Influence of elevated temperature on the species and mobility of chromium in ferrous sulfate-amended contaminated soil.

Ferrous sulfate (FeSO4) combined with acid pretreatment is usually employed to remediate contaminated soils containing Cr(VI). However, the long-term efficiency of this stabilization method is important for its sustainability. In this study, a gradient temperature-elevating exposure test was employed to investigate the stability of Cr in FeSO4-remediated soil when exposed to elevated temperatures (40 °C, 120 °C, and 500 °C), possibly caused by hot weather and/or wildfires. The results of chemical extraction and X-ray absorption near edge structure spectroscopy (XANES) showed that the Cr(VI) in contaminated soil was successfully transformed to Cr(III) after stabilization, resulting in the dramatic decrease of water-leachable Cr(VI). The stabilization efficiency was further improved under 40 °C treatment after 30 days. Subsequently, the 120 °C treatment (7 days) had relatively little effect on the Cr speciation and mobility in soils. However, even one day of 500 °C calcination resulted in the deterioration of stabilization efficiency, and the water-leachable Cr(VI) re-increased and became higher than the Chinese environmental standards (total Cr 15 mg/L, Cr(VI) 5 mg/L) for the classification of hazardous solid wastes. XANES results reflected that heating at 500 °C facilitate the formation of Cr2O3, which was mainly caused by thermal decomposition and dehydration of Cr(OH)3 in the soil. Besides, the transformation of Cr species resulted in the enhanced association of Cr with the most stable residual fraction (88.3%-91.6%) in soil. Based on chemical extraction results, it was suggested that the oxidation of Cr(III) to Cr(VI) contributed to the re-increased mobility of Cr(VI) in soil. However, the XANES results showed that almost no significant re-oxidization of Cr(III) to Cr(VI) happened after heating at 500 °C, which was probably caused by XANES linear combination fits (LCF) uncertainties. Moreover, the changes in soil properties, including a rise in pH to a slightly alkaline range and/or the decomposition of organic matter, possibly contributed to the enhanced mobility of Cr(VI) in soil. This study contributes to clarifying the mobility and transformation of Cr in contaminated soils and provides a support for the sustainable management of remediated soils.

Resource recovery and regeneration strategies for spent lithium-ion batteries: Toward sustainable high-value cathode materials.

Traditional cathode recycling methods have become outdated amid growing concerns for high-value output and environmental friendliness in spent Li-ion battery (LIB) recycling. Our study presents a closed-loop approach that involves selective sulfurization roasting, water leaching, and regeneration, efficiently transforming spent ternary Li batteries (i.e., NCM) into high-performance cathode materials. By combining experimental investigations with density functional theory (DFT) calculations, we elucidate the mechanisms within the NCM-C-S roasting system, providing a theoretical foundation for selective sulfidation. Utilizing in situ X-ray diffraction techniques and a series of consecutive experiments, the study meticulously tracks the evolution of regenerating cathode materials that use transition metal sulfides as their primary raw materials. The Li-rich regenerated NCM exhibits exceptional electrochemical performance, including long-term cycling, high-rate capabilities, reversibility, and stability. The closed-loop approach highlights the sustainability and environmental friendliness of this recycling process, with potential applications in other cathode materials, such as LiCoO2 and LiMn2O4. Compared with traditional methods, this short process approach avoids the complexity of leaching, solvent extraction, and reverse extraction, significantly increasing metal utilization and Li recovery rates while reducing pollution and resource waste.

Extraction of Se(iv) and Se(vi) from aqueous HCl solution by using a diamide-containing tertiary amine.

Here, we investigated the mechanism underlying the extraction of Se(iv) and Se(vi) from aqueous HCl solutions by N-2-ethylhexyl-bis(N-di-2-ethylhexyl-ethylamide)amine (EHBAA). In addition to examining extraction behavior, we also elucidated structural properties of the dominant Se species in solution. Two types of aqueous HCl solutions were prepared by dissolving a SeIV oxide or a SeVI salt. X-ray absorption near edge structure analyses revealed that Se(vi) was reduced to Se(iv) in 8 M HCl. Using 0.5 M EHBAA, ∼50% of Se(vi) was extracted from 0.5 M HCl. In contrast, Se(iv) was hardly extracted from 0.5 to 5 M HCl; however, at molar concentrations above 5 M, the extraction efficiency of Se(iv) increased drastically, reaching ∼85%. Slope analyses for the distribution ratios of Se(iv) in 8 M HCl and Se(vi) in 0.5 M HCl showed that apparent stoichiometries of Se(iv) or Se(vi) to EHBAA were 1 : 1 and 1 : 2, respectively. Extended X-ray absorption fine structure measurements revealed that the inner-sphere of the Se(iv) and Se(vi) complexes extracted with EHBAA was [SeOCl2] and [SeO4]2-, respectively. Together, these results indicate that Se(iv) is extracted from 8 M HCl with EHBAA via a solvation-type reaction, whereas Se(vi) is extracted from 0.5 M HCl via an anion-exchange-type reaction.

Chemical speciation changes of an all-solid-state lithium-ion battery caused by roasting determined by sequential acid leaching.

All-solid-state lithium-ion batteries (ASS-LIBs) are expected to replace current liquid-based LIBs in the near future owing to their high energy density and improved safety. It would be preferable if ASS-LIBs could be recycled by the current recycling processes used for liquid-based LIBs, but this possibility remains to be determined. Here, we subjected an ASS-LIB test cell containing an argyrodite-type solid electrolyte (Li6PS5Cl) and nickel-manganese-cobalt-type active material (Li(Ni0.5Mn0.3Co0.2)O2) to roasting, a treatment process commonly used for recycling of the valuable metals from liquid-based LIBs, and investigated the changes in chemical speciation. Roasting was performed at various temperatures (350-900 °C), for various times (60-360 min), and under various oxygen fugacity (air or O2) conditions. The chemical speciation of each metal element after roasting was determined by sequential elemental leaching tests and X-ray diffraction analysis. Li formed sulfates or phosphates over a wide temperature range. Ni and Co followed very complicated reaction paths owing to coexistence of S, P, and C, and they formed sulfides, phosphates, and complex oxides. The optimum conditions for minimizing formation of insoluble compounds, such as complex oxides, were a roasting temperature of 450-500 °C and a roasting time of 120 min. The results indicated that although ASS-LIBs can be treated by the same roasting processes as those used for current liquid-based LIBs, the optimal roasting conditions have narrow ranges. Thus, careful process control will be needed to achieve high extraction percentages of the valuable metals from ASS-LIBs.

Waste-Based Ceramsite for the Efficient Removal of Ciprofloxacin in Aqueous Solutions.

Ciprofloxacin (CIP), a compound with bioaccumulation toxicity and antibiotic resistance, is frequently detected in water at alarming concentrations, which is becoming an increasing concern. In this study, a low-cost ceramsite was developed from industrial solid wastes through sintering to remove CIP from wastewater. The effects of adsorbent dosage, initial pH, contact time, initial CIP concentration, and temperature were explored. More than 99% of CIP (20-60 mg/L) was removed at around pH 2-4 by the ceramsite. The kinetic data fitted well with the pseudo-second-order model, revealing that chemisorption was the main rate-determining step. The isotherm data was better described by the Freundlich model, suggesting that CIP was removed by the formation of multiple layers on the heterogeneous surface. Moreover, the removal efficiency was practically higher than 95% during five regeneration cycles, when different regeneration methods were used, including calcination, HCl, and NaOH washing, indicating that the ceramsite exhibited outstanding reusability in removing CIP. The primary mechanism of CIP removal by the ceramsite was found to be the synergism of adsorption and flocculation, both of which depended on the release of Ca2+ from the ceramsite. In addition, strong Ca-CIP complexes could be formed through surface complexation and metal cation bridging between Ca2+ and different functional groups in CIP.

Chemokine expression in human 3-dimensional cultured epidermis exposed to PM2.5 collected by cyclonic separation.

Fine particulate matter (PM2.5) exposure has a risk of inducing several health problems, especially in the respiratory tract. The skin is the largest organ of the human body and is therefore the primary target of PM2.5. In this study, we examined the effects of PM2.5 on the skin using a human 3-dimensional cultured epidermis model. PM2.5 was collected by cyclonic separation in Yokohama, Japan. Global analysis of 34 proteins released from the epidermis revealed that the chemokines, chemokine C-X-C motif ligand 1 (CXCL1) and interleukin 8 (IL-8), were significantly increased in response to PM2.5 exposure. These chemokines stimulated neutrophil chemotaxis in a C-X-C motif chemokine receptor 2-dependent manner. The oxidative stress and signal transducer and activator of transcription 3 pathways may be involved in the increased expression of CXCL1 and IL-8 in the human epidermis model. Interestingly, in the HaCaT human keratinocyte cell line, PM2.5 did not affect chemokine expression but did induce IL-6 expression, suggesting a different effect of PM2.5 between the epidermis model and HaCaT cells. Overall, PM2.5 could induce the epidermis to release chemokines, followed by neutrophil activation, which might cause an unregulated inflammatory reaction in the skin.

Geochemical Modeling of Heavy Metal Removal from Acid Mine Drainage in an Ethanol-Supplemented Sulfate-Reducing Column Test.

A passive treatment process using sulfate-reducing bacteria (SRB) is known to be effective in removing heavy metals from acid mine drainage (AMD), though there has been little discussion of the mechanism involved to date. In this work, a sulfate-reducing column test was carried out using supplementary ethanol as an electron donor for microorganisms, and the reaction mechanism was examined using geochemical modeling and X-ray absorption fine structure (XAFS) analysis. The results showed that Cu was readily removed from the AMD on the top surface of the column (0-0.2 m), while Zn and Cd depletion was initiated in the middle of the column (0.2-0.4 m), where sulfide formation by SRB became noticeable. Calculations by a developed geochemical model suggested that ethanol decomposition by aerobic microbes contributed to the reduction of Cu, while sulfide produced by SRB was the major cause of Zn and Cd removal. XAFS analysis of column residue detected ZnS, ZnSO4 (ZnS oxidized by atmospheric exposure during the drying process), and CuCO3, thus confirming the validity of the developed geochemical model. Based on these results, the application of the constructed geochemical model to AMD treatment with SRB could be a useful approach in predicting the behavior of heavy metal removal.

Highly Efficient Cd2+ Removal Using Tobermorite with pH Self-Adjustment Ability from Aqueous Solution.

Cadmium (Cd), as a type of heavy metal, can increase the incidence of many diseases, even in low concentrations. In this study, tobermorite was hydrothermally synthesized and then applied to adsorb Cd2+ from an aqueous solution. The physicochemical characteristics of the synthesized tobermorite were detected, and the results indicated that the well-crystallized tobermorite had a lot of mesopores and a large specific surface area of 140.92 m2/g. It acquired a pH self-adjustment ability via spontaneously releasing Ca2+ and OH- into the aqueous solution. The effects of different factors on Cd2+ removal were investigated. For Cd2+, the removal efficiency could reach 99.71% and the maximum adsorption capacity was 39.18 mg/g using tobermorite. The adsorption data was best fitted with the pseudo-second-order kinetic and Langmuir isotherm models. In addition, there was no strict limit on the solution pH in Cd2+ adsorption because the tobermorite could adjust the solution pH to an alkaline atmosphere spontaneously. The efficient removal of Cd2+ using tobermorite was a result of surface complexation and ion exchange.

Coprecipitation mechanisms of Zn by birnessite formation and its mineralogy under neutral pH conditions.

Birnessite (δ-Mn(IV)O2) is a great manganese (Mn) adsorbent for dissolved divalent metals. In this study, we investigated the coprecipitation mechanism of δ-MnO2 in the presence of Zn(II) and an oxidizing agent (sodium hypochlorite) under two neutral pH values (6.0 and 7.5). The mineralogical characteristics and Zn-Mn mixed products were compared with simple surface complexation by adsorption modeling and structural analysis. Batch coprecipitation experiments at different Zn/Mn molar ratios showed a Langmuir-type isotherm at pH 6.0, which was similar to the result of adsorption experiments at pH 6.0 and 7.5. X-ray diffraction and X-ray absorption fine structure analysis revealed triple-corner-sharing inner-sphere complexation on the vacant sites was the dominant Zn sorption mechanism on δ-MnO2 under these experimental conditions. A coprecipitation experiment at pH 6.0 produced some hetaerolite (ZnMn(III)2O4) and manganite (γ-Mn(III)OOH), but only at low Zn/Mn molar ratios (< 1). These secondary precipitates disappeared because of crystal dissolution at higher Zn/Mn molar ratios because they were thermodynamically unstable. Woodruffite (ZnMn(IV)3O7•2H2O) was produced in the coprecipitation experiment at pH 7.5 with a high Zn/Mn molar ratio of 5. This resulted in a Brunauer-Emmett-Teller (BET)-type sorption isotherm, in which formation was explained by transformation of the crystalline structure of δ-MnO2 to a tunnel structure. Our experiments demonstrate that abiotic coprecipitation reactions can induce Zn-Mn compound formation on the δ-MnO2 surface, and that the pH is an important controlling factor for the crystalline structures and thermodynamic stabilities.

Involvement of polycyclic aromatic hydrocarbons and endotoxin in macrophage expression of interleukin-33 induced by exposure to particulate matter.

Air pollutants are important factors that contribute to the development and/or exacerbation of allergic inflammation accompanied by asthma, but experimental evidence still needs to be collected. Interleukin 33 (IL-33) is closely involved in the onset and progression of asthma. In this study, we examined the effects of particulate matter (PM) on IL-33 expression in macrophages. PM2.5 collected in Yokohama, Japan by the cyclone device significantly induced IL-33 expression in human THP-1 macrophages, and the induction was clearly suppressed by pretreatment with the aryl hydrocarbon receptor (AhR) antagonist CH-223191 or the Toll-like receptor 4 (TLR4) antagonist TAK-242. PM2.5-induced IL-33 expression was significantly attenuated in AhR-knockout or TLR4-mutated macrophages, suggesting an important role of polycyclic aromatic hydrocarbons (PAHs) and endotoxin in IL-33 stimulation. PM samples derived from tunnel dust slightly but significantly induced IL-33 expression, while road dust PM did not affect IL-33 expression. The PAH concentration in tunnel dust was higher than that in road dust. Tunnel dust or road dust PM contained less endotoxin than PM2.5 collected in Yokohama. These data suggest that the potency of IL-33 induction could depend on the concentration of PAHs as well as endotoxin in PMs. Caution regarding PAHs and endotoxin levels in air pollutants should be taken to prevent IL-33-induced allergic inflammation.

Separation of cathode particles and aluminum current foil in lithium-ion battery by high-voltage pulsed discharge Part II: Prospective life cycle assessment based on experimental data.

This series of papers addresses the recycling of cathode particles and aluminum (Al) foil from positive electrode sheet (PE sheet) dismantled from spent lithium-ion batteries (LIBs) by applying a high-voltage pulsed discharge. As concluded in Part I of the series (Tokoro et al., 2021), cathode particles and Al foil were separated in water based on a single pulsed power application. This separation of LIB components by pulsed discharge was examined by means of prospective life cycle assessment and is expected to have applications in LIB reuse and recycling. The indicators selected were life cycle greenhouse gas (LC-GHG) emissions and life cycle resource consumption potential (LC-RCP). We first completed supplementary experiments to collect redundant data under several scale-up circumstances, and then attempted to quantify the uncertainties from scaling up and progress made in battery technology. When the batch scale of pulsed discharge separation is sufficiently large, the recovery of cathode particles and Al foil from PE sheet by pulsed discharge can reduce both LC-GHG and LC-RCP, in contrast to conventional recycling with roasting processes. Due to technology developments in LIB cathodes, the reuse of positive electrode active materials (PEAM) does not always have lower environmental impacts than the recycling of the raw materials of PEAM in the manufacturing of new LIB cathodes. This study achieved a proof of concept for resource consumption reduction induced by cathode utilization, considering LC-GHG and LC-RCP, by applying high-voltage pulsed discharge separation.

Separation of cathode particles and aluminum current foil in Lithium-Ion battery by high-voltage pulsed discharge Part I: Experimental investigation.

To enable effective reuse and recycling processes of spent lithium-ion batteries (LiBs), here we develop a novel electrical method based on a high-voltage pulsed discharge to separate cathode particles and aluminum (Al) foil. A cathode particle sample was mechanically separated from a LiB, cut into 30-mm × 80-mm test pieces, and subjected to a high-voltage electrical pulse discharge from either end in water. At a voltage of 25 kV, 93.9% of the cathode particles separated from the Al foil. These particles were easily recovered by sieving at 2.36 mm because the Al foil retained its shape. Some Al contaminated the particles owing to generation of hot plasma and subsequent shock waves; however, the Al concentration in the recovered cathode particles was limited to 2.95%, which is low enough to allow for further cobalt and nickel recovery by hydrometallurgical processing. The results of heat balance calculations obtained from the current waveforms suggested that polyvinylidene fluoride, the main component of the adhesive in the cathode particle layers, melted and lost its adhesion through Joule heating of the Al foil at the maximum current of 19.0 kA at 25 kV. Almost 99% of the recovered cathode particles maintained their chemical composition and form after separation, and therefore could potentially be directly reused in LiBs.

Understanding the biogeochemical mechanisms of metal removal from acid mine drainage with a subsurface limestone bed at the Motokura Mine, Japan.

Subsurface limestone beds (SLBs) are used as a passive treatment technique to remove toxic metals from acid mine drainage (AMD). In this study, we investigated the mechanisms and thermodynamics of metal (manganese, copper, zinc, cadmium, and lead) precipitation in the SLB installed at the Motokura Mine. Field surveys in 2017 and 2018 showed that the pH of the SLB influent (initially 5-6) increased to approximately 8 in the drain between 24 and 45 m from the inlet. This increase was caused by limestone dissolution and resulted in the precipitation of hydroxides and/or carbonates of copper, zinc, and lead, as expected from theoretical calculations. Manganese and cadmium were removed within a pH range of approximately 7-8, which was lower than the pH at which they normally precipitate as hydroxides (pH 9-10). X-ray absorption near-edge structure analysis of the sediment indicated that δ-MnO2, which has a high cation-exchange capacity, was the predominant tetravalent manganese compound in the SLB rather than trivalent compound (MnOOH). Biological analysis indicates that microorganism activity of the manganese-oxidizing bacteria in the SLB provided an opportunity for δ-MnO2 formation, after which cadmium was removed by surface complexation with MnO2 (≡ MnOH0 + Cd2+ ⇄ ≡ MnOCd+ + H+). These findings show that biological agents contributed to the precipitation of manganese and cadmium in the SLB, and suggest that their utilization could enhance the removal performance of the SLB.

Insight into the Mechanism of Arsenic(III/V) Uptake on Mesoporous Zerovalent Iron-Magnetite Nanocomposites: Adsorption and Microscopic Studies.

Mesoporous zerovalent iron-magnetite nanocomposites (ZVI-MNCs) were developed to circumvent the limitations of magnetite, such as its susceptibility to phase transition in air-water interfaces. High-resolution transmission electron microscopy images revealed the presence of Fe0 and Fe3O4 in the as-prepared adsorbent. High-resolution X-ray photoelectron spectroscopy (HR-XPS) Fe 2p deconvoluted spectra showed that electron transfer between Fe0 and Fe3O4 controlled the magnetite transformation. The isotherm equilibrium data for As(III) and As(V) are described by the Sips model, which suggests single- and multilayer formation onto a heterogeneous surface with different binding sites, whereas adsorption is controlled by a pseudo-second-order kinetic model, which indicates chemisorption. The maximum sorption capacities (qm) for As(III) and As(V) are 632.6 and 1000 µmol g-1, respectively, which are larger than the qm of similar adsorbents. The greater qm for As(V) is attributed to a higher multilayer formation and a stronger bonding force compared with As(III). The arsenic uptake capacity showed that the as-prepared adsorbent was effective over a wide pH range, and an optimal uptake capacity was recorded between pH 5.0 and 9.0 for As(III) and 3.0 and 7.0 for As(V). The adsorbent exhibited a remarkable regeneration performance for As(III) and As(V) uptake. Several microscopic analytical tools, including Fourier transform infrared spectroscopy, HR-XPS, and X-ray absorption near-edge structure together with zeta potential, confirmed that the binding mode of As(III) and As(V) on ZVI-MNCs was predominantly inner-sphere coordination. Partial redox transformation occurred for As(III) and As(V) on nearly 10 nm of the adsorbent, which indicates that a surface redox mechanism contributed partially to arsenic uptake on the near surface of the ZVI-MNCs. Extended X-ray absorption fine structure spectral analysis proposed that a corner-sharing monodentate mononuclear (1V) complex occurred for As(III) with a small portion of a corner-sharing bidentate binuclear (2C) complex, whereas As(V) formed a corner-sharing bidentate binuclear (2C) complex with octahedral Fe bonding.

Effect of Cellulose Nanocrystals Extracted from Oil Palm Empty Fruit Bunch as Green Admixture for Mortar.

This paper aims to examine the effect of cellulose nanocrystals (CNCs) derived from oil palm empty fruit bunch fiber (EFB) incorporating cement mortar on its structural performances. Cellulose nanocrystals (CNCs) were extracted from α-cellulose extracted from EFB using an acid hydrolysis process with a concentration of acid used was 64% w/v under the temperature of 45 °C for 60 minutes. The Cellulose nanocrystals (CNCs) were mixed into the cement mortar ranging from 0 to 0.8% w/w and its mechanical properties were determined. The developed CNCs mortar was characterized for their compressive and flexural properties as well as microstructure. The influence of CNCs concentration, curing method, dispersion of CNCs on mortar's mechanical performance was thoroughly examined to find out the optimum condition. Overall results revealed that an addition of 0.4% cellulose nanocrystals has shown to increase the compressive and flexural strength to 46% and 20%, respectively cured under the wrapping method. The hydration of cementitious composites also improved significantly with the addition of CNCs by the formation of highly crystalline of portlandite observed under the XRD test. This present work demonstrates the importance of palm oil empty fruit bunch waste as a sustainable resource of cellulose nanocrystals admixture to achieve structural strength of cement mortar and promotes green technologies in construction.

Kinetics and mechanism of selenate and selenite removal in solution by green rust-sulfate.

This work investigated the removal of selenite and selenate from water by green rust (GR) sulfate. Selenite was immobilized by simple adsorption onto GR at pH 8, and by adsorption-reduction at pH 9. Selenate was immobilized by adsorption-reduction to selenite and zero valent selenium (Se0) at both pH 8 and 9. In the process, GR oxidized to a mixture of goethite (FeOOH) and magnetite (Fe3O4). The kinetics of selenite and selenate sorption at the GR-water interface was described through a pseudo-second-order model. X-ray absorption spectroscopy data enabled to elucidate the concentration profiles of Se and Fe species in the solid phase and allowed to distinguish two removal mechanisms, namely adsorption and reduction. Selenite and selenate were reduced by GR through homogeneous solid-phase reaction upon adsorption and by heterogeneous reaction at the solid-liquid interface. The selenite reduced through heterogeneous reduction with GR was adsorbed onto GR but not reduced further. The redox reaction between GR and selenite/selenate was kinetically described through an irreversible second-order bimolecular reaction model based on XAFS concentration profiles. Although the redox reaction became faster at pH 9, simple adsorption was always the fastest removal mechanism.

Investigation and evaluation of the detachment of printed circuit boards from waste appliances for effective recycling.

To establish an effective recycling process for waste appliances, the process of recovering printed circuit boards (PCBs) containing valuable elements in comminution was investigated and evaluated. The present study performed comminution tests using three different types of waste appliances: smartphones, microwave ovens and electrical rice cookers. Comminution tests showed that a drum-type agitation mill operated at a mid-range rotation speed could achieve a relatively high recovery ratio of PCBs and inhibit excessive breakage of PCBs. Following these experiments, simulations using the discrete element method with a particle-based rigid-body model were conducted to evaluate the comminution performance of the drum-type agitation mill. Experimental and simulation results confirm that the processes of detachment of PCBs from waste appliances and subsequent breakage can be expressed by kinetic equations related to collision energy. It is concluded from these results that the kinetic equations obtained in experiments and simulations can be used to evaluate the recovery process of PCBs from waste appliances.

Comparison of the Extractabilities of Tetrachloro- and Tetrabromopalladate(II) Ions with a Thiodiglycolamide Compound.

Using N,N,N',N'-tetra-2-ethylhexyl-thiodiglycolamide (TEHTDGA) in n-dodecane as the extractant, we compared the percentages of Pd(II) extracted from HCl and HBr solutions, and analyzed the structures of the Pd(II)-extractant complexes. For comparison, similar experiments were performed with di-n-hexyl sulfide (DHS), a well-known sulfide-type extractant. TEHTDGA extracted Pd(II) from both HCl and HBr solutions much faster than DHS. The Pd(II)/(TEHTDGA or DHS) stoichiometry in the organic phase was 1:2. For TEHTDGA, the extractability of Pd(II) from HBr solution was inferior to that from HCl solution, whereas the opposite was true for DHS. However, FT-IR spectroscopy and EXAFS measurements indicated that the inner-sphere structure of Pd(II) in the TEHTDGA complex was almost the same as that in the DHS system: in both cases, two of the halide ions in the tetrachloro- or tetrabromopalladate(II) ion were replaced by the sulfur atoms of two extractant molecules.

Sorption mechanisms of chromate with coprecipitated ferrihydrite in aqueous solution.

Hexavalent chromium (Cr(VI)) attracted researchers' interest for its toxicity, natural availability and removal difficulty. Nevertheless, its sorption mechanism is not clearly understood yet. In this work, we elucidated the sorption mechanism of the co-precipitation of chromates with ferrihydrite through quantitative analysis. The influence of Cr/Fe molar ratio on sorption was investigated by zeta potential measurements, X-ray diffraction (XRD) and X-ray adsorption fine-structure analysis (XAFS). Coprecipitation at pH 5 showed almost twice the sorption density of adsorption at pH 5. In co-precipitation, a shift of the XRD peak due to inner-sphere sorption of chromate was observed at Cr/Fe molar ratio 0.5. For adsorption, the same peak shift was confirmed at Cr/Fe molar ratio of 1. Zeta potential at pH 5 suggested that the sorption mechanism changed at Cr/Fe molar ratio 0.25 for coprecipitation and at Cr/Fe molar ratio of 1 for adsorption. Fitting of Cr and Fe K-edge extended X-ray adsorption fine-structure suggested that ferrihydrite immobilized Cr(VI) via outer sphere surface complexation for lower Cr/Fe ratios and via inner-sphere surface complexation for higher molar ratios. At higher molar ratios, bidentate binuclear CrFe bonds were well established, thus resulting in the expansion of the ferrihydrite structure.

Silicate Removal in Aluminum Hydroxide Co-Precipitation Process.

The removal mechanisms of silicate using an aluminum hydroxide co-precipitation process was investigated and compared with an adsorption process, in order to establish an effective and validated method for silicate removal from wastewater. Adsorption isotherms, XRD and FT-IR analyses showed that silicate uptake occurred by adsorption to boehmite for initial Si/Al molar ratios smaller than two, but by precipitation of poorly crystalline kaolinite for the ratios larger than two, in both co-precipitation and adsorption processes. Silicate was removed by two steps: (i) an initial rapid uptake in a few seconds; and (ii) a slow uptake over several hours in both processes. The uptake rate in the first step was higher in the co-precipitation process than in adsorption process, presumably due to increased silicate adsorption to boehmite and rapid precipitation of kaolinite. These results suggest that silicate removal using aluminum salts could be effectively achieved if the pH adjustment and aluminum concentration are strictly controlled.