Bensulfuron-methyl (BSM) residues in soil threaten the rotation of BSM-sensitive crops. Microbial biofilms formed on crop roots could improve the ability of microbes to survive and protect crop roots. However, the research on biofilms with the purpose of mitigating or even eliminating BSM damage to sensitive crops is very limited. In this study, one BSM-degrading bacterium, Hansschlegelia zhihuaiae S113, colonized maize roots by forming a biofilm. Root exudates were associated with increased BSM degradation efficiency with strain S113 in rhizosphere soil relative to bulk soil, so the interactions among BSM degradation, root exudates, and biofilms may provide a new approach for the BSM-contaminated soil bioremediation. Root exudates and their constituent organic acids, including fumaric acid, tartaric acid, and l-malic acid, enhanced biofilm formation with 13.0–22.2% increases, owing to the regulation of genes encoding proteins responsible for cell motility/chemotaxis (fla/che cluster) and materials metabolism, thus promoting S113 population increases. Additionally, root exudates were also able to induce exopolysaccharide production to promote mature biofilm formation. Complete BSM degradation and healthy maize growth were found in BSM-contaminated rhizosphere soil treated with wild strain S113, compared to that treated with loss-of-function mutants ΔcheA-S113 (89.3%, without biofilm formation ability) and ΔsulE-S113 (22.1%, without degradation ability) or sterile water (10.7%, control). Furthermore, the biofilm mediated by organic acids, such as l-malic acid, exhibited a more favorable effect on BSM degradation and maize growth. These results showed that root exudates and their components (such as organic acids) can induce the biosynthesis of the biofilm to promote BSM degradation, emphasizing the contribution of root biofilm in reducing BSM damage to maize.

Fine particulate matter (PM2.5) samples were collected using a high-volume air sampler and pre-combusted quartz filters during May 2013 to January 2014 at a background rural site (47∘35 N, 133∘31 E) in Sanjiang Plain, Northeast China. A homologous series of dicarboxylic acids (C2-C11) and related compounds (oxoacids, α-dicarbonyls and fatty acids) were analyzed by using a gas chromatography (GC) and GC-MS method employing a dibutyl ester derivatization technique. Intensively open biomass-burning (BB) episodes during the harvest season in fall were characterized by high mass concentrations of PM2.5, dicarboxylic acids and levoglucosan. During the BB period, mass concentrations of dicarboxylic acids and related compounds were increased by up to >20 times with different factors for different organic compounds (i.e., succinic (C4) acid > oxalic (C2) acid > malonic (C3) acid). High concentrations were also found for their possible precursors such as glyoxylic acid (ωC2), 4-oxobutanoic acid, pyruvic acid, glyoxal, and methylglyoxal as well as fatty acids. Levoglucosan showed strong correlations with carbonaceous aerosols (OC, EC, WSOC) and dicarboxylic acids although such good correlations were not observed during non-biomass-burning seasons. Our results clearly demonstrate biomass burning emissions are very important contributors to dicarboxylic acids and related compounds. The selected ratios (e.g., C3/C4, maleic acid/fumaric acid, C2/ωC2, and C2/levoglucosan) were used as tracers for secondary formation of organic aerosols and their aging process. Our results indicate that organic aerosols from biomass burning in this study are fresh without substantial aging or secondary production. The present chemical characteristics of organic compounds in biomass-burning emissions are very important for better understanding the impacts of biomass burning on the atmosphere aerosols.

The two forage species used in New Zealand pastoral agricultural systems, chicory (Cichorium intybus) and plantain (Plantago lanceolata) show differential ability to absorb and translocate cadmium (Cd) from roots to shoots. Chicory can accumulate Cd from even low Cd soils to levels that might exceed regulatory guidelines for Cd in fodder crops and food. Chicory and plantain were grown in soil-filled rhizocolumns under increasing Cd levels (0 (Control), 0.4, 0.8 and 1.6 mg Cd/kg soil) for 60 days and showed variable secretion of oxalic, fumaric, malic and acetic acids as a function of Cd treatment. Plant roots secrete such Low Molecular Weight Organic Acids into the rhizosphere soil, which can influence Cd uptake. Chicory showed significantly (P < 0.05) lower secretion of fumaric acid, and higher secretion of acetic acid than plantain at all Cd treatments. We propose that the significant secretion differences between the two species can explain the significantly (P < 0.05) higher shoot Cd concentration in chicory for all Cd treatments. Understanding the mechanism for increased uptake in chicory may lead to breeding or genetic modification which yield low Cd uptake cultivars needed to mitigate the risk of Cd accumulation in pastoral agricultural food chains from this increasingly important fodder crop.

Chlorpyrifos (CP) is a widely used organophosphate (OP) insecticide and a potent environmental neurotoxin. This research focuses on the potential of bacteria, both native to agricultural soil and part of a designed consortium composed of laboratory strains, to completely degrade CP and its toxic metabolites. Metabolite production and degradation kinetics analysis through gas chromatography-mass spectrophotometry (GCMS) analysis was conducted on native soil samples and compared to soil spiked with different combinations of bacterial consortia over 7 days to determine the effectiveness of CP degradation in both non-augmented and augmented soil. GCMS analysis of augmented soil samples inoculated with putative microbial CP degradation activity identified four CP metabolites, including 3,5,6-trichloropyridinol (TCP), phosphorothioic acid, fumaric acid, and ethanol. Non-augmented ranch and crop field soil also displayed a greater native degradation capacity than garden soil, possibly due to greater pesticide exposure. CP-inoculated soil spiked with a 3-strain consortium exhibited the highest degradation rate, with 78.55% of CP degraded within 48 h. Overall, degradation kinetics for augmented and non-augmented soil samples showed that CP had an average half-life of 1.03 and 5.45 days, respectively. The outcome of this study suggests that while native agricultural populations are capable of CP degradation, supplementing contaminated soil with a bacterial consortium consisting of Pseudomonas putida CBF10-2, Ochrobactrum anthropi FRAF13, and Rhizobium radiobacter GHKF11 could be a highly efficient and safe biological approach to facilitating rapid and efficient CP degradation in agriculture.

Cadmium (Cd) accumulation, antioxidant activity (AOA), chlorophyll fluorescence (F) and organic acid distribution in Chlorophytum comosum and Callisia fragrans plants exposed to artificially added Cd (40, 160 and 320 mg kg⁻¹) were examined in pot experiment. At the highest Cd concentration, C. comosum accumulated in roots and the aboveground parts up to 1331 and 1054 mg Cd kg⁻¹ DW, and C. fragrans up to 1427 and 1263 mg Cd kg⁻¹ DW, respectively, which are quite near at the level of hyperaccumulator. Cd accumulation in both plant species increased significantly with the increment of soil Cd dosage, and the distribution was roots > shoots > stolons. Values of BC showed rising trend indicating an accumulation potential of both species. The root AOA was positively correlated to Cd addition, especially in C. comosum. Higher values of free SA were found in roots with a significant enhancement at concentrations of 40 and 160 mg kg⁻¹ Cd. It was observed that citric acid significantly reacted in both species, while fumaric acid only in C. comosum in response to Cd which may contribute to Cd chelation. Our data indicate that both species are suitable for phytoextraction of Cd from contaminated soils which increases their value as ornamentals.

Toxic Microcystis species are the main bloom-forming cyanobacteria in freshwaters. It is imperative to develop efficient techniques to control these notorious harmful algal blooms (HABs). Here, we present a simple, efficient, and environmentally safe algicidal way to control Microcystis blooms, by using intermediate carboxylic acids from the tricarboxylic acid (TCA) cycle. The citric acid, alpha-ketoglutaric acid, succinic acid, fumaric acid, and malic acid all exhibited strong algicidal effects, and particularly succinic acid could cause the rapid lysis of Microcystis in a few hours. It is revealed that the Microcystis-lysing activity of succinic acid and other carboxylic acids was due to their strong acidic activity. Interestingly, the acid-lysed Microcystis cells released large amounts of phycocyanin, about 27-fold higher than those of the control. On the other hand, the transcription of mcyA and mcyD of the microcystin biosynthesis operon was not upregulated by addition of alpha-ketoglutaric acid and other carboxylic acids. Consider the environmental safety of intermediate carboxylic acids. We propose that administration of TCA cycle organic acids may not only provide an algicidal method with high efficiency and environmental safety but also serve as an applicable way to produce and extract phycocyanin from cyanobacterial biomass.

Eisenia fetida earthworms were exposed to sub-lethal levels of imidacloprid for 48 h via contact filter paper tests and soil tests. After the exposure, ¹H nuclear magnetic resonance (NMR) metabolomics was used to measure earthworm sub-lethal responses by analyzing the changes in the polar metabolite profile. Maltose, glucose, malate, lactate/threonine, myo-inositol, glutamate, arginine, lysine, tyrosine, leucine, and phenylalanine relative concentrations were altered with imidacloprid exposure in soil. In addition to these metabolites (excluding leucine and phenylalanine), fumarate, ATP, inosine, betaine, scyllo-inositol, glutamine, valine, tryptophan, alanine, tyrosine, and isoleucine relative concentrations shifted with imidacloprid exposure during contact tests. Metabolite changes in E. fetida earthworms exposed to imidacloprid showed a non-linear concentration response and an upregulation in gluconeogenesis. Overall, imidacloprid exposure in soil induces a less pronounced response in metabolites glucose, maltose, fumarate, adenosine-5′-triphosphate (ATP), inosine, scyllo-inositol, lactate/threonine, and tyrosine in comparison to the response observed via contact tests. Thus, our study highlights that tests in soil can result in a different metabolic response in E. fetida and demonstrates the importance of different modes of exposure and the extent of metabolic perturbation in earthworms. Our study also emphasizes the underlying metabolic disruption of earthworms after acute sub-lethal exposure to imidacloprid. These observations should be further examined in different soil types to assess the sub-lethal toxicity of imidacloprid to soil-dwelling earthworms.

To estimate the pollution of As and Pb in the Songhua River which flows through the major rice-producing regions in China, the present study investigated the level and release of As and Pb in surficial sediments which collected from nine sites in Songhua River (M₁–M₉). The concentration of As and Pb was ranged as follows: As = 3.104~15.01 μg/g, Pb = 20.10~37.42 μg/g; the average concentration: As = 6.466 ± 3.077 μg/g, Pb = 28.88 ± 5.077 μg/g. By analysis vertically, the average concentration of As was 5.166 ± 1.496 μg/g in the upstream, 5.815 ± 1.793 μg/g in the midstream, and 9.716 ± 4.977 μg/g in the downstream. The average concentration of Pb was 27.83 ± 4.552 μg/g in the upstream, 28.66 ± 6.333 μg/g in the midstream, and 30.99 ± 4.837 μg/g in the downstream. It indicated that the concentration of As and Pb increased gradually from upstream to downstream. As existed mainly as insoluble state and Pb existed mainly as sulfide and organic combining state in surficial sediments, and the species of As and Pb could transform with the change of the circumstance. The release of quantity of As was higher than Pb. The pH of 6 was not conducive to the release of As and Pb. When the temperature was 35 and 6 °C, the release of As and Pb in surficial sediments were restrained, respectively. Fumaric acid and citric acid played an important role in promoting the release of As, but not conducive to Pb. Furthermore, the reasonable aeration rate was beneficial to the release process of As and Pb in surficial sediment. By kinetic analysis, the Elovich equation (Ct = 84.931–8.952lnt) could be used to describe the dynamic process of the release of As in a relatively short time. The Elovich equation (C ₜ = 2.724 + 1.3724lnt) and double constant rate equation (lnC T = 1.4646 + 0.1522lnT) could well describe the dynamics process of the release of Pb.

The microbial production of fumaric acid by Rhizopus arrhizus NRRL 2582 has been evaluated using soybean cake from biodiesel production processes and very high polarity (VHP) sugar from sugarcane mills. Soybean cake was converted into a nutrient-rich hydrolysate via a two-stage bioprocess involving crude enzyme production via solid state fermentations (SSF) of either Aspergillus oryzae or R. arrhizus cultivated on soybean cake followed by enzymatic hydrolysis of soybean cake. The soybean cake hydrolysate produced using crude enzymes derived via SSF of R. arrhizus was supplemented with VHP sugar and evaluated using different initial free amino nitrogen (FAN) concentrations (100, 200, and 400 mg/L) in fed-batch cultures for fumaric acid production. The highest fumaric acid concentration (27.3 g/L) and yield (0.7 g/g of total consumed sugars) were achieved when the initial FAN concentration was 200 mg/L. The combination of VHP sugar with soybean cake hydrolysate derived from crude enzymes produced by SSF of A. oryzae at 200 mg/L initial FAN concentration led to the production of 40 g/L fumaric acid with a yield of 0.86 g/g of total consumed sugars. The utilization of sugarcane molasses led to low fumaric acid production by R. arrhizus, probably due to the presence of various minerals and phenolic compounds. The promising results achieved through the valorization of VHP sugar and soybean cake suggest that a focused study on molasses pretreatment could lead to enhanced fumaric acid production.

Lead (Pb) stress adversely affects in planta nutrient homeostasis and metabolism when present at elevated concentration in the surrounding media. The present study was aimed at investigation of organic acid exudations, elemental contents, growth, and lipid peroxidation in two wild plants (Amaranthus viridis L. and Portulaca oleracea L.), exhibiting differential root to shoot Pb translocation, under Pb stress. Plants were placed in soil spiked with lead chloride (PbCl₂) concentrations of 0, 15, 30, 45, or 60 mg Pb/kg soil, in rhizoboxes supplied with nylon nets around the roots. The plant mucilage taken from root surfaces, mirroring the rhizospheric solution, was analyzed for various organic acids. Lead stress resulted in a release of basified root exudates from both plants. Exudates of P. oleracea roots showed a higher pH. In both plants, the pH rising effect was diminished at the highest Pb treatment level. The exudation of citric acid, glutamic acid (in both plants), and fumaric acid (in P. oleracea only) was significantly increased with applied Pb levels. In both plant species, root and shoot Pb contents increased while nutrients (Ca, Mg, and K) decreased with increasing Pb treatment levels, predominantly in A. viridis. At 60 mg Pb/kg soil, shoot Na content of A. viridis was significantly higher as compared to untreated control. Higher Pb treatment levels decreased plant fresh and dry masses as well as the quantity of photosynthetic pigments due to enhanced levels of plant H₂O₂ and thiobarbituric acid reactive substances in both species. Photosynthetic, growth, and oxidative stress parameters were grouped into three distinct dendrogram sections depending on their similarities under Pb stress. A positive correlation was identified between Pb contents of studied plants and secretion of different organic acids. It is concluded that Pb stress significantly impaired the growth of A. viridis and P. oleracea as a result of nutritional ion imbalance, and the response was cultivar-specific and dependent on exogenous applied Pb levels. Differential lipid oxidation, uptake of nutrients (Ca, Mg, and K) and exudation of citric acid, fumaric acid, and glutamic acid could serve as suitable physiological indicators for adaptations of P. oleracea to Pb enriched environment. The findings may help in devising strategies for Pb stabilization to soil colloids.