Low Molecular Weight Organic Acids Research Articles

Unveiling the impact of low-molecular-weight organic acids on enrofloxacin sorption in North China agricultural soil: Insights and implications

Low-molecular-weight organic acids (LMWOAs) play a crucial role as components of dissolved organic matter in soil, influencing the sorption/desorption, degradation, and plant uptake of diverse pollutants within the agricultural soil ecosystem. This study delves into the sorption behavior and mechanism of the fluoroquinolone antibiotic enrofloxacin (ENR) on agricultural soil in North China, focusing on the impact of LMWOAs. Through batch equilibrium experiments, we explored the sorption/desorption kinetics of ENR under varying conditions such as temperature, pH, ion strength, and ion type, with the addition of acetic acid, oxalic acid, and citric acid individually. Our findings reveal that the sorption and desorption kinetics of ENR—whether with or without LMWOAs—conformed well to the pseudo-second-order kinetic model (R2 ≥ 0.997). The presence of LMWOAs notably enhanced ENR sorption while impeding desorption in soil, with oxalic acid demonstrating the highest promotion effect followed by acetic acid and citric acid. Moreover, the sorption capacity and affinity of ENR decreased with rising solution pH, dropping from 96.8%-98.5% to 30.9%–34.4%. Acidic conditions favored ENR retention in soil, with inhibition of sorption escalating alongside increasing ionic strength. LMWOAs, soil solution pH, and coexisting ions emerge as pivotal factors shaping ENR sorption behavior. Furthermore, LMWOA presence intensified desorption hysteresis of ENR on soil, with a desorption hysteresis coefficient (HI) ≤ 0.124. These results suggest that LMWOAs restrict ENR mobility in the local soil environment, heightening the risk of its accumulation in soil and crops. This study offers valuable insights into the intricate interplay among LMWOAs, ENR sorption dynamics, and environmental outcomes, underscoring the importance of understanding such complexities in agricultural soil management.

Transport of reduced PBAT microplastics in saturated porous media: Synergistic effects of enhanced surface energy and roughness

Microplastic (MP) pollution presents significant global environmental challenges, exacerbated by reduction aging processes in anoxic environments, thereby increasing environmental risks and potential threats to human health. However, the mechanisms underlying the transport of reduced MPs remain poorly understood. In this study, laboratory-scale column experiments were conducted to investigate the transport behavior of polybutylene adipate terephthalate (PBAT), a common biodegradable MPs, and its reduced products obtained through the aging process mediated by two typical reducing agents, NaBH4 and Na2S, under varying conditions (ionic strength (IS), divalent cations, and low molecular weight organic acids (LMWOAs)). The results indicated that reduction aging improved the hydrophilicity of PBAT by increasing the surface roughness (roughness factor increased from 1.300 to 1.642) and surface energy (from 51.80 to 107.03 mN m−1), thereby increasing the mobility of reduced PBAT (with recovery rate increased from 53.77 % to 63.18 %). Increased IS decreased the mobility of reduced PBAT by decreasing the surface negative charge density. Divalent cations inhibited the mobility of both pristine and reduced PBAT in porous media, with pristine PBAT, containing more oxygen functional groups, exhibiting stronger inhibition. Furthermore, LMWOAs promoted the retention of reduced PBAT in porous media, which was dependent on the type of LMWOAs. This study revealed the alterations in MPs properties caused by reduction aging and their effects on transport mechanisms, offering new insights into the transport behavior and environmental risks of reduced MPs.

The Role of Low-Molecular-Weight Organic Acids in Metal Homeostasis in Plants.

Low-molecular-weight organic acids (LMWOAs) are essential O-containing metal-binding ligands involved in maintaining metal homeostasis, various metabolic processes, and plant responses to biotic and abiotic stress. Malate, citrate, and oxalate play a crucial role in metal detoxification and transport throughout the plant. This review provides a comparative analysis of the accumulation of LMWOAs in excluders, which store metals mainly in roots, and hyperaccumulators, which accumulate metals mainly in shoots. Modern concepts of the mechanisms of LMWOA secretion by the roots of excluders and hyperaccumulators are summarized, and the formation of various metal complexes with LMWOAs in the vacuole and conducting tissues, playing an important role in the mechanisms of metal detoxification and transport, is discussed. Molecular mechanisms of transport of LMWOAs and their complexes with metals across cell membranes are reviewed. It is discussed whether different endogenous levels of LMWOAs in plants determine their metal tolerance. While playing an important role in maintaining metal homeostasis, LMWOAs apparently make a minor contribution to the mechanisms of metal hyperaccumulation, which is associated mainly with root exudates increasing metal bioavailability and enhanced xylem loading of LMWOAs. The studies of metal-binding compounds may also contribute to the development of approaches used in biofortification, phytoremediation, and phytomining.

Co-transport of citrate-modified biochar nanoparticles and released plant-available silicon in saturated porous media: Effect of LMWOAs and solution chemistry

Citrate-modified biochar nanoparticles (CBCNPs) represent a promising amendment with plant-available silicon (PASi) releasing capacity. However, the co-transport behavior with released PASi remain poorly understood. This study investigated their co-transport in saturated porous media under various solution chemistry and low molecular weight organic acids (LMWOAs). Experimental and two-site kinetic model results revealed that higher ionic strength caused favorable aggregation and size-selective, hindering CBCNPs transport. Divalent Ca2+ ions retained CBCNPs more effectively than K+ due to stronger charge screening and cation bridging. The pH buffering capacity of CBCNPs resulted in consistent transport behavior across a broad pH range (4–8). XDLVO calculation clarified the impact mechanisms of IS, ion types and pH on CBCNPs transport. Furthermore, LMWOAs exhibited a time-dependent blocking effect on CBCNPs transport. Oxalic acid (OA) and citric acid (CA) facilitated CBCNPs transport though mechanisms beyond XDLVO, including steric hindrance, competitive adsorption, and surface hydrophilicity. The presence of LMWOAs significantly hindered PASi co-transport, with the inhibitory effect ranked as acetic acid (AA) ≈ CA > OA > absence of organic acids. The inhibition is attributed to the blocking effect and formation of Si-organic acid complexes, as evidenced by breakthrough curves and density functional theory calculations. This study provides novel insights into the co-transport of CBCNPs with released PASi through mutual mechanisms, indicating both potential environmental benefits and risks.

Hydrocarbons, Hydrogen, and Organic Acids Generation by Ball Milling and Batch Incubation of Sedimentary Rocks

Pulverized rock samples are widely used in laboratory experiments, e.g., to assess microbial or abiotic processes in batch incubation tests. However, it is unclear if ball-milled samples accurately reflect in-situ conditions and if observed processes are affected by by-products artificially generated during the sample preparation procedure. As such, this study examined the effects of dry ball milling on the release of gases, which include C1-C4 hydrocarbons, carbon dioxide (CO2), hydrogen (H2), and low molecular weight organic acids (LMWOAs) from different sedimentary rocks. The experiments involved pulverization using a gas-tight zirconium oxide planetary ball mill followed by wet and dry batch incubation and thermal desorption up to 200 o C. During milling, all sedimentary rocks, except a low organic carbon sandstone sample, yielded methane (CH4), ethane (C2H6), propane (C3H8), butane (C4H10), H2, CO2, and unsaturated hydrocarbons, e.g., ethene (C2H4). Sandstones only yielded H2, CH4, and CO2. Stable carbon isotope signatures of these products are similar to thermogenic gases. The gases were also detected in subsequent wet incubation experiments (after gases from milling had been removed). Additionally, formate, acetate, and citrate, were detected in all samples except for sandstone. Pyruvate, malate, and succinate were also detected in some samples. Thermal desorption products of powdered limestone, shale, and pyrite concretion samples included organic acids, such as acetate and formate, which were higher in milled samples than in crushed particles (∼1 mm). The original geological thermal maturity of the studied sedimentary rock samples was low (below “oil window”) and, thus, considerably below “gas window”, suggesting that most of the detected gases were generated during ball milling. H2 generated during ball milling may be derived from the reduction of water from fluid inclusion or phyllosilicates, involving the formation of reactive mineral surfaces or radicals. Notably, the concentrations of gaseous hydrocarbons derived from milling are relatively high and comparable to “wet” gases. At the same time, these data indicate that substantial amounts of gases and LWMOAs might be artificially generated during laboratory batch experiments with milled samples. Hence, ball milled rock samples must be used with caution if assessing (bio-)geochemical processes for natural environments.

Effect of Low Molecular Weight Organic Acids and Liming on Phosphorus Adsorption in Acidic Tea Soils in the Black Sea Region, Türkiye

ABSTRACT Agricultural productivity is significantly hindered by the limited availability of phosphorus in acidic soils due to the presence of aluminum and iron phosphates. Soil liming is commonly employed to enhance soil fertility. However, modifying the pH might also impact the interactions involving existing soil organic matter, leading to changes in the effective concentrations of competing low-molecular-weight acids (LMWOACs) participating in phosphorus adsorption. This study explored the impacts of citric, oxalic, and malic acids in acidic soils from tea cultivation regions within the Eastern Black Sea. These soils had undergone various levels of liming and were incubated for 15 months to assess their effects on phosphorus (P) adsorption in 7 acidic soils. The experimental sorption data were utilized to calculate the soil Langmuir and Freundlich adsorption parameters. In addition, the influences of organic acids and liming levels on the Freundlich and Langmuir model parameters were subjected to ANOVA analysis. The findings indicated that citric acid demonstrated the highest efficiency in diminishing phosphorus adsorption among the tested organic acids, followed by oxalic and malic acids. Three carboxyl groups (−COOH) in citric acid facilitated the formation of more complexes with adsorbed phosphorus on the soil surface. Furthermore, the 100% LR ratio of liming notably decreased phosphorus adsorption, especially in the lower end of the isotherms. Therefore, it can be concluded that the combination of LMWOACs and liming treatments could be used to overcome P deficiency in acid soils with very high P sorption ability.

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.

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.

The mechanism of citric acid and oxalic acid on dissolution of high-silicon iron tailings

In the indoor static environment, citric acid and oxalic acid, two kinds of low molecular weight organic acids were used to dissolve silicon and iron, which were two valuable elements in iron tailings. The results showed that the iron tailings used in this study were high silicon type iron tailings with 76.1 % silicon content and 11.31 % iron content. Both acids were soluble to ferrosilicon, but their solubility to iron was higher. Compared with the two, oxalic acid had stronger silicon solubility, reaching 35.98 μg/mL after 24d. The solubility of citric acid to iron was stronger, reaching 483.51 μg/mL after 24d. The dissolution of silicon and total iron in iron tailings by oxalic acid, citric acid and mixed acid conforms to first-order kinetics and belongs to surface dissolution reaction. After the dissolution of oxalic acid, silicon and iron ions might exist in the form of metasilic acid, iron oxalate and trioxalate potassium ferrite. Oxalic acid reacted with Fe2+ to precipitate, which might be the reason for the higher Fe3+ in the solution. The silicon and iron ions after citric acid dissolution might exist in the form of ferric citrate, ferric citrate complex, ferrous hexafluorosilicate, and more Fe2+ products might be the reason for the higher Fe2+ in the solution.

A novelty strategy for AMD prevention by biogas slurry: Acetate acid inhibition effect on chalcopyrite biooxidation and leachate

With the widespread application of anaerobic digestion technology, biogas slurry become the main source of organic amendments in practice. Comprehensive studies into the inhibitory effects of low molecular weight (LMW) organic acids, essential components in biogas slurry, on the sulfide minerals biooxidation and its bioleaching (AMD) have been lacking. In this study, acetic acid (AA) served as a representative of LMW organic acids in biogas slurry to investigate its impact on the inhibition of chalcopyrite biooxidation by Acidithiobacillus ferrooxidans (A. ferrooxidans). It was shown that AA could slow down the chalcopyrite biooxidation and inhibit the jarosite formation on the mineral surface. Compared with the control group (0 ppm AA), the sulfate increment in the leachate of the 50 ppm, 100 ppm, and 200 ppm AA-treated groups decreased by 36.4%, 66.8%, and 69.0%, respectively. AA treatment (≥50 ppm) could reduce the oxidation of ferrous ions in the leachate by one order of magnitude. At the same time, the bacterial concentration of the leachate in the 50 ppm, 100 ppm, and 200 ppm AA-treated groups decreased by 70%, 93%, and 94%, respectively. These findings provide a scientific basis for new strategies to utilize biogas slurry for mine remediation and contribute to an enhanced comprehension of organic amendments to prevent AMD in situ in mining soil remediation.

Impact of low molecular weight organic acids on heavy metal(loid) desorption in biochar-amended paddy soil.

Low molecular weight organic acids (LMWOAs) are important soil components and play a key role in regulating the geochemical behavior of heavy metal(loid)s. Biochar (BC) is a commonly used amendment that could change LMWOAs in soil. Here, four LMWOAs of oxalic acid (OA), tartaric acid (TA), malic acid (MA), and citric acid (CA) were evaluated for their roles in changing Cd and SB desorption behavior in contaminated soil with (S1-BC) or without BC (S1) produced from Paulownia biowaste. The results showed that OA, TA, MA, and CA reduced soil pH with rising concentrations, and biochar partially offset the pH reduction by LMWOAs. The LMWOAs reduced Cd desorption from the soil at low concentrations but increased Cd desorption at high concentrations, and CA was the most powerful in this regard. The LMWOAs had a similar effect on Sb desorption, and CA was the most effective species of LMWOAs. Adding BC to the soil affects Cd and Sb dynamics by reducing the Cd desorption but increasing Sb desorption from the soil and increasing the distribution coefficient (Kd) values of Cd but lowering the Kd values of Sb. This study helped understand the effects of LMWOAs on the geochemical behavior of Cd and Sb in the presence of biochar, as well as the potential risks of biochar amendment in enhancing Sb desorption from contaminated soil.

Critical roles of low-molecular-weight organic acid in enhancing hydroxyl radical production by ferrous oxidation on γ-Al2O3 mineral surface

Recognizing the pervasive presence of alumina minerals and low-molecular-weight organic acids (LMWOAs) in the environment, this study addressed the gap in the interaction mechanisms within the ternary system involving these two components and Fe(II). Specifically, the impacts of LMWOAs on hydroxyl radicals (•OH) production and iron species transformation during Fe(II) oxidation on γ-Al2O3 mineral surface were examined. Results demonstrated that adding 0.5 mM oxalate (OA) or citrate (CA) to the γ-Al2O3/Fe(II) system (28.1 μM) significantly enhanced •OH production by 1.9-fold (51.9 μM) and 1.3-fold (36.2 μM), respectively, whereas succinate (SA) exhibited limited effect (30.7 μM). Raising OA concentration to 5 mM further promoted •OH yield to 125.0 μM after 24 h. Deeper analysis revealed that CA facilitated the dissolution of adsorbed Fe(II) and its subsequent oxygenation by O2 through both one- and two-electron transfer mechanisms, whereas OA enhanced the adsorption of dissolved Fe(II) and more efficient two-electron transfer for H2O2 production. Additionally, LMWOAs presence favored the formation of iron minerals with poor crystallinity like ferrihydrite and lepidocrocite rather than well-crystallized forms such as goethite. The distinct impacts of various LMWOAs on Fe(II) oxidation and •OH generation underscore their unique roles in the redox processes at mineral surface, consequently modulating the environmental fate of prototypical pollutants like phenol.

Enhanced biodegradation of benzo[a]pyrene with Trametes versicolor stimulated by citric acid.

Polycyclic aromatic hydrocarbons (PAHs) are a class of persistent organic pollutants with carcinogenic, mutagenic and teratogenic effects. The white-rot fungi in the fungal group have significant degradation ability for high molecular weight organic pollutants. However, exogenous fungi are easily antagonized by indigenous microorganisms. Low molecular weight organic acids, a small molecular organic matter secreted by plants, can provide carbon sources for soil microorganisms. Combining organic acids with white rot fungi may improve the nutritional environment of fungi. In this study, immobilized Trametes versicolor was used to degrade benzo[a]pyrene in soil, and its effect on removing benzo[a]pyrene in soil mediated by different low molecular weight organic acids was investigated. The results showed that when the degradation was 35days, the removal effect of the experimental group with citric acid was the best, reaching 43.7%. The degradation effect of Trametes versicolor on benzo[a]pyrene was further investigated in the liquid medium when citric acid was added, and the effects of citric acid on the biomass, extracellular protein concentration and laccase activity of Trametes versicolor were investigated by controlling different concentrations of citric acid. In general, citric acid can act as a carbon source for Trametes versicolor and promote its extracellular protein secretion and laccase activity, thereby accelerating the mineralization of benzo[a]pyrene by Trametes versicolor. Therefore, citric acid can be used as a biostimulant in the remediation of PAHs contaminated soil with Trametes versicolor.

Tomato yield and soil chemical properties influenced by low–molecular–weight organic acids in calcareous soil

<p>Calcareous soils have restrictive characteristics that limit and pose a challenge for crop production; in this environment, plants can exude low-molecular-weight organic acids (LMWOAs). This study aimed to verify the influence of exogenously applied LMWOAs in calcareous soils on tomato yield and the chemical characteristics of soil and leachate. <em>Solanum lycopersicum</em> L. seedlings were grown in pots containing calcareous soil in a greenhouse, fertilized by drip irrigation with Steiner nutrient solution in which the treatments 0.1 mM citric acid (CA), 0.1 mM oxalic acid (OA), 0.01 mM salicylic acid (SA) and a control without LMWOAs (T0) were prepared, applied during the whole growth cycle. The experiment was repeated four times, with twenty replicates per treatment, under a completely randomized design. The yield per plant was quantified, while pH and microbial respiration (RMS) were measured in the soil. The pH, electrical conductivity (EC), oxidation-reduction potential (ORP), carbonate (CO<sub>3</sub><sup>2–</sup>), and bicarbonate (HCO<sub>3</sub><sup>–</sup>) contents were quantified in the leachates. SA application reduced the soil pH (8.75). SA and CA improved the fruit yield per plant by 11% and 33%, respectively (p < 0.05). CA induced a 1.7% reduction in leachate pH (p < 0.05) and a 15.9% increase in HCO<sub>3</sub><sup>–</sup> content (p < 0.05). SA decreased EC and CO<sub>3</sub><sup>2–</sup> concentrations by 8.9 and 23.1% (p < 0.05), but increased HCO<sub>3</sub><sup>–</sup> content by 23.1 % (p < 0.05). The use of LMWOAs as a strategy in the management of calcareous soils can promote favorable conditions for tomato yield per plant.</p>

Role of malic acid in enhancing the efficiency of barley (Hordeum vulgare L.) and alfalfa (Medicago sativa L.) plants for phytoremediation of salt affected soil

Soil salinization is a growing global problem that influences plant growth and crop productivity. Most of the reclamation efforts in the past have focused on the installation of surface drainage systems. Other management approaches, such as excessive leaching and chemical amendments, have also been used on a limited scale to enhance the productivity of these soils. Phytoremediation can be cost-effective and environmentally sound technology.A laboratory experiment was carried out to study the role of malic acid which is low molecular weight organic acid (LMWOA) in enhancing the efficiency of barley and alfalfa plants for the phytoremediation of salt-affected soil. Seeds of barley and alfalfa were cultured in pots and irrigated with full strength Hoagland nutrient solution with three concentrations of seawater (SW) (10%, 20% and 30%) and a mixture of seawater with malic acid (MA) at 2, 4 and 6 mM l-1 (MA+SW), Hoagland solution was used as control. After twelve weeks, plants were harvested, and three types of soils (barley soil, alfalfa soil, and plant-free soil) were subjected to physical and chemical analysis for EC (electrical conductivity), TOC (total organic carbon), pH, potassium, sodium, and chloride ions. Results indicated a significant decrease was recorded in soil EC, pH, potassium, sodium, and chloride ions and a significant increase in soil TOC in barley and alfalfa soil compared with plant-free soil. Treatments with (MA+SW), especially at (2+10%) resulted in a significant increase in ions availability and phytoremediation activity in barley and alfalfa soils comparing with plant-free soil.

Effects of organic acid application and ectomycorrhizal symbiosis on growth and morphological parameters of <em>Pinus pseudostrobus</em>

Background: Many landscapes, both natural and anthropogenic, are dominated by degraded soils that have low phosphorus availability due to low overall phosphorus concentration or to phosphorus sequestration by iron-rich minerals. Questions and / or Hypotheses: Does the application of low molecular weight organic acids improve phosphorus availability and plant growth in phosphorus-poor soils, and is this effect modulated by ectomycorrhizal fungi? Studied species / data description /Mathematical model: Pinus pseudostrobus and its ectomycorrhiza Pisolithus arhizus, in addition to six sodium salts of organic acids. Study site and dates: The experiment was carried out in a shade house (35 % shade) in Morelia, Michoacán in 2015. Methods: We conducted experiments with Pinus pseudostrobus and its ectomycorrhiza Pisolithus arhizus in addition to six sodium salts of organic acids. Sodium salts of citrate, oxalate, acetate, tartrate, succinate and malate were added to the soil at 0, 4, 8, 16, 32 and 64 micromolar concentrations. Results: The salts of the organic acids—particularly tartrate and malate-solubilized phosphorus and improved plant growth after 12 months in the absence of P. arhizus. When plants were inoculated with P. arhizus, the effect of most organic acids was either detrimental or non-significant. However, citrate, tartrate and succinate improved biomass and morphological parameters. Conclusions: These results suggest that adding appropriate organic acids to heavily degraded soils can aid P. pseudostrobus establishment and its benefits are higher than the association with mycorrhiza for young plants during the initial stages of fungal colonization.

Mechanisms of Metal Immobilization in the Soil by a Phosphate Compound with Low Molecular Weight Organic Acids Present

ABSTRACT It is important to consider how phosphate-based metal immobilization differs from traditional soil incubation because of the presence of low molecular weight organic acids (LMWOAs) in the rhizosphere. Therefore, in an incubation study, the impacts of 3% NaH2PO4 (a P compound), tartaric acid (TA), oxalic acid (OA), and combinations of P and TA/OA on cadmium (Cd), lead (Pb), and zinc (Zn)’s geochemical redistribution and availability in metal-contaminated soils were studied. The mechanisms of metal immobilization were also explored. P, a low TA (TA2), and P plus a low TA (p-TA2) significantly reduced Cd, Pb, and Zn’s acid-extractable and available (CaCl2-extractable) forms compared to the control (CK), with p-TA2 being the most effective. At high TA (>TA5–TA20), all OA levels (OA2–OA20), and P plus high TA/OA concentrations, trends reversed. Treatments became more negative as pH increased, particularly p-TA2, indicating that the main mechanism for immobilizing metals was electrostatic adsorption. However, XRD showed that the P material alone formed Cd-P, Pb-P, and Zn-P minerals, implying that sorption and precipitation were the primary metal immobilizing techniques. In conclusion, p-TA2 has the potential to effectively immobilize metals in contaminated soils. However, when treating metal-contaminated soils with P, rhizospheric LMWOAs must be considered.

Effects of low-molecular-weight organic acids on the transformation and phosphate retention of iron (hydr)oxides

The retention and mobilization of phosphate in soils are closely associated with the adsorption of iron (hydr)oxides and root exudation of low-molecular-weight organic acids (LMWOAs). This study investigated the role of LMWOAs in phosphate mobilization under incubation and field conditions. LMWOAs-mediated iron (hydr)oxide transformation and phosphate adsorption experiments revealed that the presence of LMWOAs decreased the phosphate adsorption capacity of iron (hydr)oxides by up to ~74 % due to the competition effect, while LMWOAs-induced iron mineral transformation resulted in an approximately six-fold increase in phosphate retention by decreasing the crystallinity and increasing the surface reactivity. Root simulation in rhizobox experiments demonstrated that LMWOAs can alter the contents of different extractable phosphate species and iron components, leading to 10 % ~ 30 % decreases in available phosphate in the near root region of two tested soils. Field experiments showed that crop covering between mango tree rows promoted the exudation of LMWOAs from mango roots. In addition, crop covering increased the contents of total phosphate and available phosphate by 9.08 % ~ 61.20 % and 34.33 % ~ 147.33 % in the rhizosphere soils of mango trees, respectively. These findings bridge the microscale and field scale to understand the delicate LMWOAs-mediated balance between the retention and mobilization of phosphate on iron (hydr)oxide surface, thereby providing important implications for mitigating the low utilization efficiency of phosphate in iron-rich soils.

A quantitative analysis on thermochemical sulfate reduction products of two model compounds: Implications for reaction mechanism and alteration process of hydrocarbons

Thermochemical sulfate reduction (TSR) is an important redox reaction that markedly alters hydrocarbons in deep reservoirs. Although the major achievements that involve reaction mechanism, process, and geochemical characteristics were attained in the last 50 years, a quantitative TSR model that includes major products was not built, which restricts the understanding of the reaction mechanism and the generation process of hydrocarbons in TSR. In this study, two series of thermal simulation experiments of the TSR involving n-octadecane (n-C18) and n-dodecylbenzene (C12B) with MgSO4 and H2O in a confined gold-tube system were conducted, and all the major products in different phases, particularly oxygen-containing compounds, were quantitatively analyzed. The results indicated that the high-molecular-weight (HMW) oxygenated compounds in heavy products were predominated by ketones, followed by alcohol and acids, and the low-molecular-weight (LMW) organic acids in water mainly comprised acetic acids, followed by formic acid and propionic acid. Both oxygen-containing compounds prompted the TSR process but in different ways. The accumulation of HMW oxygenated compounds in the non-autocatalytic stages was essential for initiating the catalyzed reaction of TSR. In addition, the oxygenated compounds of hydrocarbons enhance polarity, making hydrocarbons easier to contact with HSO4− or [MgSO4] CIP. The LMW organic acids possibly prompted the TSR process by acidifying the water and thus facilitating the formation of HSO4− and [MgSO4] CIP. The oxidation reaction during TSR possibly converted HMW oxygenated compounds to LMW organic acids and CO2. The quantitative analysis of products in TSR revealed that TSR destroyed the hydrocarbons more rapidly but in a different way from thermal cracking and that the generation process of hydrocarbon types in TSR was in the following order: heavy hydrocarbon, gaseous hydrocarbon/light hydrocarbon/solid bitumen, and gaseous hydrocarbon/solid bitumen. Compared with oil cracking, the TSR promoted the oil reservoir to rapidly progress to more mature stages. The hydrocarbon precursor and reaction extent affected the generation process and the character of all products in the TSR. These results can provide an improved understanding of the TSR mechanism and process and be useful in the evaluation of petroleum potential for TSR-altered oils.

Effects of sertraline hydrochloride with As(III) or Cd on rhizosphere micro-environment and root endophytes in rice

This study investigated the effects of the antidepressant sertraline hydrochloride (Ser-HCI) on rice physiology when combined with arsenic (III) or cadmium. Hydroponic experiments revealed that combined lower concentrations (0.2 and 0.6 mg L−1) of Ser-HCl and As (III) or Cd increased rice biomass and reduced pH and low molecular weight organic acids. The fluorescence intensity was enhanced with Ser-HCl and As-only treatments, with a significant difference (p < 0.05) in the dissolved organic matter index. There was a decrease in endophyte-specific operational taxonomic units, with proteobacteria dominating the rice root endophytes. The addition of Ser-HCl resulted in the Verrucomicrobiota increasing by 6.4 times, which was positively correlated with malic acid and negatively correlated with pH. Functional annotation highlighted alterations in carbohydrate metabolism pathways. This study provides insights into the interactive effects of Ser-HCl on rice when combined with As (III) or Cd, addressing gaps in our understanding of the impact of antidepressants on plant systems.