Enhanced remediation of BDE-209 in contaminated mangrove sediment by planting and aquaculture effluent.

Toxic and persistent flame retardant (BDE-209) and aquaculture effluent (AE) are ubiquitous in coastal environments, but how their co-existence influences their fate is not yet investigated. This study investigated AE effects on remediation and uptake of BDE-209 by Kandelia obovata (Ko) and Avicennia marina (Am), true and dominant mangrove species. After 12-months, a significant removal of BDE-209 was achieved in planted mangrove sediment and the removal was significantly enhanced by AE addition, possibly due to the enhancement of nitrogen (N) and phosphorous (P) content in sediment. Residual percentages of parent BDE-209 in Ko and Am planted sediments without AE were 61.4% and 70.9%, respectively, but decreased to 46.9% and 48.0% with AE addition after 12-months. A similar trend was found in unplanted sediment, with 86.5% and 65.3% of BDE-209 retained in sediments without and with AE addition, respectively. The results demonstrated that AE addition not only increased the debromination of BDE-209 in all treated sediments with the production of debrominated congeners (de-PBDEs) like di- to nona-BDEs in unplanted and planted sediments, but also enhanced the take up of BDE-209 in Ko root, and de-PBDEs in both Ko and Am, thus enhancing the phytoremediation of BDE-209 in contaminated sediments.

Developing interim water quality criteria for emerging chemicals of concern for protecting marine life in the Greater Bay Area of South China.

This study aimed to establish marine water quality criteria (MWQC) for emerging chemicals of concern (ECCs) for protecting aquatic life in the Greater Bay Area (GBA) of South China. Despite the frequent occurrence and elevated concentrations of these ECCs in the GBA, there is a lack of regional MWQC for these contaminants. We screened 21 common ECCs that were classified into the following six groups: (1) new persistent organic contaminants; (2) brominated flame retardants; (3) perfluoroalkyl and polyfluoroalkyl substances; (4) pharmaceutically active compounds (PhACs); (5) plasticizers; and (6) personal care products. Globally, MWQC for PhACs remain largely unavailable despite their increasing occurrence in marine environments. Using an integrative scientific approach, we derived interim MWQC for the GBA with specific protection goals. The approach described herein can be applied for the derivation of MWQC for ECCs and the establishment of guidelines for ecological risk assessment in the GBA and other regions.

Diphenamid photodegradation using Fe(III) impregnated N-doped TiO2/sulfite/visible LED process: Influence of wastewater matrix, kinetic modeling, and toxicity evaluation.

Sulfite-based photocatalysis has been recently employed as a promising technology for the treatment of organic pollutants via the generation of reactive radicals. In this contribution, the effect of wastewater matrix constituents and toxicity evaluation were systematically investigated in the FeIII impregnated N-doped TiO2 (FeN-TiO2)/sulfite/visible LED (Vis LED) process in the presence of diphenamid (DPA) as a model organic pollutant. The results showed that the presence of HCO3-, SO42-, NO3-, and F- had no detrimental effect on DPA degradation. Conversely, the presence of Cr(VI), NO2-, Cl-, and Br- caused a stronger retardation effect. The effect of natural organic matter such as humic acid (HA) was inert at normal concentrations. Interestingly, the retardation effect of inorganic ions can be quantified at any given ion concentration based on the linear correlations between the DPA decay (first-order kinetic constants) and concentration of ion species. Toxicity tests on Synechocystis sp., Microcystis flos-aquae, and Nostoc sp. algae revealed that higher toxicity was noticed at 240 min treatment time accompanied by lower toxicity with prolonging the treatment time for all selected algae except for Microcystis flos-aquae. In addition, novel two-phase mathematical models were successfully proposed to predict the accumulation of intermediates depending on their evolution profile.

Effects of aquaculture effluents on fate of 2,2',4,4',5-pentabromodiphenyl ether (BDE-99) in contaminated mangrove sediment planted with Kandelia obovata.

The problems of aquaculture effluent (AE) and polybrominated diphenyl ethers (PBDEs) are common in coastal areas. The fate of 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), a dominant PBDE congener, in mangrove sediments and the effects of AE on it have never been reported. A 12-months microcosm study was conducted and more than 55% of the BDE-99 in contaminated sediment was removed at the end. The removal percentages depended on treatments, with the highest removal in the treatment planted with Kandelia obovata (Ko) and irrigated with AE (WPAE), followed by Ko planted but without AE (WP), unplanted with AE (NPAE) and unplanted without AE (NP). Hydroxylation of BDE-99 was observed in all treatments, with a preference in the para position bromine substitution, followed by meta position and the lowest was ortho bromine substitution. BDE-99 was also debrominated to lower brominated congeners like tri- and di-BDEs congeners. Different from parent BDE-99, ortho-substituted BDE-28 and -15 were more dominant than that of para-substituted BDE-17 and -7, suggesting that para-substituted congeners could further be debrominated. The AE addition enhanced root uptake of PBDEs in Ko. These findings suggested that the addition of AE and planting Ko could be an effective way to remedy BDE-99 in contaminated sediments.

Could mangrove plants tolerate and remove BDE-209 in contaminated sediments upon long-term exposure?

Polybrominated diphenyl ethers (PBDEs) such as BDE-209, the commonest congener, are known to be toxic. A 24-months study using mangrove mesocosms with mixed mangrove species, namely Avicennia marina (Am), Aegiceras corniculatum (Ac) and Kandelia obovata (Ko), or without any plant was conducted to examine toxicity, removal, translocation and uptake of BDE-209. At month 24, BDE-209 stimulated the production of root superoxide radical (O2-*), and leaf and root malondialdehyde (MDA) of Ko, enhanced leaf O2-* of Ac, but did not affect the production of O2-* and MDA in Am. These findings indicated that the tolerance to BDE-209 was species-specific, with Am being the most tolerant and Ko the most sensitive species. In leaf and root, BDE-209 stimulated peroxidase (POD) activity in both Ac and Ko, and superoxide dismutase (SOD) in Am. After 24-months, more than 60% and 40% of BDE-209 in contaminated sediments were removed in planted and unplanted groups, respectively, with more PBDEs in upper than bottom sediment layers. This study demonstrates that planting tolerant species such as Avicennia marina with high uptake could remedy PBDEs in contaminated sediments.

Growth and antioxidative response of two mangrove plants to interaction between aquaculture effluent and BDE-99.

Mangroves are subject to contamination of polybrominated diphenyl ethers (PBDEs) due to waste and wastewater disposal, and aquaculture effluent (AE) from nearby aquaculture activities. However, the response of mangrove plants to these two stresses and their interaction has seldom been reported. A six-month microcosm study, planted with either Kandelia obovata (Ko) or Avicennia marina (Am), the two most dominant species in South China mangrove swamps, was conducted to investigate the effects of BDE-99, and the interactions of BDE-99 (one of the most abundant PBDE congeners) and AE on growth and physiological responses of these plants. In addition to mixed stressors, both stressors were also applied individually. Results showed that Avicennia was more tolerant to BDE-99 contamination than Kandelia, as reflected by the reduced biomass, but increased superoxide radical (O2-⁎) release and malondialdehyde (MDA) content in Kandelia. Addition of AE alleviated toxicity of BDE-99 in Kandelia by promoting biomass but lowering oxidative stress and MDA production. The hormesis model also demonstrated that the interaction between BDE-99 and AE on leaf and root MDA and O2-⁎ content in both Kandelia and Avicennia were mostly antagonistic. Activities of catalase (CAT), superoxide dismutase (SOD) and peroxidase (POD) in both leaf and root of Kandelia were reduced by BDE-99. On the contrary, BDE-99 significantly enhanced the three enzyme activities in Avicennia root at month 3. Addition of AE also significantly enhanced root CAT, POD and SOD activities, and leaf SOD in both plant species to remove excess ROS produced under BDE-99 exposure. These results indicated that the tolerance of mangrove plants to oxidative stresses depended on antioxidative enzymes that were inducible.

A combined effect of polybrominated diphenyl ether and aquaculture effluent on growth and antioxidative response of mangrove plants.

Mangrove wetland receives nutrient-rich aquaculture effluent (AE) from nearby farming activities and polybrominated diphenyl ethers (PBDEs) from the production and usage of flame retardants. The effects of BDE-209 (the most common PBDE congener), AE and their combination on two true mangrove species, namely Kandelia obovata and Avicennia marina, were compared in a 6-month microcosm study. Results showed that K. obovata was more sensitive to these contaminants than A. marina, as reflected by its enhanced production of leaf superoxide (O2-∗) by BDE-209 and root malondialdehyde (MDA) by the combined BDE-209 and AE treatment. The hormesis model showed that the combined effects of BDE-209 and AE on the production of MDA, O2-∗ and catalase (CAT) activity in K. obovata and A. marina were antagonistic except root O2-∗ in A. marina, but the effects on leaf superoxide dismutase (SOD) activity in K. obovata, and root SOD and peroxidase (POD) activities in A. marina were synergistic. The defense mechanisms differed between treatment and species. The activities of SOD and POD were the main mechanisms to defend K. obovata and A. marina against BDE-209, but CAT in K. obovata and POD in A. marina were more important in defending the combined BDE-209 and AE treatment.

Biochar accelerates microbial reductive debromination of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) in anaerobic mangrove sediments.

A common congener of polybrominated diphenyl ethers, 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), is a prevalent, persistent and toxic pollutant. It could be removed by reduction debromination by microorganisms but the rate is often slow. The study hypothesized that spent mushroom substrate derived biochar amendment could accelerate the microbial reductive debromination of BDE-47 in anaerobic mangrove sediment slurries and evaluated the mechanisms behind. At the end of 20-week experiment, percentages of residual BDE-47 in slurries amended with biochar were significantly lower but debromination products were higher than those without biochar. Such stimulatory effect on debromination was dosage-dependent, and debromination was coupled with iron (Fe) reduction. Biochar amendment significantly enhanced the Fe(II):Fe(III) ratio, Fe(III) reduction rate and the abundance of iron-reducing bacteria in genus Geobacter, thus promoting bacterial iron-reducing process. The abundances of dehalogenating bacteria in genera Dehalobacter, Dehalococcoides, Dehalogenimonas and Desulfitobacterium were also stimulated by biochar. Biochar as an electron shuttle might increase electron transfer from iron-reducing and dehalogenating bacteria to PBDEs for their reductive debromination. More, biochar shifted microbial community composition in sediment, particularly the enrichment of potential PBDE-degrading bacteria including organohalide-respiring and sulfate-reducing bacteria, which in turn facilitated the reductive debromination of BDE-47 in anaerobic mangrove sediment slurries.

Antioxidative response of Kandelia obovata, a true mangrove species, to polybrominated diphenyl ethers (BDE-99 and BDE-209) during germination and early growth.

A 3-months microcosm experiment with mangrove sediment spiked with PBDEs and planted with propagules of Kandelia obovata was conducted to investigate PBDE toxicity and antioxidative responses of the germinated seedlings. BDE-99 suppressed germination rate, leaves formation and growth of mangrove seedlings. The leaves and roots of BDE-99 treated seedlings had significantly higher superoxide (O2-) release, malondialdehyde (MDA) and total polyphenol (TP) content, and peroxidase (POD) activity than the control. BDE-209 increased activities of all three antioxidative enzymes, catalase (CAT), POD and superoxide dismutase (SOD) in roots, but in leaves, only CAT activity was stimulated. The MDA content of BDE-209 treated seedlings was less than the control. PBDEs were found in plant tissues of the treated seedlings. These results indicated that even though PBDEs were taken up in tissues, K. obovata, due to its antioxidative defense enzymes, could tolerate PBDEs and could be used for the bioremediation of PBDE-contaminated environments.

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 polybrominated diphenyl ethers and plant species on nitrification, denitrification and anammox in mangrove soils.

Little is known about polybrominated diphenyl ethers (PBDEs) and planting affect biogeochemical processes, and their impact on microbial nitrogen (N) transformation in soil. A 12-month microcosm experiment was conducted to understand the effects of a mixture of PBDEs at two contamination levels, 2 and 20 mg kg(-1)dry weight representing low and high soil contamination, respectively, using two mangrove plant species, namely Kandelia obovata (Ko) and Bruguiera gymnorrhiza (Bg), on nitrification, denitrification and anammox in mangrove soils. No significant changes in these N transformation processes were found at month 3 and at a low level of PBDEs in both plant species, suggesting that short-term exposure to 2 mg kg(-1) contamination did not affect microbial N transformation. At month 12, a high level of PBDE contamination significantly decreased the nitrification potential activity and the copy numbers of archaeal amoA and bacterial amoA gene in Ko soil, but such inhibitory effect was not significant in Bg soil. On the contrary, the denitrification-related parameters, including the activities of nitrate reductase and nitrite reductase, potential denitrification activity and copy numbers of nirK, nirS and nosZ gene, were stimulated by a high level of PBDE contamination in both Ko and Bg soils, and the stimulation was higher in the more anaerobic Bg soil. Different from denitrification, a high level of PBDE contamination decreased the copy numbers of anammox bacterial 16S rRNA gene in Bg soil but not in Ko soil; this was possibly related to the lower nitrate concentration in Bg soil that might inhibit the growth of anammox bacteria. These results indicated that the effects of PBDEs on microbial N transformation were plant species-specific, with the nitrifying microorganisms in Ko soil more susceptible to PBDE contamination, while denitrification and anammox in Bg soil were more sensitive.