Behavior Of Arsenic Research Articles

Effect of sulfidogenesis on ferrihydrite geochemistry and associated arsenic fate.

The behavior of arsenic (As) in groundwater is closely related to the sulfidation of ferrihydrite. In the ternary ferrihydrite-As-sulfide system, ferrihydrite can either initially adsorb As before sulfide reduction or first encounter sulfide and then interact with the aqueous As, altering As fate. However, their relative contributions to the mineralogical transformation of ferrihydrite and subsequently associated As mobilization/redistribution remain poorly understood. Therefore, batch experiments combined with chemical, microscopic, and spectroscopic analyses were conducted to clarify the geochemistry of ferrihydrite and its influence on As behavior. Results indicated that in the pre-sorption groups, the secondary minerals were predominantly presented in amorphous phase due to the retardative effect of As. At low sulfide concentrations (S/Fe=0.04), the content of residual ferrihydrite was large, which favored As immobilization. At high sulfide concentrations (S/Fe=0.8), however, As was initially released into the solution and subsequently re-immobilized by secondary minerals. The adsorption capacity of the secondary minerals for As decreased with the increase in amorphous mackinawite formation. In the pre-sulfidation groups, rapid ferrihydrite reduction promoted the formation of crystalline minerals, significantly reducing their adsorption capacity. At low sulfide concentrations, the released As was partially adsorbed on the surface of crystalline goethite and lepidocrocite. At high sulfide concentrations, magnetite formed and favored As immobilization through its incorporation into magnetite particles. These results provide important insights into the geochemistry of Fe, S, and As in groundwater systems.

The mechanism of arsenic behaviour in the soil-plant system and its interaction with biogenic macroelements of plants under conditions of toxic stress

ABSTRACT The mobility of arsenic compounds in the soil-plant system and its interaction with biogenic macroelements K, P, Ca, Mg, Si, S, Na in plants under conditions of toxic stress have been studied. This is illustrated by the wheatgrass Elytrigia repens. It has been established that the root system is responsible for protecting the aerial part of wheatgrass from excess arsenic, and it is of great importance for phytostabilisation of arsenic pollution therefore indicating the increased tolerance of this plant. The intensity of As accumulation in plants depends on its speciation in the soil. Antagonism of the main essential elements (K, P) to the accumulation of As in wheatgrass shoots is observed. It can lead to disruption of metabolic processes in plant cells. It has been shown that changes in the K+/Na + values may lead to violation of osmotic processes in the aerial plant organs and contribute to their degradation not only under salt stress but also under the influence of higher concentrations of As in the plants. In areas intensively contaminated with arsenic, a decrease in the K/Na value in the above-ground organs of wheatgrass can be used as a criterion for the degree of phytotoxicity.

Geochemical Constraints on Arsenic and Rare Earth Elements in Groundwater of Ganges Delta, Nadia District, West Bengal

ABSTRACT Geochemical studies of groundwater from 302 tubewells and aquifer sediments of the Ganges delta plain of Quaternary age are conducted. The geochemical behaviour of Fe, Mn, SO42-, arsenic (As), REEs, and Eu parameters in groundwater indicates two contrasting environments: (i) a more oxic condition in the fluvial environment of the Jalangi River in the northern part, and (ii) a less oxidizing/reducing environment in the palaeo-lacustrine environment towards south of the study area. Arsenic concentration in groundwater is more in palaeo-lacustrine environment due to (i) reductive desorption from Fe-oxyhydroxide in the high pH reducing environment and (ii) mobilization by ion exchange with the help of fertilizer used in agricultural activities. Both these phenomena are attributed to the strong spatial correlation of arsenic (As) with pH, PO4, and SO4. However, the dissimilar nature of REE pattern in groundwater and aquifer sediment indicates that REE geochemistry of groundwater is being modified by the “reductive dissolution of Fe-oxyhydroxides” in sediment which releases REE into the groundwater. We conclude that desorption and “reductive dissolution of Fe-oxyhydroxide” controls release of As and REE into the groundwater in both oxic and reducing aquifer conditions in the Ganges delta.

Adsorption and migration behaviors of heavy metals (As, Cd, and Cr) in single and binary systems in typical Chinese soils

In this study, the competitive adsorption and migration behaviors of arsenic (As), cadmium (Cd), and chromium (Cr) in typical Chinese soils were investigated. It was observed that Hainan, Shanxi, and Zhejiang Mengjiadai soils exhibited the highest adsorption capacities for As (563 μg/g), Cd (653 μg/g), and Cr (383 μg/g), respectively. Heavy metals (HMs) adsorption capacities were predicted by Extreme gradient boosting (XGBoost) models, and the Shapley additive explanation (SHAP) was employed to elucidate the effect of soil physicochemical properties on target values. Due to redox and complexation reaction, the primary factor affecting adsorption has changed from free state manganese (Mn) in single As system to antimony (Sb) in As/Cd and As/Cr systems. Furthermore, the maximum adsorption capacity (Qm) of As increased by 49.4 % with the addition of Cd into Heilongjiang soil. Finally, the migration process of HMs in Heilongjiang, Hebei, and Hainan soils was simulated by column experiments. With a relatively large dispersion coefficient (D = 29.630 cm2/h) and small retardation factor (Rh = 0.030), Cr penetrated fastest in Heilongjiang soil. This research demonstrates that both the types and coexistence of HMs may affect the HMs behaviors in soil.

Research progress on environmental behavior of arsenic in Qinghai-Tibet Plateau soil

The Qinghai-Tibet Plateau, with its high altitude and cold climate, is one of the most fragile ecological environments in China and is distinguished by its naturally elevated arsenic (As) levels in the soil, largely due to its rich mineral and geothermal resources. This review provides a comprehensive analysis of As content, focusing on its distribution, environmental migration, and transformation behavior across the plateau. The review further evaluates the distribution of As in different functional areas, revealing that geothermal fields (107.2 mg/kg), mining areas (53.8 mg/kg), and croplands (39.3 mg/kg) have the highest As concentrations, followed by river and lake sediments and adjacent areas (33.1 mg/kg). These elevated levels are primarily attributed to the presence of As-rich minerals, such as arsenopyrite and pyrite. Additionally, human activities, including mining and geothermal energy production, exacerbate the release of As into the environment. The review also highlights the role of local microorganisms, particularly those from the phyla Proteobacteria and Actinobacteria, which possess As metabolic genes that facilitate As translocation. Given the unique climatic conditions of the plateau, conventional methods for As control may not be fully effective. However, the review identifies promising remediation strategies that are environmentally adaptable, such as the use of local microorganisms, specific adsorbents, and integrated technologies, which offer potential solutions for managing and utilizing As-contaminated soils on the plateau.

Effects of Nitrogen Fertilizer Application on Soil Properties and Arsenic Mobilization in Paddy Soil

Anthropogenic nitrogen (N) fertilization may substantially alter arsenic (As) behavior in the soil. However, a comprehensive understanding of how the soil As cycle responds to external N addition remains elusive. This study investigates the effects of various N fertilizers on soil properties and As mobility in paddy soil. Regardless of N sources, the concentrations of soluble As and SPLP-extractable As decreased with all N applications. Similarly, soil acidification occurred and dissolved iron (Fe) increased in most treatments, except for KNO3 addition. However, only the KNO3 application could reduce As desorption from soil minerals based on phosphate extraction. Also, KNO3 enhanced both soil catalase (S-CAT) and dehydrogenase (S-DEH) activities. Other N treatments decreased S-CAT activities, but increased S-DEH activities. Principal components analysis indicated that phosphate extractable As was associated with NH4+-N concentration and S-DEH activity, while the concentrations of soluble As and SPLP-extractable As were associated with pH, S-CAT activity, and dissolved Fe. These results demonstrated that the soil properties induced by the N application are the main drivers of As desorption in paddy soil and that KNO3 application is more eco-friendly than other N sources in As-contaminated paddy soil. This study shed light on the reasonable application of N-bearing fertilizers and the importance of soil properties to assess As mobility in As-contaminated paddy soil.

Arsenic accumulation in spolic technosols in the area of a large copper smelting plant in the Middle Urals

Relevance. The necessity to study arsenic behaviour in soils as one of the main pollutants of depositing environments in areas of mining and metallurgical industry. In recent decades, arsenic emissions into the environment have reached a huge scale, so this element attracts the attention of researchers around the world. But in spite of all the studies of this problem, there are still some aspects that need to be clarified to understand the geochemistry of arsenic. This paper deals with spolic technosols with critically high arsenic content in the soil profile with alternating water-logged and dry conditions. As one of the main soil-forming elements, orthosteins contain significant amounts of iron and manganese compounds and are capable of adsorption and involvement of the elements in nodule formation. Aim. To determine the influence of orthosteins on arsenic accumulation in soil subjected to intensive anthropogenic load. Object. Ortsteins spolic technosols in the zone of operation of copper smelting plant and background soils not exposed to pollution. Methods. Arsenic was determined by inversion voltammetry method. Morphological characterisation and patterning of the orthosteins were performed by scanning electron microscopy using a Thermo Fisher Phenom XL G2 Desktop SEM unit. Results. The study of morphological features of orthosteins revealed differences in soils subjected to greater anthropogenic load. Arsenic was not detected inside the orthosteins in all studied soils. Also arsenic concentrations in the total mass of ortstein is up to 40–50% of the soil mass. This fact indicates the accumulation of arsenic by surface adsorption and the appearance of orthosteins as a geochemical barrier. The data obtained in the course of this work can contribute to the search for ways to clean up soils contaminated with arsenic, as well as provide an understanding of the basic processes of the behaviour of this element in soil formation.

Arsenic behavior in soil-plant system under the manure application with the combination of antibiotic and roxarsone

Limited attention has been given to the interaction between antibiotics and arsenic in the soil-plant system. In this investigation, Medicago sativa seedlings were grown in soil treated with cow manure containing oxytetracycline (OTC) or sulfadiazine (SD), as well as arsenic (introduced through roxarsone, referred to as ROX treatment). The study revealed a notable increase in As(III) and dimethylarsinic acid (DMA(V)) levels in rhizosphere soils and plant root tissues as arsenic contamination intensified in the presence of antibiotics, while concentrations of As(V) and monomethylarsonic acid (MMA(V)) decreased. Conversely, elevated antibiotic presence resulted in higher levels of As(V) but reduced DMA concentrations in both rhizosphere soils and plant root tissues in the presence of arsenic. The arsenic biotransformation gene aioA was inhibited by arsenic contamination when antibiotics were present, and suppressed by antibiotic contamination in the presence of arsenic, especially in SD treatments, resulting in reduced expression levels at higher SD concentrations. Conversely, the arsM gene exhibited consistent upregulation under all conditions. However, its expression was found to increase with higher concentrations of ROX in the presence of antibiotics, decrease with increasing SD concentrations, and initially rise before declining with higher levels of OTC in the presence of arsenic. Bacterial genera within the Proteobacteria phylum, such as Geobacter, Lusitaniella, Mesorhizobium, and Methylovirgula, showed significant co-occurrence with both aioA and arsM genes. Correlation analysis demonstrated associations between the four arsenic species and the two arsenic biotransformation genes, emphasizing pH as a critical factor influencing the transformation and uptake of different arsenic species in the soil-plant system. The combined stress of antibiotics and arsenic has the potential to modify arsenic behavior and associated risks in soil-plant systems, highlighting the necessity of considering this interaction in future research endeavors.

Reductive dissolution of As-bearing iron oxides: Mediating mechanism of fulvic acid and dissimilated iron reducing bacteria

Fulvic acid (FA) and iron oxides often play regulating roles in the geochemical behavior and ecological risk of arsenic (As) in terrestrial ecosystems. FA can act as electron shuttles to facilitate the reductive dissolution of As-bearing iron (hydr)oxides. However, the influence of FA from different sources on the sequential conversion of Fe/As in As-bearing iron oxides under biotic and abiotic conditions remains unclear. In this work, we exposed prepared As-bearing iron oxides to FAs derived from lignite (FAL) and plant peat (FAP) under anaerobic conditions, tracked the fate of Fe and As in the aqueous phase, and investigated the reduction transformation of Fe(III)/As(V) with or without the presence of Shewanella oneidensis MR-1. The results showed that the reduction efficiency of Fe(III)/As(V) was increased by MR-1, through its metabolic activity and using FAs as electron shuttles. The reduction of Fe(III)/As(V) was closely associated with goethite being more conducive to Fe/As reduction compared to hematite. It is determined that functional groups such as hydroxy, carboxy, aromatic, aldehyde, ketone and aliphatic groups are the primary electron donors. Their reductive capacities rank in the following sequence: hydroxy> carboxy, aromatic, aldehyde, ketone> aliphatic group. Notably, our findings suggest that in the biotic reduction, Fe significantly reduction precedes As reduction, thereby influencing the latter's reduction process across all incubation systems. This work provides empirical support for understanding iron's role in modulating the geochemical cycling of As and is of significant importance for assessing the release risk of arsenic in natural environments.

Suppression of OsSAUR2 gene expression immobilizes soil arsenic bioavailability by modulating root exudation and rhizosphere microbial assembly in rice

One of the factors influencing the behavior of arsenic (As) in environment is microbial-mediated As transformation. However, the detailed regulatory role of gene expression on the changes of root exudation, rhizosphere microorganisms, and soil As occurrence forms remains unclear. In this study, we evidence that loss-of-function of OsSAUR2 gene, a member of the SMALL AUXIN-UP RNA family in rice, results in significantly higher As uptake in roots but greatly lower As accumulation in grains via affecting the expression of OsLsi1, OsLsi2 in roots and OsABCC1 in stems. Further, the alteration of OsSAUR2 expression extensively affects the metabolomic of root exudation, and thereby leading to the variations in the composition of rhizosphere microbial communities in rice. The microbial community in the rhizosphere of Ossaur2 plants strongly immobilizes the occurrence forms of As in soil. Interestingly, Homovanillic acid (HA) and 3-Coumaric acid (CA), two differential metabolites screened from root exudation, can facilitate soil iron reduction, enhance As bioavailability, and stimulate As uptake and accumulation in rice. These findings add our further understanding in the relationship of OsSAUR2 expression with the release of root exudation and rhizosphere microbial assembly under As stress in rice, and provide potential rice genetic resources and root exudation in phytoremediation of As-contaminated paddy soil.

Understanding arsenic behavior in alluvial aquifers: Evidence from sediment geochemistry, solute chemistry and environmental isotopes

The hydro-geochemistry and isotopic variations in groundwater, coupled with sediment geochemistry, were investigated in the Middle Gangetic Plain, India, to better understand the aquifer dynamics that influence the arsenic (As) evolution and mobilization. Eighty-four groundwater samples, thirteen River water samples, and two sediment cores (33 mbgl) were studied. The samples were analyzed for major ions and trace metals, including As and stable isotopic variability (δ2H, δ18O, and δ13C). The study area was categorized into older and younger alluvium based on existing geomorphological differences. Younger alluvium exhibits higher As enrichment in sediment and groundwater, ranging of 2.59–31.52 mg/kg and bdl to 0.62 mg/L. Groundwater samples were thermodynamically more stable with As(OH)3 species ranging from 88.5% to 91.4% and FeOOH from 69% to 81%, respectively. PHREEQC and mineralogical analysis suggested goethite and siderite act as a source and sink for As. However, statistical analysis suggested reductive dissolution as the primary mechanism for As mobilization in the study area. Spatio-temporal analysis revealed elevated concentrations of As in the central and northeastern regions of the study area. Stable isotope (δ2H and δ18O) analysis inferred active recharge conditions primarily driven by precipitation. The depleted d-excess value and enriched δ18O in the groundwater of younger alluvium indicate the effect of groundwater recharge with significant evaporation enrichment. Groundwater recharge potentially decreased the quantity of arsenic in groundwater, whereas evaporation enrichment increased it. Rainwater infiltration during recharge introduces oxygenated water into the aquifer, leading to changes in the redox conditions and facilitating biogeochemical reactions. The carbon isotope (δ13C) results suggest that high microbial activity in younger alluvium promotes As leaching from sediment into the groundwater.

The photocatalytic oxidation of As(III) on birnessite

Birnessite is regarded as an efficient oxidizing agent that would significantly influence the environmental fate of elements such as arsenic. This study compared the chemical and photocatalytic oxidation of As(III) over birnessite. During the chemical oxidation, As(III) was oxidized to As(V), while Mn(IV) was reduced to Mn(II), subsequently forming MnOOH. The coverage of the reactive sites by MnOOH inhibited the chemical oxidation of residual As(III). At pH 5.0, after 360 min of reaction, 61% of As(III) was oxidized to As(V), and the oxidation of As(III) decreased with an increase in pH. The photocatalytic oxidation of As(III), where almost all As(III) could be oxidized to As(V) over a pH range of 5.0–8.0 and 360 min, was much more efficient compared to chemical oxidation. In contrast to chemical oxidation, the formation of MnOOH slightly affected the photocatalytic performance of birnessite. It was demonstrated that •O2− radicals and holes (hvb+) played an important role in the photocatalytic oxidation of As(III) over birnessite. Our findings confirmed that light dramatically promoted the oxidation of As(III) by birnessite, broadening the understanding of the environmental behaviors of arsenic.

The alternation of flood and ebb tide induced arsenic release and migration from coastal tidal flat sediments in Yellow Sea wetlands: An ex-situ study

Periodic floods and ebb tides driven by seawater affect arsenic (As) behavior in coastal wetlands, which is not fully understood. In this study, we combined DGT, high-throughput sequencing, and real-time quantitative polymerase chain reaction (qPCR) techniques for the first time to investigate the effects of flood and ebb tide on As transformation and mobility in a typical coastal tidal flat wetland by laboratory experiments. In the flood-tide stage, more As was released into the water solution, and As(III) concentration in water solution was notably higher (51 μg/L) than in the ebb-tide stage, especially in SA (sodium acetate addition) treatment. As-methylation also occurred in this stage. The release of As was attributed to the reductive dissolution of amorphous and crystalline Fe oxides bound As induced by microbes. Fusibacter, Sva1033, Bradyrhizobium, Ralstonia, and Desulfobacter were primarily involved in the reduction of As, Fe, and S. The copy numbers of arsC were 20–148 times higher than arrA, suggesting that the detoxification reduction pathway was the primary mechanism of direct As-reduction in the flood-tide stage. However, 2-D high-resolution DGT techniques revealed that the concentrations of As(III) and total As in pore water of sediments in the ebb-tide stage were higher than those in the flood-tide stage. The detected aioA gene indicated that As was oxidized in the sediment surface, resulting in As stabilization by crystalline iron minerals, whereas more As(III) were accumulated in pore water. The reduction pathway mediated by arrA may play a prominent role in the ebb-tide stage. This study provides new insights into As release processes in coastal wetlands in seawater environments, which further deepens our understanding of As biogeochemical cycling behavior in different natural environments.

Adsorption behavior of lead, cadmium, and arsenic on manganese-modified biochar: competition and promotion.

Biochar adsorption of heavy metals has been a research hotspot, yet there has been limited reports on the effect of heavy metal interactions on adsorption efficiency in complex systems. In this study, the adsorbent was prepared by pyrolysis of rice straw loaded with manganese (BC-Mn). The interactions of Pb, Cd and As adsorption on BC-Mn were systematically studied. The results of the adsorption isotherms for the binary metal system revealed a competitive adsorption between Pb and Cd, resulting in decreased Pb (from 214.38mg/g to 148.20mg/g) and Cd (from 165.73mg/g to 92.11mg/g). A notable promotion occurred between As and Cd, showing an increase from 234.93mg/g to 305.00mg/g for As and 165.73mg/g to 313.94mg/g for Cd. In the ternary metal system, Pb inhibition did not counteract the promotion of Cd and As. Furthermore, the Langmuir isotherm effectively described BC-Mn's adsorption process in monometallic, binary, and ternary metal systems (R2 > 0.9294). Zeta and FTIR analyses revealed simultaneous competition between Pb and Cd for adsorption on BC-Mn's -OH sites. XPS analysis revealed that As adsorption by BC-Mn facilitated the conversion of MnO2 and MnO to MnOOH, resulting in increased hydroxyl radical production on BC-Mn's surface. Simultaneously, Cd combined with the adsorbed As to form ternary Cd-As-Mn complexes, which expedited the removal of Cd. These results help to provide theoretical support as well as technical support for the treatment of Pb-Cd-As contaminated wastewater.

Redox Behavior of Arsenic (III) and Copper (II) Mixtures on Ultraflat Au (111) Thin Film Electrodes

The electrochemical behavior of arsenic on gold (Au) electrodes surfaces is of great interest as As is well-recognized as a highly toxic and relatively ubiquitous ground water species. The United States Environmental Protection Agency (USEPA) and World Health Organization (WHO) drinking water standards for arsenic are 10 PPB, or 𝜇g L-1 [1]. These minute ion concentrations necessitate the use of analytical methods with high sensitivity and a low susceptibility to cross interferences. Electrochemical stripping voltammetry is a well-established electroanalytical method for arsenic ions [2]. Polycrystalline gold electrodes are often used due to their high redox stability and relatively low overpotential for hydrogen evolution. We recently explored the use of ultra-flat, thin film, Au(111) electrodes to replace polycrystalline Au for As stripping voltammetry. Previous studies on oriented single crystals showed relatively narrow stripping peaks with greatly improved peak to background ratios on the (111) surfaces [3]. We observed comparatively similar or better stripping behavior on the Au(111) thin film electrodes with correspondingly far less gold usage per electrode. Unfortunately, copper is a known interference for arsenic stripping electroanalysis, with a strong affinity for UPD deposition on gold. We therefore studied the deposition behavior of Cu on Au(111) thin film electrodes and the co- deposition of Cu and As on the Au(111) thin film electrodes to evaluate cross interference effects. Copper redox behavior in 0.5M H2SO4 was characterized by cyclic voltammetry, electro- deposition and linear stripping voltammetry (LSV) measurements. Strong Cu UPD behavior was observed on Au(111) thin films with sharper, better defined redox peaks than polycrystalline electrodes. Arsenic and Cu ions were also co-deposited over a wide range of Cu (II) and As (III) concentrations. Complex redox behavior was observed with strong indications of Cu-As alloy formation. This was confirmed via angle resolved, X-ray Photoemission Spectroscopy (XPS) measurements. Our results also indicate that the electrodeposition efficiency during LSV of As is increased by the co-deposition of Cu. The results of this study have important implications for understanding the nature of Cu (II) interference with electrochemical detection of trace As (III) in water.[1] USEPA. National Secondary Drinking Water Regulations. 2009. https://www.epa.gov/sdwa/drinking-water- regulations-and-contaminants (accessed.[2] USEPA. METHOD 7063: ARSENIC IN AQUEOUS SAMPLES AND EXTRACTSBY ANODIC STRIPPING VOLTAMMETRY (ASV). 1996.[3] Casuse-Driovínto, T. Q.; Rizo, R.; Benavidez, A.; Brearley, A. J.; Cerrato, J. M.; Garzon, F. H.; Herrero, E.; Feliu, J. M. Increased Sensitivity and Selectivity for As(III) Detection at the Au(111) Surface: Single Crystals and Ultraflat Thin Films Comparison. The Journal of Physical Chemistry C 2022, 126 (48), 20343-20353. DOI: 10.1021/acs.jpcc.2c05541.

Thermodynamic analysis of Ti, As-containing systems based on E-pH diagrams and partial pressures

Abstract
 The removal of arsenic from the technological circulation of metallurgical enterprises is a technologically necessary process, leading from year to year to the formation of new volumes of arsenic-containing objects. One of the forms of extracting arsenic from the production stage is arsenates of various metals, which are difficult and poorly soluble compounds. This approach also does not solve environmental issues in general. Thus, titanium arsenates under storage and burial conditions are subject to hydrolysis, which leads to gradual pollution and poisoning of the environment with arsenic-containing compounds. The practical value of titanium and its compounds in economic activities forces us to look for ways to rationally use arsenic-containing titanium compounds.
 The article is the first to carry out a thermodynamic analysis of the behavior of arsenic and titanium based on potential-pH diagrams and partial pressures. The course and directions of chemical reactions in titanium- and arsenic-containing systems, the conditions for the stability of their constituent phases, the thermodynamic parameters of the behavior of the participating components, their compounds, the range of their stability, and the redox processes of the formation of chemical products have been studied.
 The regions of existence of titanium arsenate are determined, and chemical and electrode reactions for the production of titanium arsenate from titanium and arsenic compounds are considered. The results of the work confirm both the effectiveness of using titanium compounds to remove arsenic from solutions in the form of poorly soluble manganese arsenate, and the possibility of regenerating titanium in the form of oxides and bases.
 Key words: thermodynamic systems, diagrams, arsenic compounds, titanium compounds, titanium arsenate.

Sustainable removal of arsenic from waters by adsorption on blue crab, Portunus segnis (Forskål, 1775) chitosan-based adsorbents

Chitosan is the common name of a linear, copolymer of β-(1−4)-linked d-glucosamine and N-acetyl-d-glucosamine whose molecular structure comprises a backbone linked through glycosidic bonds. This polysaccharide has received a lot of attention due to its potential to remove heavy metals. In this context, this work was carried out with the aim of studying the efficacy of blue crab, Portunus segnis (Forskål, 1775) chitosan produced previously by the authors via a studied biological process to remove arsenic from aqueous solutions and therefore to be promoted in the environmental sector as effective ingredients for water decontamination. Batch experiments were performed to examine the effects of multiple parameters. Equilibrium isotherms were fitted using the Langmuir and Freundlich equation and finally, column experiments based on adsorption capacity were applied to better describe the adsorption process. The adsorption efficiency of powder from blue crab by-products, biological chitosan (BC) and commercially available chitosan (CC) was compared with that of magnetic chitosan (BMC) which was also prepared by a cross-linking reaction using glutaraldehyde (GTA) in the presence of magnetite. Features of each chitosan forms were analyzed by a field emission-scanning electron microscopy (FE-SEM). The BMC has been found to be effective in removing arsenic. Indeed, both BMC and CC showed improved adsorption behavior of arsenic after the addition of magnetic nanoparticles. The arsenic removal behavior of most materials can be explained by a pseudo-second-order kinetic model mechanism. The pH of the arsenic solution depends on the acid-base state of the adsorbent, which further influences the adsorption performance.

Iron oxide-supported gold nanoparticle electrode for simultaneous detection of arsenic and sulfide on-site

The environmental behavior of arsenic (As) has garnered significant attention due to its hazardous nature. The fate of As often couples with sulfide, thus co-detecting arsenic and sulfide on-site is crucial for comprehending their geochemical interactions. While electrochemical methods are suitable for on-site chemical analysis, there currently exists no electrode capable of simultaneously detecting both arsenic and sulfide. To address this, we developed a dual-metal electrode consisting of iron oxide-encased carbon cloth loaded with gold nanoparticles (Au/FeOx/CC) using the electrochemical deposition method. This electrode enables square wave stripping voltammetry (SWASV) binary detection of As and sulfide. Comparison experiments reveal that the reaction sites for sulfide primarily reside on FeOx, while the interface synergy of iron oxide and gold nanoparticles enhances the response to arsenite (AsIII). Arsenate (AsV) is directly reduced to As0 on Fe0, obviating the need for an external reducing agent. The electrode achieves detection limits of 1.5 μg/L for AsV, 0.25 μg/L for AsIII, and 11.6 μg/L for sulfide at mild conditions (pH 7.8). Field validation was conducted in the Tengchong geothermal hot spring region, where the electrochemical method exhibited good correlation with the standard methods: Total As (r = 0.978 vs. ICP-MS), AsIII (r = 0.895 vs. HPLC-ICP-MS), and sulfide (r = 0.983 vs. colorimetric method). Principal component analysis and correlation analysis suggest that thioarsenic, could potentially be positive interferents for AsIII. However, this interference can be anticipated and mitigated by monitoring the abundance of sulfide. The study provides new insights and problems for the electrochemical detection of coexisted As and sulfide.

Picropharmacolite and arsenolite from the Mareshnitsa ore occurrence, Eastern Rhodopes – new minerals for Bulgaria

New for Bulgaria arsenic minerals picropharmacolite and arsenolite from the Mareshnitsa ore occurrence, Eastern Rhodopes are presented. Their formation is due to the oxidation of arsenopyrite, which is abundant in the samples. The composition of the picropharmacolite from Mareshnitsa differs from the picropharmacolite from other deposits around the world. It is characterized by relatively few impurities and excess of Mg, which substitute part of Ca. This is resulting in smaller a parameter of the unit cell. The presence of these two new arsenic minerals sheds additional light on the behaviour of arsenic in the area.

Dissolved organic matter and Fe/Mn enhance the combination and transformation of As in Lake Chaohu Basin

The phenomenon of algal blooms resulting from lake eutrophication has the potential to increase the concentration of dissolved organic matter (DOM) and consequently influence the environmental behaviour of arsenic (As). In the subtropical region, the interplay between DOM, Fe/Mn and As becomes complex as Fe/Mn-rich substances from soils and sediments enter eutrophic lakes. The mechanisms by which DOM-Fe/Mn interactions affect the transformation of As species remain uncertain. Therefore, the Chaohu Lake Basin was selected as a representative case study site to investigate the levels of DOM, As, Fe and Mn in the water and to establish their associations. In addition, the interaction mechanism between DOM-Fe/Mn and As was investigated by elucidating the transformation behaviour of DOM-Fe/Mn on As species in a controlled laboratory environment. The results showed that in cases where the coexistence of Fe and Mn concentrations was relatively low (e.g. Fe < ∼0.5 mg/L and Mn < ∼0.6 mg/L), the concentration of As in water would increase proportionally with the simultaneous increase of both Fe and Mn concentrations (As < 5 μg/L). However, when the concentration of either Fe or Mn reached 10 mg/L, the proportion of As complexed by DOM increased significantly, reaching 99.73% and 99.66%, respectively. In the configuration of a metallic bridge, the elements Fe and Mn act as connectors between negatively charged DOM and As, thereby increasing the adsorption capacity of DOM for As. The alcohol and alkene functional groups present on the DOM-Fe/Mn surface show a preference for binding with free species of As in aqueous environments. In addition, the reductive groups on the surface of DOM not only directly convert As(V) to As(III), but also facilitate the reduction of Fe(III) to Fe(II), resulting in the indirect conversion of As(V) to As(III). Thus, this study provides a comprehensive understanding of the transport and transformation processes of arsenic in subtropical eutrophic lakes.