Enhancement effect of nanoscale zero-valent iron addition on microbial degradation of BDE-209 in contaminated mangrove sediment.

Chemical and biological methods have been employed to remedy polybrominated diphenyl ether contamination, but the removal of decabromodiphenyl ether (BDE-209) by either method still has limitations. The present study aims to evaluate the combined effect of nanoscale zero-valent iron (nZVI) (from 0.1 to 10%) reduction and microbial debromination on BDE-209 removal in mangrove sediments under an anaerobic condition. During the 12-months incubation, nZVI significantly enhanced BDE-209 removal, with 17.03% to 41.99% reduction in sterilized sediments. The reduction was even higher in non-sterilized sediments with living indigenous microorganisms, achieving 15.80%, 33.50%, 55.83% and 66.95% removal of BDE-209 at 0 (control without nZVI), 0.1%, 1% and 10% nZVI, respectively. In control sterilized sediments, no debromination was found, and debromination occurred according to spiked levels of nZVI, with BDE-153 being the dominant congener. The concentrations of debrominated congeners in non-sterilized sediments also increased with nZVI levels, but were significantly higher than the respective sterilized sediment. The relative proportions of different debrominated congeners in non-sterilized sediments depended on nZVI levels, with BDE-99 being the dominant congener in low nZVI amended sediments but shifted to BDE-153 under high nZVI. Higher concentrations of ferrous iron (Fe2+) were detected in both sterilized and non-sterilized sediments spiked with more nZVI, and their concentrations significantly correlated with BDE-209 removal. Growth of total bacteria in sediments with 1% and 10% nZVI was inhibited within first two months, but their numbers resumed to that in the control at the end of 12 months. The present study demonstrates the synergy between chemical and microbiological methods, and a combination of nZVI and indigenous microorganisms could be an efficient and feasible mean to remedy BDE-209 in contaminated sediments.

Growth and Cd uptake by rice (Oryza sativa) in acidic and Cd-contaminated paddy soils amended with steel slag.

Contamination of rice (Oryza sativa) by Cd is of great concern. Steel slag could be used to amend Cd-contaminated soils and make them safe for cereal production. This work was conducted to study the effects of steel slag on Cd uptake and growth of rice plants in acidic and Cd-contaminated paddy soils and to determine the possible mechanisms behind these effects. Pot (rhizobag) experiments were conducted using rice plants grown on two acidic and Cd-contaminated paddy soils with or without steel slag amendment. Steel slag amendment significantly increased grain yield by 36-45% and root catalase activity, and decreased Cd concentrations in brown rice by 66-77% compared with the control, in both soils. Steel slag amendment also markedly decreased extractable soil Cd, Cd concentrations in pore-water and Cd translocation from roots to above-ground parts. It also significantly increased soil pH, extractable Si and Ca in soils and Ca concentrations in roots. Significant positive correlations were found between extractable soil Cd and Cd concentrations in rice tissues, but it was negatively correlated with soil pH and extractable Si. Calcium in root tissues significantly and negatively correlated with Cd translocation factors from roots to straw. Overall, steel slag amendment not only significantly promoted rice growth but decreased Cd accumulation in brown rice. These benefits appear to be related to improvements in soil conditions (e.g. increasing pH, extractable Si and Ca), a reduction in extractable soil Cd, and suppression of Cd translocation from roots to above-ground parts.

Vertical distribution of dehalogenating bacteria in mangrove sediment and their potential to remove polybrominated diphenyl ether contamination.

The removal and degradation of polybrominated diphenyl ethers (PBDEs) in sediments are not clear. The vertical distribution of total and dehalogenating bacteria in sediment cores collected from a typical mangrove swamp in South China and their intrinsic degradation potential were investigated. These bacterial groups had the highest abundances in surface sediments (0-5cm). A 5-months microcosm experiment also showed that surface sediments had the highest rate to remove BDE-47 than deeper sediments (5-30cm) under anaerobic condition. The deeper sediments, being more anaerobic, had lower population of dehalogenating bacteria leading to a weaker BDE-47 removal potential than surface sediments. Stepwise multiple regression analysis indicated that Dehalococcoides spp. were the most important dehalogenating bacteria affecting the anaerobic removal of BDE-47 in mangrove sediments. This is the first study reporting that mangrove sediments harbored diverse groups of dehalogenating bacteria and had intrinsic potential to remove PBDE contamination.

Effects of alkaline and bioorganic amendments on cadmium, lead, zinc, and nutrient accumulation in brown rice and grain yield in acidic paddy fields contaminated with a mixture of heavy metals.

Paddy soils and rice (Oryza sativa L.) contaminated by mixed heavy metals have given rise to great concern. Field experiments were conducted over two cultivation seasons to study the effects of steel slag (SS), fly ash (FA), limestone (LS), bioorganic fertilizer (BF), and the combination of SS and BF (SSBF) on rice grain yield, Cd, Pb, and Zn and nutrient accumulation in brown rice, bioavailability of Cd, Pb, and Zn in soil as well as soil properties (pH and catalase), at two acidic paddy fields contaminated with mixed heavy metals (Cd, Pb, and Zn). Compared to the controls, SS, LS, and SSBF at both low and high additions significantly elevated soil pH over both cultivation seasons. The high treatments of SS and SSBF markedly increased grain yields, the accumulation of P and Ca in brown rice and soil catalase activities in the first cultivation season. The most striking result was from SS application (4.0 t ha-1) that consistently and significantly reduced the soil bioavailability of Cd, Pb, and Zn by 38.5-91.2 % and the concentrations of Cd and Pb in brown rice by 20.9-50.9 % in the two soils over both cultivation seasons. LS addition (4.0 t ha-1) also markedly reduced the bioavailable Cd, Pb, and Zn in soil and the Cd concentrations in brown rice. BF remobilized soil Cd and Pb leading to more accumulation of these metals in brown rice. The results showed that steel slag was most effective in the remediation of acidic paddy soils contaminated with mixed heavy metals.

Contributions of Abiotic and Biotic Processes to the Aerobic Removal of Phenolic Endocrine-Disrupting Chemicals in a Simulated Estuarine Aquatic Environment.

The contributions of abiotic and biotic processes in an estuarine aquatic environment to the removal of four phenolic endocrine-disrupting chemicals (EDCs) were evaluated through simulated batch reactors containing water-only or water-sediment collected from an estuary in South China. More than 90% of the free forms of all four spiked EDCs were removed from these reactors at the end of 28 days under aerobic conditions, with the half-life of 17α-ethynylestradiol (EE2) longer than those of propylparaben (PP), nonylphenol (NP) and 17ß-estradiol (E2). The interaction with dissolved oxygen contributed to NP removal and was enhanced by aeration. The PP and E2 removal was positively influenced by adsorption on suspended particles initially, whereas abiotic transformation by estuarine-dissolved matter contributed to their complete removal. Biotic processes, including degradation by active aquatic microorganisms, had significant effects on the removal of EE2. Sedimentary inorganic and organic matter posed a positive effect only when EE2 biodegradation was inhibited. Estrone (E1), the oxidizing product of E2, was detected, proving that E2 was removed by the naturally occurring oxidizers in the estuarine water matrixes. These results revealed that the estuarine aquatic environment was effective in removing free EDCs, and the contributions of abiotic and biotic processes to their removal were compound specific.

Chlorophyll catalyse the photo-transformation of carcinogenic benzo[a]pyrene in water.

Algal blooms cause great damage to water quality and aquaculture. However, this study showed that dead algal cells and chlorophyll could accelerate the photo-transformation of benzo[a]pyrene (BaP), a ubiquitous and persistent pollutant with potently mutagenic and carcinogenic toxicities, under visible light irradiation. Chlorophyll was found to be the major active substance in dead algal cells, and generated a high level of singlet oxygen to catalyse the photo-transformation of BaP. According to various BaP metabolites formed, the degradation mechanism was proposed as that chlorophyll in dead algal cells photo-oxidized BaP to quinones via photocatalytic generation of singlet oxygen. The results provided a good insight into the role of chlorophyll in the photo-transformation of organic contaminants and could be a possible remediation strategy of organic pollutants in natural environment.

One-step extraction and derivatization liquid-phase microextraction for the determination of chlorophenols by gas chromatography-mass spectrometry.

A sample pretreatment method for the determination of 18 chlorophenols (CPs) in aqueous samples by derivatization liquid-phase microextraction (LPME) was investigated using gas chromatography-mass spectrometry. Derivatization reagent was spiked into the extraction solvent to combine derivatization and extraction into one step. High sensitivity of 18 CPs derivatives could be achieved after optimization of several parameters such as extraction solvent, percentage of derivatization reagent, extraction time, pH, and ionic strength. The results from the optimal method showed that calibration ranging from 0.5 to 500microgL(-1) could be achieved with the RSDs between 1.75% and 9.39%, and the limits of detection (LOD) are ranging from 0.01 to 0.12microgL(-1) for the CPs. Moreover, the proposed LPME method was compared with solid-phase microextraction (SPME) coupled with on-fiber derivatization technique. The results suggested that using both methods are quite agreeable. Furthermore, the recoveries of LPME evaluated by spiked environmental samples ranged from 87.9% (3,5-DCP) to 114.7% (2,3,5,6-TeCP), and environmental water samples collected from the Pearl River were analyzed with the optimized LPME method, the concentrations of 18 CPs ranged from 0.0237microgL(-1) (3,5-DCP) to 0.3623microgL(-1) (2,3,6-TCP).

Determination of hydroxy metabolites of polycyclic aromatic hydrocarbons by fully automated solid-phase microextraction derivatization and gas chromatography-mass spectrometry.

A fully automated sample pretreatment method was developed for the detection of mono and dihydroxy metabolites of polycyclic aromatic hydrocarbons (PAHs) by gas chromatography-mass spectrometry in the selected ion monitoring mode. Direct immersion solid-phase microextraction for the extraction of target compounds and the headspace on-fiber silylation with N,O-bis(trimethylsilyl)trifluoroacetamide were performed automatically by a multipurpose autosampler (MPS2). The operating conditions including extraction time, derivatization time, ionic strength, pH, and incubation temperature were optimized. Calibration responses of nine metabolites of PAHs over a concentration range of 0.1-100 microg L(-1) with a correlation coefficient of 0.999 were obtained. The detection limits of the nine metabolites in mini pore water, minimal salts medium and soil extract culture medium were in the range of 0.001-0.013, 0.002-0.024 and 0.002-0.134 microg L(-1), respectively, while the respective quantification limits were 0.003-0.044, 0.005-0.081 and 0.008-0.447 microg L(-1). The reliability was confirmed by the traditional solid-phase extraction method. The proposed method could be used to analyze the metabolites of PAHs degraded by microorganisms such as algae and to determine the biodegradation pathways of PAHs.

A case study on fuel oil contamination in a mangrove swamp in Hong Kong.

Mangroves commonly found along tropical and subtropical coastlines are susceptible to oil pollution. In December 2000, around 500 1 m tall Kandelia candel saplings at the age of 3-5 years old located at the foreshore region of Sheung Pak Nai swamp, Hong Kong SAR, were found to be damaged by oil pollution. More than 80% of the saplings were either dead or washed away and leaving less than 5% healthy saplings with dense green leaves. Elevated concentrations of light n-alkanes (ranging from n-C14 to n-C20), pristane and phytane were recorded in surface sediments collected in December 2000. The ratio between light and total n-alkanes was 0.4. The total petroleum hydrocarbons (60-80 microg g(-1) TPH) and unresolved complex mixtures (60-70 microg g(-1) UCM) were higher than the background values of other mangrove sediments in Hong Kong, which were 40 and 20 microg g(-1), respectively. In certain root zone sediments, TPH concentrations were above 1000 microg g(-1). These results suggest that surface sediments in Sheung Pak Nai were contaminated by petroleum oil, most likely by illegal discharge of fuel oil which occurred between 1998 and 2002. One year later, in December 2001, unhealthy saplings had recovered and re-grown. The concentrations of TPH and UCM in sediments declined to around 40 microg g(-1), pristane and phytane dropped by 80%, and the ratio of light to total n-alkanes was 0.15, suggesting that residual oil in sediments was weathered leading to a remarkable recovery of the unhealthy saplings.

Fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp in Hong Kong following an oil spill.

The fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp (Yi O) in Hong Kong after an oil spill accident was investigated. The concentrations and profiles of PAHs in surface sediments collected from five quadrats (each of 10 m x 10 m) covering different degrees of oil contamination and the most contaminated mangrove leaves were examined in December 2000 (30 days after the accident) and March 2001 (126 days later). The concentrations of total PAHs in surface sediments ranged from 138 to 2,135 ng g(-1), and PAHs concentrations decreased with time. In the most contaminated sediments, total PAHs dropped from 2,135 (30 days) to 1,196 ng g(-1) (120 days), and the decrease was smaller in less contaminated sediments. The percentage reduction in sediment PAHs over three months (44%) was less significant than that in contaminated leaves (85%), indicating PAH in or on leaves disappeared more rapidly. The PAH profiles were very similar in sediments collected from quadrats Q1 and Q2 with benzo[a]anthracene and pyrene being the most abundant PAH compounds, but were different in the other three quadrats. The proportion of the light molecular weight PAHs to total PAHs increased after three months, especially phenanthrene. Results suggest that physical and photo-chemical weathering (tidal washing and photo-oxidation) of crude oil in surface sediments and on plant leaves were important processes in the first few months after the oil spill. The PAH contamination in Yi O swamp came from both petrogenic and pyrolytic sources. The petrogenic characteristic in the most contaminated sediment was confirmed with high values of phenanthrene to anthracene ratio (>10) and low values of fluoranthene to pyrene ratio (0.3-0.4).