Mechanistic insight into the impact of interaction between goethite and humic acid on the photooxidation and photoreduction of bifenthrin.

Numerous application of pyrethroid insecticides has led to their accumulation in the environment, threatening ecological environment and human health. Its fate in the presence of iron-bearing minerals and natural organic matter under light irradiation is still unknown. We found that goethite (Gt) and humic acid (HA) could improve the photodegradation of bifenthrin (BF) in proper concentration under light irradiation. The interaction between Gt and HA may further enhance BF degradation. On one hand, the adsorption of HA on Gt may decrease the photocatalytic activity of HA through decreasing HA content in solution and sequestering the functional groups related with the production of reactive species. On the other hand, HA could improve the photocatalytic activity of Gt through extending light absorption, lowing of bandgap energy, hindering the recombination of photo-generated charges, and promoting the oxidation and reduction reaction on Gt surface. The increased oxygen vacancies on Gt surface along with the reduction of trivalent iron and the nucleophilic attack of hole to surface hydroxyl group contributed to the increasing photocatalytic activity of Gt. Electron paramagnetic resonance and quenching studies demonstrated that both oxidation species, such as hydroxyl radical (•OH) and singlet oxygen (1O2), and reducing species, such as hydrogen atoms (H•) and superoxide anion radical (O2•-), contributed to BF degradation in UV-Gt-HA system. Mass spectrometry, ion chromatography, and toxicity assessment indicated that less toxic C23H22ClF3O3 (OH-BF), C9H10ClF3O (TFP), C14H14O2 (OH-MBP), C14H12O2 (MBP acid), C14H12O3 (OH-MBP acid), and chloride ions were the main degradation products. The production of OH-BF, MPB, and TFP acid through oxidation and the production of MPB and TFP via reduction were the two primary pathways of BF degradation.

Mechanism of interaction between ascorbic acid and soil iron-containing minerals for peroxydisulfate activation and organophosphorus flame retardant degradation.

Soil constituents may play an important role in peroxydisulfate (PDS)-based oxidation of organic contaminants in soil. Iron-containing minerals (Fe-minerals) have been found to promote PDS activation for organics degradation. Our study found that ascorbic acid (H2A) could enhance PDS activation by soil Fe-minerals for triphenyl phosphate (TPHP) degradation. Determination and characterization analyses of Fe fractions showed that H2A could induce the reductive dissolution of solid Fe-minerals and the increasing of oxygen vacancies/hydroxyl groups content on Fe-minerals surface. The increasing of divalent Fe (Fe(II)) accelerated PDS activation to generate reactive oxygen species (ROS). Electron paramagnetic resonance (EPR) and quenching studies showed that sulfate radicals (SO4•-) and hydroxyl radicals (HO•) contributed significantly to TPHP degradation. The composition and content of Fe-minerals and soil organic matter (SOM) markedly influenced ROS transformations. Surface-bond and structural Fe played the main role in the production of Fe(II) in reaction system. The high-concentration SOM could result in ROS consumption and degradation inhibition. Density functional theory (DFT) studies revealed that H2A is preferentially adsorbed at α-Fe2O3(012) surface through Fe-O-C bridges rather than hydrogen bonds. After absorption, H atoms on H2A may further be migrated to adjacent O atoms on the α-Fe2O3(012) surface. With the transformation of H atoms to the α-Fe2O3(012) surface, the Fe-O-C bridge is broken and one electron is transferred from the O to Fe atom, inducing the reduction of trivalent Fe (Fe(III)) atom. MS/MS2 analysis, HPLC analysis, and toxicity assessment demonstrated that TPHP was transformed to less toxic 4-hydroxyphenyl diphenyl phosphate (OH-TPHP), diphenyl hydrogen phosphate (DPHP), and phenyl phosphate (PHP) through phenol-cleavage and hydroxylation processes, and even be mineralized in reaction system.

Activation of persulfate with natural organic acids (ascorbic acid/catechin hydrate) for naproxen degradation in water and soil: Mechanism, pathway, and toxicity assessment.

In this study, we investigated the effects of different natural organic acids (NOAs), L-ascorbic acid (AA) and (+)-catechin hydrate (CAT), on the activation of persulfate (PDS) for the oxidation of naproxen (NAP) in water and soil. We found that only AA-activated PDS process had a significant degradation efficiency of NAP in water. High AA concentration (500 µM) inhibited the degradation of NAP, whereas high levels of PDS (7.5 mM) and acidic conditions (pH=3-7) were beneficial for NAP degradation. In soil, both CAT and AA promoted PDS activation and NAP degradation. Low soil organic matter and high Fe/Mn-mineral contents were favorable for NAP degradation by AA-activated PDS. Column experiments confirmed that NAP was readily transported and degraded under porous medium conditions using AA-activated PDS. Moreover, we revealed that SO4•- and HO• were the dominant reactive species for NAP degradation by AA-activated PDS. Intermediate products of NAP in the AA-activated PDS process were analyzed and the reactive sites of NAP were predicted. E. coli growth tests verified that the intermediate products in the AA-activated PDS process were less toxic than NAP. Our results highlight the high potential of NOAs-activated PDS process for the remediation of NAP-contaminated water and soil.

Soil microbial stoichiometry and community structure responses to long-term natural forest conversion to plantations in a subtropical region.

Soil microbial stoichiometry reflects carbon (C) and nutrient (e.g., nitrogen (N) and phosphorus (P)) elemental balances under land-use change (LUC). However, how soil microbial community (SMC) structure and stoichiometry respond to long-term LUC in forests is still unclear. Here, we investigated three 36-year-old typical plantations, Cryptomeria fortunei, Metasequoia glyptostroboides, and Cunninghamia lanceolata, and the natural forest to assess their soil microbial stoichiometry and SMC structure. Three plots (30×30 m2) were randomly set in each forest site. In each plot of every forest site, soil samples of three depths (0-10, 10-30, and 30-60 cm) were collected. Dissolved organic C, N, and P (abbreviated as DOC, DON, and DOP, respectively) and environmental factors were measured. We also detected microbial biomass C, N, and P as well as SMC structure. The results showed that the soil microbial C:N:P stoichiometry had a strong or strict homeostasis regardless of soil depth and exhibited decoupling from the SMC structure at each depth. The SMC structure across forest types was mainly driven by mean annual soil temperature (MAST) and DOC at 0-10 cm depth, by soil water content and MAST at 10-30 cm depth, and by DOC to DOP ratio at 30-60 cm depth. Thus, SMC structure could be jointly regulated by available resources and environment. These results suggest that the C dynamics in forests tend to gain resilience or re-equilibrium over more than three decades after forest conversion. These findings highlight the importance of reforested plantations forest management for sustaining soil C over a long term.

Ferrous-activated persulfate oxidation of triclosan in soil and groundwater: The roles of natural mineral and organic matter.

Contamination of antimicrobial agents such as Triclosan (TCS) in soil and groundwater possess high risk to human health and ecological systems. Present study systematically studied the degradation of TCS in soil and groundwater by Fe2+ activated persulfate (Fe2+/PS) oxidation process and special attention was paid on revealing the influence of remediation process on soil physicochemical and microbial characteristics. Experimental results demonstrated that TCS was readily degraded in soil upon Fe2+/PS oxidation system. Higher Fe2+/PS concentration and lower pH value may promote the TCS degradation. Besides added Fe2+, the naturally present Fe (III)-O and dissolved Fe from iron containing minerals may also activate PS for TCS degradation. SO4•-, HO•, R• and 1O2 were identified to be involved in the reaction system while addition of Fe2+-chelating agents, e.g., oxalic acid and ethylene diamine tetraacetic acid (EDTA) may slightly promote the degradation. Low concentration of Cl- facilitated TCS degradation and high concentration of Cl- slowed down the degradation. The presence of HCO3- may inhibit the degradation. Fe2+/PS oxidation process may partly reduce the soil organic matter content and diversely affect the composition of various C functional groups on soil. It also induced the breakdown of large soil aggregates and reduced the soil porosity, especially at macroporosity region. Phospholipid Fatty Acid test indicated that soil microbial community structure has been altered and the actinomycetes, fungi and Gram-negative bacteria decreased largely. The feasibility of remediation of TCS using Fe2+/PS oxidation in various natural groundwater samples was evaluated. Finally, five degradation intermediates of TCS by Fe2+/PS oxidation in soil were enriched by solid phase extraction and were identified by liquid chromatography-triple quadrupole mass spectrometry for proposing detailed transformation pathways.

Degradation of Atrazine, Simazine and Ametryn in an arable soil using thermal-activated persulfate oxidation process: Optimization, kinetics, and degradation pathway.

This study examined the feasibility of applying thermal-activated persulfate (PS) oxidation for remediation of soil co-contaminated with s-triazine herbicides including Atrazine (ATZ), Simazine (SIM) and Ametryn (AME). Homogeneous activation using heating method (50 °C) was selected. Results showed that thermal-activated PS oxidation process may successfully degrade ATZ in soil and degradation efficiency was increased along the arising activation temperature. Higher PS dosages and depressed initial pH were beneficial for degradation while increasing initial ATZ concentration may hamper the degradation. The oxidation process may lead to changes of surface functional groups on soil. The presence of Cl-, HCO3- and H2PO4- at both of low and high concentrations may inhibit the degradation of ATZ. Soil depths may apparently influence the ATZ degradation which followed 0-10 < 10-30 < 30-60 cm mainly depending on the soil organic matter (SOM) contents. Thermal-activated PS may effectively degrade ATZ, SIM and AME under co-contaminated condition and the more favorable of ethyl group towards SO4- than isopropyl and methylation groups was detected. Both of SO4- and HO were identified to be responsible for degradation. Finally, degradation intermediates of ATZ, SIM and AME were identified by LC-Q-TOF-MS and detailed transformation pathways for three pesticides were proposed, respectively.

Effects of biochar particle size and concomitant nitrogen fertilization on soil microbial community structure during the maize seedling stage.

Biochar is widely used as a soil amendment, either alone or in association with fertilizer. However, the effects of biochar particle size on the soil microbial community are largely unclear. Biochar was divided into two groups according to diameter sizes: < 1 mm and 2.5-5 mm (labeled as CB1 and CB5, respectively). A pot experiment was established in which maize (Zea maize L.) was treated with CB1, CB5, and/or external nitrogen (N, NH4NO3). At the end of the seedling period (45 days), analyses of soil microbial community structure and other soil and crop properties were conducted. The biochar (regardless of N addition) enhanced microbial biomass and activity. CB1 had a stronger capacity than CB5 to modify soil microbial community structure by promoting soil microbial groups (e.g., fungi, Gram-negative bacteria), which is likely due to CB1 undergoing a series of more intense processes (e.g., nutrient release, mineralization) than CB5. However, this difference was diminished or disappeared when N was added, mainly due to the masking effect of soil acidification that was induced by N fertilization. Collectively, fine biochar has a stronger effect on soil microbial community than coarse biochar. Particle size only affects soil microbial community structure when biochar is applied alone; it has no effect when biochar is applied in association with chemical N fertilizer, at least during the seedling period. The relationship between particle size and soil microbial community needs to be considered when using biochar for soil amendment.

Biodegradation of 2-hydroxyl-1,4 naphthoquinone (lawsone) by Pseudomonas taiwanensis LH-3 isolated from activated sludge.

2-hydroxy-1,4 naphthoquinone (lawsone) is widely used and induces environmental pollutions during its production and application. In the present study, a lawsone-degrading bacterium strain, LH-3 was successfully isolated from the activated sludge. Based on the 16S rRNA gene analysis, the strain LH-3 phylogenetically belonged to the Pseudomonas taiwanensis. It could degrade 200 mg L-1 lawsone completely in 9 h with an inoculum quantity of 1% (v/v). The effects of environmental conditions on the degradation process and the degradation pathway were systematically investigated. LH-3 could maintain its high degradation efficiency under high salt condition. The identified intermediates of salicylic acid, 2-hydroxy-4-oxo-chroman-2-carboxylic acid, and catechol elucidated the potential degradation pathway. Furthermore, the immobilized LH-3 strain cells prepared with alginate gel and biochar performed excellent stability in nine successive degradation runs. It could sucessfully survive in laboratory scale sequencing batch reactor and become to be the dominant species. This study clearly revealed that LH-3 could serve as an attractive candidate for the microbial remediation of lawsone-containing wastewater.

Effect of forestry-waste biochars on adsorption of Pb(II) and antibiotic florfenicol in red soil.

Biochars derived from Pinus massoniana and Cunninghamia lanceolata trunks (abbreviated as PB and CB, respectively) were used to investigate their potential capabilities to improve lead (Pb(II)) and antibiotic florfenicol (FLO) immobilization in soil. Results shows that, after incubation for 60 days, the maximum adsorption capacities (Q m ) of biochar-treated soils (soil-PB and soil-CB) for Pb(II) was increased by 27 and 14 %, respectively, compared with pristine soil sample. In the case of FLO, however, the Q m of biochar-treated soils were enhanced by 266 and 206 % for soil-PB and soil-CB, respectively. The increased Pb(II) adsorption was mainly due to the enhanced interactions between Pb(II) and oxygen-containing functional groups and aromatic structures in biochars. Whereas, the improvement of FLO adsorption was achieved through electrostatic interaction, hydrogen bonding, and van der Waals forces interactions between FLO molecule and biochars. Regardless of the similarities in chemical compositions between two biochars, significantly higher surface area and total pore volume of PB than CB biochar may be the key factors accounting for the differences in adsorption efficiencies for Pb(II) and FLO between Soil-PB and Soil-CB.

Sulfate radical-based oxidation of fluoroquinolone antibiotics: Kinetics, mechanisms and effects of natural water matrices.

Widespread occurrence of fluoroquinolone antibiotics (FQs) in surface water, groundwater, soil and sediment has been reported and their remediation is essentially needed. Sulfate radical (SO4-) based advanced oxidation processes (SR-AOPs) are promising technologies for soil and groundwater remediation. In this study, the degradation kinetics, mechanisms, and effects of natural water matrices on heat-activated persulfate (PS) oxidation of FQs were systematically investigated. Experimental results clearly demonstrated that 92% of CIP was removed within 180 min (pH = 7, 60 °C). Higher temperature and lower pH facilitated the degradation of ciprofloxacin (CIP). The piperazine moiety of CIP was identified as the reactive site for SO4- attack by comparison with substructural analogs, flumequine (FLU) and 1-(2-fluorophenyl) piperazine (FPP). A comparison of the degradation of CIP, norfloxacin (NOR), enrofloxacin (ENR) and ofloxacin (OFL) confirmed that the presence of cyclopropane ring also influence the degradation of FQs. Water matrix significantly influenced the degradation of CIP and ENR, and the degradation rate followed the order of Milli-Q water (pH = 7) > groundwater > artificial seawater > artificial surface water > lake water. Degradation products of CIP in different water matrix were enriched by solid phase extraction (SPE) and then analyzed by liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-MS/MS). Detailed transformation pathways of CIP were proposed and were compared with respect to different water matrices. Four transformation pathways including stepwise piperazine ring oxidation, OH/F substitution, hydroxylation, and cyclopropane ring cleavage were proposed for CIP degradation. Results clearly show that the water matrix influenced the degradation of FQs appreciably, a phenomenon that should be taken into consideration when applying SR-AOPs for remediation of soil and groundwater contaminated by FQs.

Natural ageing process accelerates the release of Ag from functional textile in various exposure scenarios.

Natural ageing process occurs throughout the life cycle of textile products, which may possess influences on the release behavior of additives such as silver nanoparticles (Ag NPs). In this study, we assessed the releasability of Ag NPs from a Ag NPs functionalized textile in five different exposure scenarios (i.e. tap water (TW), pond water (PW), rain water (RW), artificial sweat (AS), and detergent solution (DS) along with deionized water (DW) as reference), which were very likely to occur throughout the life cycle of the textile. For the pristine textile, although the most remarkable release was found in DW (6-15 µg Ag/g textile), the highest release rate was found in RW (around 7 µg Ag/(g textile·h)). After ageing treatment, the total released Ag could be increased by 75.7~386.0% in DW, AS and DS. Morphological analysis clearly showed that the Ag NPs were isolated from the surface of the textile fibre due to the ageing treatment. This study provides useful information for risk assessment of nano-enhanced textile products.