•The Fe-S-PCP coexisting anoxic system was built up with different Fe/S mole ratios.•Fe(III) reduction was initiated first and complete during the stage I incubation.•Sulfate reduction was enhanced during the stage II incubation.•The dechlorination rate of PCP decreased with the increase of sulfate concentration.•Our study provides improved strategy for remediation of PCP polluted soils.An anaerobic soil slurry incubation experiment was conducted by controlling different Fe/S mole ratios (1/3, 1/2, 1/1, 2/1, 3/1, 8/1 and the control without sulfate) through the addition of sodium sulfate, to investigate the effect of sulfate and iron reduction on the reductive dechlorination of pentachlorophenol (PCP). Two sequential incubation periods were carried out with the stage I incubation conducted under a low electron donor concentration (0.5 mM lactate) and stage II incubation conducted under increased electron donor supply with lactate at 20 mM. During stage I, the production of Fe(II) occurred markedly while sulfate reduction and PCP dechlorination rate were low, with the highest dechlorination rates of PCP only 11.0% among all treatments at the end of stage I incubation. During stage II, both PCP dechlorination and sulfate reduction were greatly enhanced in all treatments, while the concentration of Fe(II) changed slightly. The rate of PCP dechlorination decreased (from 87.7% to 34.2%) with the increase of sulfate concentration (from Fe/S mole ratio of 8/1 to 1/3). Our study suggested that the presence of a certain amount of sulfate might facilitate PCP dechlorination in the range of Fe/S mole ratios greater than 1 when compared with the control without SO42−. With the investigation of the dechlorination of PCP under the Fe-S-PCP coexisting condition with different Fe/S mole ratios, our study may provide improved strategy for optimizing the remediation of flooded soils and sediments polluted by PCP.

Impacts of a commercially available decay-facilitating microbial inoculum on carbon (C) and nitrogen (N) mineralization were evaluated during decomposition of rice straw in a paddy soil.Two incubation experiments were conducted for 105 days with a typical low-yield high-clay soil in central China to monitor effects of straw and the inoculum on CO2 evolution, as well as dissolved organic C (DOC), NH4+, NO3−, and pH under conditions of 15 °C 70 %, 25 °C 40 %, 25 °C 70 %, 25 °C 100 %, and 35 °C 70 % of water-holding capacity (WHC) with adequate N, supplied as urea or manure, respectively.Treatments of 25 °C 70 % WHC, 25 °C 100 % WHC, and 35 °C 70 % WHC generally achieved significant higher CO2 evolution while treatment of 25 °C 40 % WHC had least. This was more evident with added manure compared to urea (P < 0.05). The inoculum generally increased the decomposition of C inputs and the largest increases were in the initial 28 day in treatments 25 °C 70 % WHC, 25 °C 100 % WHC, and 35 °C 70 % WHC; only the 25 °C 40 % WHC actually immobilized C. The CO2 release rates were positively correlated with DOC, but with different slopes within treatments. Despite equivalent N application rates, manure treatments had significantly less N (including NO3−, NH4+, and total dissolved N) than those with urea. Incubation of 25 °C 40 % WHC decreased soil pH the least, probably due to relative low moisture causing delayed nitrification.The results implied that the inoculum, especially fungi, would adjust to edaphic and N fertilization in regulating organic C mineralization, during which water potential would exhibit a great role in regulating substrate and nutrient availability.

Carbon isotopic analysis and molecular-based methods were used in conjunction with geochemical data sets to assess the dechlorination of pentachlorophenol (PCP) when coupled to biogeochemical processes in a mangrove soil having no prior history of anthropogenic contamination. The PCP underwent 96% dechlorination in soil amended with acetate, compared to 21% dehalogenation in control soil. Carbon isotope analysis of residual PCP demonstrated an obvious enrichment of 13C (εC, −3.01 ± 0.1%). Molecular and statistical analyses demonstrated that PCP dechlorination and Fe(III) reduction were synergistically combined electron-accepting processes. Microbial community analysis further suggested that enhanced dechlorination of PCP during Fe(III) reduction was mediated by members of the multifunctional family of Geobacteraceae. In contrast, PCP significantly suppressed the growth of SO42– reducers, which, in turn, facilitated the production of CH4 by diversion of electrons from SO42– reduction to methanogenesis. The integrated data regarding stoichiometric alterations in this study gives direct evidence showing PCP, Fe(III), and SO42– reduction, and CH4 production are coupled microbial processes during changes in soil redox.

Vertical variations of pentachlorophenol (PCP) dissipation and microbial community were investigated in a paddy soil with the addition of electron acceptors (NO3–, SO42–) and donors (crop residues). Crop residues enhanced PCP dissipation by supplying dissolved organic carbon (DOC) as an electron donor, whereas NO3– and SO42– inhibited it. The dissipation of PCP in electron donor treatments resulted in the accumulation of 3,4,5-trichlorophenol (3,4,5-TCP) except for wheat residues. The abundance and diversity of phospholipid fatty acids (PLFAs) decreased with increasing soil depth. The succession of predominant PLFAs shifted from aerobic bacteria to anaerobic bacteria when electron acceptors were changed to electron donors. The saturated/monounsaturated fatty acids (S/M) ratio increased with soil depth, which probably implied that nutrient turnover rate declined after the accumulation of 3,4,5-TCP. The results showed that the addition of electron donors and acceptors modified the microbial communities, which then further influenced the degradation pathway of PCP.

A laboratory incubation under constant temperature and humidity was conducted to estimate the impacts of nitrogen (N) fertilizers on the acidification of two acid soils (Plinthudult and Paleudalfs) in south China.The experiment had three treatments, i.e., control (CK), addition of urea (U), and addition of ammonium sulfate (AS). We measured soil pH, nitrate (NO3−), ammonium (NH4+), exchangeable hydrogen ion (H+), and aluminum ion (Al3+) concentrations at various intervals during the 90 days of incubation. Soil buffering capacity (pHBC) was also measured at the end of the experiment.The application of N fertilizers resulted in soil acidification. The U treatment caused greater acidification of the Plinthudult soil than the AS treatment, while there were no differences between U and AS treatments on the acidification of the Paleudalfs. At the end of the trial, the pHBC of Plinthudult in AS treatment was greater than that in CK and U treatments, which may be due to the buffering system of NH4+ and NH4OH. However, the pHBC of Paleudalfs was unchanged between treatments. The dynamics of exchangeable H+ and Al3+ corresponded to that of soil pH. Correlation analysis showed that both soil exchangeable H+ and soil exchangeable Al3+ were significantly related to soil pH.Application of urea and ammonium sulfate caused acidification in both soils and increased soil exchangeable Al3+ and H+ concentrations in the Paleudalfs. The application of urea increased exchangeable Al3+, and ammonium sulfate increased pHBC in the Plinthudult.

Biochars have been considered as useful soil amendments due to their beneficial properties in improving soil fertility, carbon (C) sequestration, and soil decontamination. In our study, a series of biochars produced from different types of feedstocks at two pyrolysis temperatures (300 and 500 °C) were characterized to evaluate their different potentials as soil amendments.Ten types of feedstocks were used to prepare biochars at the pyrolysis temperatures of 300 and 500 °C, for 2 h. Chemical and physical analyses, X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier Transform Infrared (FTIR) analyses were conducted to determine differences in biochar properties. Then, soil incubation studies were used to investigate the relationships between these biochar properties and their different ameliorant values in soil.The pH, ash, total C, total potassium, total phosphorus, total base cation concentrations, surface areas, and total pore volumes of biochars produced at 500 °C were higher than at 300 °C, while the reverse applied for yields, total oxygen and total hydrogen, and average pore widths and particle sizes. Cluster analysis suggested that biochars derived from similar feedstock types belonged in the same category. The SEM, XRD, and FTIR analyses of typical biochars from the different categories suggested both variations and similarities in their characteristics. In addition, the results from soil incubation experiments were consistent with the conclusions made from biochar characteristics analysis.Biochars derived from swine manures, fruit peels, and leaves with high pH and macro-nutrients appeared appropriate to increase soil pH and soil nutrient availability; whereas, biochars from wetland plant residues with high C concentrations and Brunauer–Emmett–Teller were better for soil C sequestration and contaminant adsorption.

Sorption and desorption of butachlor were simultaneously investigated on synthesized pure amorphous hydrated Fe oxides (AHOs Fe), and soils both with and without surface coating of AHOs Fe, with special interest towards how amorphous sesquioxides affect and contribute to butachlor retention in soils.The AHOs Fe was artificially synthesized pure materials. Two soils with contrasting physicochemical properties selected for study were black soil and latosol, belonging to permanent charged soil and variable charged soil, respectively. Both soils were further treated using AHOs Fe for detecting the differentiation from native soils regarding butachlor retention produced after the soils were surface-coated by AHOs Fe. A sorption experiment was conducted using a batch equilibrium technique, and desorption was carried out immediately following sorption by three sequential dilution. Hysteresis index (HI) values were calculated to investigate desorption hysteresis by developing desorption isotherms concentration dependent and time dependent, respectively.The sorption capacity for butachlor increased in the order of AHOs Fe, uncoated soils, and soils with surface coating of AHOs Fe. The sorption capacity of both soils significantly increased after surface coating by AHOs Fe (p < 0.01), with a bigger increase achieved by black soil (52.0 %) as compared with that by latosol (45.3 %). Desorption of butachlor was coincidently hysteretic on AHOs Fe, and soils both uncoated and coated, whereas variation in desorption hysteresis was different between AHOs Fe and soils with increasing butachlor sorption loading, indicating different sorption mechanisms were operative for AHOs Fe and soils across the entire butachlor concentration range. Hysteresis of butachlor desorption was weakened after the soils were surface coated by AHOs Fe, as suggested by the changed HI values.With high specific surface area and highly reactive surfaces, the “active” AHOs Fe originally has a relatively high sorption capacity and affinity for butachlor. While in natural soils, where the inevitable association derived from soil organic matter (SOM) would restrain AHOs Fe from sequestrating butachlor directly, AHOs Fe may likely contribute in a mediator way by coordinating active sites both on and within SOM. This may enhance the availability of sorption domains both on and within soils, thereby achieved an enhanced but more reversible retention for butachlor in soils after their surfaces were coated by AHOs Fe. This study has extended the observations of the role of noncrystalline sesquioxides in retention of pesticides such as butachlor from pure clay mineral systems to natural soils.

Adsorption and desorption are important processes that influence the transport, transformation, and bioavailability of atrazine in soils. Equilibrium batch experiments were carried out to investigate the adsorption–desorption characteristics of atrazine. The objectives of this study were to (1) determine and quantify the main soil parameters governing atrazine adsorption and desorption phenomena; (2) find the correlativity between the identified soil parameters; and (3) investigate the universal desorption hysteresis traits.Fifteen soils with contrasting physico-chemical characteristics were collected from 11 provinces in eastern China. The equilibrium time was 24 h both for adsorption and desorption experiments. Atrazine was detected by Waters 2695/UV HPLC.Adsorption isotherms of atrazine could be well described by the Freundlich equation (r ≥ 0.994, p < 0.01). The total organic carbon (TOC) was the first independent variable that described 53.0 % of the total variability of Kf, followed by the pH (9.9 %), and the clay (4.0 %) and silt (1.2 %) contents, separately; while the primary soil properties that affect desorption parameters included the TOC, pH, free Fe2O3 (Fed) and the sand content, with the biggest contribution achieved by the TOC (ranged from 48.5–78.1 %). The results showed that when the content ratio of clay to TOC (RCO) was less than 40, the atrazine adsorption was largely influenced by the organic matrix, while when the RCO was greater than 40, they were vital affected by the clay content.Adsorption–desorption isotherms of atrazine in soils were nonlinear. The content of TOC, clay, and iron oxides, as well as the pH value were the key soil parameters affecting the adsorption–desorption of atrazine in soil, among which the RCO especially exhibited relevance. Additionally, the desorption hysteresis existed for atrazine retention in all 15 tested soils, and the hysteretic effect enhanced with the increasing time for desorption. This would be ascribed to the heterogeneity physical–chemical properties of these soils.

•Microbial community was greatly influenced by PCP in the mangrove soil.•Bacteroidetes, Proteobacteria and Firmicutes were active during PCP transformation.•The growth of some methanogens was stimulated in PCP treatments.•PCP dechlorination was coupled with soil biogeochemical redox (C, Fe, S) processes.The aim was to investigate the influence of pentachlorophenol (PCP) on the soil microbial communities and the coupled mechanism between PCP reductive dechlorination and soil redox under anaerobic condition. Accordingly, a slurry incubation experiment was carried out in which bacterial and archaeal communities were detected by MiSeq amplicon sequencing. The original microbial community balance was gradually disrupted and new microbial structure was reconstructed subsequently through self-regulation and acclimation during PCP transformation, coupling with the changes of soil biogeochemical redox dynamics. The phylum Bacteroidetes predominated during the earlier PCP dechlorination period and then was progressively replaced by Proteobacteria and Firmicutes groups when PCP was mostly transformed into 2,3,4,5-TeCP and 3,4,5-TCP. Heatmap and hierarchical cluster analysis revealed the Clostridium-like, Geobacter-like and Dehalococcoides-like organisms enriched concurrently during PCP reductive dechlorination processes. The relative abundance changes of the redox-active microorganisms, together with their relevance to the corresponding biogeochemical redox processes, showed that PCP dechlorination, Fe(III) and SO42 − reduction, as well as methanogenesis were coupled terminal electron accepting processes. The combined analysis of the microbial function, the affinity for substrates (H2 and acetate) and the sensitivity for PCP toxicity by microorganisms might explain why electron transport chain has changed in soil biogeochemical redox process. Our study offers a comprehensive description of the impact of PCP on the soil microbial community structures, which could be very useful for understanding the regulation of soil nutrient and energy transfer during biogeochemical cycling processes in soils with significant inputs of exogenous pollutants.Download high-res image (99KB)Download full-size image