Low Molecular Weight Organic Acids Research Articles

Synergetic effects of Mn(II) production and site availability on arsenite oxidation and arsenate adsorption on birnessite in the presence of low molecular weight organic acids

Manganese oxides and organic acids are key factors affecting arsenic mobility, but As(III) oxidation and adsorption in the coexistence of birnessite and low molecular weight organic acids (LMWOAs) are poorly understood. Herein, As(III) immobilization by birnessite was investigated with/without LMWOAs (including tartaric (TA), malate (MA), and succinic acids (SA) with two, one and zero hydroxyl groups, respectively). In the low-As(III) system with less Mn(II) production, LMWOAs generally inhibited As(III) oxidation. The slower decrease in As(III) concentration in TA-amended batches resulted from stronger bonding interaction between TA and edge sites, evidenced by higher removal of TA than MA and SA in solutions and the higher proportion of shifted C-OH component in solids. In high-As(III) systems with abundant Mn(II) production, higher concentrations of dissolved Mn and Mn(III) in LMWOA-amended batches than in LMWOA-free batches revealed that LMWOA-induced complexing dissolution caused the release of adsorbed Mn(II), which was conducive to As(III) oxidation and As(V) adsorption onto the edge sites. The lowest concentrations of dissolved Mn and Mn(III) in TA-amended batches indicated that the hydroxyl group constrained complexing dissolution. This study reveals that concentrations of produced Mn(II) determined the roles of LMWOAs in As(III) behavior and highlights the impacts of the hydroxyl group on arsenic mobility.

Robust reactive oxygen species production in interfacial reaction between organic acids and biochar: The combined effect of electron acceptance and electron conduction

Interfacial electron transport and reactive oxygen species (ROS) generation in the redox action between biochar (BC) and low-molecular-weight organic acids (LMWOAs) have been overlooked during the utilization of BC in soil amelioration/remediation. Herein, BC and N-doped BC (NBC) with various physicochemical properties were prepared at pyrolysis temperatures of 350, 550 and 750 °C (namely BC/NBC350, 550 and 750) and their interactions with LMWOAs were systematically investigated. Results of ROS quenching and electrochemical cell experiments revealed that BC/NBC could strongly interact with LMWOAs, especially ascorbic acid (AA), and acted as an electron shuttle to mediate one electron transfer from AA to oxygen to generate O2•−, followed by the robust generation of H2O2 and •OH. Interestingly, the generation rates of •OH and H2O2 in the NBC-AA system were significantly higher than that in the BC-AA system, of which the NBC550-AA system exhibited the best performance, enabling its superior ability in bisphenol A degradation. Different from conventional wisdom, the electron shuttle capacity depended on a combined aromatization degree and electron-accepting capacity of BC/NBC. These findings complement the interfacial electron transfer mechanism during the natural BC-LMWOAs interaction and provide new inspiration for the development of green and efficient organic pollutant removal technologies.

Mechanism of synergistic remediation of soil phenanthrene contamination in paddy fields by rice-crab coculture and bioaugmentation with Pseudomonas sp.

Polycyclic aromatic hydrocarbons (PAHs) are persistent and harmful pollutants with high priority concern in agricultural fields. This work constructed a rice-crab coculture and bioaugmentation (RCM) system to remediate phenanthrene (a model PAH) contamination in rice fields. The results showed that RCM had a higher remediation performance of phenanthrene in rice paddy compared with rice cultivation alone, microbial addition alone, and crab-rice coculture, reaching a remediation efficiency of 88.92 % in 42 d. The concentration of phenanthrene in the rice plants decreased to 6.58 mg/kg, and its bioconcentration effect was efficiently inhibited in the RCM system. In addition, some low molecular weight organic acids of rice root increased by 12.87 %∼73.87 %, and some amino acids increased by 140 %∼1150 % in RCM. Bioturbation of crabs improves soil aeration structure and microbial migration, and adding Pseudomonas promoted the proliferation of some plant growth-promoting rhizobacteria (PGPRs), which facilitated the degradation of phenanthrene. This coupling rice-crab coculture with bioaugmentation had favorable effects on soil enzyme activity, microbial community structure, and PAH degradation genes in paddy fields, enhancing the removal of and resistance to PAH contamination in paddy fields and providing new strategies for achieving a balance between production and remediation in contaminated paddy fields.

Rhizosphere environmental factors regulated the cadmium adsorption by vermicompost: Influence of pH and low-molecular-weight organic acids

Vermicompost is a promising amendment for immobilization of cadmium (Cd) in soils; however, its effectiveness can be influenced by rhizosphere environment conditions, such as pH and the presence of low-molecular-weight organic acids (LMWOAs). In this study, a batch experiment was conducted to examine the characteristics of Cd adsorption by vermicompost at different pH (pH = 3, 5, and 7) and after the addition of different LMWOAs (oxalic acid; citric acid; malic acid). Furthermore, a series of morphology and structural analyses were conducted to elucidate the mechanisms of observed effects. The results showed that the adsorption capacity of vermicompost for Cd increased as pH increased, and chemisorption dominated the adsorption process. Changes in pH altered adsorption performance by affecting the -OH groups of alcohol/phenol and the -CH2 groups of aliphatics. Further, the addition of oxalic acid promoted Cd adsorption, and the effect was concentration dependent. Modifying the verimicompost surface with more adsorption sites might be the main reason. Conversely, citric acid and malic acid showed the ability to inhibit Cd adsorption by vermicompost. Citric acid caused a blocking effect by covering flocculent substances on the vermicompost surface while reducing surface adsorption sites by dissolving mineral components such as iron oxides. However, the action of malic acid did not appear to be related to changes in morphology or the structure of vermicompost. Overall, the results of this study partially explain the limited effectiveness of Cd immobilization within the rhizosphere by vermicompost, and provide theoretical support for regulating rhizosphere environments to improve the effectiveness of vermicompost immobilization of Cd.

The Dissolution Behavior of Feldspar Minerals in Various Low-Molecular-Weight Organic Acids.

Feldspar is a high-abundance mineral in the earth's crust, and its natural weathering and dissolution processes are an important phenomenon on the earth's surface. This study focused on the dissolution behavior of silicon (Si) and aluminum (Al) in feldspar minerals (microcline and albite) when exposed to low-molecular-weight organic acids (LMWOAs). Various analytical techniques, including atomic absorption spectrophotometer, X-ray diffraction, scanning electron microscope, and Fourier-transform infrared spectroscopy, were employed to investigate these processes. The results revealed that the concentration of Si and Al released from alkali feldspar increased after treatment with LMWOAs, exhibiting non-stoichiometric dissolution. The Si/Al release ratio from feldspar deviated from the expected value of three. Among the LMWOAs tested, oxalic acid was found to be more effective in dissolving aluminum, while citric acid showed greater efficacy in dissolving silicon. Notably, the composite acid demonstrated the highest capacity for feldspar dissolution, with values of 538 μM (Si) and 287 µM (Al) after treatment for 720 h, respectively. The dissolution data for Si and Al in the organic acid solution was fittingly described by a first-order equation, with high correlation coefficients (R2 ≥ 0.992). The characterization of feldspar powders indicated that the (040) crystal plane of feldspar was particularly susceptible to attack by organic acids. In the presence of these acids, the chemical bonds Si (Al)-O, Si-Si(Al), and O-Si(Al)-O shifted to higher wavenumbers. Additionally, the surface corrosion morphology of feldspar exhibited distinct nanostructures, which became more pronounced with increasing exposure time. It was also observed that the reactivity of feldspar increased over time. These findings provide valuable insights into the natural dissolution process of feldspar and offer a new perspective for the study of this phenomenon.

Sensitive method for total selenium determination in garlic and nuts by UV–photochemical vapor generation coupled to atomic absorption spectrometry using mild conditions

Photochemical vapor generation (PVG) coupled on–line to atomic absorption spectrometry using a flow injection mode was investigated for the determination of total Se in garlic and nut samples. In the presence of low molecular weight organic acid solutions, Se(IV) is converted by UV irradiation to volatile species which are transported to the heated quartz tube atomizer. Formic and acetic acids were tested as photochemical reagents and a mixture of 1.5 % (v/v) formic and 5 % (v/v) acetic acid was the best alternative. Central composite design was employed for parameters optimization. The effect of potential interfering elements such as hydride–forming elements, transition metals and nitric acid was investigated to ascertain possible effects of the matrix on Se(IV) signal. Under optimized conditions a detection limit (LOD) of 33 ng g–1 (3σ) was reached. Samples of garlic and nuts purchased at a local market were analyzed and Se concentrations spanned the range 0.36–248 µg g–1. These results were compared with ICP–MS measurements utilizing an elliptical joint confidence region (EJCR) with bilinear least squares analysis, and good results were obtained.

Quantitative relationship between soil pH and electrical conductivity values and cadmium phytoavailability for Chinese cabbage under simulated conditions

Pot experiments were conducted to investigate the impacts of continuous addition of different concentrations of calcium chloride (CaCl2) and/or low-molecular-weight organic acids (LMWOAs) on soil pH, electrical conductivity (EC), and cadmium (Cd) transformation. These factors subsequently affected Cd phytoavailability in a system consisting of Cd-contaminated soil and Chinese cabbage (Brassica chinensis L.). The results indicate that CaCl2 addition had a greater impact on reducing soil pH value, increasing soil EC value, and enhancing Cd phytoaccumulation in Chinese cabbage compared to LMWOAs. When soil pH dropped by 0.3 unit and the soil EC increased by 500 µS cm−1, the Cd concentration in the Chinese cabbage shoots was 3 times higher than that in the control group. Throughout two planting terms of Chinese cabbage, the addition of CaCl2 (1.6–3.2 g kg−1) and LMWOAs (≤ 1.0 g kg−1) led to phytoextracted Cd concentration exceeding exchangeable Cd concentration in soil samples before the pot experiment. Regarding phytoextracted Cd, desorption from carbonate-bound Cd contributes more than desorption from bound to organic matter Cd and adsorption to Fe/Mn oxide Cd. This study underscores the influence of soil pH and EC value variations and Cd transformation on Cd phytoavailability. Special attention should be given to leafy vegetables grown in Cd-contaminated soil, as the phytoavailable Cd concentration reaches approximately 2.0 µg kg−1, which may lead to Cd levels surpassing acceptable limits for Chinese cabbage.

The Dissolution Mechanism of Low-Molecular-Weight Organic Acids on the Sillimanite.

The interaction between low-molecular-weight organic acids (LMWOAs) and minerals in nature has been widely studied; however, limited research has been conducted on the dissolution mechanism of sillimanite in the presence of different organic acids. In this study, the interaction between the sillimanite sample and LMWOAs (citric acid, oxalic acid, and citric/oxalic mixture) at the same pH was investigated. The dissolution rate of Si and Al was high during the initial reaction time, then slowed down in the presence of LMWOAs. The dissolution data for Si and Al from sillimanite in the LMWOAs fit well with the first-order equation (Ct = a(1 - exp(-kt))) (R2 > 0.991). The dissolution process of sillimanite in the organic acids was controlled by the surface chemical reaction step. The dissolution concentration of Si in aqueous citric acid was higher than that in oxalic acid. In contrast, the dissolution concentration of Al in oxalic acid was more than that in citric acid. The maximum concentrations of Si and Al in the presence of composite organic acids were 1754 μmol/L and 3904 μmol/L. The sillimanite before and after treatment with LMWOAs were studied using X-ray diffraction (XRD) and scan electron microscopy (SEM). These results are explained by the characterization of the sillimanite. Under the single acid solution, the (210) crystal plane with a high areal density of Al in sillimanite was easily dissolved by the oxalic acid, while the (120) in sillimanite with a high areal density of Si was more easily dissolved by citric acid. In the composite organic acids, the Si-O bond and Al-O bond in sillimanite were attacked alternately, leading to the formation of some deeper corrosion pits on the surface of sillimanite. The results are of interest in the dissolution mechanisms of sillimanite in the low-molecular-weight organic acids and the environmentally friendly activation of sillimanite.

Root chemistry and microbe interactions contribute to metal(loid) tolerance of an aromatic plant – Vetiver grass

Aromatic plants, such as vetiver grass (Chrysopogon zizanioides), possess strong abilities to resist environmental stresses. However, whether such abilities stem from the interaction between specific chemical characteristics and the associated microbes in roots and rhizosphere remains unclear. We conducted pot experiments to analyze stress-tolerant parameters, organic compounds, and bacterial communities in roots and rhizosphere of vetiver under typical metal(loid) stress [cadmium (Cd), arsenic (As), or Cd + As] over time. The results showed that the vetiver displayed limited toxic symptoms in terms of oxidative stress-antioxidant balance and chlorophyll content. The root low-molecular-weight organic acids (LMWOAs), fatty acids, and sterols were highly sensitive to growth stage (increased from the 4-month to the 8-month stage), and less sensitive to metal(loid) stress. The sugar contents in the rhizosphere soils also notably increased over time. Such endo and rhizosphere chemical changes strongly correlated with and enriched the functional bacteria including Streptomyces, which can resist stress and promote plant growth. The compound-bacteria interaction highly depended on growth stage. Vetiver demonstrated a progressive adaptation to stresses through metabolite modulation and cellular defense reinforcement. Our study evidenced that vetiver shapes the interaction between organic compounds and bacterial community in the root-soil interface and provides notable stress-resistant functions.

Transport of polystyrene nanoplastics with different functional groups in goethite-coated saturated porous media: Effects of low molecular weight organic acids and physicochemical properties

The influence of low molecular weight organic acids (LMWOAs) and goethite on the migration of nanoplastics in the soil environment remains poorly understood. To elucidate the mechanism of influence, the study investigated the impact of LMWOAs on the migration ability of functionalized polystyrene nanoplastics (PSNPs-NH2/COOH) in quartz sand (QS) and goethite (α-FeOOH)-coated quartz sand (FOS). We investigated the effect of changes in iron valence induced by LMWOAs on the migration of PSNPs. The results revealed that the migration ability of polystyrene nanoplastics (PSNPs) declined as the ionic strength (IS) increased and the pH decreased, primarily due to the compression of the double layer and protonation reactions. The migration of PSNPs is facilitated by LMWOAs through distinct mechanisms in the two media. Specifically, LMWOAs were adsorbed on the FOS and QS surfaces through complexation and hydrogen bonding, respectively. At pH 4.0, LMWOAs exhibit redox activity, resulting in the generation of additional Fe(III). This redox process enhances the electrostatic attraction between the media and PSNPs, thereby reducing the competition at specific points and spatial resistance associated with LMWOAs. In contrast to FOS, LMWOAs at pH 4.0 reduced the migration ability of PSNPs in QS, following the trend of MA > TA > CA. This difference was attributed to the pKa of LMWOAs and the weak hydrogen bonding on the QS surface. The relevant mathematical models effectively validate the migration results. The above conclusions suggest that LMWOAs can alter the valence state of iron on the surface of goethite, thereby influencing the migration of plastic particles in environmental media.

Effect of low molecular weight organic acids on the lead and chromium release from widely-used lead chromate pigments under sunlight irradiation

Lead chromate pigments are commonly used yellow inorganic pigments. They can pose environmental risks as they contain toxic heavy metals lead and chromium. Low molecular weight organic acids (LMWOAs), as widespread dissolved organic matter (DOM), affect the lead and chromium release from the pigment in water. In this work, the role of LMWOAs in the photodissolution of commercial lead chromate pigment was investigated. The pigment underwent significant photodissolution under simulated sunlight exposure with LMWOAs, and subsequently released Cr(III) and Pb(II). The photodissolution process is caused by the reduction of Cr(VI) by photogenerated electrons of the lead chromate pigment. The LMWOAs promoted photodissolution of the pigment by improving the electron-hole separation. The formation of Cr(III)-contained compounds leads to a slower release of chromium than lead. The photodissolution kinetics increase with decreasing pH and increasing LMWOAs concentration. The photodissolution of lead chromate pigment was basically positively related to the total number of hydroxyl and carboxyl groups in LMWOAs. The LMWOAs with stronger affinity to lead chromate pigment, lower adiabatic ionization potential (AIP) and higher energy of the highest occupied molecular orbital (EHOMO) are favorable to Cr(VI) reduction by photogenerated electrons and pigment photodissolution. 2.39% of chromium and 10.34% of lead released from the lead chromate pigment in natural conditions during a 6-h sunlight exposure. This study revealed the photodissolution mechanism of lead chromate pigment mediated by LMWOAs with different molecular structures, which helps understand the environmental photochemical behavior of the pigment. The present results emphasize the important role of DOM in the heavy metals release from commercial inorganic pigments.

Metabolic insights into how multifunctional microbial consortium enhances atrazine removal and phosphorus uptake at low temperature

Agricultural soils in the black soil region of northeast China often face negative stress due to low temperatures, pesticide contamination, and inadequate nutrient supply. In this study, a new cold-tolerant strain of Peribacillus simplex C1 (C1) was selectively isolated from atrazine contaminated soil. The artificially constructed microbial consortium (CPD) [C1, phosphorus-solubilizing bacterium Enterobacter sp. P1, and atrazine-degrading bacterium Acinetobacter lwoffii DNS32] demonstrated the most effective performance in enhancing atrazine degradation and phosphorus-solubilizing capacity when the initial inoculation ratio of 5:1:2 at 15 °C. CPD enhanced energy-related metabolic pathways and increased choline production to regulate bacterial adaptation to temperature decrease. Additionally, the strains could selectively utilize carbon sources (low molecular weight organic acids) or nitrogen sources (some metabolites of atrazine) provided by each other to enhance growth. Furthermore, strain C1 enhanced membrane fluidity through increased expression of the unsaturated fatty acids. Pot experiments demonstrated that CPD assisted soybean seedlings in resisting dual stresses of low temperature and atrazine contamination by inducing the expression of genes related to photosynthesis, membrane permeability, phosphorus response, and cold tolerance.

Identification of cadmium phytoavailability in response to cadmium transformation and changes in soil pH and electrical conductivity

Owing to complex changes in the soil environment, determining cadmium (Cd) phytoavailability is challenging. We devised a soil-wheat system to monitor alterations in soil pH, electrical conductivity (EC), and Cd transformation under various rates of calcium chloride and/or low-molecular-weight organic acids (LMWOAs) addition. The findings indicate that decreasing soil pH value, increasing soil EC value, and Cd transformation affect the phytoextraction of Cd. The exchangeable Cd and transformation of Cd under shifts in soil pH and EC contribute differentially to the phytoextracted Cd. The level of potentially phytoavailable Cd was identified through complete wheat cultivation in which the soil pH decreased by 0.47 unit and soil EC increased by 600-1000 μS cm−1, resembling the concentration of 0.01 M LMWOAs extractable Cd, when transitioning from paddy to dryland soil. Based on considering the phytoextracted Cd as the phytoavailable Cd throughout a complete wheat growth term, the threshold for phytoavailable Cd in soil, ensuring the safety of wheat grain (limit: 0.1 mg kg−1), is determined to be 2.90 μg kg−1. Maintaining control over Cd phytoavailability in soil emerges as the key factor in ensuring the safety of wheat grain cultivation.

Effect of common low-molecular-weight organic acid on the photodegradation of sertraline by ferrihydrite

Sertraline is one of the most commonly used antidepressant pharmaceuticals with ubiquitous distribution in the aqueous environment. However, the environmental behavior of sertraline in the co-presence of low-molecular-weight organic acid (LMWOA) and iron oxide mineral is still poorly understood. In this study, the photodegradation of sertraline was systematically investigated in a common photosensitizing system (ferrihydrite (Fh)-LMWOA). Six LMWOAs, including citrate acid (CA), tartrate acid (TA), malate acid (MA), lactate acid (LA), succinate acid (SA) and malonic acid (MOA) were chosen as the representatives. Our results implied that the different Fe3+ dissolution rates would lead to rather different sertraline degradation patterns following the order of Fh-CA > Fh-TA > Fh-MA > Fh-LA > Fh-SA > Fh-MOA. The reaction was initiated by the interaction between LMWOA and Fh via ligand-promoted-dissolution mechanism. Furthermore, the Fe3+ dissolution rates also showed a strong correlation with the metal-organic complexation constants, indicating that the photodegradation process is strongly related to the complexation ability of LMWOA with Fe3+. •OH, O2•- and CO2•- were detected, indicating that they contributed to the photodegradation of sertraline. •OH was demonstrated to be the dominant Reactive oxygen species (ROS) for the degradation of sertraline, and the detailed transformation pathways were proposed based on the product analysis and theoretical calculation. According to the ecological structure activity relationship estimation, the photodegradation products of sertraline possessed lower toxicity compared to the parent compound. These findings contribute to a more comprehensive understanding of the environmental fate of sertraline and evaluate its potential ecotoxicity in natural systems.

Dramatically enhanced phenol degradation upon FeS oxygenation by low-molecular-weight organic acids

Oxidizing potential of FeS for organic contaminants degradation due to hydroxyl radicals (•OH) production has been recently documented, but the oxidizing efficiency was limited. Here, we revealed that low-molecular-weight organic acids (LMWOAs) can immensely enhance phenol degradation during FeS oxygenation due to increased utilization efficiency of FeS electron for •OH production. Upon oxygenation of 0.5 g/L FeS, phenol degradation boosted from 7.1% without LMWOAs to 91.5%, 84.6% and 95.0% with the addition of 1 mM oxalate, citrate and EDTA, respectively. Electron utilization efficiency of Fe(II) for •OH production dramatically rose from 0.3% with FeS alone to respective 2.0%, 2.5% and 2.7% in the LMWOAs systems. An increase in oxalate concentrations benefited •OH formation and phenol degradation. Coexisting oxalate led to an additional •OH production pathway from Fe(II)-oxalate oxidation, which expanded the O2 reduction to H2O2 from a two- to one-electron transfer process. Meanwhile, electron transfer from FeS to dissolved Fe(III)-oxalate promoted the redox cycling of Fe(III)/Fe(II), thus supplying the Fe(II) oxidation for •OH production. Moreover, the presence of oxalate decreased the crystallinity and particles size of lepidocrocite generated from FeS oxidation. Consequently, this study shed lights on the LMWOAs-enhanced contaminant degradation in either natural or engineered FeS oxidation systems.

Photochemical vapor generation of Zinc and Gallium

Photochemical vapor generation (PVG) of Zinc (Zn) and Gallium (Ga) was firstly reported in this study. The main parameters influencing PVG of Zn and Ga were investigated with inductively coupled plasma mass spectrometry (ICP-MS), such as the type and concentration of low molecular weight organic acids (LMWOAs), the concentration of transition metal ions and their synergistic effects, the wavelength and time of UV irradiation, and pH of sample solution. Formic acid (FA) and Cu2+ were required for the generation of volatile species of Zn and Ga. In addition, the effects of interfering ions on the PVG of Zn and Ga were investigated. Good precisions with 2.3% and 2.7% were obtained under the selected conditions for replicate measurement of 200 ng mL−1 Zn and Ga standard solution (n = 7), respectively. The limits of detection (LOD, 3σ, n = 11) were calculated to be 8.8 ng mL−1 and 0.77 ng mL−1 for Zn and Ga with PVG-ICP-MS measurement, respectively. Carbonyl compounds were speculated to be formed in this study. Moreover, nanoparticles containing Cu, Zn or Ga were found in liquid solution after UV irradiation, which may be useful for investigating the formation of natural nanoparticles in environment as well as the isotope fractionation of Zn and Ga in photochemical processes.

The release of Cd, Cu, Fe, Mn, Ni, Pb, and Zn from clay loam and sandy loam soils under the influence of various organic amendments and low-molecular-weight organic acids

Low-molecular-weight organic acids (LMWOAs) interact with potentially toxic elements (PTEs) and affect their mobility; however, the effect of different amendments on PTEs release from soils when added along with LMWOAs is still unclear. In this study, two soils (a clay loam and a sandy loam) amended with sugar beet bagasse ash (SBBA), poultry manure (PM), sewage sludge (SS) from Kermanshah city (SSK), and SS from Toyserkan city (SST) at a rate of 5 %. In these treatments we studied release of Cd, Cu, Fe, Mn, Ni, Pb, and Zn with citric, oxalic, and malic acids added at 10 different rates each, i.e., 0.1, 1, 2.5, 5, 10, 30, 40, 50, 70, and 100 mmol L−1. We found that the percentage of PTEs release was higher for citric, followed by oxalic and malic acids. The highest amount of PTEs released in both soils decreased in the following order: SST > SBBA > SSK > PM. The percentage of PTEs complexed with LMWOAs and the log activity of PTEs species mostly increased with decreasing pH. It could be concluded that the application of PM is more environmentally friendly than that of the other amendments. Since Cd had the highest percentage of release in all treated soils and LMWOAs, more consideration should be given to Cd to prevent environmental pollution.

Amendment of organic acids significantly enhanced hydroxyl radical production during oxygenation of paddy soils

Recently, hydroxyl radical (•OH) production during soil redox fluctuations has been increasingly reported, but the low efficiency of contaminant degradation is the barrier for engineering remediation. The widely distributed low-molecular-weight organic acids (LMWOAs) might greatly enhance •OH production due to their strong interactions with Fe(II) species, but it was less investigated. Herein, we found that LMWOAs amendment (i.e., oxalic acid (OA) and citric acid (CA)) significantly enhanced •OH production by 1.2 −19.5 times during oxygenation of anoxic paddy slurries. Compared with OA and acetic acid (AA) (78.4 −110.3 μM), 0.5 mM CA showed the highest •OH accumulation (140.2 μM) due to the elevated electron utilization efficiency derived from its strongest capacity for complexation. Besides, increasing CA concentrations (within 6.25 mM) dramatically enhanced the •OH production and imidacloprid (IMI) degradation (increased by 48.6%), and further decreased due to the extensive competition from excess CA. Compared to 0.5 mM CA, the synergistic effects of acidification and complexation induced by 6.25 mM CA rendered more formation of exchangeable Fe(II) that easily coordinated with CA, and thus significantly enhanced its oxygenation. This study proposed promising strategies for regulating natural attenuation of contaminants using LMWOAs in agricultural fields, especially soils with frequent occurrence of redox fluctuations.

Assessment of natural low molecular weight organic acids in facilitating cadmium phytoextraction by Lepidium didymus (Brassicaceae).

The present study examined the ability of three naturally occurring low molecular weight organic acids (tartaric, TA; citric, CA; and oxalic, OA) to improve the efficiency of cadmium (Cd) phytoextraction in Lepidium didymus L. (Brassicaceae). The plants were grown in soil containing three different concentrations, i.e., 35, 105, and 175mgkg-1, of total Cd and 10mM of TA, CA, and OA. After 6weeks, plant height, dry biomass, photosynthetic traits, and metal accumulation were determined. All three organic chelants significantly increased the Cd accumulation in L. didymus plants; however, the greatest accumulation was seen with TA (TA > OA > CA). In general, Cd accumulation was the highest in the roots, followed by the stems, and the leaves. Highest BCFStem was observed upon the addition of TA (7.02) and CA (5.90) at Cd35, compared to Cd-alone (3.52) treatment. The BCF was the highest in the stem (7.02) and leaves (3.97) under Cd35 treatment supplemented with TA. The BCFRoot in the plants under different chelant treatments were in the following order: Cd35 + TA (~ 100) > Cd35 + OA (~ 84) > Cd35 + TA (~ 83). The stress tolerance index and translocation factor (root-stem) were maximal at Cd175 with TA and OA supplementation, respectively. The study concludes that L. didymus could be a viable option for Cd-remediation projects, and the addition of TA improved its phytoextraction efficiency.

Chemical-microbial effects of acetic acid, oxalic acid and citric acid on arsenic transformation and migration in the rhizosphere of paddy soil

Low-molecular-weight organic acids (LMWOAs) are essential components of rice roots exudates and an important source of soil organic carbon. The chemical-microbial pathway by which LMWOA affects arsenic (As) cycling in the rhizosphere of paddy soils is still unclear. In this study, three typical LMWOAs (acetic acid (AA), oxalic acid (OA), and citric acid (CA)) in rice root exudates were added to As-contaminated soil at a concentration of 10 mM, mimicking the rhizosphere environment. The results showed that the addition of AA and OA inhibited the mobilization of As in the rhizosphere soil. After 14 days of incubation, the content of As in the porewater of AA and OA decreased by 40% and 22%, respectively, compared with the control. AA hindered the mobilization of As in soil via promoting the formation of secondary minerals. The addition of OA inhibits the mobilization of As via increasing the proportion of As (V) in porewater and promoting the formation of secondary minerals in soil. In addition, OA addition not only significantly increased the aioA gene abundance but also notably enriched the microorganisms containing As (III) methylation functional genes (arsM). The addition of CA greatly expedited the release of As from the soil solid phase through the solubilization of Fe/Mn minerals via the effects of both soil chemistry and microbial action. Furthermore, linear discriminant analysis effect size (LEfSe) revealed the possibility that bacteria such as Burkholderia, Magnetospirillum, and Mycobacterium were involved in the reduction or methylation of As in the rhizosphere of paddy soil. This study revealed the internal causes of LMWOAs regulating As transformation and mobilization in flooded paddy soil and provided theoretical support for reducing As accumulation in rice by breeding rice varieties with high AA and OA secretions.