Transformation Of Species Research Articles

Unexpected Nanoscale CeO2 Structural Transformations Induced by Ecologically Relevant Phosphate Species

In the present study, the dissolution and microstructural transformation of CeO2 nanoparticles (NPs) in a phosphate-containing milieu were investigated. The dissolution behaviour of 2 nm and 5 nm CeO2 NPs in phosphate buffer solutions was found to differ markedly from that observed in 0.01 M NaClO4. Through synchrotron X-ray diffraction analysis and X-ray absorption spectroscopy, the interaction between CeO2 NPs and phosphate species was examined, revealing the transformation of the oxide into sodium-cerium double phosphate, with cerium predominantly existing in the Ce(IV) state. According to scanning and transmission electron microscopy observations, thus formed Na-Ce(IV) phosphate consists of spindle-like aggregates of nanocrystalline rods, presumably formed during phosphate anions sorption on the initial CeO2 surface. Pair distribution function analysis revealed that Na-Ce(IV) phosphate has a three-dimensional framework crystal structure, similar to NaTh2(PO4)3, as reported earlier, with large channels along the c-axis containing disordered sodium atoms. This study represents the first detailed analysis of phosphate-induced speciation and microstructural transformation of CeO2 NPs, resulting in the formation of Ce(IV) phosphate. Similar processes may occur in natural ecosystems upon the introduction of CeO2 NPs.

Anthropocentrism and Inheritance in Our Mutual Friend: Return, Recognition, Reanimation

Abstract In decentering “Man,” a category long rhetorically constructed as the privileged species of a divine creator, Charles Darwin’s theory of natural selection necessitated a reexamination of how human subjectivity should be represented in fiction. This article uses the example of Charles Dickens’s Our Mutual Friend (1864) to track and scientifically contextualize how anthropocentrism is constructed and interrogated in fiction after publication of On the Origin of Species (1859). Competing nineteenth-century theories of species transmutation recognized physiological fluidity and variation within species and type, yet unlike Darwin, they sought to define uniquely human qualities of mind. Literary narratives, such as Dickens’s final completed novel, engaged this intellectual project—attempting to stabilize a dominant form of human subjectivity while recognizing shifting varieties of being. Protagonist John Harmon is oddly vacant as an imagined human consciousness; his actions create or resolve conflict within the story, but he fails to demonstrate any stable motivation. Depicting the initial misrecognition, and eventual recognition, of an English heir newly returned from abroad, Our Mutual Friend articulates cultural anxieties about the potential mutability of identity and type and the origins and durability of English dominance. Its post-Darwinian model of consciousness challenges traditional realist valorization of the individualistic, agential subject.

Molecular understanding of speciation transformation of phosphorus and sulfur in food waste digestate during hydrothermal treatment

Recovering phosphorus (P) and sulfur (S) from biowaste is a key strategy to address the current P resources shortage and soil S deficiency. Food waste digestate (FWD) contains high contents of P and S, while its direct application is severely limited by available nutrient leaching loss and pollutant exposure. Hydrothermal treatment (HT) is an effective technique for biowaste disposal, enabling detoxification and resource recovery. The study systematically investigated the speciation transformation of P and S in FWD during HT, using chemical extraction and in-situ X-ray absorption near-edge structure (XANES) spectroscopy. The results revealed that up to 98% of P in FWD was enriched in the solid product (hydrochar) after HT, with organic P and labile P being converted into stable Ca-bound forms, predominantly hydroxyapatite. This transformation reduced the risk of P leakage loss compared to untreated FWD. Interestingly, the S speciation evolution exhibited more complexity. The highest S proportion in hydrochar of 73.6% was observed at 140 °C under HT. As the temperature increased from 140 °C to 180 °C, S in the hydrochar gradually dissolved into the liquid phase, attributed to unstable aliphatic compounds (mercaptan) and the sulfides oxidizing to sulfates. Above 180 °C, intermediate oxidation states and sulfates were reduced and formed metal sulfides. These findings have important implications for understanding the viability of HT for FWD disposal and the value-added utilization of FWD.

Pyrite functionalized Black Soldier Fly feces biochar for mine soil quality improvement and heavy metals immobilization

Frequent mining activities have led to an increasing transfer of heavy metals to the soil. Pyrite functionalized Black Soldier Fly feces biochar composite material (BFFS) was synthesized to immobilize Cu and Pb in contaminated mine soil and improve soil quality in our study. Incubation experiments showed that BFFS significantly reduced the leaching rates by 96 % and 90 % for Cu and Pb, respectively, when compared to the control after 220 days. Speciation transformation analysis further revealed that BFFS could significantly reduce easily labile fractions of Cu and Pb, and transformed to recalcitrant fractions. Moreover, BFFS significantly improved the quality of mine soil combined with soil quality index analysis. The potential toxicity and bioavailability of Cu and Pb can still be effectively reduced by BFFS, even during a 90-day field experiment. In addition, the mine soil improved by BFFS further promoted the survival and growth of ramie. Multiple characterization analyses and related experiments indicated that ion exchange, adsorption, complexation, and coprecipitation mainly contribute to the high efficiency immobilization of Cu and Pb by BFFS. These findings could bring some fresh perspectives on the development of immobilization materials and related technologies for the economical, green and sustainable remediation of heavy metals contaminated mine soil.

Enhanced passivation of lead and cadmium from contaminated farmland using biochar with tailored pore properties: Performance and mechanisms

The porous biochar (PBCPB) was prepared by one-step KHCO3-activated pyrolysis of corn stalks, which showed excellent passivation properties for Pb/Cd in soil (48.99 % or 46.74 %). Characterization results revealed that the PBCPB possessed a dense and network-like pore structure with a huge specific surface area of 1342.07 m2/g, which was conducive to the passivation of Pb/Cd. Batch experiments showed that PBCPB had excellent adsorption properties with the maximum absorption capacity of 117.61/48.24 mg/g. After 30 d of remediation, the bioavailable-Pb/Cd contents in 5.0 % of PBCPB treatment were reduced by 47.06 % and 58.42 %, respectively. The speciation transformation results uncovered that the contents of unstable Pb/Cd components gradually decreased with the increase of PBCPB dosages, ultimately transforming into stable residual components. In addition, the PBCPB could effectively increase the contents of soil available nutrients and enhance functional enzyme activities, which contributed to promoting the growth of cucumber seedlings. Meanwhile, PBCPB strongly alleviated the oxidative damage of Pb/Cd to cucumber seedlings by significantly reducing the Pb/Cd accumulation and antioxidant oxidase activity of cucumber seedlings. Furthermore, precipitation, complexation, as well as cation-π interaction were the primary passivation mechanisms of PBCPB for Pb/Cd. Overall, the study provided a reasonable design of porous carbon-based materials for the remediation of Pb/Cd-contaminated soil.

Deep learning-based simultaneous bioavailability assessment and speciation analysis of dissolved organic copper

Algal copper uptake (i.e., Cu bioavailability) in the euphotic zone plays a vital role in algal photosynthesis and respiration, affecting the primary productivity and the source and sink of atmospheric carbon. Algal Cu uptake is controlled by natural dissolved organic Cu (DOCu) speciation (i.e., complexed with the dissolved organic matter) that conventionally could be tested by model prediction or molecular-level characterizations in the lab, while DOCu uptake are hardly directly assessed. Thus, the new chemistry-biology insight into the mechanisms of the Cu uptake process in algae is urgent. The DOCu speciation transformation (organic DOCu to free Cu(II) ions), enzymatic reduction-induced valence change (reduction of free Cu(II) to Cu(I) ions), and algal Cu uptake at the algae-water interface are imitated. Herein, an intelligent system with DOCu colorimetric sensor is developed for real-time monitoring of newly generated Cu(I) ions. Deep learning with whole sample image-based characterization and powerful feature extraction capabilities facilitates colorimetric measurement. In this context, the Cu bioavailability with 7 kinds of organic ligands (e.g., amino acids, organic acids, carbohydrates) can be predicted by the mimetic intelligent biosensor within 15.0 min i.e., the DOCu uptake and speciation is successfully predicted and streamlined by the biomimetic approach.

Improvements in recovery of rare earth elements (REEs) from coal via fluidized-bed combustion: Thermal alteration of REE mineralogy and its impact on element extractability

The extraction of rare earth elements (REE) from coal ash has attracted significant attention, but satisfactory solutions have not yet been achieved. Indeed, the REE extractability is largely determined by the transformation behavior of REE during coal combustion. This study found that the controlled combustion conditions of circulated fluidized-bed boiler (CFB) can both utilize the heating value and enhance the recovery of REE from coal. Tests were conducted using a bituminous coal with REE concentration of approximately 149 ppm in an industrial 35 t/h CFB boiler with controlled boiler loads and coal sources. Advanced automated image analysis by scanning electron microscopy (AIA-SEM) and sequential leaching procedure were employed to clarify the speciation transformation behavior of REE in boilers and investigate the effects of these transformations on the leachability of REE. Approximately 75 % of REE partitioned into fly ash and enriched in particles < 45 μm (∼710 ppm) after combustion. Acid leaching tests under mild conditions (1 M HCl at 60 ℃ and S/L = 1:25) performed on coal, bulk ashes, and sieved ashes revealed an improvement in REE leaching ratio from coal (21.34 %) to fly ash (71.07 %). Particle size played a crucial role in acid extractability, particularly for middle and heavy REE in cyclone ash but had no influence on those in fly ash. The dominant forms of REE in coal including Ca-REE fluorocarbonates (36.7 %), aluminophosphates (12.0 %), and organic-bound REE (approximately 20 %) significantly decreased, contributing to the formation of leachable rare earth oxides (∼65 %) in ash. Furthermore, the small size of REE mineral grains in coal (over 50 % below 5 μm) and extensive mineral fragmentation occurring in boiler resulted in the enrichment and enhanced REY leachability in fine ash.

Adsorption Potential, Speciation Transformation, and Risk Assessment of Hg-, Cd-, and Pb-Contaminated Soils Using Biochar in Combination with Potassium Dihydrogen Phosphate.

The objective of this study is to develop a remediation technology for composited heavy metal-contaminated soil. Biochars (BC300, BC400, and BC500) derived from corn were combined with potassium dihydrogen phosphate (KH2PO4) to immobilize and remove heavy metal ions, including mercury (Hg2+), cadmium (Cd2+), and lead (Pb2+). The adsorption kinetics of metal ions in aqueous solutions with different concentrations was tested, and the fitting effects of the two models were compared. The findings demonstrate that the joint application of biochar and KH2PO4 could markedly enhance the immobilization efficacy of Pb2+, whereas the utilization of KH2PO4 on its own exhibited a more pronounced immobilization impact on Cd2+. Furthermore, the present study underscores the shortcomings of various remediation techniques that must be taken into account when addressing heavy metal-contaminated soils. It also emphasizes the value of comprehensive remediation techniques that integrate multiple remediation agents. This study offers a novel approach and methodology for addressing the intricate and evolving challenges posed by heavy metal contamination in soil. Its practical value and potential for application are significant.

Influence of Four Veterinary Antibiotics on Constructed Treatment Wetland Nitrogen Transformation.

The use of wetlands as a treatment approach for nitrogen in runoff is a common practice in agroecosystems. However, nitrate is not the sole constituent present in agricultural runoff and other biologically active contaminants have the potential to affect nitrate removal efficiency. In this study, the impacts of the combined effects of four common veterinary antibiotics (chlortetracycline, sulfamethazine, lincomycin, monensin) on nitrate-N treatment efficiency in saturated sediments and wetlands were evaluated in a coupled microcosm/mesocosm scale experiment. Veterinary antibiotics were hypothesized to significantly impact nitrogen speciation (e.g., nitrate and ammonium) and nitrogen uptake and transformation processes (e.g., plant uptake and denitrification) within the wetland ecosystems. To test this hypothesis, the coupled study had three objectives: 1. assess veterinary antibiotic impact on nitrogen cycle processes in wetland sediments using microcosm incubations, 2. measure nitrate-N reduction in water of floating treatment wetland systems over time following the introduction of veterinary antibiotic residues, and 3. identify the fate of veterinary antibiotics in floating treatment wetlands using mesocosms. Microcosms containing added mixtures of the veterinary antibiotics had little to no effect at lower concentrations but stimulated denitrification potential rates at higher concentrations. Based on observed changes in the nitrogen loss in the microcosm experiments, floating treatment wetland mesocosms were enriched with 1000 μg L-1 of the antibiotic mixture. Rates of nitrate-N loss observed in mesocosms with the veterinary antibiotic enrichment were consistent with the microcosm experiments in that denitrification was not inhibited, even at the high dosage. In the mesocosm experiments, average nitrate-N removal rates were not found to be impacted by the veterinary antibiotics. Further, veterinary antibiotics were primarily found in the roots of the floating treatment wetland biomass, accumulating approximately 190 mg m-2 of the antibiotic mixture. These findings provide new insight into the impact that veterinary antibiotic mixtures may have on nutrient management strategies for large-scale agricultural operations and the potential for veterinary antibiotic removal in these wetlands.

Endogenous iron-enriched biochar derived from steel mill wastewater sludge for tetracycline removal: Heavy metals stabilization, adsorption performance and mechanism

Steel mill wastewater sludge, as an iron-enriched solid waste, was expected to be converted into iron-enriched biochar with acceptable environmental risk by pyrolysis. The purpose of our study was to evaluate the chemical speciation transformation of heavy metals in biochar under various pyrolysis temperatures and its reutilization for tetracycline (TC) removal. The experimental data indicated that pyrolysis temperature was a key factor affecting the heavy metals speciation and bioavailability in biochar, and biochar with pyrolysis temperature at 450 °C was the most feasible for reutilization without potential risk. The endogenous iron-enriched biochar (FSB450) showed highly efficient adsorption towards TC, and its maximum adsorption capacity could reach 240.38 mg g−1, which should be attributed to its excellent mesoporous structure, abundant functional groups and endogenous iron cycling. The endogenous iron was converted to a stable iron oxide crystalline phase (Fe3O4 and MgFe2O4) by pyrolysis, which underwent a valence transition to form a coordination complex with TC by electron shuttling in the FSB450 matrix. The study provides a win-win approach for resource utilization of steel wastewater sludge and treatment of antibiotic contamination in wastewater.

Driving factors for distribution and transformation of heavy metals speciation in a zinc smelting site

Heavy metal pollution at an abandoned smelter pose a significant risk to environmental health. However, remediation strategies are constrained by inadequate knowledge of the polymetallic distribution, speciation patterns, and transformation factors at these sites. This study investigates the influence of soil minerals, heavy metal occurrence forms, and environmental factors on heavy metal migration behaviors and speciation transformations. X-ray diffraction analysis revealed that the minerals associated with heavy metals are mainly hematite, franklinite, sphalerite, and galena. Sequential extraction results suggest that lead and zinc are primarily present in the organic-sulfide fractions (F4) and residual form (F5) in the soil, accounting for over 70% of the total heavy metal content. Zinc displayed greater instability in carbonate-bound (16%) and exchangeable (2%) forms. The migration and diffusion patterns of heavy metals in the subsurface environment were visualized through the simulation of labile state heavy metals, demonstrating high congruence with groundwater pollution distribution patterns. The key environmental factors influencing heavy metal stable states (F4 and F5) were assessed by integrating random forest models and redundancy analysis. Primary factors facilitating Pb transformation into stable states were available phosphorus, clay content, depth, and soil organic matter. For Zn, the principal drivers were Mn oxides, soil organic matter, clay content, and inorganic sulfur ions. These findings enhance understanding of the distribution and transformation of heavy metal speciation and can provide valuable insights into controlling heavy metal pollution at non-ferrous smelting sites.

Effects of biodegradable microplastics on arsenic migration and transformation in paddy soils: a comparative analysis with conventional microplastics

The combined pollution of microplastics (MPs) and arsenic (As) in paddy soils has attracted more attention worldwide. However, there are few comparative studies on the effects of biodegradable and conventional MPs on As migration and transformation. Therefore, conventional (polystyrene, polyethylene, polyvinyl chloride) and biodegradable (polybutadiene styrene, polylactic acid, polybutylene adipate terephthalate) MPs were selected to explore and demonstrate their influences and mechanism on As migration from paddy soils to overlying water and As speciation transformation through microcosmic experiment with measuring the changes of As chemical distribution, physicochemical indexes and microbial community in paddy soils. The results showed that biodegradable MPs enhanced As migration and transformation more effective than conventional MPs during 60 d. Biodegradable MPs indirectly increased the content of As(Ⅲ) and bioavailable As by changing the microbial community structure and affecting the biogeochemical cycles of carbon, nitrogen, sulfur and iron in soils, and promoted the As migration and transformation. PBS showed the strongest promoting effect, transforming to more As(Ⅲ) (11.43%) and bioavailable As (4.28%) than control. This helps to a better understanding of the effects of MPs on As biogeochemical cycle and to clarify the ecological and food safety risks of their combined pollution in soils.

Legacy Mercury Re-emission and Subsurface Migration at Contaminated Sites Constrained by Hg Isotopes and Chemical Speciation.

The re-emission and subsurface migration of legacy mercury (Hg) are not well understood due to limited knowledge of the driving processes. To investigate these processes at a decommissioned chlor-alkali plant, we used mercury stable isotopes and chemical speciation analysis. The isotopic composition of volatilized Hg(0) was lighter compared to the bulk total Hg (THg) pool in salt-sludge and adjacent surface soil with mean ε202HgHg(0)-THg values of -3.29 and -2.35‰, respectively. Hg(0) exhibited dichotomous directions (E199HgHg(0)-THg = 0.17 and -0.16‰) of mass-independent fractionation (MIF) depending on the substrate from which it was emitted. We suggest that the positive MIF enrichment during Hg(0) re-emission from salt-sludge was overall controlled by the photoreduction of Hg(II) primarily ligated by Cl- and/or the evaporation of liquid Hg(0). In contrast, O-bonded Hg(II) species were more important in the adjacent surface soils. The migration of Hg from salt-sludge to subsurface soil associated with selective Hg(II) partitioning and speciation transformation resulted in deep soils depleted in heavy isotopes (δ202Hg = -2.5‰) and slightly enriched in odd isotopes (Δ199Hg = 0.1‰). When tracing sources using Hg isotopes, it is important to exercise caution, particularly when dealing with mobilized Hg, as this fraction represents only a small portion of the sources.

Combined Remediation Effects of Sewage Sludge and Phosphate Fertilizer on Pb-Polluted Soil from a Pb-Acid Battery Plant.

Pb soil pollution poses a serious health risk to both the environment and humans. Immobilization is the most common strategy for remediation of heavy metal polluted soil. In this study, municipal sewage sludge was used as an amendment for rehabilitation of Pb-contaminated soils, for agricultural use, near a lead-acid battery factory. The passivation effect was further improved by the addition of phosphate fertilizer. It was found that the leachable Pb content in soils was decreased from 49.6 mg kg-1 to 16.1-36.6 mg kg-1 after remediation of sludge for 45 d at applied dosage of municipal sewage sludge of 4-16 wt%, and further decreased to 14.3-34.3 mg kg-1 upon extension of the remediation period to 180 d. The addition of phosphate fertilizer greatly enhanced the Pb immobilization, with leachable Pb content decreased to 2.0-23.6 mg kg-1 with increasing dosage of phosphate fertilizer in range of 0.8-16 wt% after 180 d remediation. Plant assays showed that the bioavailability of Pb was significantly reduced by the soil remediation, with the content of absorbed Pb in mung bean roots decreased by as much as 87.0%. The decrease in mobility and biotoxicity of the soil Pb is mainly attributed to the speciation transformation of carbonate, Fe-Mn oxides and organic matter bound Pb to residue Pb under the synergism of reduction effect of sludge and acid dissolution and precipitation effect of phosphate fertilizer. This study suggests a new method for remediation of Pb-contaminated soil and utilization of municipal sewage sludge resources.

Mercury speciation transformation mediated by thiolated biochar in high salinity groundwater: Interfacial processes, influencing factors, and mechanisms

Groundwater, a vital freshwater source, faces mercury contamination threats, impacting ecosystems and human health. Removing low concentrations of mercury from high-salinity groundwater has always been a challenge. This study demonstrates the effectiveness of thiol-modified biochar (BCS) in decontaminating mercury from saline groundwater by mediating mercury speciation transformation. Initially, mercury species (e.g., HgClOH, Hg(OH)2, HgCl2, HgOHCO3–) selectively attach to thiol groups, leading to an increase in surface zeta potential and a reduction in electrostatic attraction to calcium species (e.g., CaCO3 and CaSO4). Then, cations bound to thiol groups (e.g., Na+, Ca2+, and CaHCO3+) undergo ion exchange with mercury species (e.g., Hg2+, HgOH+, and HgCl+). Finally, mercury species (e.g., Hg(OH)2, HgSO4, and HgS) gradually precipitate or co-precipitate with calcium minerals (e.g., calcite, aragonite, and vaterite). Compared with biochar (BC), BCS exhibits a larger mercury adsorption capacity (qm = 4.30 ± 0.13 mg g−1) and a faster initial reaction rate (h2 = 4.12 × 10–2 mg g−1 min−1). BCS withstands pH variations, small organic molecules, and coexisting heavy metal ions but exhibits slightly reduced performance in higher ionic strength and with large organic molecules. Additionally, BCS serves as an effective permeable reactive barrier against flowing mercury-contaminated groundwater, the Adams-Bohart and Yan models effectively describe the breakthrough curves. These findings provide scientific support for BCS’s application in remediating high-salinity and trace mercury-contaminated groundwater.

Alumina inhibits pyrite oxidative dissolution by regulating solid film passivation layer and S, Fe, and Al speciation transformation

The oxidation of pyrite results in the formation of a solid film passivation layer on its surface. This layer effectively hinders the direct interaction between H2O, O2, and the pyrite surface, thereby impeding the oxidation dissolution of pyrite. There are few studies on whether alumina (Al2O3), a common aluminum-containing oxide, affects the formation of a solid film passivation layer on the surface of pyrite and inhibits the oxidation dissolution of pyrite. This research investigates the impact of Al2O3 incorporation on the speciation transformation of S, Fe, and Al on the surface of pyrite during oxygen pyrite process. The oxidation of pyrite followed the “polysulfide-thiosulfate” complex oxidation pathway. When <1.5 g/L Al2O3 was introduced, it increase pyrite oxidation, whereas ≥1.5 g/L Al2O3 prevented pyrite oxidation. The process of Al2O3 dissolution results in the consumption of H+ and the subsequent release of Al3+. This, in turn, facilitates the hydrolysis of Fe3+ and Al3+ to generate a secondary mineral layer on the pyrite surface. As a result of the accumulation of S promotes the formation of polysulfide chemical (FeSn) or iron deficiency sulfide (Fe1-xS), resulting in the formation of a solid film passivation layer composed of sulfur film and secondary mineral layer. The results demonstrated that Al2O3 can promote the formation of a solid film passivation layer on the surface of pyrite, which has significant implications for controlling the oxidation dissolution process of pyrite and offers a new perspective for the source control of acid mine drainage.

Rates and pathways of iodine speciation transformations at the Bermuda Atlantic Time Series

The distribution of iodine in the surface ocean – of which iodide-iodine is a large destructor of tropospheric ozone (O3) – can be attributed to both in situ (i.e., biological) and ex situ (i.e., mixing) drivers. Currently, uncertainty regarding the rates and mechanisms of iodide (I-) oxidation render it difficult to distinguish the importance of in situ reactions vs ex situ mixing in driving iodine’s distribution, thus leading to uncertainty in climatological ozone atmospheric models. It has been hypothesized that reactive oxygen species (ROS), such as superoxide (O2•−) or hydrogen peroxide (H2O2), may be needed for I- oxidation to occur at the sea surface, but this has yet to be demonstrated in natural marine waters. To test the role of ROS in iodine redox transformations, shipboard isotope tracer incubations were conducted as part of the Bermuda Atlantic Time Series (BATS) in the Sargasso Sea in September of 2018. Incubation trials evaluated the effects of ROS (O2•−, H2O2) on iodine redox transformations over time and at euphotic and sub-photic depths. Rates of I- oxidation were assessed using a 129I- tracer (t1/2 ~15.7 Myr) added to all incubations, and 129I/127I ratios of individual iodine species (I-, IO3-). Our results show a lack of I- oxidation to IO3- within the resolution of our tracer approach – i.e., &amp;lt;2.99 nM/day, or &amp;lt;1091.4 nM/yr. In addition, we present new ROS data from BATS and compare our iodine speciation profiles to that from two previous studies conducted at BATS, which demonstrate long-term iodine stability. These results indicate that ex situ processes, such as vertical mixing, may play an important role in broader iodine species’ distribution in this and similar regions.

The fate of Arsenic associated with the transformation of iron oxides in soils: The mineralogical evidence

The influence of iron (oxyhydr)oxides on the transformation and migration of arsenic(As) has garnered significant attention. Previous work has largely focused on the transformation of iron oxides related to As fate at molecular and mechanistic levels. However, studies examining the interplay between As concentration and iron oxides transformation within complex soil system are sparse. This study investigates the transformation of iron oxides in soils with varying As concentration during microbial dissimilatory iron reduction (DIR), employing humic acid (HA) as electron shuttle and assesses the impact on As speciation transformation. Comparative analyses indicate that in soils with high As concentration (>1000 mg/kg), the secondary transformation of iron (oxyhydr)oxides to other forms, such as the conversion of ferrihydrite to goethite and lepidocrocite, or schwertmannite to goethite, is impeded. Consequently, the formation of goethite and lepidocrocite, which would typically re-stabilize As, is inhibited, leading to elevated release of As(III). On the other hand, an increase in magnetite formation in soils with low As concentration (<100 mg/kg) appears to re-stabilize As effectively. Furthermore, the formation of new secondary iron (oxyhydr)oxides in soils with As concentration <200 mg/kg enhances fraction F5, which subsequently contributes to the re-immobilization of As, sequestering it within the soil matrix. This process results in a lower release of As(III) from soils with As concentration below 200 mg/kg. These findings enhance the understanding of the interdependent relationship between the transformation of iron oxides and the fate of As in complex soil systems.

Evolution and speciation transformation of chlorine during automobile shredder residue pyrolysis

Disposal of automobile shredder residue (ASR) via pyrolysis enables the recovery of valuable products; however, the production of hazardous pollutants and low-value products is inevitable due to its high chlorine content. In this work, chlorine evolution behavior and the conversion mechanism during ASR pyrolysis between 480 and 600 °C were systematically studied. The experimental results for organic chlorine (Org-Cl) showed that released chlorinated gases were complex, and HCl only accounted for 35% of the gas phase products, while short-chain hydrocarbons with carbon atoms between two and four accounted for 52%. Chlorine was predominantly retained in the char, and Org-Cl was the primary contributor to the residual chlorine, accounting for over 50% of the char. The content of inorganic chlorine (InO-Cl) was low in the raw sample but significantly increased in the char. Through the distinction between organic and inorganic chlorine content in char, it was confirmed that Org-Cl could be converted to InO-Cl due to complex secondary reactions with metallic compounds. The conversion was favored by increasing the Org-Cl content and the temperature. Our findings clarified the evolution mechanism of chlorine and the transformation from Org-Cl to InO-Cl, thus providing guidance for chlorine regulation and the efficient recycling of metal resources.

Unveiled the Structure-Selectivity Relationship for Carbon Dioxide Reduction Triggered by Bi-Doped Cu-Based Nanocatalysts.

To investigate synergistic effect between geometric and electronic structures on directing CO2RR selectivity, water phase synthetic protocol and surface architecture engineering strategy are developed to construct monodispersed Bi-doped Cu-based nanocatalysts. The strongly correlated catalytic directionality and Bi3+ dopant can be rationalized by the regulation of [*COOH]/[*CO] adsorption capacities through the appropriate doping of Bi3+ electronic modulator, resulting in volcano relationship between FECO/TOFCO and surface EVBM values. Spectroscopic study reveals that the dual-site binding mode ([Cu─μ─C(═O)O─Bi3+]) enabled by Cu1Bi3+ 2 motif in single-phase Cu150Bi1 nanocatalyst drives CO2-to-CO conversion. In contrast, the study of dynamic Bi speciation and phase transformation in dual-phase Cu50Bi1 nanocatalyst unveils that the Bi0-Bi0 contribution emerges at the expense of BOC phase, suggesting metallic Bi0 phase acting as [H]˙ formation center switches CO2RR selectivity toward CO2-to-HCOO- conversion via [*OCHO] and [*OCHOK] intermediates. This work provides significant insight into how geometric architecture cooperates with electronic effect and catalytic motif/phase to guide the selectivity of electrocatalytic CO2 reduction through the distinct surface-bound intermediates and presents molecular-level understanding of catalytic mechanism for CO/HCOO- formation.