Low Molecular Weight Organic Acids Research Articles

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.

MnO2/TiO2-Catalyzed ozonolysis: enhancing Pentachlorophenol degradation and understanding intermediates

Pentachlorophenol is a pesticide widely known for its harmful effects on sewage, causing harm to the environment. In previous studies, our group identified adsorption as a crucial factor in catalytic ozonation processes, and subsequent observations revealed the catalyst’s role in reducing toxicity during degradation. In this research, we quantified organochlorine intermediates and low molecular weight organic acids generated under optimal pH conditions (pH 9), with and without the catalyst. Additionally, we assessed the reactivity of these intermediates through theoretical calculations. Our findings indicate that the catalyst reduces the duration of intermediates. Additionally, the presence of CO2 suggests enhanced mineralization of pentachlorophenol, a process notably facilitated by the catalyst. Theoretical calculations, such as Fukui analysis, offer insights into potential pathways for the dechlorination of aromatic molecules by radicals like OH, indicating the significance of this pathway.

Study on biodegradation of polyurethane coating on PCB by Aspergillus brasiliensis in space

Polyurethane (PU) is a commonly used conformal coating for printed circuit boards (PCBs). Filamentous fungi present in the space station environment are capable of degrading PU coatings, thereby posing a threat to the safety of electronic components. Therefore, we conducted a 90-day interaction test between Aspergillus brasiliensis and PU-coated PCBs in the China Space Station (CSS) and a controlled environment on the ground. This research aimed to investigate the alterations in the physiological properties of A. brasiliensis on PCB surfaces and the deterioration behavior of PU coating systems in the space microgravity environment. The results show that many fungal parameters, such as growth, morphology, cell ultrastructure, and low molecular weight organic acids (LMWOA) accumulation showed strong changes after spaceflight compared to ground controls. Distinct corrosion morphological features were found in the internal coatings by FIB/SEM analysis, suggesting the existence of a particular deterioration mechanism in the microgravity environment, which requires further investigation.

Distribution Characteristics of Low-Molecular-Weight Organic Acids in Reclaimed Soil Filled with Fly Ash: A Study.

This study aims to assess the contents of different kinds of low-molecular-weight organic acids (LMWOAs) in reclaimed soil filled with fly ash in the Huainan mining area in China using high-performance liquid chromatography (HPLC). Using a mobile phase consisting of 0.1% phosphoric acid and acetonitrile in a volume ratio of 98:2, the detection was performed at a wavelength of 210 nm for 15 min. In addition, a cluster analysis was performed on the detected LMWOAs in the reclaimed soil. The correlations between the LMWOA and nutrient contents in the reclaimed soil were also analyzed. In total, eight and seven LMWOAs were detected in the reclaimed soil and filled fly ash, respectively. In contrast, no LMWOAs were detected in the fresh fly ash from a thermal power plant. The order of total LMWOA contents at different sampling points followed the order of farmland control soil > 1# (Triticum aestivum) > 4# (Phragmites australis) > 5# (Vigna radiata) > 2# (Sorghum bicolor) > 3# (Tamarix ramosissima) > fly ash-filled soil. The farmland control soil and fly ash-filled soil exhibited the highest and lowest LMWOA contents of 648.22 and 85.09 μg·g-1, respectively. The LMWOA contents in the reclaimed soil followed the order of oxalic acid > tartaric acid > malonic acid > lactic acid > acetic acid > citric acid > propionic acid > succinic acid. Indeed, oxalic acids exhibited the highest total amount of 1445.79 μg·g-1 and succinic acids exhibited the lowest total amount of 6.50 μg·g-1. The LMWOA contents in the reclaimed soil decreased with increasing soil depth, showing statistically significant differences between the 0-10 and 10-40 cm soil layers (p < 0.05). According to the obtained clustering results, the detected LMWOAs can be divided into two categories. The first category consisted of oxalic acid, while the second category included the remaining LMWOAs. The soil LMWOA contents of 4# (Phragmites australis) and 5# (Vigna radiata) were significantly different from those at the other sampling points. According to the Pearson correlation analysis results, the occurrence and characteristics of the soil LMWOAs can be controlled by regulating the pH values and available nutrient contents in the soil, thereby improving the eco-environmental conditions of the reclaimed rhizosphere.

Physiological and Enzymatic Antioxidant Responses of Solanum tuberosum Leaves to Arbuscular Mycorrhizal Fungal Inoculation under Water Stress.

Solanum tuberosum is one of the most widely cropped plant species worldwide; unfortunately, drought is one of the major constraints on potato productivity because it affects the physiology, biochemical processes, and yield. The use of arbuscular mycorrhizal fungi (AMF) has exhibited beneficial effects on plants during drought. The objective of this study was to analyse the effect of AMF inoculation on two genotypes of potato plants exposed to water stress, and the photosynthetic traits, enzymatic antioxidant activity, and exudation of low-molecular-weight organic acids (LMWOAs) of potato plants inoculated with two strains of AMF, Claroideoglomus claroideum (CC) and Claroideoglomus lamellosum (HMC26), were evaluated. Stomatal conductance exhibited a similar trend in the CC and HMC26 treatments for both potato genotypes; moreover, the photosynthetic rate significantly increased by 577.9% between the 100% soil humidity (S0) and 40% soil humidity (S2) stress levels for the VR808 genotype under the CC treatment. The activities of the enzymes catalase (CAT) and ascorbate peroxidase (APX) showed similar trends. In this study, there were different responses among genotypes and treatments. Inoculation with CC under S2 stress levels is a promising potential approach for improving potato growth under drought conditions.

Influence of cations and low molecular weight organic acids on Cs(I) adsorption on montmorillonite and vermiculite

To predict the mobility of radiocesium (RCs) in the environment, it is essential to understand the adsorption and desorption processes. In this study, we focused on the effects of certain environmental factors, including typical cations (K+, Na+, and NH4+) and low molecular weight organic acids (LMWOAs) such as acetic acid, malic acid, and citric acid on the behavior of RCs on montmorillonite and vermiculite. The results showed that montmorillonite possesses the strongest adsorption capacity for Cs+ than that of vermiculite. Since K+ and NH4+ exhibit similar physicochemical properties to Cs+, there is a significant inhibition of Cs+ adsorption on montmorillonite and vermiculite during the competitive interaction with K+ and NH4+. Compared to NH4Cl, the desorption ratios of Cs+ on montmorillonite and vermiculite are higher in the presence of KCl as the background solution. Low molecular weight organic acids can cover the surfaces of montmorillonite and vermiculite to different extents, which effectively blocks the adsorption sites for Cs+, and leads to an obvious decrease in the adsorption and desorption of Cs+. Due to the high expandable performance, Cs+ is primarily reversibly adsorbed by montmorillonite. Nevertheless, the adsorption of Cs+ on vermiculite exhibits typical irreversible characteristics due to the interlayer collapse. After the adsorption of LMWOAs on montmorillonite and vermiculite, the irreversible adsorption of Cs+ is increased obviously, mainly due to the blocking effect of organic matters on the adsorption sites with high affinity to Cs+.

Mechanism of tartaric acid mediated dissipation and biotransformation of tetrabromobisphenol A and its derivatives in soil

Biotransformation is a major dissipation process of tetrabromobisphenol A and its derivatives (TBBPAs) in soil. The biotransformation and ultimate environmental fate of TBBPAs have been widely studied, yet the effect of root exudates (especially low-molecular weight organic acids (LMWOAs)) on the fate of TBBPAs is poorly documented. Herein, the biotransformation behavior and mechanism of TBBPAs in bacteriome driven by LMWOAs were comprehensively investigated. Tartaric acid (TTA) was found to be the main component of LMWOAs in root exudates of Helianthus annus in the presence of TBBPAs, and was identified to play a key role in driving shaping bacteriome. TTA promoted shift of the dominant genus in soil bacteriome from Saccharibacteria_genera_incertae_sedis to Gemmatimonas, with a noteworthy increase of 24.90–34.65% in relative abundance of Gemmatimonas. A total of 28 conversion products were successfully identified, and β-scission was the principal biotransformation pathway for TBBPAs. TTA facilitated the emergence of novel conversion products, including 2,4-dibromophenol, 3,5-dibromo-4-hydroxyacetophenone, para-hydroxyacetophenone, and tribromobisphenol A. These products were formed via oxidative skeletal cleavage and debromination pathways. Additionally, bisphenol A was observed during the conversion of derivatives. This study provides a comprehensive understanding about biotransformation of TBBPAs driven by TTA in soil bacteriome, offering new insights into LMWOAs-driven biotransformation mechanisms.

Role of low-molecular-weight organic compounds on photochemical formation of Mn(III)-ligands in aqueous systems: Implications for BPA removal

Aqueous trivalent manganese [Mn(III)], an important reactive intermediate, is ubiquitous in natural surface water containing humic acid (HA). However, the effect of low-molecular-weight organic acids (LMWOAs) on the formation, stability and reactivity of Mn(III) intermediate is still unknown. In this study, six LMWOAs, including oxalic acid (Oxa), salicylic acid (Sal), catechol (Cat), caffeic acid (Caf), gallic acid (Gal) and ethylene diamine tetraacetic acid (EDTA), were selected to investigate the effects of LMWOAs on the degradation of BPA induced by in situ formed Mn(III)-L in the HA/Mn(II) system under light irradiation. The chromophoric constituents of HA could absorb light radiation and generate superoxide radical to promote the oxidation of Mn(II) to form Mn(III), which was further involved in transformation of BPA. Our results implied that different LMWOAs did significantly impact on Mn(III) production and its degradation of BPA due to their different functional group. EDTA, Oxa and Sal extensively increased the Mn(III) concentration from 50 to 100 μM compared to the system without LMWOAs, following the order of EDTA > Oxa > Sal, and also enhanced the degradation of BPA with the similar patterns. In contrast, Cat, Caf and Gal had an inhibitory effect on the formation of Mn(III), which is likely because they consumed the superoxide radicals generated from irradiated HA, resulting in the inhibition of Mn(II) oxidation and further BPA removal. The product identification and theoretical calculation indicated that a single electron transfer process occurred between Mn(III)-L and BPA, forming BPA radicals and subsequent self-coupling products. Our results demonstrated that the LMWOAs with different structures could alter the cycling process of Mn via complexation and redox reactions, which would provide new implications for the removal of organic pollutants in surface water.

Distinct photochemistry of adsorbed and coprecipitated dicarboxylates with ferrihydrite: Implications for iron reductive dissolution and carbon stabilization

Although ligand-promoted photodissolution of ferrihydrite (FH) has long been known for low molecular weight organic acids (LMWOAs), such as oxalate (Oxa) and malonate (Mal), photochemistry of coprecipitated FH with Oxa and Mal remains unknown, despite the importance of these mineral-organic associations in carbon retention has been acknowledged recently. In this study, ferrihydrite-LMWOAs associations (FLAs) were synthesized under circumneutral conditions. Photo-dissolution kinetics of FLAs were compared with those of adsorbed LMWOAs on FH surface and dissolved Fe-LMWOAs complexes through monitoring Fe(II) formation and organic carbon decay. For aqueous Fe(III)-LMWOAs complexes, Fe(II) yield was controlled by the initial concentration of LMWOAs and nature of photochemically generated carbon-centered radicals. Inner-sphere mononuclear bidentate (MB) configuration dominated while LMWOAs were adsorbed on the FH surface. MB complex of FH-Oxa was more photoreactive, leading to the rapid depletion of Oxa. Oxa can be readsorbed but in the form of binuclear bidentate and outer-sphere complexation, with much lower photoreactivity. While LMWOAs was coprecipitated with FH, the combination mode of LMWOAs with FH includes surface adsorption with a mononuclear bidentate structure and internal physical inclusion. Higher content of LMWOAs in the FLAs promoted the photo-production of Fe(II) as compared to pure FH, while it was not the case for FLAs containing moderate amounts of LMWOAs. The distinct photochemistry of adsorbed and coprecipitated Fe-LMWOAs complexes is attributed to ligand availability and configuration patterns of LMWOAs on the surface or entrapped in the interior structure. The present findings have significant implications for understanding the photochemical redox cycling of iron across the interface of Fe-organic mineral associates.

Peroxydisulfate-Driven Reductive Dechlorination as Affected by Soil Constituents: Free Radical Formation and Conversion.

We report a previously unrecognized but efficient reductive degradation pathway in peroxydisulfate (PDS)-driven soil remediation. With supplements of naturally occurring low-molecular-weight organic acids (LMWOAs) in anaerobic biochar-activated PDS systems, degradation rates of 12 γ-hexachlorocyclohexanes (HCH)-spiked soils boosted from 40% without LMWOAs to a maximum of 99% with 1 mM malic acid. Structural analysis revealed that an increase in α-hydroxyl groups and a diminution in pKa1 values of LMWOAs facilitated the formation of reductive carboxyl anion radicals (COO•-) via electrophilic attack by SO4•-/•OH. Furthermore, degradation kinetics were strongly correlated with soil organic matter (SOM) contents than iron minerals. Combining a newly developed in situ fluorescence detector of reductive radicals with quenching experiments, we showed that for soils with high, medium, and low SOM contents, dominant reactive species switched from singlet oxygen/semiquinone radicals to SO4•-/•OH and then to COO•- (contribution increased from 30.8 to 66.7%), yielding superior HCH degradation. Validation experiments using SOM model compounds highlighted critical roles of redox-active moieties, such as phenolic - OH and quinones, in radical formation and conversion. Our study provides insights into environmental behaviors related to radical activation of persulfate in a broader soil horizon and inspiration for more advanced reduction technologies.

The dissipation of organophosphate esters mediated by ryegrass root exudate oxalic acid in soil: Analysis of enzymes activities, microorganism

Complex rhizoremediation is the main mechanism of phytoremediation in organic-contaminated soil. Low molecular weight organic acids (LMWOAs) in root exudates have been shown to increase the bioavailability of contaminants and are essential for promoting the dissipation of contaminants. The effects of root exudates on the dissipation of organophosphate esters (OPEs) in soil are unclear. Consequently, we studied the combined effects of root exudates, soil enzymes and microorganisms on OPEs (tri (1-chloro-2-propyl) phosphate (TCPP) and triphenyl phosphate (TPP)) dissipation through pot experiments. Oxalic acid (OA) was confirmed to be the main component of LMWOAs in root exudates of ryegrass. The existence of OA increased the dissipation rate of OPEs by 6.04%–25.50%. Catalase and dehydrogenase activities were firstly activated and then inhibited in soil. While, urease activity was activated and alkaline phosphatase activity was inhibited during the exposure period. More bacteria enrichment (e.g., Sphingomonas, Pseudomonas, Flavisolibacter, Pontibacter, Methylophilus and Massilia) improved the biodegradation of OPEs. In addition, the transformation paths of OPEs hydrolysis and methylation under the action of root exudates were observed. This study provided theoretical insights into reducing the pollution risk of OPEs in the soil.

Effects of root-derived organic acids on sorption of pharmaceutically active compounds in sandy topsoil

The presence and fate of pharmaceutically active compounds (PhACs) in agricultural fields are rarely investigated. The present study highlights that root-derived low-molecular-weight organic acids (LMWOAs) affect the mobility of PhACs in cultivated humic Arenosol. Sorption experiments are conducted using three PhACs characterised by different physicochemical properties: carbamazepine (CBZ), 17α-ethinylestradiol (EE2), and diclofenac-sodium (DFC). The results suggest that the adsorption of EE2 is more intense than the other two PhACs, whereas DFC and CBZ are primarily dominated by desorption. LMWOAs mainly provide additional low-energy adsorption sites for the PhACs, and slight pH changes do not significantly affect the sorption mechanism. During competitive adsorption, the high-energy sites of the adsorbents are initially occupied by EE2 owing to its high adsorption energy (∼15 kJ/mol). The new low-energy binding sites enhance the adsorption of DFC (from 8.5 % to 72.0 %) and CBZ (from 31.0 % to 70.0 %) during multicomponent adsorption. LMWOAs not only affect adsorption by modifying the pH but also provide additional binding sites that allow the PhACs to remain in the root environment for a longer period. As the concentration of LMWOAs temporarily changes, so does the availability of PhACs in the root zone. Environmental changes in the humic horizon enhance the mobility of the adsorbed PhACs, which renders them continuously available for uptake by plants, thus increasing the possibility of PhACs entering the human food chain.

Seasonal distributions and possible sources of low molecular weight organic acids in PM2.5 from a typical mining city after decade green mining developing in Southeastern Hubei, Central China

Low molecular weight (LMW) organic compounds are prevalent in the atmospheric aerosols. Human activities and natural sources could significantly influence aerosol compositions and concentrations, particularly in a typical mining and metallurgy city. In this study, we measured dicarboxylic acids, ω-oxocarboxylic acids, pyruvic acid, α-dicarbonyls, and fatty acids in PM2.5 from Huangshi, China throughout one year. The results indicated that oxalic acid and glyoxylic acid were the most abundant dicarboxylic acid and ω-oxocarboxylic acid, respectively, across all seasons. Following nearly a decade of environmentally conscious economic development in Huangshi, it is observed that organic compounds primarily accumulated in PM2.5 due to the combustion of fossil fuels for mining-related activities and biogenic emissions. Furthermore, anthropogenic activities, including emissions related to traffic, biomass burning, and plastic incineration, significantly influence the composition of organic aerosols. Natural processes, such as atmospheric oxidation during long-distance transport, predominantly from North China, Mongolia, Russia, and Kazakhstan, also play a substantial role. The findings underscore the transitioning energy structures, modes of transport, and oxidation processes during long-distance transport have already begun to influence the composition of LMW organic compounds. The insights gained from this study offer valuable information for researchers and governmental authorities to understand the molecular composition and potential sources of LMW organic acids in the context of green mining development. This knowledge can aid in the formulation of targeted policies for the prevention and control of carbonaceous pollution in similar mining regions globally.

Modelling diagenetic reactions and secondary porosity generation in sandstones controlled by the advection of low‐molecular‐weight organic acids

AbstractHigher secondary porosity was observed in the centre of a sandstone unit in the Eocene Shahejie Formation fan delta front sandstones from the Bozhong Depression, Bohai Bay Basin. This differs from past studies showing secondary porosity mainly in the marginal parts of sandstones adjacent to shales. This study utilized reactive transport models involving low‐molecular‐weight organic acids (LMWOA) to discuss potential processes resulting in the contrary distribution of secondary porosity. An interface model simulating LMWOA diffusion from adjacent shales to the sandstone resulted in secondary porosity in sandstones adjacent to shales. In contrast, an advection model simulating advective transport of LMWOA parallel to the sandstone bedding successfully generated higher secondary porosity in the central part. The central part of the sandstone exhibited better grain sorting (greater depositional porosity) and significantly less early carbonate cements compared to the marginal sandstone parts. Consequently, the central part had greater porosity prior to the dissolution through LMWOA. The initially higher porosity in the central part allowed for a higher advective flux of LMWOA‐rich water and associated lower pH, resulting in decreased oligoclase saturation, higher oligoclase dissolution rates and ultimately higher secondary porosity. This study indicates that grain sorting during sediment deposition, early carbonate cementation, LMWOA production in adjacent shales, and advection processes collectively control the diagenetic reactions and the distribution of secondary porosity in sandstones.

Effects of flooding and warming on soil nitrogen fraction transformation under low‐molecular‐weight organic acid inputs

AbstractFlooding and climate warming lead to the increase of low‐molecular‐weight organic acid (LMWOA) inputs to soil. However, it is unclear what the effects of flooding and climate warming on soil nitrogen fraction transformation under LMWOA input are. Fluvisol was collected in the riparian zone of the Three Gorges Reservoir to conduct an incubation experiment with the treatments of three LMWOAs at five contents, two hydrological environments and two temperatures. Compared with LMWOA input of 0 mg kg−1, the soil nitrogen in ion exchangeable fraction (IEF‐N), strong oxidant extractable fraction (SOEF‐N) and non‐transformable nitrogen (NTF‐N) were increased by 35.77, 54.71 and 25.49 mg kg−1, respectively, under LMWOA input of 40 mmol kg−1. Soil nitrogen in the weak acid extractable fraction (WAEF‐N) was decreased by 117.41 mg kg−1. Microbial biomass nitrogen (MBN) was increased by 25.29 mg kg−1, and calcium carbonate (CaCO3) was decreased by 8.03 g kg−1. The contents of IEF‐N, NTF‐N and amorphous iron oxides were higher under the flooding environment than under the drying environment. In contrast, opposite results were observed for soil nitrogen in the strong alkali extractable fraction (SAEF‐N), SOEF‐N and MBN. IEF‐N and NTF‐N contents were higher at 20°C than at 30°C, and the contents of SOEF‐N and MBN were higher at 30°C than at 20°C. WAEF‐N was dissolved by LMWOA through CaCO3 dissolution. The dissolved WAEF‐N was partly transformed into SOEF‐N and NTF‐N by microbial assimilation and humification. Flooding desorbed SAEF‐N through the crystalline transformation of iron oxides. Flooding inhibited the transformation of IEF‐N to SOEF‐N and promoted the formation of NTF‐N, while warming did the opposite. The results provide a perspective of the bound state between soil and nitrogen for understanding the soil nitrogen cycling and help to assess the impacts of climate warming and flooding on soil nitrogen loss from soil to the surrounding water.

An environmentally friendly strategy for reducing the environmental risks of heavy metals adsorbed by kaolinite

Plenty of heavy metals (HMs) that are adsorbed on clay minerals (such as kaolinite), in addition to low molecular-weight organic acids (such as oxalic acid (OA)) with high activities, are widespread in the natural environment. In the present study, the effects of OA on the environmental behaviors of Pb2+/Cd2+ adsorbed by kaolinite have been investigated. The effectiveness and mechanisms of calcium silicate (CS) and magnesium silicate (MS) in reducing the environmental risks of the HMs have also been studied. The results showed that the releases of Pb2+/Cd2+ increased with an increasing concentration of OA. When different dosages of CS/MS were added to the aging system, a redistribution of HMs took place and the free form of Pb2+/Cd2+ decreased to very low levels. Also, the unextractable Pb2+/Cd2+ increased to high levels. Furthermore, a series of characterizations showed that the released HMs were re-captured by the CS/MS. In addition, the CS immobilized the OA in the solution during the aging process, which also facilitated an immobilization of the carbon element in the environment. In general, the present study has contributed to a further understanding of the transport behaviors of the HMs in natural environments, and of the interactions between CS (or MS), the environmental media, and the heavy metal contaminants. In addition, this study has also provided an eco-friendly strategy for an effective remediation of heavy metal pollution.

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.