Heavy metals and polycyclic hydrocarbon compounds in benthic organisms of the Upper Gulf of Thailand

Concentrations of heavy metals and polycyclic aromatic hydrocarbons (PAHs) were measured in bivalves collected in the Upper Gulf of Thailand. PAHs detected included acenaphthene, acenaphthylene, benzo[a]pyrene, fluoranthene, methylphenanthrene, phenanthrene and triphenylene. Benzo[a]pyrene was detected in all species at concentrations varying from 1.0 to 8.2 ng·g^?1. Concentrations of cadmium, cobalt, copper, lead and nickel were significantly lower in bivalves from the Gulf than in green mussels collected from the mouth of the Chao Phraya River. No correlation was found between metal concentrations in animals and sediment, with the exception of copper. Copper concentrations in polychaetes and clams appeared to correlate with the copper:iron ratio of sediments. High rates of degradation were observed when radiolabelled chlorobenzene, phenanthrene and chrysene were added to water and sediment of the Chao Phraya River. Rates were lower in the waters and sediment of the Gulf of Thailand. The calculated half-lives of chlorobenzene in the Gulf of Thailand and the Chao Phraya River were about 130 and 68 days, respectively.     

PAHs contamination and bacterial communities in mangrove surface sediments of the Jiulong River Estuary, China

Sixteen sediment samples collected from eight transects in a mangrove swamp of the Jiulong River Estuary, Fujian, China were investigated for their content of polycyclic aromatic hydrocarbons (PAHs) and the biodegradation potential of the indigenous microorganisms. The bacterial community structures in the mangrove sediments and in enrichment cultures were also investigated. The results showed that the total PAHs concentration of mangrove sediments ranged from 280 to 1074 ng g(-1) dry weight, that the PAHs composition pattern in the mangrove sediments was dominated by high molecular weight PAH components (4-6 rings), and that Benzo[ghi]perylene and Indeno[1,2,3-cd]pyrene were the most dominant at different stations. Abundant PAH-degrading bacteria were found in all the stations, the values of phenanthrene-degrading bacteria ranged from 5.85 x 10(4) to 7.80 x 10(5) CFU g(-1) dry weight, fluoranthene-degrading bacteria ranged from 5.25 x 10(4) to 5.79 x 10(5) CFU g(-1) dry weight, pyrene-degrading bacteria ranged from 3.10 x 10(4) to 6.97 x 10(5) CFU g(-1) dry weight and the benzo(a)pyrene-degrading bacteria ranged from 5.25 x 10(4) to 7.26 x 10(5) CFU g(-1) dry weight. DGGE analysis of PCR-amplified 16S rDNA gene fragments confirmed that there was a remarkable shift in the composition of the bacterial community due to the addition of the different model PAH compound phenanthrene (three ring PAH), fluoranthene(four ring PAH), pyrene(four ring PAH) and benzo(a)pyrene(five ring PAH) during enrichment batch culture. Eleven strains were obtained with different morphology and different degradation ability. The presence of common bands for microbial species in the cultures and in the native mangrove sediment DNA indicated that these strains could be potential in situ PAH-degraders.     

Comet assay for the detection of genotoxicity in blood cells of flounder (Paralichthys olivaceus) exposed to sediments and polycyclic aromatic hydrocarbons

To investigate the genotoxic effect of marine sediments on aquatic organism, sediment samples were collected from 13 sites along the coast of Gwangyang Bay (Korea). Concentrations of polycyclic aromatic hydrocarbons (PAHs) in sediments were determined and the relationship between exposure of flounder blood cells to sediment extracts and DNA single-strand breakage in the blood cells was examined using the comet assay. Levels of DNA damage were proportionally increased by exposure concentration and the highest sediment-associated DNA damage was observed at the station showing the highest PAHs contamination. DNA damage in blood cells exposed to five types of PAHs (benzo[a]pyrene, fluoranthene, anthracene, pyrene and phenanthrene) and in flounder (Paralichthys olivaceus) exposed to benzo[a]pyrene (BaP) for 0, 2 and 4 days were assessed by measuring comet tail length. The tail lengths of five PAHs-exposed groups at 50 and 100 ppb were significantly different from the non-exposed group, and the genotoxic effect of BaP correlated with both concentration and duration of exposure. Throughout the study, significant differences in DNA breakage were recorded between cells exposed to sediment extracts or PAHs and non-exposed control. This study demonstrated the comet assay as a successful tool in monitoring contamination of marine sediments and assessing genotoxicity of PAHs in marine organisms, either in vitro or in vivo.     

Effectiveness of bacterial inoculum and mangrove plants on remediation of sediment contaminated with polycyclic aromatic hydrocarbons

The remediation of mangrove sediment contaminated with mixed polycyclic aromatic hydrocarbons (PAHs) having 3-, 4- and 5-rings by natural attenuation, bioaugmentation, phytoremediation and its combination was compared by greenhouse microcosm studies. At Days 90 and 154, the decreases of PAHs in contaminated mangrove sediment by phytoremediation, planted with one-year old Aegiceras corniculatum, and bioaugmentation, the inoculation of PAH-degrading bacterial strains isolated from mangrove sediment, either SCSH (Mycobacterium parafortuitum) or SAFY (Sphingobium yanoikuyae), were not better than that by natural attenuation (the non-vegetated and un-inoculated microcosms). The populations of SCSH and SAFY in sediment could not be maintained even with repeated inoculation, suggesting that the two isolates were not able to compete with the indigenous microbes and had little enhancement effect. Although some PAHs were accumulated in roots, root uptake only accounted for <15% of the spiked PAHs and the effect of plants on remediation were also insignificant. At the end of the 154-day experiment, the mass balance calculation revealed that the overall losses of PAHs by phytoremediation were comparable to that by bioaugmentation but were lower than that by natural attenuation, especially for the high molecular weight PAHs. Under natural attenuation, around 90% fluorene, 80% phenanthrene, 70% fluoranthene, 68% pyrene and 32% benzo[a]pyrene in contaminated sediment were removed. These results demonstrated that the mangrove sediment itself had sufficient indigenous microorganisms capable of naturally remedying PAH contamination.     

Marine-derived filamentous fungi and their potential application for polycyclic aromatic hydrocarbon bioremediation

Eight marine-derived fungi that were previously selected for their abilities to decolorize RBBR dye were subjected to pyrene and benzo[a]pyrene degradation. The fungus Aspergillus sclerotiorum CBMAI 849 showed the best performance with regard to pyrene (99.7%) and benzo[a]pyrene (76.6%) depletion after 8 and 16 days, respectively. Substantial amounts of benzo[a]pyrene (>50.0%) depletion were also achieved by Mucor racemosus CBMAI 847. Therefore, these two fungal strains were subjected to metabolism evaluation using the HPLC-DAD-MS technique. The results showed that A. sclerotiorum CBMAI 849 and M. racemosus CBMAI 847 were able to metabolize pyrene to the corresponding pyrenylsulfate and were able to metabolize benzo[a]pyrene to benzo[a]pyrenylsulfate, suggesting that the mechanism of hydroxylation is mediated by a cytochrome P-450 monooxygenase, followed by conjugation with sulfate ions. Because these fungi were adapted to the marine environment, the strains that were used in the present study are considered to be attractive targets for the bioremediation of saline environments, such as ocean and marine sediments that are contaminated by PAHs.     

太湖沉积物理化性质及营养盐的时空变化

在不同季节,采集太湖梅梁湾和贡湖湾沉积物柱状样,研究沉积物Eh、pH、总氮、总磷以及有机质四季垂向剖面分布变化特征.研究结果表明,在表层下(0-3 cm),Eh随沉积物深度的增加迅速下降,很快进入还原状态.沉积物剖面上pH变化幅度不大,在6.4-7.8之间,冬季沉积物pH均有所降低.太湖沉积物中含有丰富的营养盐,总氮和总磷最高浓度分别为2.68和0.864 mg/g,其剖面分布特征表明,沉积物表层总氮和总磷含量远高于底层,其含量随深度增加而降低,但四季变化趋势不明显.沉积物中有机质含量在10 cm以上变化幅度较大,随着沉积物深度的增加,有机质含量明显减少,季节变化幅度不大.比较不同采样点发现,位于梅梁湾生态系统试验区内的S1位点沉积物氮磷内源负荷最大.     

Biliary fluorescent aromatic compounds (FACs) measured by fixed wavelength fluorescence (FF) in several marine fish species from the NW Mediterranean

The fixed wavelength fluoresce (FF) method was used to estimate the levels of fluorescent aromatic compounds (FACs) in the bile of fourteen fish species of commercial and/or ecological interest. Sampling was carried out in the NW Mediterranean at depths ranging from 50 to 1000 m during four seasonal cruises. During the summer sampling period, some species were also collected from another site (Vilanova fishing grounds) for comparison. Baseline levels of the polycyclic aromatic hydrocarbons (PAHs) naphthalene, phenanthrene, pyrene and benzo[a]pyrene were measured. Some seasonality was observed, with reduced FF levels in summer and no differences among sites, consistent with sediment PAH levels. We discuss our results in relation to fish phylogeny, season, depth, diet, trophic level and swimming capacity. Overall FF levels indicated differences among species; the suprabenthic feeders from shallow and deep communities, and Mullus barbatus in particular, displayed elevated FF values and are potential candidates for additional monitoring studies.     

Baseline levels of benzo(a)pyrene in southern California mussels

Marine mussels accumulate the carcinogen benzo(a)pyrene from contaminated environments. Baseline studies in California indicate that levels of the carcinogen in mussels are at or near zero, except in areas of human activity. This finding runs counter to previous suggestions that benzo(a)pyrene is widely distributed in marine organisms.     

Biodegradation of polycyclic aromatic hydrocarbons by a halotolerant bacterial strain Ochrobactrum sp. VA1

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants in the environment and are derived from both man-made and natural resources. The present study is focused on the degradation of PAHs by a halotolerant bacterial strain under saline conditions. The bacterial strain VA1 was isolated from a PAH-degrading consortium that was enriched from marine water samples that were collected from different sites at Chennai, India. In the present study, a clearing zone formed on PAH-amended mineral salt agar media confirmed the utilization of PAH by the bacterial strain VA1. The results show that the strain VA1 was able to degrade anthracene (88%), phenanthrene (98%), naphthalene (90%), fluorene (97%), pyrene (84%), benzo(k)fluoranthene (57%) and benzo(e)pyrene (50%) at a 30 g/L NaCl concentration. The present study reveals that the VA1 strain was able to degrade PAHs in petroleum wastewater under saline conditions. The promising PAH-degrading halotolerant bacterial strain, VA1, was identified as Ochrobactrum sp. using biochemical and molecular techniques.     

Composition and sources of pollutant hydrocarbons in the Severn Estuary

Hydrocarbon distributions in sediment from the Severn Estuary can be explained mainly in terms of a pollutant origin. The aliphatic hydrocarbon distribution is similar to that found in biodegraded crude oils. The distribution of polycyclic aromatic hydrocarbons, including the carcinogen benzo(a)pyrene, is similar to that derived from the pyrolysis of fossil fuels, especially petroleum.     

Cooxidation of Benzo(a)pyrene and Phenols on Activated Sludges

In the presence of the cancerogenic benzo(a)pyrene (4 × 10^?7 mole/1) the rate the of biochemical oxidation of phenols and a mixture of oil-shale alkylresorcinols (5 × 10^?5 mole/1) on activated sludges adapted to these phenols is reduced up to 30%. The oxidation of benzo(a)pyrene occurs at a high rate, the rate constant on both sludges being 6.8 × 10⁸ mole/1 · sec and exceeds the index of the processes of its selfpurification by two orders. The high efficiency of the biooxidation of benzo(a)pyrene is retained at a repeated use of the same biomass, thus no additional regeneration being needed. Some products of the, biooxidation of benzo(a)pyrene, such as 1,6- and 3,6-quinone, derivatives of chrysene and naphthalene, are identified.     

Cooxidation of Carcinogenic Benzo(a) Pyrene and Phenols by Horseradish Peroxidase (Armoracia lapathifolia)

The catalytic activity of horseradish (Armoracia lapathifolia) peroxidase in the oxidation reactions of benzo(a)pyrene (BP) and phenols, separately and in admixture, has been studied. Experiments were carried out with model phenols from industrial sewage (phenol, m-, p-cresols, catechol, hydroquinone, resorcinol, orcinol), keeping to the real concentration ratio of reagents, 0.5 mM for phenols, 0.1 nM for benzo(a)pyrene. The total oxidation process for all reagents tested is described by the second-order formal kinetic equation up to 60 … 90% of their conversion. Addition of peroxidase increases the rate of oxidation of benzo(a)pyrene and phenols 2 … 6 times as compared with the control test (with hydrogen peroxide), whereas a linear dependence of the rate of benzo(a)pyrene oxidation on the enzyme concentration is observed. By cooxidation a mutual inhibition of benzo(a)pyrene and phenols is established whose degree depends on the phenol-chemical structure and varies in the range of 23 … 58% for BP under the influence of phenols and 35 … 80% for phenols under the influence of benzo(a)pyrene. The results obtained permit a supposition that peroxidase containing plants are capable of simultaneously transforming carcinogenic benzo(a)pyrene and toxic phenols in water reservoirs and in the soil, thus promoting the detoxication of environment.     

Polycyclic aromatic hydrocarbons in coastal sediments of southwest Taiwan: An appraisal of diagnostic ratios in source recognition

Fifty-seven surface sediment samples were collected from the coast of southwest Taiwan and analyzed for polycyclic aromatic hydrocarbons (PAHs). Concentrations of total PAHs (28 PAH compounds) ranged from 15 to 907 ng g⁻¹ dry weight. Diagnostic ratios showed that PAHs in the sediments of the Gaoping estuary were predominantly of petroleum origin, whereas sediments from the Kaohsiung coast contained principally combustion-derived PAHs. Principal component analysis indicated that emissions from automobiles and coal burning were the main sources of combustion-derived PAHs. The relatively high ratios of perylene/penta-aromatic PAH isomers in sediments from the Tainan coast and some off-shore stations on the Kaohsiung coast suggest a significant diagenetic PAH contribution. The study shows that certain diagnostic ratios are useful and sensitive in delineating the distribution of PAHs from specific sources in southwest Taiwan. The phenanthrene/anthracene ratio is a better indicator than the methylphenanthrenes/phenanthrene ratio for tracing petrogenic PAHs, and the benzo(a)anthracene/chrysene and indeno(1,2,3-c,d)pyrene/benzo(g,h,i)perylene ratios are more specific than the benzo(a)pyrene/benzo(e)pyrene and benzo(b)fluoranthcene/benzo(k)fluoranthcene ratios in distinguishing PAHs from various pyrogenic sources.     

Role of a moderately halophilic bacterial consortium in the biodegradation of polyaromatic hydrocarbons

Polycyclic aromatic hydrocarbons are ubiquitous pollutants in the environment, and most high molecular weight PAHs cause mutagenic, teratogenic and potentially carcinogenic effects. While several strains have been identified that degrade PAHs, the present study is focused on the degradation of PAHs in a marine environment by a moderately halophilic bacterial consortium. The bacterial consortium was isolated from a mixture of marine water samples collected from seven different sites in Chennai, India. The low molecular weight (LMW) PAHs phenanthrene and fluorine, and the high molecular weight (HMW) PAHs pyrene and benzo(e)pyrene were selected for the degradation study. The consortium metabolized both LMW and HMW PAHs. The consortium was also able to degrade PAHs present in crude oil-contaminated saline wastewater. The bacterial consortium was able to degrade 80% of HMW PAHs and 100% of LMW PAHs in the saline wastewater. The strains present in the consortium were identified as Ochrobactrum sp., Enterobacter cloacae and Stenotrophomonas maltophilia. This study reveals that these bacteria have the potential to degrade different PAHs in saline wastewater.     

Vitamin B12 and Reduced Titanium for Remediation of Residual Chlorinated Solvents: Field Experiment

A first pilot-scale field experiment using vitamin B₁₂ and reduced titanium was conducted in an in situ vertical circulation column at CFB Borden. The objective of the experiment was to test the applicability of the technology for restoring aquifer source zones contaminated by chlorinated solvents—tetrachloroethene (PCE) and 1,1,1-trichloroethane (1,1,1-TCA)—in a mixture of dense nonaqueous phase liquids (DNAPLs). Vitamin B₁₂ promotes the reductive dechlorination of chlorinated organics. A highly reducing and slightly alkaline environment must be maintained (Eh < - 480 mV and 7 < pH < 9) to maximize the rate of degradation. In this field test, PCE and 1,1,1-TCA degraded to a limited extent under experimental conditions, with 1,1,1-TCA degrading more readily. Indigenous bacteria were found to metabolize citrate, which caused titanium to precipitate, limiting degradation. The addition of glucose at the end of a second field season effectively limited citrate degradation and helped recover the optimal redox potential by keeping reduced titanium in solution. A laboratory column was used to confirm field results. The column also produced a significant biomass, which provided an additional source of organic carbon onto which the solvents sorbed.     

Heavy metals mobility in harbour contaminated sediments: the case of Port-en-Bessin

Metallic contaminants associated with sediments showed various behaviours depending on physicochemical conditions. A contaminated sediment core from a harbour in the Bay of Seine was sampled to derive information about metal solubilization from anoxic sediment. In these anaerobic surroundings, physicochemical processes depended on the organic matter cycle, on vertical variation of redox conditions and on precipitation conditions of iron and manganese. In the studied core, anoxic conditions were developed at -15 cm depth. A three-step sequential extraction procedure, modified from the BCR method (now the SM&T), was applied to the anoxic sediment in order to evaluate the potential mobility of fixed metals. Zinc was the most labile metal, recovered in the first extraction stages, and was associated with the non-residual fraction of sediment. Lead was the least labile metal, with up to 70% associated with the residual fraction of the sediment. Copper was associated with organic matter, and its mobility was controlled by the concentration and degradation of the organic fraction. Discharge of organic-rich dredged sediments at sea results in degradation of contained organic matter and may affect the environmental impact of these metals significantly. These results therefore help to improve the waste management of such contaminated sediments.     

DDT, PAH and PCB in sediments from the intertidal zone of the Bohai Sea and the Yellow Sea

Current contents of persistent organic contaminants, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and the congeners (naphthalene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo(a)anthracene, benzo(a)pyrene and benzo(e)pyrene), DDTs and metabolites in the intertidal sediments of the Bohai Sea and the Yellow Sea were studied. The mean levels of DDTs, PAHs and PCBs were 177.52, 877.2 and 3.4 ng g-1 dry weight, respectively. The spatial trends of the contaminant residue levels were analysed too.     

Distribution and source differentiation of PAHs and PCBs among size and density fractions in contaminated harbor sediment particles and their implications in toxicological assessment

Sediment samples collected from Kaohsiung Harbor (Taiwan) were analyzed for 15 priority polycyclic aromatic hydrocarbons (PAHs) and 118 individual polychlorinated biphenyl (PCB) congeners in various particle size fractions and two density fractions. The PAHs in the low density fraction were a much more sensitive and effective indicator of the PAH source than those in the sediment as a whole. Hierarchical cluster analysis of PAH analytes in the low density sediments revealed significant differences in compositional patterns between locations and among size fractions. In the sediment samples from both study sites, the low density fraction particles had up to 155 and 150 times higher concentrations of PAHs and PCBs, respectively, than those in the corresponding high density fractions. In addition, the total toxic benzo[a]pyrene and 2,3,7,8-tetrachlorodibenzodioxin (TCDD, dioxin) equivalents in the sediment low density fractions were much higher (up to 170 and 273 times, respectively) than the corresponding high density fractions.     

Oxidation of Benzo(a) Pyrene Catalyzed by Phenol Oxidases of Alga Nitella sp. and Potato Tubers

The kinetics of oxidation of carcinogenic benzo(a)pyrene (0.1 nM solution in phosphate buffer) catalyzed by enzyme protein of soil and water plants (potato tubers and alga Nitella sp.) has been studied. The benzo(a)pyrene oxidation rate is determined by the phenoloxidase activity of the enzyme protein from both sources to an equal degree and expressed by the Michaelis-Menten equation. The values for k_cat and apparent K_m were (0.97 ± 0.14) Ms^?1 and 33 ± 6 μM, respectively. The presence of other compounds (including protein substances) in acetone preparations of potato tubers considerably suppresses its catalytic activity in relation to benzo(a)pyrene. Consequently, in the polluted biosphere some water plants, such as alga Nitella sp., and potato tuber can transform carcinogenic benzo(a)pyrene (BP). As oxidation products, all three BP-quinones, i.e. 1,6-, 3,6-and 6,12-diones, were identified.     

PAH-degrading microbial consortium and its pyrene-degrading plasmids from mangrove sediment samples in Huian, China

PAH-degrading microbial consortium and its pyrene-degrading plasmids were enriched from the sediment samples of Huian mangroves. The consortium YL showed degrading abilities of 92.1%, 87.6%, 92.3%, and 95.8% for pyrene, fluoranthene, phenanthrene, and fluoene at 50 mg l(-1) after 21 days incubation, respectively. The dynamics of pH changes in the cultures was consistent with that of PAH concentration change. Bacillus cereus Py5 and Bacillus megaterium Py6 were isolated from the consortium and observed consuming 65.8% and 33.7% of pyrene (50 mg l(-1)) within three weeks, respectively. The enriched Escherichia coli DH5alpha cells containing the plasmids of YL were demonstrated to degrade 85.7% of the original pyrene concentration at the 21st day.