Thiol-functionalized black carbon as effective and economical materials for Cr(VI) removal: Simultaneous sorption and reduction.

Hazardous Cr(VI) continues to pose critical concerns for environmental and public health, demanding the development of effective remediation methods. In this study, thiol-functionalized black carbon (S-BC) was proposed for Cr(VI) removal by mixing thioglycolic acid (TGA) with black carbon (BC) derived from rice straw residue at 80 °C for 8 h. Using a 1:40 (g mL-1) BC-to-TGA ratio, the resulting S-BC40 sample demonstrated significantly enhanced Cr(VI) sorption capacities of 201.23, 145.78, and 106.60 mg g-1 at pH 3.5, 5.5, and 7.5, surpassing its BC counterpart by 2.0, 2.3, and 2.2 times. Additionally, S-BC40 converted all sorbed Cr into Cr(III) species at pH ≥ 5.5, resulting in an equal distribution of Cr(OH)3 and organic Cr(III) complexes. However, approximately 13% of Cr sorbed on BC remained as Cr(VI) at pH 3.5 and 7.5. Both C-centered and S-centered thiyl radicals might contribute to Cr(VI) reduction; however, sufficient C-S groups replenished via thiol-functionalization was the key for the complete Cr(VI) reduction on S-BC samples as pH ≥ 5.5. Thanks to the exceptional Cr(VI) sorption capacity, affordability, and accessibility, thiol-functionalization stands out as a promising modification method for BC. It presents a distinct opportunity to concurrently achieve the objectives of efficient Cr(VI) remediation and waste recycling.

Cross-redox and simultaneous removal of Cr(VI) and As(III): Influences of Fe(II), Fe(III), oxalic acid, and dissolved organic carbon.

Hexavalent chromium [Cr(VI)] and arsenite [As(III)] are hazardous to both human and ecosystem. While their cross-redox reaction decreases both their toxicities, the interferences from ubiquitous substances like Fe (Fe(II) and Fe(III)) and organic compounds (oxalic acid and soil-extracted dissolved organic carbon (DOC)) on such interaction are rarely reported; thence, inspires the investigation in this study. Results showed that the cross-redox, in the absence of interfering substances, only occurred at pH≤2.0, with reaction orders of 0.676 and 0.783 in respect to the concentration of Cr(VI) and As(III). The pseudo-reaction constant, k', of such reaction was recorded at 0.087 m1.377/(mmol0.459 min). With the addition of Fe(II), the rate of Cr(VI) reduction is promoted in conjunction with suppressed As(III) oxidation. Upon neutralizing to pH 6.0, such reduced Cr can be entirely removed via Fe(II)-assisted adsorption and/or co-precipitation. Meanwhile, the elimination of aqueous As is relatively inferior (36 %), attributed to the largely preserved As(III), which is less susceptible to adsorptive/co-precipitative removal. Unlike Fe(II), Fe(III) did not alter Cr(VI)-As(III) cross-redox path, but triggered high adsorptive and/or co-precipitative removals of Cr and As (90 %). In contrast, both organically-altered systems exhibits plummeted As(III) oxidation, under distinctive mechanisms: oxalic acid competes with As(III) in the redox interactions while DOC reduces As(V) into As(III). Also, DOC would undergo complexion with metals and/or blocked the adsorption or co-precipitation sites, leading to even lower Cr and As precipitation. This study unravelled the interference from ubiquitous species in the co-removal of Cr(VI) and As(III), which provides insightful remediation for heavy metal contaminations.

Chemical synthesis of unique intermetallic TiFe nanostructures originating from the morphology of oxide precursors.

In this study, intermetallic TiFe nanostructures were chemically prepared from Ti-Fe oxide precursors using a CaH2 reducing agent in molten LiCl at as low as 600 °C. The used precursor was spherical oxide nanoparticles or commercial FeTiO3 bulk powder. After the reduction treatment, the former precursor was changed to an aggregation of TiFe nanoparticles with a particle size of 44-46 nm. Surprisingly, the latter precursor was reduced to a layered morphology composed of TiFe nanoparticles with a particle size of 47-65 nm. An intermetallic compound with a unique layered morphology was found for the first time, and the layered morphology could have originated from the morphology of the FeTiO3 precursor in which the Fe2+ and Ti4+ ions occupied alternating layers perpendicular to the trigonal c-axis. The precursor originated morphology was enabled by the proposed low reduction temperature method, and the environment-friendliness of the proposed method was finally evaluated using life-cycle assessment (LCA).

Modeling the time-lag effect of sea surface temperatures on ciguatera poisoning in the South Pacific: Implications for surveillance and response.

Ciguatera poisoning (CP), arising from ciguatoxins produced by toxic dinoflagellate Gambierdiscus, is one of the most common food-borne diseases in the South Pacific. Climate change as well as its related events have been hypothesized to a higher abundance and wider presence of toxic dinoflagellates, hence a higher risk of the disease. Yet existing studies assessing the relationship between climate factors and CP are limited or based on old data. In this study, we used prewhitened cross-correlation analysis and auto-regressive integrated moving-average (ARIMA) modeling to develop predictive models of monthly CP incidence in Cook Islands and French Polynesia, two ciguatera-endemic regions in the South Pacific, utilizing the latest epidemiological data. Results reveal the significant time-lagged associations between the monthly CP incidence rate and several indicators relating to sea surface temperature (SST). In particular, SST anomaly is proven to be a strong positive predictor of an increased ciguatera incidence for both countries. If these time-lags can be supported by more investigations, it will allow health authorities to take appropriate actions, to limit or avoid an epidemic risk, especially on high-risk climate scenarios.

Redox reactions between chromium(VI) and hydroquinone: Alternative pathways for polymerization of organic molecules.

Chromium (VI) reduction by organic compounds is one of the major pathways to alleviate the toxicity and mobility of Cr(VI) in the environment. However, oxidative products of organic molecules receive less scientific concerns. In this study, hydroquinone (H2Q) was used as a representative organic compound to determine the redox reactions with Cr(VI) and the concomitant oxidative products. Spectroscopic analyses showed that Cr(III) hydroxides dominated the precipitates produced during redox reactions of Cr(VI) and H2Q. For the separated filtrates, the acidification induced the oxidative polymerization of organic molecules, accompanied with the complexation with Cr(III). The aromatic domains dominated the chemical structures of the black and fluffy organic polymers, which was different to the natural humic acids due to the shortage of aliphatic chains. Results of linear combination fitting (LCF) for Cr K-edge X-ray absorption near edge structure (XANES) spectra demonstrated that up to 90.4% of Cr inventory in precipitates derived after the acidification of filtrates was Cr(III) complexed with humic-like polymers, suggesting that Cr(III) possibly acted as a linkage among organic molecules during the polymerization processes of H2Q. This study demonstrated that Cr(VI) may lead to the polymerization of organic molecules in an acidic solution, and thus, it could raise scientific awareness that the oxidative decomposition of organic molecules may not be the only pathway while interacting with the strong oxidant of Cr(VI).

Removal and simultaneous reduction of Cr(VI) by organo-Fe(III) composites produced during coprecipitation and coagulation processes.

Composites formed during the coprecipitation and/or coagulation of ubiquitous dissolved organic matter (DOM) and Fe in natural and waste water systems might be potential scavengers for Cr(VI) in terms of sorption and reduction. Our objective here was to determine sorption and simultaneous reduction of Cr(VI) on organo-Fe(III) composites (OFC) in relation coprecipitated pH and C/(C + Fe) ratios. Results showed the greatest Cr sorption of 51.8 mg g-1 on the OFC sample that was precipitated at pH 3 and contained the C/(C + Fe) molar ratio of 0.71. Wherein the Cr(VI) removal subsequent to the coprecipitation was dominated by the sorption on Fe hydroxides. Although amounts of total sorbed Cr decreased with increasing C/(C + Fe) molar ratio, the reverse trend on Cr(VI) reducibility compensated the Cr(VI) removal capability of OFC samples. With C/(C + Fe) molar ratios ≥ 0.89, the increasing amounts of coprecipitated organic matter that homogeneously distributed with Fe domains on OFC surfaces could trigger a significantly pronounced Cr reduction. Collectively, our results suggested an alternative method for Cr(VI) remediation by manipulating C/Fe ratios in suspensions. After the sorption of most Cr(VI) on Fe hydroxides, increasing C/Fe ratio in systems could further improve the Cr(VI) removal efficiency by the reduction of remaining Cr(VI) to Cr(III).

Use 3-D tomography to reveal structural modification of bentonite-enriched clay by nonionic surfactants: Application of organo-clay composites to detoxify aflatoxin B1 in chickens.

Although nonionic surfactants are relatively eco-friendly compared with cationic and anionic surfactants, few studies have investigated their application in modified clay. Herein we prepared organo-clay composites (OCCs) by mixing bentonite-enriched clay (BEC) with nonionic surfactants (Brij 30 and Igepal CO-890) and determined if these modifications would enable chickens to detoxify aflatoxin B1 (AFB1). For the first time, in situ three-dimensional (3-D) microstructures of modified BEC was characterized in suspension using transmission X-ray microscopy. Although X-ray diffraction patterns indicated the expansion in the spacing between planes of atoms (basal spacing) of surfactant-modified BEC, 3-D images indicated shrinkage in its microscale porous framework with increasing surfactant additions from 1 to 30 wt%. Such declining trends in porous dimensions caused by the dehydration in interlayer galleries of clays positively correlated with sorption amounts of AFB1 on OCCs. After chickens had consumed amended feeds for 11 weeks, AFB1 concentrations in liver, kidney, and plasma were significantly lower than in the control treatment. Thus, we suggest using BEC with 1 wt% surfactant addition, an amendment to chicken feeds, to detoxify AFB1. Modifying BEC with nonionic surfactants show the promise in mitigating AFB1 accumulation in chickens, which should improve food safety and reduce environmental contamination.

Adsorption mechanisms of chromate and phosphate on hydrotalcite: A combination of macroscopic and spectroscopic studies.

Hydrotalcite (HT) is a layered double hydroxide (LDH), which is considered as a potential adsorbent to remove anion contaminants. In this study, adsorption of chromate (CrO4) and phosphate (PO4) on HT was conducted at various pH and temperatures. Related adsorption mechanisms were determined via the isotherm, kinetic, and competitive adsorption studies as well as the Cr K-edge X-ray absorption fine-structure (XAFS) spectroscopy. The maximum adsorption capacities for CrO4 and PO4 on HT were 0.16 and 0.23 mmol g-1. Regarding adsorption kinetics, CrO4 and PO4 adsorption on HT could be well described by the second order model, and the rate coefficient of CrO4 and PO4 on HT decreased significantly with the increasing pH from 5 to 9. The adsorption kinetics for CrO4 and PO4 were divided into fast and slow stages with the boundary at 15 min. This biphasic adsorption behavior might be partially attributed to multiple reactive pathways including anion exchange and surface complexation. Fitting results of Cr K-edge EXAFS analysis showed a direct bonding between CrO4 and Al on HT surfaces. Such a surface complexation appeared to be the rate-limiting step for CrO4 adsorption on HT. By contrast, the diffusion through the hydrated interlayer space of HT was the major rate-limiting step for PO4. This study determined the adsorption behaviors of CrO4 and PO4 on HT, including the initial transfer process and the subsequent adsorption mechanisms. Such information could improve the strategy to use HT as the potential adsorbent for the remediation of anionic pollutants.

Adsorption of tetracycline on Fe (hydr)oxides: effects of pH and metal cation (Cu2+, Zn2+ and Al3+) addition in various molar ratios.

Iron (Fe) (hydr)oxides control the mobility and bioavailability of tetracycline (TC) in waters and soils. Adsorption of TC on Fe (hydr)oxides is greatly affected by polyvalent metals; however, impacts of molar metal/TC ratios on TC adsorptive behaviours on Fe (hydr)oxides remain unclear. Results showed that maximum TC adsorption on ferrihydrite and goethite occurred at pH 5-6. Such TC adsorption was generally promoted by the addition of Cu2+, Zn2+ and Al3+. The greatest increase in TC adsorption was found in the system with molar Cu/TC ratio of 3 due to the formation of Fe hydr(oxide)-Cu-TC ternary complexes. Functional groups on TC that were responsible for the complexation with Cu2+shifted from phenolic diketone groups at Cu/TC molar ratio < 1 to amide groups at Cu/TC molar ratio ≥ 1. For the addition of Al3+, the complexation only took place with phenolic diketone groups, resulting in the enhanced TC adsorption at a molar Al/TC ratio of 1. However, TC adsorption decreased for Al/TC molar ratio > 1 as excess Al3+ led to the competitive adsorption with Al/TC complexes. For the Zn2+ addition, no significant correlation was found between TC adsorption capacity and molar Zn/TC ratios.

Capacity and recycling of polyoxometalate applied in As(III) oxidation by Fe(II)-Amended zero-valent aluminum.

Arsenic remediation is often initiated by oxidizing As(III) to As(V) to alleviate its toxicity and mobility. Due to the easy availability, zero-valent Al (ZVAl) like Al can was considered as potential alternatives to facilitate As(III) oxidation. This study determined the capability and recycling of polyoxometalate (POM) to catalyze As(III) oxidation in Fe(II)-amended ZVAl systems. POM acquired electrons from ZVAl more effectively at pH 1 than at pH 2. While 76% of the reduced POM [POM(e-)] reacted with O2(g) to generate H2O2 at pH 1, only 60% of POM(e-) was used to produce H2O2 at pH 2. The remaining POM(e-) was oxidized by the generated H2O2. Such additional consumption of POM(e-) and H2O2 led to the incomplete As(III) oxidation in the system without residual ZVAl and emphasized the need for a continuous electron supply from ZVAl to compensate the depletion of POM(e-). After the hydrolyzation at pH 6.0, the XANES data evidenced that not only As(V) but WO4 released from the POM retained on surfaces of Al/Fe hydroxides. The competition for sorption sites on Al/Fe hydroxides between As(V) and WO4 led to the incomplete As removal. Despite the loss of WO4, the POM re-polymerized at pH 1 still showed the comparable capability to catalyze As(III) oxidation with original POM. This study revealed electron transfer pathways from ZVAl to As(III) as catalyzed by POM and evidenced the effective POM recycling after As removal, which lowers the cost of POM application and turns the ZVAl/Fe(II)/POM/O2 system into a practical strategy for As remediation.

Stabilization of Natural Organic Matter by Short-Range-Order Iron Hydroxides.

Dissolved organic matter (DOM) is capable of modifying the surfaces of soil minerals (e.g., Fe hydroxides) or even forming stable co-precipitates with Fe(III) in a neutral environment. The DOM/Fe co-precipitation may alter biogeochemical carbon cycling in soils if the relatively mobile DOM is sorbed by soil minerals against leaching, runoff, and biodegradation. In this study, we aimed to determine the structural development of DOM/Fe co-precipitates in relation to changes in pH and C/(C + Fe) ratios using XRD, XPS, Fe K-edge XAS, FTIR, and C-NEXAFS techniques. The results showed that in the system with bulk C/(C + Fe) molar ratios ≤0.65, the ferrihydrite-like Fe domains were precipitated as the core and covered by the C shells. When the C/(C + Fe) molar ratio ranged between 0.71 and 0.89, the emerging Fe-C bonding suggested a more substantial association between Fe domains including edge- and corner-sharing FeO6 octahedra and DOM. With C/(C + Fe) bulk molar ratios ≥0.92, only corner-sharing FeO6 octahedra along with Fe-C bonding were found. The homogeneously distributed C and Fe domains caused the enhancement of Fe and C solubilization from co-precipitates. The C/(C + Fe) ratios dominated structural compositions and stabilities of C/Fe co-precipitates and may directly affect the Fe and C cycles in soils.

Accumulation of heavy metals and trace elements in fluvial sediments received effluents from traditional and semiconductor industries.

Metal accumulation in sediments threatens adjacent ecosystems due to the potential of metal mobilization and the subsequent uptake into food webs. Here, contents of heavy metals (Cd, Cr, Cu, Ni, Pb, and Zn) and trace elements (Ga, In, Mo, and Se) were determined for river waters and bed sediments that received sewage discharged from traditional and semiconductor industries. We used principal component analysis (PCA) to determine the metal distribution in relation to environmental factors such as pH, EC, and organic matter (OM) contents in the river basin. While water PCA categorized discharged metals into three groups that implied potential origins of contamination, sediment PCA only indicated a correlation between metal accumulation and OM contents. Such discrepancy in metal distribution between river water and bed sediment highlighted the significance of physical-chemical properties of sediment, especially OM, in metal retention. Moreover, we used Se XANES as an example to test the species transformation during metal transportation from effluent outlets to bed sediments and found a portion of Se inventory shifted from less soluble elemental Se to the high soluble and toxic selenite and selenate. The consideration of environmental factors is required to develop pollution managements and assess environmental risks for bed sediments.

Molecular Structures of Al/Si and Fe/Si Coprecipitates and the Implication for Selenite Removal.

Aluminum and iron oxides have been often used in the coagulation processes during water purification due to their unique surface properties toward anions. In the presence of silica, the coprecipitation of Al/Si or Fe/Si might decrease the efficiency of wastewater purification and reuse. In this study, surface properties and molecular structures of Al/Si and Fe/Si coprecipitates were characterized using spectroscopic techniques. Also, the selenite removal efficiency of Al/Si and Fe/Si coprecipitates in relation to their surface and structural properties was investigated. While dissolved silicate increased with increasing pH from Fe/Si coprecipitates, less than 7% of silicate was discernible from Al/Si samples over the range from acidic to alkaline conditions. Our spectroscopic results showed that the associations between Al and Si were relatively stronger than that between Fe and Si in coprecipitates. In Al/Si coprecipitates, core-shell structures were developed with AlO6/AlO4 domains as the shells and Si frameworks polymerized from the SiO2 as the cores. However, Si framework remained relatively unchanged upon coprecipitation with Fe hydroxides in Fe/Si samples. The Si core with Al shell structure of Al/Si coprecipitates shielded the negative charges from SiO2 and thereby resulted in a higher adsorption capacity of selenite than Fe/Si coprecipitates.