the anthropogenic impact on metal concentrations in the bottom sediments of the Juam reservoir, Korea, and in stream sediments in its catchment, and to estimate the potential mobility of selected metals (Fe, Mn, Cu, Ni, Pb and Zn) using sequential extraction. A comparison of the metal concentrations in the stream sediments with mean background values in sediments collected from first- or second-order creeks shows that Pb, Cu and Ni are the most affected by anthropogenic inputs. The 206Pb/207Pb ratios of the bottom and core sediments (means: 1.2320±0.0502 and 1.2212±0.0040, respectively) suggest that Pb contamination is mainly due to the waste discharge of abandoned coal and metal mines rather than industrial and airborne sources. Considering the proportion of metals bound to the exchangeable, carbonate and reducible fractions, the comparative mobility of metals is suggested to decrease in the order Mn>Pb>Zn>Ni>Fe≫Cu.