New insight into the mechanism underlying the effect of biochar on phenanthrene degradation in contaminated soil revealed through DNA-SIP.

Biochar has been widely used for the remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soil, but its mechanism of influencing PAH biodegradation remains unclear. Here, DNA-stable isotope probing coupled with high-throughput sequencing was employed to assess its influence on phenanthrene (PHE) degradation, the active PHE-degrading microbial community and PAH-degradation genes (PAH-RHDα). Our results show that both Low-BC and High-BC (soils amended with 1 % and 4 % w/w biochar, respectively) treatments significantly decreased PHE biodegradation and bioavailable concentrations with a dose-dependent effect compared to Non-BC treatment (soils without biochar). This result could be attributed to the immobilisation of PHE and alteration of the composition and abundance of the PHE-degrading microbial consortium by biochar. Active PHE degraders were identified, and those in the Non-BC, Low-BC and High-BC microcosms differed taxonomically. Sphaerobacter, unclassified Diplorickettsiaceae, Pseudonocardia, and Planctomyces were firstly linked with PHE biodegradation. Most importantly, the abundances of PHE degraders and PAH-RHDα genes in the 13C-enriched DNA fractions of biochar-amended soils were greatly attenuated, and were significantly positively correlated with PHE biodegradation. Our findings provide a novel perspective on PAH biodegradation mechanisms in biochar-treated soils, and expand the understanding of the biodiversity of microbes involved in PAH biodegradation in the natural environment.

Mechanism of salicylic acid in promoting the rhizosphere benzo[a]pyrene biodegradation as revealed by DNA-stable isotope probing.

Benzo[a]pyrene (BaP) is a typical high-molecular-weight PAH with carcinogenicity. Rhizoremediation is commonly applied to remove soil BaP, but its mechanism remains unclear. The role of inducers in root exudates in BaP rhizoremediation is rarely studied. Here, to address this problem, we firstly investigated the effect of the inducer salicylic acid on BaP rhizoremediation, rhizosphere BaP degraders, and PAH degradation-related genes by combining DNA-stable-isotope-probing, high-throughput sequencing, and gene function prediction. BaP removal in the rhizosphere was significantly increased by stimulation with salicylic acid, and the rhizosphere BaP-degrading microbial community structure was significantly changed. Fourteen microbes were responsible for the BaP metabolism, and most degraders, e.g. Aeromicrobium and Myceligenerans, were firstly linked with BaP biodegradation. The enrichment of the PAH-ring hydroxylating dioxygenase (PAH-RHD) gene in the heavy fractions of all 13C-treatments further indicated their involvement in the BaP biodegradation, which was also confirmed by the enrichment of dominant PAH degradation-related genes (e.g. PAH dioxygenase and protocatechuate 3,4-dioxygenase genes) based on gene function prediction. Overall, our study demonstrates that salicylic acid can enhance the rhizosphere BaP biodegradation by altering the community structure of rhizosphere BaP-degrading bacteria and the abundance of PAH degradation-related genes, which provides new insights into BaP rhizoremediation mechanisms in petroleum-contaminated sites.

Occurrence and risk assessment of currently used organophosphate pesticides in overlying water and surface sediments in Guangzhou urban waterways, China.

Organophosphate pesticides (OPPs) are one type of the most massively used pesticides and ubiquitously detected in aquatic environments, which may pose potential risks to the aquatic organisms and human health. In the present study, the spatiotemporal distribution and potential risks of OPPs were investigated in overlying water and surficial sediments from urban waterways of Guangzhou. For all studied sites, in general, four target OPPs (i.e., malathion, chlorpyrifos, terbufos, and diazinon) were present in the overlying water, with malathion and chlorpyrifos as major components. Higher concentrations of the four OPPs were found for the water and sediments collected in the dry season compared to the wet season, possibly because of the dilution effect of heavy rains. The results of Pearson's analyses and principal coordinate analyses (PCoA) suggested similar sources for target OPPs in the water and sediments across the Guangzhou urban waterways. Potential ecological risks of the OPPs to three representative taxons (algae, aquatic invertebrates, and fish) were evaluated via toxic units (TUs) and risk quotients (RQs), while risk assessment on human health was performed using hazard index (HI). Although TU results showed no acute risks to the aquatic organisms in the overlying water and surface sediments, RQ results of the mixture showed high risks to the aquatic invertebrate and fish in all water samples. Individual HI values and cumulative HI values were on the order of 10-6-10-3 for children and adults, suggesting no potential risks to either children or adults through drinking and bathing.

Temporal-spatial distribution of synthetic pyrethroids in overlying water and surface sediments in Guangzhou waterways: potential input mechanisms and ecological risk to aquatic systems.

Temporal-spatial distribution of synthetic pyrethroids (SPs) in overlying water and surface sediments and ecological risk to aquatic systems were investigated, where paired water and surface sediments were collected during dry and wet periods in Guangzhou urban waterways. Eight target SPs (i.e., tefluthrin, bifenthrin, cyhalothrin, permethrin, cyfluthrin, cypermethrin, esfenvalerate, and deltamethrin), with cypermethrin and permethrin as major components, were ubiquitously detected in both water (dissolved and particle phases, separately) and sediments. Significant increases of ΣSP (sum of eight SPs) concentrations were observed in both water and sediment from the dry period to the wet period. The spatial distribution of SPs was mostly impacted by land-use type, with the highest ΣSP concentrations in the residential areas, which indicates the massive application of pyrethroids in household mosquito control. It is demonstrated that SPs preferred to be adsorbed to the particles, and rainfall-induced runoff was suggested as an important mechanism that moved SPs to the receiving waterways. A rising trend on sediment concentrations of SPs in the Guangzhou area in the last decade implied increasing application of pyrethroid insecticides, with cypermethrin and permethrin as the dominant components, where the contamination of SPs was positively related with urbanization rate (e.g., resident population and green coverage area). A special emphasis was placed on the potential effects of both individual SPs and their mixtures in three trophic levels (i.e., algae, daphnia, and fish) using toxic units (TUs) and risk quotients (RQs) for water and sediments. In spite of no acute effects due to SPs in the sediments, the toxic units showed daphnia as the most sensitive species in water, with acute risks to daphnia exhibited in several sampling sites. The risk assessment points out that a chronic toxicity (RQ index) caused by SPs in three trophic levels (algae, daphnia, and fish) exists, especially in Daphnia magna. Graphical abstract.

Degradation of tetrabromobisphenol A in a paddy soil during sequential anoxic-oxic incubation: Kinetics, metabolites, and potential pathways.

Due to the increasing pollution of tetrabromobisphenol A (TBBPA) in paddy soils, it is of great importance to explore the degradation of TBBPA under repeated anoxic-oxic conditions. In the present study, the degradation of TBBPA (kinetics, metabolites and potential pathways) and the influence of low molecular weight organic acid i.e., lactic acid were investigated in a paddy soil during sequential anoxic-oxic incubations. Under the anoxic condition, TBBPA in the non-sterile soils was efficiently debrominated into three intermediates (including tri-BBPA, di-BBPA and mono-BBPA) and bisphenol A (BPA) with a rate constant (k) of 0.0371 d-1 and a half-life (t1/2) of 60.8 d. The debromination end product (BPA) steadily accumulated. Next, turning to the oxic conditions, the anaerobically accumulated BPA degraded rapidly, while the intermediates and TBBPA were desorbed from the bound residues and were persistent. The detection of tri-BBPA followed by di-BBPA and mono-BBPA thereafter indicated that the dehalogenation of TBBPA was likely a stepwise removal of bromine atoms. A pathway of TBBPA → tri-BBPA → di-BBPA → mono-BBPA → BPA was thus proposed for TBBPA degradation. The degradation of TBBPA and its metabolites was biologically mediated. Moreover, the biodegradation of TBBPA could be significantly accelerated by the addition of lactic acid as an exogenous carbon source and electron donor, with k being increased to 0.0766 d-1 and t1/2 being shortened to 31.9 d. The information will improve our understanding of biotic process associated with agronomic practices (such as applying organic fertilizers) contributing to TBBPA attenuation in the natural soil environment.

Improvement of zinc substitution in the reactivity of magnetite coupled with aqueous Fe(II) towards nitrobenzene reduction.

The reduction of nitrobenzene (NB) by Zn-substituted magnetite coupled with aqueous Fe(II) was studied. A series of Zn-substituted magnetites (Fe3-xZnxO4, x = 0, 0.25, 0.49, 0.74, and 0.99) were synthesized by a coprecipitation method followed by systematic analysis of the variation in structure and physicochemical properties of magnetite using XRD, TEM, TG, BET and XAFS. All of the samples had a spinel structure by Zn substitution. Zn2+ primarily occupied the tetrahedral sites, but a portion of them moved to the octahedral sites at higher Zn level. Zn substitution increased the BET specific surface area and surface hydroxyl amount. The electron balance indicated that the NB reduction was primarily through the heterogeneous reaction by Fe3-xZnxO4 and adsorbed Fe(II), where NB in aqueous solution was reduced by structural Fe2+ in magnetite recharged by adsorbed Fe(II). Various factors, such as aqueous Fe(II) concentration, magnetite stoichiometry and Zn level, were investigated to illustrate their effects on the reduction processes. Both the rate constant kobs and electron transfer amount illustrated that Zn substitution generally improved the reduction activity of the Fe3-xZnxO4/Fe(II) system, while overdose of Zn retarded the process. This issue was attributed to the variation in electron conductivity of Fe3-xZnxO4 and Zn2+ occupancy.

Reduction removal of hexavalent chromium by zinc-substituted magnetite coupled with aqueous Fe(II) at neutral pH value.

In this study, Cr(VI) removal by Zn-substituted magnetite coupled with aqueous Fe(II) through adsorption and reduction was investigated. A series of Zn-substituted magnetites (Fe3-xZnxO4, x=0, 0.25, 0.49, 0.74 and 0.99) were synthesized by a coprecipitation method, followed by systematic characterization, e.g., X-ray diffraction (XRD), thermogravimetry (TG), specific surface area and surface acid/base titration. The characterization results show that all samples had a spinel structure without an obvious alternation by Zn substitution. The BET surface area and surface site density gradually increased with Zn substitution. During Cr removal under neutral pH value, Cr(VI) was first adsorbed on the magnetite surface and then reduced to Cr(III) by Fe3-xZnxO4 and adsorbed Fe(II); finally, it was immobilized on the Fe3-xZnxO4 surface, which was verified via X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge spectroscopy (XANES) analyses and desorption experiment. With the increase in the Zn content in magnetite, the Cr removal efficiency initially decreased; then, it improved, which was ascribed to the decreasing Cr(VI) reduction and increasing Cr(VI) adsorption. This variation in activity by Zn substitution was discussed in terms of the reaction mechanism as well as the cationic microstructure and surface properties of Fe3-xZnxO4.

Using lysine adducts of human serum albumin to investigate the disposition of exogenous formaldehyde in human blood.

Formaldehyde is a human carcinogen that readily binds to nucleophiles, including proteins and DNA. To investigate whether exogenous formaldehyde produces adducts in extracellular fluids, we characterized modifications to human serum albumin (HSA) following incubation of whole blood, plasma, and saliva with formaldehyde at concentrations of 1, 10 and 100µM. The only HSA locus that showed the presence of formaldehyde modifications was Lys199. A N(6)-Lys adduct with added mass of 12Da, representing a putative intramolecular crosslink, was detected in biological fluids that had been incubated with formaldehyde but not in control fluids. An adduct representing N(6)-Lys formylation was detected in all fluids, but levels did not increase above control values over the tested range of formaldehyde concentrations. An adduct representing N(6)-Lys199 acetylation was also measured in all samples. We then applied the assay to repeated samples of human plasma from 6 nonsmoking volunteer subjects (from Berkeley, CA), and single samples of serum from 15 workers exposed to airborne formaldehyde at about 1.5ppm in a production facility and 15 control workers from Tianjin, China. Although all human plasma/serum samples contained basal levels of the products of N(6)-Lys formylation and acetylation, the putative crosslink product was not detected. Since the putative crosslink was observed in plasma incubated with formaldehyde at 1µM, this suggests that the endogenous concentration of formaldehyde in serum was much lower than reported in the literature. Furthermore, concentrations of the formyl adduct were not higher in workers exposed to formaldehyde at about 1.5ppm than in controls. Follow-up in vitro experiments with gaseous formaldehyde at 1.4ppm detected the putative crosslink in plasma but not whole blood. This combination of results suggests that N(6) formylation occurs within cells with subsequent release of adducted HSA to the systemic circulation. Comparing across human samples, levels of N(6)-Lys199 formyl adducts were present at similar concentrations in subjects from California and China (about 1mmol/mol HSA), but N(6)-Lys199 acetyl adducts were present at higher concentrations in Chinese subjects (0.34 vs. 0.13mmol/mol HSA).

Profiles, sources, and transport of polycyclic aromatic hydrocarbons in soils affected by electronic waste recycling in Longtang, south China.

We studied the profiles, possible sources, and transport of polycyclic aromatic hydrocarbons (PAHs) in soils from the Longtang area, which is an electronic waste (e-waste) recycling center in south China. The sum of 16 PAH concentrations ranged from 25 to 4,300 ng/g (dry weight basis) in the following order: pond sediment sites (77 ng/g), vegetable fields (129 ng/g), paddy fields (180 ng/g), wastelands (258 ng/g), dismantling sites (678 ng/g), and former open burning sites (2,340 ng/g). Naphthalene, phenanthrene, fluoranthene, pyrene, chrysene, and benzo[b]fluoranthene were the dominant PAHs and accounted for approximately 75 % of the total PAHs. The similar composition characteristics of PAHs and the significant correlations among individual, low molecular weight, high molecular weight, and total PAHs were found in all six sampling site types, thus indicating that PAHs originated from similar sources. The results of both isomeric ratios and principal component analyses confirmed that PAHs were mainly derived from the incomplete combustion of e-waste. The former open burning sites and dismantling sites were the main sources of PAHs. Soil samples that were taken closer to the point sources had high PAH concentrations. PAHs are transported via different soil profiles, including those in agricultural fields, and have been detected not only in 0- to 40-cm-deep soil but also in 40 cm to 80 cm-deep soil. PAH concentrations in soils in Longtang have been strongly affected by primitive e-waste recycling, particularly by former open burning activities.

Characteristics, sources, and transport of tetrabromobisphenol A and bisphenol A in soils from a typical e-waste recycling area in South China.

We studied the tetrabromobisphenol A (TBBPA) and bisphenol A (BPA) patterns and their sources and transport in different land-use soils from Longtang, South China, a typical electronic waste recycling center. We also studied the reductive debromination of TBBPA in paddy soils. TBBPA and BPA concentrations (on a dry weight basis) were undetected-220 and 0.50-325 ng/g, respectively, and both increased, by similar factors, in the following order: pond sediments < paddy soils = vegetable soils < wasteland < dismantling sites < former open burning sites. BPA concentrations were higher than TBBPA concentrations in all six land-use soils, and they correlated significantly. TBBPA and BPA were transported through the soil profiles, being found at relatively high concentrations in soil 0-40 cm deep, but only at low concentrations in soil 40-80 cm deep. The surface soil concentrations appear to have been strongly affected by crude recycling activities, and former open burning and dismantling sites were the main point sources. The areas surrounding the open burning sites and dismantling sites have been contaminated not only by the dumping of waste residues but also by fly ash deposition, even though the agricultural soils are far from the point pollution sources. Some BPA in the soils is likely to be the reductive debromination product of TBBPA because the long rainy season promotes TBBPA transformation and because BPA can persist for a long time. Incubation experiments confirmed that TBBPA could be transformed into BPA and that BPA could accumulate in waterlogged paddy soils, and this may be why BPA concentrations were higher than TBBPA concentrations in the Longtang area.

Enhancement effect of two ecological earthworm species (Eisenia foetida and Amynthas robustus E. Perrier) on removal and degradation processes of soil DDT.

Effects of two ecological earthworm species (epigeic Eisenia foetida and endogeic Amynthas robustus E. Perrier) with different densities (15 and 30 individuals per kg of soil) on the removal of soil 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) with two pollution levels (2 and 4 mg kg(-1)) were investigated. Concentrations of DDT and its metabolites, including 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane (DDD), 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (DDE), and 1-chloro-2,2-bis(4-chlorophenyl)ethylene (DDMU), were monitored after 60, 180, and 360 days of incubation. The results obtained showed that both earthworm species can significantly enhance degradation of soil DDT to its metabolites. For E. foetida, the higher earthworm density showed significantly higher rate of DDT degradation than the lower one. Anaerobic reductive dechlorination was the main degradation pathway over 180 days of incubation, while the aerobic dechlorination process was promoted between 180 and 360 days of incubation. Some earthworm amended treatments showed significantly higher microbial biomass carbon and nitrogen than the control, which suggested that earthworms might enhance the microbial degradation of DDT. Both earthworm species would have the potential to be applied to enhance the remediation of agricultural lands polluted by DDT.

Wet deposition of nitrogen and sulfur in Guangzhou, a subtropical area in South China.

With the aim of understanding the seasonal distribution of deposition fluxes of nitrogen (N) and sulfur (S) in South China, a main acid deposition region in China, precipitation samples were collected and analyzed from Guangzhou area, between March 2005 and February 2006. The estimated wet deposition of N (including ammonium nitrogen (NH(4)-N) and nitrate nitrogen (NO(3)-N)) and S (sulfate sulfur (SO(4)-S)) during the monitoring period were 40.47 kg N ha(-1) and 65.29 kg S ha(-1), respectively. The average deposition of NH(4)-N was ∼1.5 times of the NO(3)-N deposition, suggesting that the reduced and oxidized N depositions were comparable in the study area. The S and N depositions in the rainy season were greater than those in the dry season, showing great seasonal variation, which was consistent with both the distribution of precipitation and the period of fertilizer application for agriculture. The N and S wet deposition fluxes in Guangzhou were greater than those in Beijing and Zhengzhou, located in the northern China, but comparable to the level of Chongqing, located in the southwestern China, another major acid deposition region. The atmospheric N and S depositions in these cities from north to south were affected by both intensive agricultural and industrial activities.

Chemical composition and seasonal variation of acid deposition in Guangzhou, South China: comparison with precipitation in other major Chinese cities.

With the aim of understanding the origin of acid rains in South China, we analyzed rainwaters collected from Guangzhou, China, between March 2005 and February 2006. The pH of rainwater collected during the monitoring period varied from 4.22 to 5.87; acid rain represented about 94% of total precipitation during this period. The rainwater was characterized by high concentrations of SO(4)(2-), NO(3)(-), Ca(2+), and NH(4)(+). SO(4)(2-) and NO(3)(-), the main precursors of acid rain, were related to the combustion of coal and fertilizer use/traffic emissions, respectively. Ca(2+) and NH(4)(+) act as neutralizers of acid, accounting for the decoupling between high SO(4)(2-) concentrations and relatively high pH in the Guangzhou precipitation. The acid rain in Guangzhou is most pronounced during spring and summer. A comparison with acid precipitation in other Chinese cities reveals a decreasing neutralization capacity from north to south, probably related to the role and origin of alkaline bases in precipitation.

Distribution and deposition of polycyclic aromatic hydrocarbons in precipitation in Guangzhou, South China.

Polycyclic aromatic hydrocarbons (PAHs) were measured in precipitation from March to August 2005 in Guangzhou, South China. Fourteen PAHs were studied, and their total concentrations varied from 616.6 to 3486.7 ng/L in dissolved phase and from 403.8 to 3125.5 ng/L in particulate phase. The estimated deposition loading of PAHs was 3568 microg/m2 during the monitoring period. The deposition of PAHs was a potential source for Pearl River comparing with the contents of surface water. In addition, the high concentration in precipitation here implied that PAHs pollution was a potential environmental problem in Guangzhou. Most precipitation concentrations of PAHs in March (the last month in winter in Guangzhou) were higher than in the other months (in rainy season). PAHs inclined to be adsorbed to particulate phase with the increase of molecular weight in rainwater. Combustion of fossil fuel and biomass might be the major source of PAHs, while the direct leakage or volatilization from petroleum products might be insignificant.