Enhanced phytotoxicity of 4-chloro-3-methyphenol and lindane under sodium and potassium salt stresses.

Investigating the uptake of organic pollutants by plants under salt stress is critical for evaluating crop contamination, understanding the mechanism of plant uptake, and implementing phytoremediation. The uptake of a highly phytotoxic contaminant, 4-Chloro-3-Methyphenol (CMP, 45 mg L-1), from solutions by wheat seedling with or without Na+ and K+ was studied to illustrate the synergistic effect of salt on phytotoxicity of CMP, using uptake kinetics, transpiration, Ca2+ leakage and fatty acid saturation as indicators. The influence of Na+ and K+ on the uptake of lindane, a relatively low toxic contaminant, from soil was also explored. Under CMP-Na+ and CMP-K+ exposure, the concentrations of CMP in both root and shoot were lower than those under CMP exposure, as a result of the inhibition of transpiration caused by Na+ and K+ stresses. Low concentration of CMP did not reveal serious toxicity on cell membrane. No apparent difference of MDA generation in root cells was observed, due to the lethal concentration of CMP. The relatively small variation of Ca2+ leakage and fatty acid saturation degree in the root cell under exposure of CMP, CMP-Na+ and CMP-K+, compared to intracellular CMP content, suggested the enhanced phytotoxicity of CMP induced by salt. Higher MDA concentration in shoot cell under CMP-Na+ and CMP-K+ exposure compared with that under CMP exposure again showed the synergetic toxicity of CMP. High Na+ and K+ concentration significantly facilitated the uptake of lindane by wheat seedlings in soils, indicating that it could boost the permeability of cell membrane, thereby increasing the toxicity of linande to wheat seedlings. The short-term effect of low salt concentration on the uptake of lindane was not obvious, but long-term exposure also led to increased uptake. In conclusion, the presence of salt could amplify the phtotoxicity of organic contaminant via several mechanisms.

Triclosan targets miR-144 abnormal expression to induce neurodevelopmental toxicity mediated by activating PKC/MAPK signaling pathway.

Although the previous research confirmed that triclosan (TCS) induced an estrogen effect by acting on a novel G-protein coupled estrogen-membrane receptor (GPER), the underlying mechanisms by which downstream pathways induce neurotoxicity remain unclear after TCS activation of GPER. By employing a series of techniques (Illumina miRNA-seq, RT-qPCR, and artificial intervention of miRNA expression), we screened out four important miRNAs, whose target genes were directly/indirectly involved in neurodevelopment and neurobehavior. Especially, the miR-144 up-regulation caused vascular malformation and severely affected hair-cell development and lateral-line-neuromast formation, thereby causing abnormal motor behavior. After microinjecting 1-2-cell embryos, the similar phenotypic malformations as those induced by TCS were observed, including aberrant neuromast, cuticular-plate development and motor behavior. By KEGG pathway enrichment analysis, these target genes were demonstrated to be mainly related to the PKC/MAPK signaling pathway. When a PKC inhibitor was used to suppress the PKC/MAPK pathway, a substantial alleviation of TCS-induced neurotoxicity was observed. Therefore, TCS acts on GPER to activate the downstream PKC/MAPK signaling pathway, further up-regulating miR-144 expression and causing abnormal modulation of these nerve-related genes to trigger neurodevelopmental toxicity. These findings unravel the molecular mechanisms of TCS-induced neurodegenerative diseases, and offer theoretical guidance for TCS-pollution early warning and management.

Variations in Hydraulic Conductivity of Montmorillonite in Dual-Cation Electrolyte Solutions.

The hydraulic conductivity of Na-montmorillonite in dual-cation solutions of Na+ and Mn+ (Mn+ = K+, Ca2+, Zn2+ and Al3+) with a constant ionic strength of 0.1 mol/L was determined. The focus of this study was on the influence of Mn+ on the grain-size distribution of montmorillonite and hence its hydraulic conductivity. All the tested cations showed a high affinity towards montmorillonite, and the high valency favored the exchange between Mn+ and Na+. The hydraulic conductivity of montmorillonite increased to the maxima and then decreased in a left-skewed log-normal shape as the cation exchange progressed. The grain size of montmorillonite concurrently decreased monotonically with the cation exchange. The XRD patterns of montmorillonite confirmed the occurrence of demixing of Na+ and K+ in the interlayers. It is proposed that the rearrangement and reaggregation of grains during cation exchange occurred, leading to variations in the hydraulic conductivity of montmorillonite.

Induction of lipid metabolism dysfunction, oxidative stress and inflammation response by tris(1-chloro-2-propyl)phosphate in larval/adult zebrafish.

As an important organophosphate flame retardant, tris(1-chloro-2-propyl)phosphate (TCPP) is ubiquitous in the environment leading to inevitable human exposure. However, there is a paucity of information regarding its acute/chronic effects on obesity, lipid homeostasis, and hepatocellular carcinoma, especially regarding the underlying molecular mechanisms in humans. Herein, we investigated the effects of TCPP exposure (5-25 mg/L) on lipid homeostasis in larval and adult zebrafish (Danio rerio). TCPP exposure caused remarkable lipid-metabolism dysfunction, which was reflected in obesity and excessive lipid accumulation in zebrafish liver. Mechanistically, TCPP induced the over-expression of adipogenesis genes and suppressed the expression of fatty-acid ß-oxidation genes. Consequently, excess lipid synthesis and deficient expenditure triggered oxidative damage and an inflammation response by disrupting the antioxidant system and over-expressing proinflammatory cytokine. Based on high-throughput transcriptome sequencing, we found that TCPP exposure led to enrichment of several pathways involved in lipid metabolism and inflammation, as well as several genes related to pathways of cancer. Notably, increasing expressions of Ki-67 and 53BP1 proteins, which are reliable biomarkers for recognition and risk prediction of cellular proliferation in cancer cells, were observed in liver tissues of adult zebrafish. These results imply that chronic TCPP exposure triggers a potential risk of hepatocellular carcinogenesis (HCC) progression. Collectively, these findings offer new insights into our mechanistic understanding for the health effects of organophosphorus flame retardants on humans.

Translocation versus ion trapping in the root uptake of 2,4-dichlorophenol by wheat seedlings.

Understanding of the plant uptake of ionizable organic compounds is critical to the evaluation of crop contamination, plant protection, and phytoremediation. This study investigated the time-dependent uptake of 2,4-dichlorophenol (DCP) by intact wheat seedling roots and subsequent translocation to shoots at pH 5.0 and 8.0. Sorption of DCP by cut roots and shoots at these two pHs was conducted to provide the uptake limits and the Donnan charge. For comparison, sorption was also conducted for 1,3-dichlorobenzene (DCB), a nonionizable compound having a structure similar to that of DCP. The DCB sorption isotherms were linear and independent of pH, yielding a consistent log Klip of 3.56 with both roots and shoots, reflective of the essential dominant role of lipids in plant partition uptake. Whereas the DCP sorption also showed a linear isotherm at pH 5.0 with log Klip = 2.88, the sorption at pH 8.0 was nonlinear with a concave downward shape, especially at low concentrations. With live wheat seedlings, the DCB uptake by roots and the DCB translocation to shoots rapidly approached a steady state, showing no obvious pH effect. On the DCP uptake by live plants, there was a rapid attainment of a steady state in roots at pH 5.0 coupled with a retarded transport to shoots due presumably to the polarity of DCP. At pH 8.0, the root uptake of DCP was comparatively slower and the translocation to shoots was completely inhibited due presumably to DCP ionization. At high pH, DCP was supposedly accumulated in an ionized form in root cells via an ion-trapping mechanism.

Lindane degradation in wet-dry cycling soil as affected by aging and microbial toxicity of biochar.

This study determined the degradation of lindane in soil amended with biochar to evaluate the effects of biochar aging and microbial toxicity. Two biochars were prepared at 400 and 600 °C (BC400 and BC600) and subjected to acid washing to remove nutrition (WBC400 and WBC600). After 89 days of incubation under the alternate "wet-dry" conditions, scanning electron microscopy showed that acid washing rendered biochars especially susceptible to aging with structural collapse and fragmentation, with less surface covering. Aging impeded the release of toxic substances in BC400 and BC600 with reduced toxicity to degrading microorganisms. Lindane degradation was somewhat stimulated by biochar nutrition but mainly inhibited by adsorption. Acid washing facilitated the release of toxic substances and additionally reduced lindane degradation. The variations in fatty acid saturation degree (SFA/UFA) in soils confirmed the microbial toxicity of 5% WBC400 > 5% BC400 > 5% BC600 > 5% WBC600. High-throughput DNA sequencing showed that biochar delayed the formation of dominant degrading microbial communities in soil. Lindane degradation was completed by joint Sphingomonas, Flaviolibacter, Parasegetibacter, Azoarcus, Bacillus and Anaerolinaea. These findings are helpful for better understanding the effect of biochar in soil on long-term degradation of persistent organic pollutants.

Enhanced removal of cadmium from wastewater with coupled biochar and Bacillus subtilis.

Shortcomings of individual biochar or microbial technologies often exist in heavy metal removal from wastewater and may be circumvented by coupled use of biochar and microorganisms. In this study, Bacillus subtilis and each of three biochars of different origins (corn stalk, peanut shell, and pine wood) were coupled forming composite systems to treat a cadmium (Cd, 50 mg/L) wastewater formulated with CdCl2 in batch tests. Biochar in composite system enhanced the activity and Cd adsorption of B. subtilis. Compared with single systems with Cd removal up to 33%, the composite system with corn stalk biochar showed up to 62% Cd removal, which was greater than the sum of respective single B. subtilis and biochar systems. Further analysis showed that the removal of Cd by the corn stalk composite system could be considered to consist of three successive stages, that is, the biochar-dominant adsorption stage, the B. subtilis-dominant adsorption stage, and the final biofilm formation stage. The final stage may have provided the composite system with the ability to achieve prolonged steady removal of Cd. The biochar-microorganism composite system shows a promising application for heavy metal wastewater treatment.

Accelerating Cu and Cd removal in soil flushing assisted by regulating permeability with electrolytes.

Soil flushing is one of the common in-situ remediation technologies, in which the permeability of the soil determines its feasibility. Batch extractions showed that deionized water extracted about 20% Cu and 30% Cd from a soil. Electrolytes of 100 mmol/l NaCl, 500 mmol/l NaCl, and 167 mmol/l CaCl2 promoted the extractions to about 60% and 90%, respectively, with higher concentration and valence of cations being more effective. Presence of 100 mmol/l EDTA as a chelant further enhanced the extractions to near completion. Extractions appeared to occur concurrently via ion exchange, complexation with Cl- and predominantly chelation with EDTA. Column leaching in dynamic setups with electrolyte solutions in the presence of EDTA showed similar Cu and Cd removal degrees to the batch extractions. The permeability of soils during leaching decreased by up to 80%, decelerating time-dependent Cu and Cd removal, due to soil swelling by Na+. Electrolytes in leaching solutions well defended the permeability of soil against its decrease to as low as 3.5%, maintaining Cu and Cd removal rates. Formulating flushing solution with EDTA and proper electrolytes have advantages of not only enhancing extraction degrees but accelerating heavy metal removal from soil by regulating the permeability, with the potential to be extended to soils with high clay contents and thus low natural permeability.

Blocking effect of fullerene nanoparticles (nC60) on the plant cell structure and its phytotoxicity.

Blockage of nanoparticles on plant pore structures might produce phytotoxicity and affect plant uptake indirectly. This study examined the blocking and phytotoxic effects of fullerene nanoparticles (nC60) on plants at the cellular level. The malondialdehyde content in plant was normal during nC60 exposure, implying that nC60 caused no acute phytotoxicity, while the normalized relative transpiration significantly decreased, showing that the pore structure of roots was seriously blocked by nC60. High power optical microscopy and transmission electron microscope showed that root endothelial cells were squeezed, and inner wall structures were damaged by the extrusion of nanoparticles. Low nC60 concentrations inhibited root uptake of lindane, whereas high nC60 concentrations promoted root uptake of lindane, indicating that serious pore blocking by nC60 damaged root cell structure and hence ready transport of lindane from roots to shoots. Significant alterations of fatty acid (FA) saturation degree of root cell membrane indicated that nC60 led to phytotoxicity in the root cell membrane after long-term exposure and nC60 produced phytotoxicity in the process of blocking root pore structures and interfering with cell membrane fluidity. Moreover, the plant cell structures under phytotoxicity were more likely to be damaged mechanically by the extrusion of nanoparticles. These findings may be helpful to better understand the transport pathways of nanoparticles in plants, the phytotoxicity of nanoparticles and the potential risks of nanomaterials used in agriculture.

Mechanisms of aromatic molecule - Oxygen-containing functional group interactions on carbonaceous material surfaces.

Surface oxygen-containing functional groups (OFGs) at different sites of carbonaceous materials showed different effects on the normalized monolayer adsorption capacity (QBET/A) obtained from the modified BET model. The OFGs on mesoporous surfaces inhibited the adsorption via the water competition, whereas those on the external surface promoted the adsorption due to the enhanced hydrophobic driving force and electrostatic forces, as analyzed from the adsorption molar free energy. Multiple linear relationships were established between the monolayer adsorption capacity QBET/A and the amounts of OFGs on mesoporous and the external surfaces ([O]meso and [O]external, respectively). The properties of aromatic adsorbate compounds, the polar area radio of aromatic molecule to water (PAad/w), and the log Kow together influenced the inhibition or promotion effects of OFGs. These results would allow predictions of adsorption behavior of aromatic compounds on carbonaceous materials on the basis of OFGs parameters. Theoretical calculations and simulations projected the configuration of aromatic molecules being parallel to the graphene sheets of carbonaceous materials. The symmetry-adapted perturbation theory (SAPT) energy decomposition showed that the electrostatic forces intensified with the increase of adsorbate polarity. These analyses revealed that the electrostatic forces were enhanced in the presence of OFGs and that the π-π EDA (electron donor-acceptor) was the main force.

Metal inhibition on the reactivity of manganese dioxide toward organic contaminant oxidation in relation to metal adsorption and ionic potential.

Coexisting metal ions may significantly inhibit the oxidative reactivity of manganese oxides toward organic contaminants in metal-organic multi-pollutant waters. While the metal inhibition on the oxidation of organic contaminants by manganese oxides has previously been reported, the extent of the inhibition in relation to metal properties has not been established. Six alkali, alkaline, and transition metals, as well as two testing metals were evaluated for their abilities to inhibit the reactivity of birnessite. Regardless of the pathways of phenol and diuron oxidation (polymerization vs. breakdown), the extent of metal inhibition depended mainly on the metal itself and its concentration. The observed metal inhibition efficiency followed the order of Mn2+ > Co2+ > Cu2+ > Al3+ > Mg2+ > K+, consistent with metal adsorption on birnessite. The first-order organic oxidation rate constant (kobs) was linearly negatively correlated with metal adsorption (qe) on birnessite. These observations demonstrated that the metal inhibition efficiency was determined by metal adsorption on birnessite. The slopes of the kobs-qe varied among metals and followed the order of K+ > Ca2+ > Mg2+ > Mn2+ > Cd2+ > Co2+ > Cu2+ > Al3+. These slopes defined intrinsic inhibitory abilities of metals. As metals were adsorbed hydrated on birnessite, the intrinsic inhibitory ability was significantly linearly correlated with ionic potentials of metals, leading to a single straight line. Metals with multiple d electrons in the outermost orbit with polarizing energy that promotes hydrolysis sat slightly below the line, and vice versa.

Internalization and Phytotoxic Effects of CuO Nanoparticles in Arabidopsis thaliana as Revealed by Fatty Acid Profiles.

Internalization and phytotoxic effects of CuO nanoparticles (nCuO) in plants were studied at the cellular level. Arabidopsis thaliana was hydroponically challenged by nCuO (100 mg/L), as compared to Cu2+ ions (1.2 mg/L), to account for nCuO dissolution for 96 h and 28 days to monitor Cu accumulation in the plant as well as the fatty acid (FA) profiles of the plant cell membrane. Under the same growing conditions, the nCuO exposure resulted in more Cu accumulation than did the Cu2+ exposure. Multiple microscopic techniques confirmed the internalization and sequestration of nCuO in root cell vacuoles, where transformation of Cu(II) to Cu(I)Cl occurred. Short and long exposures (96 h versus 28 days) to both nCuO and Cu2+ elevated FA saturation degrees in plant cells through oxidative stress, as verified by in situ detection of superoxide radicals, with conversions mostly from C18:3, C16:3, and C18:2 to C16:0. Only the long exposure to nCuO significantly brought about an additional elevation of FA saturation degree in root cells. These results demonstrated that the acute effects of plant exposure to nCuO were mainly produced from the stress of Cu2+ ions released from nCuO dissolution, while the chronic effects in roots were significantly developed by the nCuO particle stress. The findings in this work are novel and may offer significant implications in better understanding nanoparticle-induced phytotoxicity and potential risks in ecosystems.

Suppression of chloromethylphenol accumulation in wheat seedlings by uptake-induced phytotoxicity.

Uptake and its induced phytotoxicity are hypothesized to suppress overall organic chemical accumulation in plant. The extent and mechanism of suppression remain rather unknown. This study was conducted to evaluate, at both physiological and cellular levels, the phytotoxicity following plant exposure to an organic chemical and, in turn, the suppression of the organic chemical accumulation in the plant. Root uptake of 4-chloro-3-methylphenol (CMP) in wheat seedlings and subsequent CMP translocation to shoots were determined. Seedling transpiration and fatty acid (FA) profiles of cell membranes, along with malondialdehyde (MDA) generation and K+ release in seedling tissues, were quantified. At CMP concentrations of 15, 45, and 60 mg L-1, CMP accumulations reached maxima of about 8.1, 24.7, 40.6 mg kg-1 in shoots, and 127.4, 187.2, and 244.3 mg kg-1 in roots, respectively. Most of these accumulations were lower than those estimated from partition-based models. Seedling transpiration was reduced by about 25% (15 mg L-1) and 60% (45 mg L-1 and 60 mg L-1). As a product of lipid peroxidation, MDA level in roots changed with exposure time following an "elevation-demotion" trend. This suggested that root cells suffered initial severe lipid peroxidation and gradually lost cell functions. This resulted in an increase in FA saturation degree of root cell membranes and hence damage to root cells. This was verified by enhanced K+ release from root tissue. The "uptake-induced phytotoxicity-suppressed accumulation" cycle existed in plant uptake involving both physiological and cellular actions to maintain CMP accumulation in wheat seedlings lower than model estimation.

Quantitative relationships between the adsorptivity of carbonaceous materials in soil for Pb(II) and soil organic matter content.

Strong adsorptivity of manufactured carbonaceous materials (MCMs) mediates the behavior of heavy metals in soil. Laboratory-reported adsorptivity of MCMs often deviates from their actual abilities in soil, because soil organic matter (SOM) can change the adsorptive abilities of MCMs by coating dissolved organic matter (DOM) on the surface of the MCMs. It was considered that the influence of SOM on the adsorptivity of MCMs in soil follows a sequential pathway of SOM releasing DOM in soil solution and subsequent DOM binding onto MCMs, thereby altering MCM surface acidity and hence changing MCM adsorptivity for heavy metals. In this study, we first extracted DOM from ten topsoils collected over a broad region of China with a wide range of SOM. The DOM solutions were then used to load DOM onto four MCMs including activated carbon (AC), multiwalled carbon nanotube (MWCNT), and two biochars (BC400 and BC700), respectively, obtaining a total of 44 MCM-DOM complex samples with known amounts of bound DOM. These MCM-DOM complex samples were then determined for their surface acidities and adsorptive abilities for Pb(II). We found that there were significant correlations between DOM concentration and SOM content, between DOM binding onto MCMs and DOM concentration, between surface acidity of MCM-DOM complexes and DOM binding onto MCMs, as well as between Pb(II) adsorption on MCM-DOM complexes and surface acidity of MCM-DOM complexes. With understanding of these individual linear correlations, linear relationships between the Pb(II) adsorption and SOM content were established by combining individual correlations and by directly plotting the former against the latter. These relationships may be used to accurately predict the adsorptive abilities of MCMs for heavy metals in soils via simply determining SOM.