Behaviors of Organic Ligands and Phosphate during Biochar-Driven Nitrate Adsorption in the Presence of Low-Molecular-Weight Organic Acids.

A batch experiment was conducted to examine the behavior of nitrate, organic ligands, and phosphate in the co-presence of biochar and three common low-molecular-weight organic acids (LMWOAs). The results show that citrate, oxalate, and malate ions competed with nitrate ion for the available adsorption sites on the biochar surfaces. The removal rate of LMWOA ligands by the biochar via adsorption grew with increasing solution pH. The adsorbed divalent organic ligands created negatively charged sites to allow binding of cationic metal nitrate complexes. A higher degree of biochar surface protonation does not necessarily enhance nitrate adsorption. More acidic conditions formed under a higher dose of LMWOAs tended to make organic ligands predominantly in monovalent forms and failed to create negatively charged sites to bind cationic metal nitrate complexes. This could adversely affect nitrate removal efficiency in the investigated systems. LMWOAs caused significant release of phosphate from the biochar. The phosphate in the malic acid treatment tended to decrease over time, while the opposite was observed in the citric- and oxalic-acid treatments. This was caused by re-immobilization of phosphate in the former due to the marked increase in solution pH over time.

Mobilization of soil phosphate after 8 years of warming is linked to plant phosphorus-acquisition strategies in an alpine meadow on the Qinghai-Tibetan Plateau.

Phosphorus (P) is essential for productivity of alpine grassland ecosystems, which are sensitive to global warming. We tested the hypotheses that (1) mobilized 'calcium-bound inorganic P' (Ca-Pi ) is a major source of plant-available P in alpine meadows with alkaline soils after long-term warming, (2) mobilization of Ca-Pi is linked to effective plant carboxylate-releasing P-acquisition strategies under warming, and (3) the mobilization is also related to plant nitrogen (N)-acquisition. We conducted an 8-year warming experiment in an alpine meadow (4635 m above sea level) on the Qinghai-Tibetan Plateau. A significant increase in P concentration in both aboveground and belowground biomass indicates an increased mobilization and assimilation of P by plants under warming. We observed a significant decrease in Ca-Pi , no change in moderately-labile organic P, and an increase in highly resistant organic P after warming. There was no increase in phosphatase activities. Our results indicate that Ca-Pi , rather than organic P was the major source of plant-available P for alpine meadows under warming. Higher leaf manganese concentrations of sedges and forbs after warming indicate that carboxylates released by these plants are a key mechanism of Ca-Pi mobilization. The insignificant increase in Rhizobiales after warming and the very small cover of legumes show a minor role of N-acquisition strategies in solubilizing phosphate. The insignificant change in relative abundance of mycorrhizal fungi and bacteria related to P cycling after warming shows a small contribution of microorganisms to Ca-Pi mobilization. The significant increase in leaf N and P concentrations and N:P ratio of grasses and no change in sedge leaf N:P ratio reflect distinct responses of plant nutrient status to warming due to differences in P-acquisition strategies. We highlight the important effects of belowground P-acquisition strategies, especially plant carboxylate-releasing P-acquisition strategies on responses of plants to global changes in alpine meadows.

Biochar-driven reduction of As(V) and Cr(VI): Effects of pyrolysis temperature and low-molecular-weight organic acids.

Batch experiments were conducted to examine the differential effects of biochar pyrolysis temperature and low-molecular-weight organic acids on the reduction of As(V) and Cr(VI) driven by Pennisetum hydridum biochar. The results showed that pyrolysis temperature significantly affected the reducing strength of the biochar. Biochar produced at 500 °C had a stronger electron-donating capacity than did the biochars produced at 300 and 700 °C. In the co-presence of the biochar and a low-molecular-weight organic acid, arsenic and chromium behaved differently. Oxalic acid and malic acid tended to have better effects on enhancing biochar-driven Cr(VI) reduction, as compared to citric acid while the opposite was observed for biochar-driven As(V) reduction. Biochar produced at 300 °C was more favourable for Cr(VI) reduction, as compared to the higher-temperature biochars while the opposite was observed for As(V) reduction in the presence of low-molecular-weight organic acids. This may make the lower-temperature biochar ideal for remediating contaminated soils containing both As(V) and Cr(VI) since it could maximize Cr(VI) reduction while minimizing As(V) reduction.

Phytoextraction of cadmium-contaminated soils: comparison of plant species and low molecular weight organic acids.

To select suitable plants for phytoextraction of Cd-contaminated soils, we evaluated the phytoextraction potential of five local Cd-accumulators: Amaranthus hypochondriacus L., Solanum nigrum L., Phytolacca acinosa Roxb., Celosia argentea L., and Sedum spectabile Boreau. The plants were grown in three naturally contaminated soils with different total Cd levels (1.57, 3.89, and 22.4 mg kg-1). Throughout the experimental period, no plants showed any visible symptoms of metal toxicity. The Cd uptake of C. argentea was the greatest in the S-YS soil (105 µg plant-1) and among the greatest in the S-HC soil and S-TJ soil. Besides, C. argentea exhibited the highest bioconcentration factor (12.3) in three soils. To improve the phytoextraction efficiency of C. argentea, we applied four low molecular weight organic acids (LMWOAs): tartaric acid, malic acid, oxalic acid, and citric acid. Malic acid was more effective in enhancing Cd uptake by C. argentea than the other LMWOAs. Therefore, C. argentea may be a potential choice in actual remediation projects. Moreover, application of malic acid is an effective way to increase the phytoextraction efficiency of C. argentea.

Oxalic acid, a molecule at the crossroads of bacterial-fungal interactions.

Oxalic acid is the most ubiquitous and common low molecular weight organic acid produced by living organisms. Oxalic acid is produced by fungi, bacteria, plants, and animals. The aim of this review is to give an overview of current knowledge about the microbial cycling of oxalic acid through ecosystems. Here we review the production and degradation of oxalic acid, as well as its implications in the metabolism for fungi, bacteria, plants, and animals. Indeed, fungi are well known producers of oxalic acid, while bacteria are considered oxalic acid consumers. However, this framework may need to be modified, because the ability of fungi to degrade oxalic acid and the ability of bacteria to produce it, have been poorly investigated. Finally, we will highlight the role of fungi and bacteria in oxalic acid cycling in soil, plant and animal ecosystems.

Woody species Rhus chinensis Mill. seedlings tolerance to Pb: Physiological and biochemical response.

Screening potential plant species is a crucial consideration in phytoremediation technology. Our previous study demonstrated that Rhus chinensis Mill. seedlings had potentials for phytoremediation of Pb contaminated soil. However, its bioaccumulation and tolerance characteristics remain unclear. Seedling growth, LMWOAs secreted by roots, Pb subcellular distribution and chemical forms, and mineral elements in R. chinensis tissues were evaluated under different Pb concentrations (0, 25, 50, 100, 200 and 400 mg/L) in culture solution at 14 days after planting. R. chinensis did not show visual symptoms of Pb toxicity under lower Pb treatments; however, Pb significantly declined the growth of seedlings under higher Pb treatments. Higher Pb stress also decreased the concentrations of nitrogen in leaves, but increased the concentrations of P and K in roots. Pb stress also decreased Mn concentrations in leaves. A great quantity of Pb was uptake and mostly retained in R. chinensis roots. Nonetheless, R. chinensis can still concentrate 459.3 and 1102.7 mg/kg Pb in leaves and stems, respectively. Most of Pb in R. chinensis tissues was stored in the cell wall with HAc-, HCl-, and NaCl-extractable form. LMWOAs secreted by R. chinensis roots showed a strong positive correlation with Pb concentrations in all plant tissues and with P in roots. Our results suggested that Pb deposited in the cell wall and integration with phosphate or oxalate might be responsible for the tolerance of R. chinensis under Pb stress in short period.

Differential release of sewage sludge biochar-borne elements by common low-molecular-weight organic acids.

Biochar materials originated from sewage sludge may contain elevated levels of potentially toxic elements. There was a lack of information on the mobility of biochar-borne elements, as driven by low-molecular-weight organic acids (LMWOAs) contained in plant root exudates. A batch experiment was conducted to examine the effects of three common LMWOAs on the release of major elements and trace elements with a focus on various potentially toxic trace elements. The results showed that substantial amounts of Al, Mn, Fe, K, Na and Mg were extracted from two sewage sludge-derived biochar materials by the LMWOAs. A much higher release rate of potentially toxic trace elements was observed in the presence of LMWOAs, as compared to reported data using extractants not encountered in root exudates. The LMWOA-driven releasibility of various potentially toxic trace elements was in the following decreasing order: Zn > Ni > Pb > Cu > Cr >Co = Cd. Other trace elements that are subject to mobilization in the presence of LMWOAs included B, Ba, In, Li and Sr except Ba under oxalic acid extraction. Among the three LMWOAs, oxalic acid showed a generally stronger capacity to mobilize these metals. The findings obtained from this study provides new information that can be used for better evaluating the phyto-availability of trace elements bound to sewage sludge-originated biochar materials.

Effects of root exudates on gel-beads/reeds combination remediation of high molecular weight polycyclic aromatic hydrocarbons.

Changes in root exudates, including low molecular weight organic acids (LMWOAs), amino acids and sugars, in rhizosphere soils during the gel-beads/reeds combination remediation for high molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs) and the degree of the effects on HMW-PAH biodegradation were evaluated in this study. The results showed that the gel-beads/reeds combination remediation notably increased the removal rates of pyrene, benzo(a)pyrene and indeno(1,2,3-cd)pyrene (65.0-68.9%, 60.0-68.5% and 85.2-85.9%, respectively). During the removal of HMW-PAHs, the LMWOAs, particularly maleic acid, enhanced the biodegradation of HMW-PAHs. Arginine and trehalose monitored in reed root exudates promoted the growth of plants and microorganisms and then improved the removal of HMW-PAHs, especially pyrene. However, the contribution of reed root exudates on degradation of 5- and 6-ring PAHs was minor. These results indicated that the utilization of root exudates was certainly not the only important trait for the removal of HMW-PAHs.

A review of environmental characteristics and effects of low-molecular weight organic acids in the surface ecosystem.

Low molecular weight organic acids (LMWOAs) are prevalent on the earth's surface. They are vital intermediate products during metabolic pathways of organic matter and participate in the tricarboxylic acid cycle during life activities. Photochemical reactions are pivotal for LMWOAs' origination and play a large role in determining their diversity and their ultimate fate. Within the long time that organic matter is preserved in sediments, it can be decomposed and converted to release organic and inorganic pollutants as well as C, N, and P nutrients, which are of potential ecological risk in causing secondary pollution to lake water. The sediment pool is a comprehensive and complex compartment closely associated with overlying water by various biochemical processes, during which LMWOAs play critical roles to transport and transform elements. This article elucidates geochemical behaviors of LMWOAs in the surface environment in details, taking natural water, soil, and aerosol as examples, focusing on reviewing research developments on sources and characteristics, migration and mineralization of LMWOAs and relevant environmental effects. Simultaneously, this review article depicts the categories and contents of LMWOAs or their contribution to DOC in environmental media, and evaluates their importance during organic matter early diagenesis. Through concluding and discussing the conversion mechanisms and influencing factors, the next research orientations on LMWOAs in lake ecosystems are determined, mainly concerning relationships with hydrochemical parameters and microorganisms, and interactions with pollutants. This will enrich the knowledge on organic matter degradation and related environmental effects, and help reconstruct a theoretical framework for organic compound succession and influencing factors, providing basic data for lake eutrophication and ecological risk assessment, conducive to better control over water pollution and proper management of water quality.

Low-molecular-weight organic acids-mediated transport of neonicotinoid pesticides through saturated soil porous media: Combined effects of the molecular structures of organic acids and the chemical properties of contaminants.

Empirical information about the transport properties of neonicotinoid pesticides through the soil as affected by the ubiquitous low molecular weight organic acids (LMWOAs) is lacking. Herein, the impacts of three LMWOAs with different molecular structures, including citric acid, acetic acid, and malic acid, on the mobility characteristics of two typical neonicotinoid pesticides (Dinotefuran (DTF) and Nitenpyram (NTP)) were explored. Interestingly, under acidic conditions, different mechanisms were involved in transporting DTF and NTP by adding exogenous LMWOAs. Concretely, acetic acid and malic acid inhibited DTF transport, ascribed to the enhanced electrostatic attraction between DTF and porous media and the additional binding sites provided by the deposited LMWOAs. However, citric acid slightly enhanced DTF mobility due to the fact that the inhibitory effect was weakened by the steric hindrance effect induced by the deposited citric acid with a large molecular size. In comparison, all three LMWOAs promoted NTP transport at pH 5.0. Because the interaction between NTP with soil organic matter (e.g., via π-π stacking interaction) was masked by the LMWOAs coating on soil surfaces. Nevertheless, LMWOAs could promote the mobility of both neonicotinoid pesticides at pH 7.0 due to the steric hindrance effect caused by the deposited organic acids and the competitive retention between LMWOAs and pesticides for effective surface deposition sites of soil particles. Furthermore, the extent of the promotion effects of LMWOAs generally followed the order of citric acid > malic acid > acetic acid. This pattern was highly related to their molecular structures (e.g., number and type of functional groups and molecular size). Additionally, when the background solutions contained Ca2+, the bridging effect of cations also contributed to the transport-enhancement effects of LMWOAs. The findings provide valuable information about the mobility behaviors of neonicotinoid pesticides co-existing with LMWOAs in soil-water systems.

Effects of low-molecular-weight organic acids on the transport of polystyrene nanoplastics: An insight at the structure of organic acids.

Plastic nanoparticles are extensively used in various products, leading to inevitable pollution in soil. Understanding their transport in soils where various organic substances exist is crucial. This study examined the impact of low-molecular-weight organic acids (LMWOAs) on the transport of polystyrene nanoplastics (PS-NPs) through saturated quartz sand. The experiments involved three dibasic acids-malonic acid (MA1), malic acid (MA2) and tartaric acid (TA) - and four monobasic acids- formic acid (FA), acetic acid (AA), propanoic acid (PA) and glycolic acid (GA) -under different pH levels (4.0, 5.5, 7.0) and in the presence of cations (Na+, Ca2+). The results demonstrated that in the presence of Na+, dibasic acids significantly enhanced PS-NPs transport, with TA being the most effective, followed by MA2 and MA1. This enhancement is attributed to the adsorption of LMWOAs onto the nanoparticles and sand, creating a more negative ζ-potential, which increases the electrostatic repulsion and decreases the PS-NPs deposition, thereby facilitating the transport. Applying the Derjaguin-Landau-Verwey-Overbeek theory, higher pH levels increased the energy barrier and secondary energy minimum, decreasing PS-NPs deposition. Moreover, dibasic acids significantly enhanced the hydrophilicity of PS-NPs. Conversely, monobasic acids, except for GA, slightly reduced the hydrophilicity of PS-NPs, as indicated by a small increase in the water contact angle, hereby minimally affecting PS-NPs transport. As for GA, although it is a monobasic acid, the additional -OH group in its molecular structure promoted PS-NPs transport, similar to dibasic acids. For example, GA also significantly enhanced the hydrophilicity of PS-NPs. In the presence of Ca2+, the enhancement of PS-NPs transport by LMWOAs was comparable to that with Na+, primarily due to the complex-forming and bridging effects of Ca2+ with the organic acids and PS-NPs. These findings provide important insights into predicting and analyzing the transport behaviors of PS-NPs.

Decreased transport of nano- and micro-plastics in the presence of low-molecular-weight organic acids in saturated quartz sand.

Low-molecular-weight organic acids (LMWOAs) and nano- and micro-plastics (NPs and MPs) are both widely distributed in terrestrial systems. To better understand the influence of LMWOAs on the transport of NPs and MPs, the effects of 0.5 mM citric- (CA), malic- (MA), and tartaric- (TA) acid on the transport of nano- (0.51 µm, PS NPs) and micro- (1.1 µm, PS MPs) polystyrene particles (2 mg L-1) in saturated quartz sand were investigated. All three LMWOAs decreased the transport of PS NPs and MPs, regardless of ionic composition or strength (0.1-10 mM NaCl and 0.1-1 mM CaCl2). Further investigation revealed that the interfacial interactions between PS-quartz sand surfaces and PS-PS were altered by LMWOAs. LMWOAs adsorbed to quartz sand surfaces could serve as new deposition sites, as evidenced by the decreased transport of PS NPs and MPs in quartz sand that was subjected to pre-equilibration with selected MA, the low inhibition of PS transport with low concentrations of LMWOAs (0.1 mM), and also the adsorption of LMWOAs onto quartz sand surfaces by batch experiments. Meanwhile, the adsorption of LMWOAs on PS, hydrodynamic measurement and visual TEM observation together clarified the slight aggregation of PS NPs and MPs in suspensions, inducing the subsequent decrease in transport. Among them, the adsorption of LMWOAs onto quartz sand surfaces was found to be the main factor dominating the decreased transport of both PS NPs and MPs in saturated quartz sand.

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.

Functional group-specific reduction of Cr(VI) by low molecular weight organic acids in frozen solution: Kinetics, mechanism and DFT calculation.

Low molecular weight organic acids (LMWOA) are commonly present in natural water and play a pivotal role in the reduction of Cr(VI). In frozen solutions, the efficiency of Cr(VI) reduction is significantly enhanced due to the freezing concentration effect. However, this facilitation is found to be contingent upon the functional groups of LMWOA in this study. To be specific, LMWOA and Cr(VI) can form five-membered ring complexes, which greatly enhance electron transfer efficiency through Ligand-to-Metal Charge Transfer (LMCT). DFT calculations indicate that oxygen-containing groups located on carbon atoms at α positions play a crucial role in forming these complexes, ultimately determining the kinetics of Cr(VI) reduction. Moreover, freezing not only increases proton concentrations but also reduces free water molecule content in the liquid-like layer (LLL), thereby affecting LMWOA species through regulation of protonation and hydrolysis, and subsequently impacting reaction mechanisms. The stoichiometric ratios between LMWOA and Cr(VI) exceed theoretical values due to complexation with Cr(III). The reduction of Cr(VI) by LMWOA in frozen solutions is inhibited by soil solution, while the degree of inhibition varies among different types of LMWOA.

Enhancing phosphorus and zinc acquisition efficiency in rice: a critical review of root traits and their potential utility in rice breeding.

BACKGROUND: Rice is the world's most important cereal crop and phosphorus (P) and zinc (Zn) deficiency are major constraints to its production. Where fertilizer is applied to overcome these nutritional constraints it comes at substantial cost to farmers and the efficiency of fertilizer use is low. Breeding crops that are efficient at acquiring P and Zn from native soil reserves or fertilizer sources has been advocated as a cost-effective solution, but would benefit from knowledge of genes and mechanisms that confer enhanced uptake of these nutrients by roots. SCOPE: This review discusses root traits that have been linked to P and Zn uptake in rice, including traits that increase mobilization of P/Zn from soils, increase the volume of soil explored by roots or root surface area to recapture solubilized nutrients, enhance the rate of P/Zn uptake across the root membrane, and whole-plant traits that affect root growth and nutrient capture. In particular, this review focuses on the potential for these traits to be exploited through breeding programmes to produce nutrient-efficient crop cultivars. CONCLUSIONS: Few root traits have so far been used successfully in plant breeding for enhanced P and Zn uptake in rice or any other crop. Insufficient genotypic variation for traits or the failure to enhance nutrient uptake under realistic field conditions are likely reasons for the limited success. More emphasis is needed on field studies in mapping populations or association panels to identify those traits and underlying genes that are able to enhance nutrient acquisition beyond the level already present in most cultivars.

Seasonal Variations of Low-Molecular-Weight Organic Acids in Three Evergreen Broadleaf Rhododendron Forests.

Low-molecular-weight organic acids (LMWOAs) are widely distributed in forests. Fresh leaves, litter, humus, and the topsoil layer of representative Rhododendron delavayi (RD), Rhododendron agastum (RA), and Rhododendron irroratum (RI) in the Baili Rhododendron National Forest Park were sampled to explore their seasonal changes. The contents of oxalic, tartaric, malic, citric, acetic, lactic, succinic, and formic acids in samples from different seasons were determined by high-performance liquid chromatography. The results showed that the composition and content of the LMWOAs in the fresh leaves, litter, humus, and topsoil layer of the rhododendrons were affected by the tree species, samples, and season. The main LMWOA was oxalic acid (the average content in the samples was 195.31 µg/g), followed by malic acid (the average content in the samples was 68.55 µg/g) and tartaric acid (the average content in the samples was 59.82 µg/g). Succinic acid had the lowest content; the average content in the samples was 18.40 µg/g. The LMWOAs of the RD were the highest (the average content in the samples was 517.42 µg/g), and the LMWOAs of the RI were the lowest (the average content in the samples was 445.18 µg/g). The LMWOAs in the three rhododendron forests were in the order of fresh leaves > litter > humus > soil layers. This study showed the seasonal distribution characteristics of LMWOAs in three evergreen broadleaf rhododendron forests, and the results provide a reference for ecosystem management and the protection of wild rhododendron forests.

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.

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.

Environmental and health impacts assessment of long-term naturally-weathered municipal solid waste incineration ashes deposited in soil-old burden in Bratislava city, Slovakia.

Municipal solid waste incineration (MSWI) is an effective method for reducing the volume/mass of waste. However, MSWI ashes contain high concentrations of many substances, including trace metal (loid)s, that could be released into the environment and contaminate soils and groundwater. In this study, attention was focused on the site near the municipal solid waste incinerator where MSWI ashes are deposited on the surface without any control. Here, combined results (chemical and mineralogical analyses, leaching tests, speciation modelling, groundwater chemistry and human health risk assessment) are presented to assess the impact of MSWI ash on the surrounding environment. The mineralogy of ∼forty years old MSWI ash was diverse, and quartz, calcite, mullite, apatite, hematite, goethite, amorphous glasses and several Cu-bearing minerals (e.g. malachite, brochantite) were commonly detected. In general, the total concentrations of metal (loid)s in MSWI ashes were high, following the order: Zn (6731 mg/kg) > Ba (1969 mg/kg) ≈ Mn (1824 mg/kg) > Cu (1697 mg/kg) > Pb (1453 mg/kg) > Cr (247 mg/kg) > Ni (132 mg/kg) > Sb (59.4 mg/kg) > As (22.9 mg/kg) ≈ Cd (20.6 mg/kg). Cadmium, Cr, Cu, Pb, Sb and Zn exceeded the indication or even intervention criteria for industrial soils defined by the Slovak legislation. Batch leaching experiments with diluted citric and oxalic acids that simulate the leaching of chemical elements under rhizosphere conditions documented low dissolved fractions of metals (0.00-2.48%) in MSWI ash samples, showing their high geochemical stability. Non-carcinogenic and carcinogenic risks were below the threshold values of 1.0 and 1 × 10-6, respectively, with soil ingestion being the most important exposure route for workers. The groundwater chemistry was unaffected by deposited MSWI ashes. This study may be useful in determining the environmental risks of trace metal (loid)s in weathered MSWI ashes that are loosely deposited on the soil surface.

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.