High-resolution mass spectrometry-based non-targeted metabolomics reveals toxicity of naphthalene on tall fescue and intrinsic molecular mechanisms.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous at relatively high concentrations by atmospheric deposition, and they are threatening to the environment. In this study, the toxicity of naphthalene on tall fescue and its potential responding mechanism was first studied by integrating approaches. Tall fescue seedlings were exposed to 0, 20, and 100 mg L-1 naphthalene in a hydroponic environment for 9 days, and toxic effects were observed by the studies of general physiological studies, chlorophyll fluorescence, and root morphology. Additionally, Ultra Performance Liquid Chromatography - Electrospray Ionization - High-Resolution Mass Spectrometry (UPLC-ESI-HRMS) was used to depict metabolic profiles of tall fescue under different exposure durations of naphthalene, and the intrinsic molecular mechanism of tall fescue resistance to abiotic stresses. Tall fescue shoots were more sensitive to the toxicity of naphthalene than roots. Low-level exposure to naphthalene inhibited the electron transport from the oxygen-evolving complex (OEC) to D1 protein in tall fescue shoots but induced the growth of roots. Naphthalene induced metabolic change of tall fescue roots in 12 h, and tall fescue roots maintained the level of sphingolipids after long-term exposure to naphthalene, which may play important roles in plant resistance to abiotic stresses.

Bioleaching of silicon in electrolytic manganese residue using single and mixed silicate bacteria.

Electrolytic manganese residue (EMR) is a type of industrial solid waste with a high silicon content. The silicon in EMR can be used as an essential nutrient for plant growth, but most of the silicon is found in silicate minerals with very low water solubility, that is, it is inactive silicon and cannot be absorbed and used by plants directly. Thus, developing a highly effective and environmentally friendly process for the activation of silicon in EMR is important both for reusing solid waste and environmental sustainability. The aim of this study was to investigate the desilication of EMR using cultures of Paenibacillus mucilaginosus (PM) and Bacillus circulans (BC). The results showed that the two types of silicate bacteria and a mixed strain of them were all able to extract silicon from EMR with a high efficiency, but the desilication performance of the mixed PM and BC was the best. Fourier transform infrared spectroscopy indicated that silicate bacteria can induce a suitable micro-environment near the EMR particles and release Si into the solution through their metabolism. X-ray diffraction analysis confirmed that layered crystal minerals, such as muscovite and diopside, were more likely to be destroyed by the bacterial action than quartz, which has a frame structure. Scanning electron microscopy-energy dispersive spectrometry proved that the silicate structures were destroyed and that Si in the residue was decreased, indicating the dissolution of silicon under the action of these microorganisms. This study suggests that bioleaching may be a promising method for the activation of silicon in EMR.

Transcriptome analysis providing novel insights for Cd-resistant tall fescue responses to Cd stress.

Cadmium (Cd) is a severely toxic heavy metal and environmental pollutant. Tall fescue is a cold season turf grass which has high resistance to Cd as well as the ability to enrich it. To investigate the molecular mechanism underlying the adaptability of tall fescue to Cd stress, RNA-Seq was used to examine Cd stress responses of tall fescue at a transcriptional level. A total of 12 cDNA libraries were constructed from the total RNA of roots or leaves of tall fescue with or without Cd treatments. A total of 2594 (1768 up- and 826 down-regulated) differentially expressed genes (DEGs) were detected in the roots of Cd-stressed tall fescue compared with control roots (R_cd vs R_ck), while only 52 (29 up- and 23 down-regulated) DEGs were found in the leaves of Cd-stressed plants versus the controls (L_cd vs L_ck). The genes encoding glutathione S-transferase (GST), transporter proteins including the ABC transporter, ZRT/IRT-like protein, potassium transporter/channel, nitrate transporter, putative iron-phytosiderophore transporter, copper-transporting ATPase or transporter and multidrug and toxic compound extrusion (MATE) proteins, and numerous transcription factors were found to be significantly induced in Cd-treated roots. In addition, pathogenesis/disease-related gene mRNAs were accumulated in Cd-treated roots of tall fescue. Furthermore, the significantly enriched KEGG pathways in roots were related to 'Glutathione metabolism', 'Ribosome', 'alpha-Linolenic acid metabolism', 'Diterpenoid biosynthesis', 'Sulfur metabolism', 'Phenylpropanoid biosynthesis', 'Protein processing in endoplasmic reticulum', 'Protein export' and 'Nitrogen metabolism'. The study provides novel insights for further understanding the molecular mechanisms of tall fescue responses to Cd stress.

Distribution and phytotoxicity of soil labile aluminum fractions and aluminum species in soil water extracts and their effects on tall fescue.

Soil acidification can alter the biogeochemistry of ecosystems and adversely affect biota; however, there are still many debates about the toxicity of aluminum (Al) fractions and Al species in soil:water extracts to plants. In this study, five crude soils with different pH values (4.92-8.51) were collected, seeded with tall fescue and grown in rhizosphere boxes for 120 days. Then, soil properties, labile Al fractions and Al species in soil:water extracts were determined, and their toxicities to plants were analyzed. Our study showed that a stable exchangeable Al fraction (ExAl) pool exists and is supplied by other labile Al fractions. Dissolution of Al from adsorbed hydroxyl-Al fraction (HyAl) and organic-Al fraction (OrAl) may play important roles in soil Al toxicity, as HyAl and OrAl account for major parts of soil labile Al. Additionally, Al3+ and mononuclear hydroxyl-Al species in soil:water extracts have few effects to plants. Nevertheless, high negative correlations were found between Al-F- complexes and tall fescue biomass, indicating their toxicity in the natural soil environment. Thus, in many cases, Al3+ toxicity should not be emphasized because of its lower activity in soil water extracts. Moreover, toxicities of AlF3(aq) and AlF4- to plants should be emphasized, because they have been confirmed in soil water extracts in this study.

Bio-stabilization of arsenic in sediments by natural carbon-containing biomass: Performance and microbial metabolites.

The development of sustainable methods for the control and bio-stabilization of arsenic in sediments, without generating secondary pollution, is an urgent technological need. In this study, we utilized three types of natural carbon-containing biomass (NCCB) to explore the stabilization of arsenic through the synergistic action of native sediment microbiomes. We also examined the metabolic pathways of microorganisms following the introduction of NCCB into high-arsenic sediments, aiming to elucidate the biological processes critical for arsenic bio-stabilization. Our findings indicate that humic acid (HA) and soil organic matter (SOM) are effective in preventing the leaching of As(III) from sediments, while fulvic acid (FA) and SOM can significantly reduce the leaching of As(V). Furthermore, the introduction of NCCB into the system altered the biological metabolic processes, with notable upregulation of metabolites such as 8-hydroxyondansetron, 1,2,3,5,6,8-hexathionane, and citric acid. These results hold promise for the application of these findings in the management of arsenic in natural sediments.

Insight into adsorption process and mechanisms of Cr(III) using carboxymethyl cellulose-g-poly(acrylic acid-co-acrylamide)/attapulgite composite hydrogel.

Cr(III) as one of the most concerned potentially toxic elements, is discharged from relevant industries and Cr(VI) reduction. Hydrogel-based adsorption could be one of the promising approaches for Cr(III) removal. Featured with environmental friendliness and low cost, carboxymethyl cellulose (CMC) was employed for the hydrogel synthesis, and attapulgite (APT) could be used to strengthen its stability. However, the adsorption performance and mechanisms need to be examined. In the present study, carboxymethyl cellulose-g-poly(acrylic acid-co-acrylamide)/ attapulgite (CMC-g-p(AA-co-AM)/APT) was synthesised via in situ copolymerisation. Its efficacy for removing Cr(III) from an aqueous solution was investigated using batch adsorption experiments. Results showed that the introduction of APT enhanced the thermal stability but decreased the swelling performance of the hydrogel. The prepared hydrogel could strongly adsorb Cr(III) at a wide pH range of 3.0-7.0. Cr(III) can be efficiently removed by the composite hydrogel within 1-2 h. At low concentration, CMC-g-p(AA-co-AM)/APT could slightly adsorbed more Cr(III) than CMC-g-p(AA-co-AM). The maximum absorption of CMC-g-p(AA-co-AM) and CMC-g-p(AA-co-AM)/APT were 74.8 and 47.7 mg/g at 298 K, respectively. The negative value of ΔHo and ΔGo indicated the adsorption of Cr(III) onto the two studied hydrogels is an exothermic and spontaneous process. Ion exchange and complexation, as implied by EDS, FT-IR and XPS, combining with electrostatic attraction are the possible adsorption mechanisms for Cr(III) onto the prepared hydrogels. All the results above suggests that the composite hydrogel CMC-g-p(AA-co-AM)/APT can be a promising candidate for the removal of Cr(III) from waste water.

Highly efficient removal of Cr(VI) from aqueous solution by pinecone biochar supported nanoscale zero-valent iron coupling with Shewanella oneidensis MR-1.

Nanoscale zero-valent iron (nZVI) has been extensively used to remove various pollutants. However, the rapid deactivation due to aggregation and surface passivation severely limits its practical application. In this study, a novel composite with nZVI supported by pinecone biochar (nZVI-PBC) was successfully synthesized and used for the removal of high concentration Cr(VI) from aqueous solution in the presence of Shewanella oneidensis MR-1 (MR-1). The results showed that the nZVI-PBC coupling with MR-1 (nZVI-PBC/MR-1) exhibited an excellent removal performance for high concentration Cr(VI) compared to the nZVI-PBC alone. Under optimal conditions, 100 mg/L Cr(VI) could be removed completely by nZVI-PBC/MR-1 within 48 h, while only 39.50% of Cr(VI) was removed by nZVI-PBC alone. The improvement of Cr(VI) removal is due to the dissolution of the surface passivation layer of nZVI-PBC, formation of sorbed Fe(II) in the presence of MR-1, and an important role of extracellular polymeric substance (EPS) derived from MR-1. X-ray photoelectron spectroscopy (XPS) and Cr K-edge X-ray absorption near-edge structure spectra (XANES) confirmed that most Cr(VI) was reduced to insoluble Cr(III) and formed Cr2O3, CrxFe1-x(OH)3 and FeCr2O4 precipitates, and a small amount of unreduced Cr(VI) was immobilized through adsorption and complexation. The results suggest that nZVI-PBC/MR-1 can effectively overcome the limitations of nZVI and achieve highly efficient removal of high concentration Cr(VI).

Species identification and mutation breeding of silicon-activating bacteria isolated from electrolytic manganese residue.

A strain of silicon-activating bacteria was isolated from electrolytic manganese residue (EMR); identified as a species of Ochrobactrum by integrated microscopic morphological characteristics, biochemical index determination, and clone analysis (i.e., results of 16S rRNA sequence); and temporarily named as Ochrobactrum sp. T-07 (T-07). The optimal growth conditions of the strain T-07 were obtained as follows: temperature of 30 °C, initial pH of 7.0, shaking speed of 180 rev. min-1, and loading volume of 100 mL. In order to enhance its activation activity of silicon, T-07 went through the ultraviolet (UV) mutagenesis and nitrosoguanidine (NTG) mutagenesis breeding, and the mutant strain T-07-B with higher activity was obtained. Under the optimal fermentation condition (leaching time of 20 days, temperature of 30 °C, initial pH of 7, pulp concentration of 5%, shaking speed of 180 rev. min-1, and particle diameter of EMR ≤ 180 µm), the available silicon content in the supernatant reached 98.8 mg L-1, which was 2.4 times of the original strain T-07. Therefore, T-07 can be used as a good backup in developing biological silicon fertilizer for plants.

Electrolytic manganese residue-based cement for manganese ore pit backfilling: Performance and mechanism.

Slag backfilling with electrolytic manganese residue (EMR) is an economical and environmentally-friendly method. However, high ammonium-nitrogen and manganese ions in EMRs limit this practice. In this study, a method of highly efficient simultaneous stabilization/solidification of ultrafine EMR by making EMR-based cementitious material (named EMR-P) was proposed and tested via single-factor and response surface optimization experiments. Results show that the stabilization efficiency of NH4+ and Mn2+ were above 95%, and the unconfined compressive strength of the EMR-P was 18.85 MPa (megapascal = N/mm2). The mechanistic study concluded that the soluble manganese sulfate and ammonium sulfate in EMR were converted into the insoluble precipitates of manganite (MnOOH), gypsum (CaSO4), MnNH4PO4·H2O, and struvite (MgNH4PO4∙6 H2O), leading to the stabilization of NH4+ and Mn2+ in the EMR-P. Leaching tests of EMR-P indicated that NH4+, Mn2+, and others heavy metals in the leachate were within the permitted level of the GB/T8978-1996. The novelty of this study includes the addition of phosphate and magnesium ions to precipitate ammonium-nitrogen and the combination between calcium ions (from CaHPO4∙2 H2O) and sulfate (from the EMR) to form calcium sulfate to improve the stability and unconfined compressive strength of cementitious materials (EMR-P).

Bio-leaching of manganese from electrolytic manganese slag by Microbacterium trichothecenolyticum Y1: Mechanism and characteristics of microbial metabolites.

The related microbial metabolomics on biological recovery of manganese (Mn) from Electrolytic Manganese Slag (EMS) has not been studied. This study aimed at open the door to the metabolic characteristics of microorganisms in leaching Mn from EMS by using waste molasses (WM) as carbon source. Results show Microbacterium trichothecenolyticum Y1 (Y1) could effectively leach Mn from EMS in combination with using waste molasses as carbon and energy sources. For the first time, Y1 was identified to be capable of generating and then metabolizing several organic acids or other organic matter (e.g., fumaric acid, succinic acid, malic acid, glyoxylic acid, 3-hydroxybutyric acid, glutaric acid, L(+)-tartaric acid, citric acid, tetrahydrofolic acid, and L-methionine). The production of organic acids by Y1 bacteria was promoted by EMS with the carbon source. This study demonstrated for the first time that metabolic characteristics and carbon source metabolic pathways of Y1 in bioleaching of Mn from EMS.

Bioleaching of silicon in electrolytic manganese residue (EMR) by Paenibacillus mucilaginosus: Impact of silicate mineral structures.

Electrolytic manganese residue (EMR) is characterized by high silicon content, and thus, is an important silicon source. While considerable research has been conducted on bioleaching EMR for silicon recovery, sufficient information is not available on the impact of specific silicate mineral structures in EMR on silicon bioleaching. In the present study, the mineral composition of EMR was determined firstly, and then the leaching effect of Paenibacillus mucilaginosus on these different silicate minerals were investigated by shake flask experiments. Results showed that the silicon in EMR was mainly composed of quartz, sericite, muscovite, biotite, olivine and rhodonite; Paenibacillus mucilaginosus had a significantly different weathering and decomposition effects on different silicate minerals. Among them, sericite, muscovite and biotite with layered structure had the most obvious silicon leaching effect, followed by rhodonite with island structure, while silicon leaching from olivine with chained structure and quartz with frame structure was much more difficult. One can roughly judge the adaptability of bioleaching of silicon in EMR using Paenibacillus mucilaginosus if the main form of silicate minerals in EMR is determined.

Chromium(VI) bioreduction and removal by Enterobacter sp. SL grown with waste molasses as carbon source: Impact of operational conditions.

A technology utilizes bacteria Enterobacter sp. SL grown in an anaerobic reactor with waste molasses as carbon source to bio-reduce hexavalent chromium [Cr(VI)] in wastewater and then remove total chromium has been developed. The performance was elucidated through different initial and operating experiments conditions, and the associated mechanism of Cr(VI) reduction was explained. Results show that Cr(VI) removal is 99.91% at 25 h in the anaerobic reactor initially containing bacteria of 5% (v/v), (NH4)2Fe(SO4)2·6H2O of 0.5 g·L-1, waste molasses of 2.5 g·L-1, Cr(VI) of 100 mg·L-1, pH of 6.0, and with the operational temperature of 45 °C. After 120 h reaction, Cr(total) removal reached 91.10%. The major reduction products [FeS, Cr2O3, Cr(OH)3, S0 granules] together with microbes was removed by sludge separation with Cr(VI) in the supernatant (0.027 mg·L-1) being much lower than that (not excess 0.2 mg·L-1) of Electroplating Pollutant Emission Standard.

Efficient removal of heavy metals by synergistic actions of microorganisms and waste molasses.

In this study, two bacteria strains (Enterobacter sp. SL and Acinetobacter sp. SL-1) and waste molasses (carbon source) were used to remove Zn(II), Cd(II), Cr(VI), and Cr(Total) in the liquid solution (87 mg·L). The results showed the removal efficiencies of Cr(Total) and Cr(VI) could reach over 98.00% after reaction, and the removal efficiencies of Zn(II) and Cd(II) were all about 90.00% by the synergistic actions of microorganisms and waste molasses. In this process, waste molasses provides nutrients for microorganisms and has the characteristics and capability of Cr, Zn, and Cd. Microorganisms mainly use biological adsorption (36.95% and 45.69%) and metabolism (24.37% and 17.05% by producing humic-acid and fulvic-acid like substances) to remove Zn(II) and Cd(II), while waste molasses could to remove Cr(Total) (81.24%) and Cr(VI) (75.90%). This study has potential application value for the treatment of wastewater containing high concentrations of heavy metals.

Sediment biomarker, bacterial community characterization of high arsenic aquifers in Jianghan Plain, China.

Representative biomarkers (e.g., n-alkanes), diversity and microbial community in the aquifers contaminated by high concentration of arsenic (As) in different sediment depth (0-30 m) in Jianghan Plain, Hubei, China, were analyzed to investigate the potential mechanism of As enrichment in groundwater. The concentration of As was abundant in top soil and sand, but not in clay. The analysis of the distribution of n-alkanes, CPI values, and wax to total n-alkane ratio (Wax(n)%) indicated that the organic matter (OM) from fresh terrestrial plants were abundant in the shallow sediment. However, n-alkanes have suffered from significant biodegradation from the depth of 16 m to 30 m. The deposition of fresh terrestrial derived organic matters may facilitate the release of As from sediment to groundwater in the sediment of 0-16 m. However, the petroleum derived organic matters may do the favor to the release of As in the deeper section of borehole (16 m to 30 m). The 16S rRNA gene sequences identification indicated that Acidobacteria, Actinomycetes and Hydrogenophaga are abundant in the sediments with high arsenic. Therefore, microbes and organic matters from different sources may play important roles in arsenic mobilization in the aquifers of the study area.

[Study on the variation of arsenic concentration in groundwater and chemical characteristics of arsenic in sediment cores at the areas with endemic arsenic poison disease in Jianghan Plain].

OBJECTIVE: To understand the variation of arsenic concentration in underground water at the endemic arsenic poison disease area of Jianghan Plain so as to better understand the spatial distribution of high arsenic groundwater, hydro-chemical evolution and source of arsenic in this region. METHODS: Thirty underground water samples were collected respectively around 3 km radius of the two houses where arsenic poisoning patients lived, in Xiantao and Honghu. Sediment cores of three drillings were collected as well. Both paired t-test or paired Wilcoxon Signed Ranking Test were used to compare the arsenic concentration of water. RESULTS: The arsenic concentration in 2011-2012 appeared lower than that in 2006-2007 at the Nanhong village of Xiantao (t = 4.645 3, P < 0.000 1), but was higher (S = -150, P < 0.000 1) in the Yaohe village of Honghu. The pH value showed weak acidity with Eh as weak oxidated. Positive correlations were observed between arsenic concentration and Cl, HCO3(-), Fe, Mn. However, negative correlations were found between As and SO4(2-), NO3(-). The range of arsenic content in the sediment was 1.500 mg/kg to 17.289 mg/kg. The maximum arsenic content existed in the soil layer, while the minimum arsenic content existed in the sand layer. CONCLUSION: The concentration of arsenic varied widely with time and space at endemic arsenic poison disease area of Jianghan Plain. Characteristics of these water chemicals showed significant differences, when compared to the groundwater from Datong Basin, Shanxi Shanyin and Hetao Plain of Inner Mongolia, which presented a typical environment with high arsenic contents in the groundwater. The arsenic content in the sediment samples seemed related to the lithologic structure.

Adsorptive removal of Cd(II) from aqueous solution using natural and modified rice husk.

In this study, the natural and modified rice husk were tested to remove Cd(II) ions from water. The modified rice husk was prepared by being treated with alkali. The results showed the Cd(II) adsorption capacity was 73.96, 125.94 mg/g, respectively, for the natural and modified rice husk. The modified rice husk had faster kinetics and higher adsorption capacities than the natural rice husk, which can be attributed to the surface structural changes of the material. Equilibrium adsorption data are more consistent with the Langmuir isotherm equation than with the Freundlich equation. The Cd(II) adsorption on the two adsorbents tends to increase with the increase of pH. The optimum pH for Cd(II) adsorption is 6.5. Both pseudo-first-order and pseudo-second-order equations were able to describe properly the kinetics of Cd(II) adsorption. The desorbability of Cd(II) is about 95.8-99.1% by 0.1M HCl solution.

Suppression of phosphate liberation from eutrophic lake sediment by using fly ash and ordinary portland cement.

In this study, the effect of suppression on phosphate liberation from eutrophic lake sediment by using fly ash and ordinary Portland cement (OPC) was investigated by small scale experiment. A system including sediment, lake water, and several kinds of capping materials was designed to clarify the suppression of phosphate liberation from sediment under the anaerobic condition. The suppression efficiencies of fly ash, OPC and glass bead used as control material were also determined, and these effects were discussed. The suppression efficiency of glass bead was 44.4%, and those of fly ash and OPC were 84.4%, 94.9%, respectively. The suppression by fly ash and OPC was mainly carried out by the adsorption effect, in addition to the covering effect. The suppression efficiency depended on the amounts of the material used, and about 90% of liberated phosphate was suppressed by fly ash of 10.0 Kg m(-2), and OPC of 6.0 Kg m(-2). The concentrations of heavy metals, such as mercury, cadmium, lead, copper, zinc, chromium, silver, arsenic and nickel, in fly ash and OPC were lower than those in the environmental materials. And it was considered that the concentrations of heavy metals in fly ash and OPC were too low to influence the ecosystem in natural water region.