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.

Arsenic speciation transformation in soils with high geological background: New insights from the governing role of Fe.

In soils, the speciation transformation of As were inherently related to the behaviors of iron (oxyhydr) oxides. It is poorly understood that the effects of the transformation of iron (oxyhydr) oxides coupled with As speciation transformation during dissimilatory Fe(III) reduction (DIR) involving with humic substances (HS) as electron donor or shuttle in soils with high arsenic geological background. In this study, the relationships between the transformation of iron (oxyhydr)oxides and As speciation transformation were investigated according to the response between continuously As speciation monitoring and iron (oxyhydr) oxides identification during DIR in the soils. The results showed that F4 (arsenic incorporated with amorphous iron (oxyhydr)oxides including ferrihydrite and schwertmannite) and F5 (arsenic incorporated with crystalline iron (oxyhydr)oxides including hematite and magnetite) were the main source and sink for As(III)Dissolved during DIR. During the incubation period, Fe(II) was the dominant driving force for the reduction of As(V) in the water-soil system. The XRD analysis indicated the changes of iron oxides such as ferrihydrite, schwertmannite, hematite and magnetite were closely related to the release and reduction of As, and those iron oxides could play governing roles for As speciation transformation during DIR in soils. Different from the known mechanism in low As concentrations, a limiting effect of As concentration on iron oxides transformation was found in our incubation experiments using soils with high As geological background (∼1000 mg/kg). This work provides new insights for Fe as governing role in As speciation transformation in soils with high arsenic geological background by firstly identifying the corresponding iron (oxyhydr)oxides in operationally defined arsenic speciation incorporated with iron oxides.

Trends and environmental factors of arsenic in sediments from the five lake ecoregions, China.

The behavior and risk of arsenic (As) closely relate to its geochemical fractionation and environmental factors in sediments. The soluble (F1), reducible (F2), oxidizable (F3), and residual fraction (F4) of As were extracted in the sediments from Lake Hulun, Wuliangsuhai, and Dalinor of Inner Mongolia Plateau. Coupled with lakes from Eastern and Northeast Plain, Yunnan-Guizhou and Qinghai-Tibetan Plateau, the responses of As fractions to environmental conditions were investigated according to the spatial distribution of As fractionations in five lake ecoregions at a national scale of China. Generally, F1 was more sensitive to environmental changes, and the pH presented significantly negative effects on the amount of soluble As, while water depth played an important role in regulating the distribution of the fraction F2 and F4. The As pools in surface lake sediments presented a latitudinal zonation due to the gradient effects of climate and anthropogenic activities on nutrient decomposition, and their influence on the capacity of sediments holding As. This work indicated that nutrients played a coordinating role in regulating the impacts of climate and environmental factors on As fractionation in aquatic environments.

The role of major functional groups: Multi-evidence from the binding experiments of heavy metals on natural fulvic acids extracted from lake sediments.

Fulvic acid (FA) plays a key role in governing the environmental geochemistry behavior of heavy metals. In this work, the roles of major functional groups were investigated based on binding experiments of heavy metals on natural FA extracted from lake sediments. The results showed that the adsorption capacities were ranked as Cu2+ > Pb2+ >Cd2+. The differences of peak area at 3412, 1713, 617and 2430 cm-1 pre- and post-binding reactions in FTIR spectra suggested that phenolic, carboxyl and nitrogen-containing groups were the major functional groups providing sites binding heavy metals. Moreover, the results of bi-Langmuir model and the ionic strength effects jointly indicated that electrostatic attraction was the key mechanism during the adsorption process. The fitted results of Ligand-binding model suggested that the major functional groups in FA were classified into two types binding sites: weak (i.e. phenolic and carboxyl groups) and strong binding sites (i.e. nitrogen-containing groups). Additionally, there might be p-benzoquinone-like formed in FA which were then reduced to hydroquinone during the adsorption process, corresponding to the changing of peak area at 1614 and 830 cm-1 in FTIR spectra, the occurrence of Peak C in Fluorescence excitation-emission matrix (EEM) spectra and the ratios of H/C (<1) and O/C (≈1). The organic matter in sediments from Lake Wuliangsuhai presented similar characteristics with terrestrial plants due to the lake characterized by Phragmites australis and Potamogeton pectinatus L. being the dominant species, which shared large proportions of woody tissues as well as waxy hydrocarbons resembling that of terrestrial plants. This work is useful to insight the environmental effects of FA on heavy metals in environment.

Nature differences of humic acids fractions induced by extracted sequence as explanatory factors for binding characteristics of heavy metals.

The composition and structure of Humic acid (HA) is so heterogeneous that it brings significant barriers to investigate the interaction between HA and heavy metal ions. The isolation of HA with relatively homogeneity is a key to reveal the binding mechanisms between HA and heavy metals. In this work, ten HA fractions (HAs) were obtained by sequential alkali extraction procedure and nature differences of the extracted HAs were considered as explanatory factors for binding characteristics of Cu2+, Pb2+ and Cd2+. The results indicate that more large molecular weight (MW) HA subunits, less carboxyl and phenolic group contents, weaker aromaticity and polarity were measured with increasing extractions, inducing weaker binding capacity of HAs. Ligand binding and bi-Langmuir models indicated that the sorption capacity and binding affinity of earlier extracted HAs were higher than the latter ones. The peak area changes at 3427, 1599, and 619 cm-1 pre- and post-adsorption in FTIR spectra suggested carboxyl, phenolic and nitrogen-containing groups were involved in the adsorption process. At the same time, the peak area difference between HAs and HAs-metal (ΔS) of phenolic groups were 8.22-20.50, 6.81-21.11 and 10.66-19.80% for Cu2+, Pb2+ and Cd2+, respectively, ΔS of carboxyl groups 6.64-17.03, 8.96-16.82 and 9.45-17.85% for Cu2+, Pb2+ and Cd2+, respectively, ΔS of nitrogen-containing groups 0.33-0.48, 0.20-1.38 and 0.31-0.59% for Cu2+, Pb2+ and Cd2+, respectively. ΔS of phenolic and carboxyl groups were larger than those of nitrogen-containing groups, implying that these two groups were the predominant binding sites suppliers for metal ions, which were also supported by the results of correlation analysis. This work is helpful to insight the environmental impacts of natural organic matter and the fate of heavy metals in natural environment.

Nature differences of fulvic acid fractions induced by extracted sequence as explanatory factors for binding characteristics of Cu2.

The isolation of fulvic acid (FA) fractions with relatively homogeneity is a key to reveal the binding mechanisms between FA and heavy metals. In this work, nine FA fractions were obtained using sequential alkali extraction procedure and nature differences of the extracted FA fractions were considered as explanatory factors for binding characteristics of Cu2+. The results indicate that the contents of carboxyl and phenolic groups decrease with increasing extractions along with an opposite trend for the content of nitrogen-containing groups. The fitted results of ligand binding and bi-Langmuir models indicate that the binding sites for Cu2+ were mainly provided by carboxyl and phenolic groups, which explained the higher sorption capacity and binding affinity of earlier extracted FAs due to its higher contents of carboxyl and phenolic groups. Furthermore, the systemic characterization of FA fractions before and after adsorption indicate the nitrogen-containing groups were gradually showing their contribution in binding Cu2+ with increasing extractions. This work is very helpful to insight the environmental effects of natural organic matter and the behavior of heavy metals in natural environment.