Mechanisms of cadmium release from manganese-rich sediments driven by exogenous DOM and the role of microorganisms.

Dissolved organic matter (DOM) is a crucial component of natural sediments that alters Cd sequestration. Nevertheless, how different types of DOM fuel Cd mobilization in Mn-rich sediments has not been elucidated. In the present study, four typical DOM, fluvic acid (FA), bovine serum albumin (BSA), sodium alginate (SA), and sodium dodecyl benzene sulfonate (SDBS), were used to amend Cd-contaminated sediment to study their effects on Cd/Mn biotransformation and microbial community response. The results demonstrated that different DOM drive microbial community shifts and enhance microbially mediated Mn oxide (MnO) reduction and Cd release. The amendment of terrestrial- and anthropogenic-derived DOM (FA and SDBS) mainly contributed to enriching Mn-reducing bacteria phylum Proteobacteria, and its abundance increased by 38.16-74.47 % and 56.41-73.98 %, respectively. Meanwhile, microbial-derived DOM (BSA and SA) mainly stimulated the abundances of metal(loid)-resistant bacteria phylum Firmicutes. Accompanied by microbial community structure, diversity, and co-occurrence network shifts, the DOM concentration and oxidation-reduction potential changed, resulting in enhanced Cd mobilization. Importantly, FA stimulated Cd release most remarkably, probably because of the decreased cooperative interactions between bacterial populations, stronger reduction of MnOs, and higher aromaticity and hydrophobicity of the sediment DOM after amendment. This study linked DOM types to functional microbial communities, and explored the potential roles of different DOM types in Cd biotransformation in lake sediments.

Binding of Cd(II) to birnessite and fulvic acid organo-mineral composites and controls on Cd(II) availability.

Manganese oxide minerals (MnOs) are major controls on cadmium (Cd) mobility and fate in the environment. However, MnOs are commonly coated with natural organic matter (OM), and the role of this coating in the retention and availability of harmful metals remains unclear. Herein, organo-mineral composites were synthesized using birnessite (BS) and fulvic acid (FA), during coprecipitation with BS and adsorption to preformed BS with two organic carbon (OC) loadings. The performance and underlying mechanism of Cd(II) adsorption by resulting BS-FA composites were explored. Consequently, FA interactions with BS at environmentally representative (5 wt% OC) increase Cd(II) adsorption capacity by 15.05-37.39% (qm = 156.5-186.9 mg g-1), attributing to the enhanced dispersion of BS particles by coexisting FA led to significant increases in specific surface area (219.1-254.8 m2 g-1). Nevertheless, Cd(II) adsorption was notably inhibited at a high OC level (15 wt%). This might have derived from the supplementation of FA decreased pore diffusion rate and generated Mn(II/III) competition for vacancy sites. The dominant Cd(II) adsorption mechanism was precipitation with minerals (Cd(OH)2), and complexation with Mn-O groups and acid oxygen-containing functional groups of FA. In organic ligand extractions, the exchange Cd content decreased by 5.63-7.93% with low OC coating (5 wt%), but increased to 33.13-38.97% at a high OC level (15 wt%). These findings help better understand the environmental behavior of Cd under the interactions of OM and Mn minerals, and provide a theoretical basis for organo-mineral composite remediation of Cd-contaminated water and soil.

Manganese oxides mediated dissolve organic matter compositional changes in lake sediment and cadmium binding characteristics.

In sediment environments, manganese (Mn) minerals have high dissolved organic matter (DOM) affinities, and could regulate the changes of DOM constituents and reactivity by fractionation. However, the effects of DOM fractionation by Mn minerals on the contaminant behaviors remain unclear. Herein, the transformations of mineral phases, DOM properties, and Cd(II) binding characteristics to sediment DOM before and after adsorption by four Mn oxides (δ-MnO2, ß-MnO2, γ-MnOOH, and Mn3O4) were investigated using multi-spectroscopic tools. Results showed a subtle structural variation of Mn oxides in response to DOM reduction, and no phase transformations were observed. Two-dimensional correlation spectroscopy based on synchronous fluorescence spectra and Fourier transform infrared spectroscopy indicated that tryptophan-like substances and the amide (II) N-H groups could preferentially interact with Cd(II) for the original DOM. Nevertheless, preferential bonding of Cd(II) to tyrosine-like substances and phenolic OH groups was exhibited after fractionations by Mn oxides. Furthermore, the binding stability and capacity of each DOM fraction to Cd(II) were decreased after fractionation based on the modified Stern-Volmer equation. These differences may be attributed to DOM molecules with high aromaticity, hydrophobicity, molecular weight, and amounts of O/N-containing group were preferentially removed by Mn oxides. Overall, the environmental hazard of Cd will be more severe after DOM fractionation on Mn minerals. This study facilitates a better understanding of the Cd geochemical cycle in lake sediments under the DOM-mineral interactions, and recommends being careful with outbreaks of aquatic Cd pollution when sediments are rich in dissolved protein-like components and Mn minerals.

[Characteristics and Sources of DOM in Lake Sediments Under Different Inundation Environments].

The characteristics and sources of DOM in sediments are significantly affected by fluctuations in lake water levels. However, the impact of spatial differences on water levels remain unclear. Here, 36 sediment samples were collected from the flood passage and coastal beach of East Dongting Lake. The differences in the composition and source of DOM in sediments under perennial inundation and seasonal inundation were studied using UV-visible absorbance (UV-Vis) and fluorescent excitation-emission matrix (EEM)-parallel factor analysis (PARAFAC). Three fluorescent components of DOM in the sediment were identified. The relative abundance of protein-like components was as high as (72.95±8.94)%, including tryptophan (C2) and tyrosine (C3). However, the humic-like component (C1) abundance was (27.05±8.94)%. Compared with that in perennial inundation, DOM in seasonal inundation had a higher and lower relative abundance of protein-like components and humic-like components, respectively. Further, the aromatic and hydrophobic components were higher in perennial inundation, showing a spatial pattern of the middle>entrance>outlet of the lake, which was more conducive to the migration of pollutants. The high FI (1.93) and BIX (0.91) and low HIX (1.57) indicated that the DOM in sediments had the mixed characteristics of being mainly endogenic and relatively weakly terrigenous. This was mainly influenced by human input and sediment characteristics. The direct effect of sewage discharge was intensified by sediment exposure in the seasonal inundation zone. Additionally, the contents of clay and total nitrogen (TN) were significantly positively correlated with FI, indicating that high nutrients and clay in sediments enhanced the endogenous input of DOM (FI>1.9). The perennial inundation zone was influenced by external runoff input. At the same time, the pH and C/N were significantly positively correlated with HIX and C1, indicating that DOM in the sediments had higher terrigenic characteristics (HIX=1.38±0.57) than those in the seasonal inundation zone owing to the alkaline environment (pH>7.5) and runoff input. The results above revealed the relevant theories of the response of DOM in sediment to water quality and pollution in the process of hydrology and human activities and provide a scientific basis for the prevention and control of sediment pollution in lakes.

How do drying-wetting cycles influence availability of heavy metals in sediment? A perspective from DOM molecular composition.

Investigating the influence mechanism of drying-wetting cycles on the availability and mobility of heavy metals in sediment from the perspective of the molecular composition of dissolved organic matter (DOM) may gain a new understanding, but little current information exists. Here, we used spectral technologies, high-resolution mass spectrometry, and elemental stoichiometry method to trace the change rules of the molecular composition of DOM in the riparian sediment of the river. Results showed that the drying-wetting cycles could benefit the degradation of labile fractions (e.g., proteins, aliphatics, and lipids) of DOM and retain the fractions with high aromaticity and molecular size (e.g., lignin). The decrease in the availability of Cd after drying-wetting alternation processes was highly related to these changes in DOM composition. However, the availability of Zn and Cu remained almost unchanged, which probably resulted from the release and depletion of N and S in sediment-derived DOM under drying-wetting alternation conditions. As for Cr, its exchangeable fraction was unchanged during the drying-wetting alternation process, likely due to its high stability in the sediment. These results have implications on the environmental geochemical cycling of heavy metals in the riparian sediment with frequent drying-wetting alternation.

Cadmium immobilization in lake sediment using different crystallographic manganese oxides: Performance and mechanism.

Cd pollution in sediments poses severe threats to environmental safety and human health. Mn oxides have potential merit for the remediation of Cd pollution in sediment but have not received enough attention. Although Mn oxides have proven effective as adsorbents for removing heavy metals from water/wastewater, the performance and the underlying mechanism of Cd immobilization in sediments by Mn oxides remain unclear. Here, three crystallographic Mn oxides δ-MnO2, γ-MnOOH, and Mn3O4 were used as amendments to investigate their potential for the in situ immobilization of Cd in lake sediment. Experimental data showed that when the sediment samples were treated with synthesized Mn oxides at dosages of 2% and 6% (w/w) for 56 days, the TCLP (toxicity characteristic leaching procedure) leachable Cd in the sediment decreased by 43.9-66.81%, and the PBET (physiologically based extraction test) extractable Cd decreased by 45.16-99.40%. Additionally, the acid-soluble fraction of Cd was partially transformed to a residual fraction, resulting in a 27.55-35.49% decrease in acid-soluble Cd and a 25.16-30.36% increase in the residual Cd fraction. Sediment pH and oxidation-reduction potential were important factors affecting the bioavailability of Cd in the remediation process. Furthermore, scanning electron microscopy, X-ray diffractometer, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analysis illustrated that the interaction between the amendment and Cd mainly involved complexation with O-containing groups, ion-exchange as > OCd+, and precipitation with carbonate. The efficient remediation capacity and associated mechanism for Mn oxides provide insights for the improved restoration of heavy metal-contaminated sediment.

Effects of pyrolysis temperature on proton and cadmium binding properties onto biochar-derived dissolved organic matter: Roles of fluorophore and chromophore.

Understanding the environmental behavior of biochar-derived dissolved organic matter (BDOM) is crucial for promoting the extensive utilization of biochar and meeting the carbon neutrality targets. However, limited studies focused on the binding mechanism of protons and Cd with DOM released from biochar produced at different pyrolysis temperatures. By combining excitation-emission matrix spectroscopy and parallel factor analysis, we found that the humic-like fluorophores in BDOM had higher aromaticity, molecular weight, and contents of carboxylic and phenolic groups relative to the protein-like fluorophores. Conversely, the protein-like fluorophores exhibited a stronger binding affinity for Cd than humic-like fluorophores. With the pyrolysis temperature increased from 300 °C to 500 °C, the quenching effects of Cd on the protein-like components were enhanced significantly. Their fluorescence intensities could be quenched up to 51.64%. The results of ultraviolet-visible absorbance spectroscopy and differential absorbance spectroscopy showed that the carboxylic-like and phenolic-like chromophores were involved in the protons and Cd binding process of BDOM. The binding ability of phenolic-like chromophores with Cd was reduced as a function of increasing pyrolysis temperature. These findings implied that these carboxylic and phenolic groups were mainly contained in the non-fluorescent components. Besides, protons and Cd could also induce inter-chromophore interactions in BDOM, and the interaction was proportional to the pyrolysis temperature. These results clearly demonstrated the pyrolysis temperature-dependent changes in the protons and Cd binding properties of BDOM. More importantly, the possible risk of Cd mobility caused by the protein-like components in BDOM cannot be ignored when the biochar was applied in contaminated soils. This research extends our knowledge of the application potentiality of biochar in heavy metal polluted soil.

Fe oxides and fulvic acids together promoted the migration of Cd(II) to the root surface of Phragmites australis.

Dissolved organic matter (DOM) or iron/manganese (hydro)oxides were important factors in the migration of Cd in sediments of wetlands. DOM and Fe oxides simultaneously affect the longitudinal and transverse migration of Cd in wetlands sediments of plants was still unclear. In this study, a 14-day rhizobox experiment was conducted and the result showed that the rhizosphere effect of Cd migration was only limited to the upper layer of sediments (- 2 to - 4 cm). Fe with fulvic acid (FA) simultaneously existed can precipitate Cd(II) from supernatant to sediments downward. Fe oxides at sediment concentration could effectively prevent Cd(II) from migrating to root surface (0.21 vs 0.02 at%). While Fe oxides with FA together at sediment concentration could effectively promoted the migration of Cd(II) to root surface (0.07 vs 0.08 at%). The formation of organo-metallic complexes of Fe in the presence of FA profoundly proved this finding (increased by ~33.0%). And the polysaccharides and aromatics in organic matter were the chief functional groups participating in the incorporation of Cd and Fe oxides. The findings reveal the migration rules of Cd(II) in sediments by FA and Fe oxides and give an insight into the mechanisms of Cd(II) migration to the root surface around wetland plants.

[Promotion and Mechanisms of DOM on Copper Adsorption by Suspended Sediment Particles].

The adsorption of heavy metals by suspended sediment particles is a key process in the migration of heavy metals in lakes and is affected by various environmental conditions. To reveal the effects and mechanisms of dissolved organic matter (DOM) on the adsorption of copper ions by suspended sediment particles, a Cu(Ⅱ) adsorption test was conducted through a laboratory simulation test. The results showed that DOM promoted the adsorption of Cu(Ⅱ) onto the suspended particles. Under the respective influences of fulvic acid and DOM extracted from the sediment of the Xiangjiang River, the adsorption percentage of Cu(Ⅱ) increased from 71.51% to 75.31% and 85.69%. Scanning electron microscope-energy spectroscopy results showed that under the influence of DOM, Cu(Ⅱ) existed inside the sediment particles after being adsorbed. The results of UV-visible (UV-Vis) spectroscopy showed that Cu(Ⅱ) and DOM were first complexed and then dissociated during the adsorption reaction. The results of fluorescent excitation-emission matrix spectroscopy combined with parallel factor analysis and synchronous fluorescence spectroscopy combined with two-dimensional correlation analysis indicate that protein-like components promoted the adsorption of Cu(Ⅱ) onto the sediment suspended particles. In particular, tyrosine-like components played a critical role in promoting adsorption. However, humic-like components hardly promote this adsorption. This study has improved the theory of heavy metal migration in lakes and can be used as a basis for the prevention and control of heavy metal pollution in sediments.

Laboratory and simulation study on the Cd(â ¡) adsorption by lake sediment: Mechanism and influencing factors.

Sediments are the major sinks for Cd(Ⅱ) in the aquatic environment. Here, the detailed binding mechanisms and effects of environmental factors on Cd(Ⅱ) adsorption onto lake sediment were tested by a batch of adsorption and characteristic experiments. Sediment samples and sediment-Cd complexes were characterized using Scanning electron microscopy, Energy dispersive spectroscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffraction spectral analyses. The interactive and main effect of parameters such as pH, flow velocity, Cd(II) concentration, sediment particle size, humic acid, fulvic acid and adsorption time involved in the adsorption process were determined using two models based on response surface methodology (RSM) and a back-propagation neural network with genetic algorithm (GABP). Results showed that Cd(II) adsorption onto sediment was mainly achieved through surface complexation with O-containing groups and precipitation with carbonate and sulfide. RSM was favorable for modeling Cd(II) adsorption in lake systems because it intuitively reflected the influence of the factors and had a good fitting precision (R2 = 0.8838, RSME = 2.5496) close to that of the GABP model (R2 = 0.8959, RSME = 2.5410). pH, sediment particle size, and humic acid exerted strong influences on Cd(II) immobilized by the sediment. Overall, our findings facilitate a better understanding of Cd(II) mobility in lakes and provide a reference for controlling heavy metals derived from both aqueous and sediment sources.

Phosphate hinders the complexation of dissolved organic matter with copper in lake waters.

The properties of phosphate in lakes and their ability to cause eutrophication have been well studied; however, the effects of phosphate on the environmental behavior of other substances in lakes have been ignored. Dissolved organic matter (DOM) and heavy metals may coexist with phosphate in lakes. Herein, the mechanisms underlying the influence of phosphate on heavy metals complexation with DOM were investigated using multi-spectroscopic tools. Overall, the amount of DOM-bound Cu(Ⅱ) decreased with the increasing phosphate content. Furthermore, the fluorescence excitation and emission matrix results combined with parallel factor analysis showed that when the Cu(Ⅱ) concentration increased from 0 to 5 mg/L and 50 µM phosphate to the reaction of DOM and copper, the fluorescence intensity of tyrosine (component 1), humic-like (component 2) and tryptophan (component 3) decreased by 36.46%, 57.34%, and 74.70% compared with the treatment with no phosphate addition, respectively. This finding indicates that the binding of different fluorescent components to Cu(Ⅱ) was restricted by phosphate. Furthermore, different functional groups responded differently to Cu(Ⅱ) under different phosphate concentrations. The binding sequence of different functional groups under high concentration of phosphate (phenolic hydroxyl group＞amide (Ⅰ) ＞carbohydrates) was completely opposite to that with no phosphate. These results demonstrated that phosphate could restrict the binding affinity of heavy metals with different fluorescent substances or organic ligands of DOM, suggesting that the comigration of DOM-bound heavy metals in lakes is hindered by phosphate and the risk of heavy metal poisoning in aquatic organisms is therefore diminished.

Restriction of dissolved organic matter on the stabilization of Cu(II) by phosphate.

The precipitation of Cu(II) by phosphate and the influence of dissolved organic matter (DOM) on the precipitation are essential for the fate of Cu(II) in aquatic environments. In this study, the influence of DOM on the reaction of phosphate with Cu(II) was investigated. Here, 51.61%, 29.75%, and 24.32% of the added Cu(II) (50 µM) precipitated without DOM and with the addition of fulvic acid (FA) and humic acid (HA), respectively, owing to the reaction with phosphate (50 µM). Excitation-emission matrix spectroscopy-parallel factor (PARAFAC) and two-dimensional ultraviolet-visible correlation spectroscopy analyses were conducted to characterize the influence of DOM on the precipitation of Cu(II) with phosphate. One humic-like and two protein-like fluorescent components were identified by the PARAFAC model for FA, whereas two humic-like fluorescent components and one protein-like fluorescent component were validated for HA. The humic-like components had primary roles, whereas the protein-like components had secondary roles in limiting the precipitation of Cu(II) with phosphate. Cu(II) binding to DOM chromophores initially occurred at shorter wavelengths, and then at longer wavelengths. Phenolic and carboxylic constituents had important roles, and HA exhibited more binding sites than FA. Therefore, humic-like fluorescent components and chromophores containing phenolic and carboxylic groups and functional groups with peaks at short wavelengths (200-220 nm) were primarily responsible for restricting the precipitation of Cu(II) with phosphate.

Enhanced Biosorption of Sb(III) onto Living Rhodotorula mucilaginosa Strain DJHN070401: Optimization and Mechanism.

How to effectively remove excess Sb(III) in the water environment by biosorption is receiving close attention in the international scientific community. To obtain the maximum biosorption efficiency, response surface methodology (RSM) was employed to optimize a total of 13 factors for biosorption of Sb(III) onto living Rhodotorula mucilaginosa DJHN070401. The mechanism of biosorption and bioaccumulation was also studied. The results showed that biosorption reached 56.83% under the optimum conditions. Besides, pH, Fe2+, and temperature are significant influencing factors, and control of Ca2+ and Fe2+ has a beneficial impact on Sb(III) biosorption. The characterization explained that physical adsorption occurred readily on the loose and porous surface of DJHN070401 where carboxyl, amidogen, phosphate group, and polysaccharide C-O functional groups facilitated absorption by complexation with Sb(III), accompanied by ion exchange of Na+, Ca2+ ions with Sb(III). It was also noted that the living cell not only improved the removal efficiency in the presence of metabolic inhibitors but also prevented intracellular Sb(III) being re-released into the environment. The results of this study underpin improved and efficient methodology for biosorption of Sb(III) from wastewater.