Effects of photodegradation of dissolved organic matter on the binding of benzo(a)pyrene

Dissolved organic matter (DOM) in natural waters can bind various organic pollutants, and the affinity of this binding is strongly influenced by the chemical characteristics of the DOM and water pH. This study examined the effects of photochemically induced alteration of the DOM's chemical properties and water pH on the binding of benzo(a)pyrene (BaP). Time- and pH-series of solar-simulated irradiations were performed on a natural water sample and aqueous DOM solutions prepared from aquatic and soil humic substances. The binding affinity of BaP, expressed as a partition coefficient of a compound to DOM, decreased substantially after the DOM samples were irradiated over environmentally relevant radiation doses and pH ranges. The lowering of the pH due to the photoproduction of acidic products often partly offsets the reduction of the binding affinity caused by direct photoalteration of the DOM's chemical structure. The decrease of the binding affinity, after correction for the photoinduced pH change, was positively correlated with the decrease in the molecular weight and the aromaticity of the DOM in the course of irradiation. Increasing O(2) abundance accelerated the decrease of the binding affinity as a result of enhanced DOM photodegradation. Visible light played a more important role in reducing the molecular weight and aromaticity of the DOM than in reducing the content of dissolved organic carbon (DOC) via photoremineralization while the reverse was true for UV radiation, indicating that photochemical reduction of the binding affinity may occur in natural waters at depths greater than UV radiation can reach. A decrease of the affinity of DOM for binding BaP will increase the free dissolved fraction of BaP and thus its availability and toxicity to aquatic organisms. The results from this study may have similar implications for organic pollutants other than BaP.     

Changes in Lumbriculus variegatus metabolites under hypoxic exposure to benzo(a)pyrene,chlorpyrifos and pentachlorophenol: Consequences on biotransformation

The regulation of endogenous metabolites is still not fully understood in aquatic invertebrates exposed concurrently to toxicants and hypoxia. Despite the prevalence of hypoxia in the aquatic environment, toxicity estimations seldom account for multiple stressors thereby differing from natural conditions. In this study, we examined the influence of hypoxia (<30% O₂) on contaminant uptake and the composition of intracellular metabolites in Lumbriculus variegatus exposed to benzo(a)pyrene (B(a)P, 3 μg L⁻¹), chlorpyrifos (CPF, 100 μg L⁻¹) or pentachlorophenol (PCP, 100 μg L⁻¹). Tissue extracts of worms were analyzed for 123 metabolites by gas chromatography–mass spectrometry and metabolite levels were then related to treatments and exposure time. Hypoxia markedly increased the accumulation of B(a)P and CPF, which underlines the significance of oxygen in chemical uptake. The oxygen effect on PCP uptake was less pronounced. Succinate and glycerol-3-phosphate increased significantly (p < 0.0001) following hypoxic treatment, whereas sugars, cysteine, and cholesterol were effectively repressed. The buildup of succinate coupled with the corresponding decline in intracellular 2-oxo- and 2-hydroxy glutaric acid is indicative of an active hypoxia inducible factor mechanism. Glutamate, and TCA cycle intermediates (fumarate, and malate) were disturbed and evident in their marked suppression in worms exposed concurrently to hypoxia and PCP. Clearly, hypoxia was the dominant stressor for individuals exposed to B(a)P or CPF, but to a lesser extent upon PCP treatment. And since oxygen deprivation promotes the accumulation of different toxicants, there may be consequences on species composition of metabolites in natural conditions.     

Metabolism of benzo(a)pyrene in rat by oral administration

Orally administered ³H-benzo(a)pyrene (BP) was concentrated in liver, kidney and lung of rat. Liver contained BP-diols, BP-quinones and 3-hydroxy-BP, and extremely high amounts of BP-quinones and unmetabolized BP were found in lung until after 7 hr of administration. In kidney, BP-quinones and BP-diols were major metabolites, but not BP or 3-hydroxy-BP. Low level of metabolites as conjugates with glucuronate and more polar compounds were also detected in kidney. These results suggested that an orally administered BP was metabolized to BP-diols and 3-hydroxy-BP mainly in liver, to BP-quinones mainly in lung, and to BP-diols and glucuronides or more polar compounds mainly in kidney.     

Effects of H19/SAHH/DNMT1 on the oxidative DNA damage related to benzo[a]pyrene exposure

Environmental Science and Pollution Research - The mechanisms that long noncoding RNA (lncRNA) H19 binding to S-adenosylhomocysteine hydrolase (SAHH) interacted with DNA methyltransferase 1 (DNMT1)...     

Effects of riboflavin on the phototransformation of benzo[a]pyrene

Riboflavin (Vitamin B2) is a natural dye-sensitizer habitually present in natural waters. Effects of riboflavin as photosensitizer on the transformation of benzo[a]pyrene (BaP) (10 microM) in the aqueous-organic solvent (water/acetonitrile/methanol 50/40/10) were investigated in this study. The photolysis half life of BaP in solution containing 50 microM riboflavin was 5 min, compared to 98 min in the absence of riboflavin. The rate of phototransformation of BaP increased as the concentration of riboflavin was raised from 10 microM to 100 microM under both natural sunlight and UVA irradiation. The half life of BaP in the presence of 50 microM riboflavin was 10.6 min and 43.1 min when exposed to visible range of natural sunlight and UVA irradiation respectively. Riboflavin decomposes under natural sunlight. Lumichrome, a principal photoproduct of riboflavin, was shown to photosensitize BaP under natural sunlight after photolysis of riboflavin. Our study indicated that other photoproducts from riboflavin, such as lumiflavin, were also involved in the phototransformation of BaP under sunlight when riboflavin diminished. The major photoproducts in the photolysis of BaP were identified as 1,6-benzo[a]pyrene-dione, 3,6-benzo[a]pyrene-dione, 6,12-benzo[a]pyrene-dione by using high performance liquid chromatography (HPLC). All these products were detected in the samples which were irradiated under different light sources and in the presence or absence of riboflavin. The possible phototransformation mechanism was discussed.     

Decomposition of benzo (a) pyrene deposited on glass fiber filters and exposed to sunlight

Measurements of Benzo (a) Pyrene deposited on glass fiber filters exposed to solar radiation indicate a time dependent exponential decrease. Possible impl$\text{i}$ cations of this phenomenon in the measurements of B(a)P in particulate samples are discussed.     

Effect of copper(II) on biodegradation of benzo[a]pyrene by Stenotrophomonas maltophilia

Benzo[a]pyrene (BaP) biodegradation by Stenotrophomonas maltophilia was studied under the influence of co-existed Cu(II) ions. About 45% degradation was achieved within 3 d when dealing with 1 mg L^?1 BaP under initial natural pH at 30 °C; degradation reached 48% in 2 d at 35 °C. Efficacy of BaP biodegradation reached the highest point at pH 4. In the presence of 10 mg L^?1 Cu(II) ions, the BaP removal ratio was 45% on 7th day, and maintained stable from 7 to 14 d at 30 °C under natural pH. The favorable temperature and pH for BaP removal was 25 °C and 6.0 respectively, when Cu(II) ions coexisted in the solutions. Experiments on cometabolism indicated that S. maltophilia performed best when sucrose was used as an additional carbon source. GC–MS analysis revealed that the five rings of BaP opened, producing compounds with one or two rings which were more bioavailable.     

Removal of pyrene and benzo(a)pyrene from contaminated water by sequential and simultaneous ozonation and biotreatment.

The removal of pyrene and benzo(a)pyrene from contaminated water by sequential and simultaneous ozonation-bioremediation techniques was investigated. During the sequential treatment, ozonation using 0.5 or 2.5 mg/L ozone was used as a pretreatment process, whereas, during the simultaneous treatment process, ozonation of hydrocarbon-contaminated water at a predetermined duration using 0.5 mg/L ozone was made in the presence of microbial biomass. Ozonation was not beneficial for the removal of pyrene. However, despite a decreased specific biodegradation rate, ozonation improved the overall elimination of benzo(a)pyrene during both treatment processes. The overall removal of benzo(a)pyrene increased from 23 to 91% after exposure of the water to 0.5 mg/L ozone for 30 minutes during the simultaneous treatment process and further to 100% following exposure to 2.5 mg/L ozone for 60 minutes during the sequential treatment mode, demonstrating the benefits of combined ozonation-biological treatment for the removal of polycyclic aromatic hydrocarbons.     

Responses of antioxidant systems and LPO level to benzo(a)pyrene and benzo(k)fluoranthene in the haemolymph of the scallop Chlamys ferrari

The effects of benzo(a)pyrene (BaP), benzo(k)fluoranthene (BkF) and their mixture on antioxidant enzyme activities and lipid peroxidation (LPO) levels of haemolymph of scallop (Chlamys ferrari) were studied. The superoxide dismutase (SOD) activities of 0.5 microg/L and 1.0 microg/L were significantly higher than controls (P<0.05), while it increased at beginning and then dropped (lower than controls) in the end at 10.0 microg/L and 50.0 microg/L PAHs groups. The catalase (CAT) activities were very little during the whole experimental time. The glutathione peroxidase (GPx) activities in each PAHs group all increased significantly (P<0.05). LPO levels all increased significantly (P<0.05) with time at each PAHs group except for the 0.5 microg/L group of less than hour 12. The toxicity of PAHs in a descending order was BaP>BkF>mixture of BaP and BkF. The changes in antioxidant enzyme activities and LPO level in haemolymph could reflect the detoxification functions and damage levels of whole organism.     

CMAQ simulations of the benzo(a)pyrene distribution over Europe for 2000 and 2001

In order to investigate benzo(a)pyrene (B(a)P) concentrations in ambient air in Europe and the respective deposition fields an expanded version of the Community Multiscale Air Quality (CMAQ) Modelling system has been used to simulate these fields for the years 2000 and 2001. Significant differences exist between different regions in Europe and between winter and summer concentrations. Modelled B(a)P concentrations are highest in Central Europe, South Ukraine and around Moscow. Wet deposition shows mainly the same regional distribution as the concentrations. Simulated concentrations and depositions are compared to measurements at selected sites of the EMEP network and of the German Federal Environmental Agencies. The measurements are on average underestimated by 50%. The temporal evolution and the regional distribution of B(a)P are captured by the model. In the approach presented here, particle bound B(a)P undergoes degradation by reactions with ozone. In order to assess the importance of the degradation process the results are compared to a model run where no degradation of particle bound B(a)P is considered. It was found that the inclusion of heterogeneous reactions of B(a)P with ozone results in a reduction of the modelled air concentration by approx. a factor of 5.     

Degradation mechanisms of benzo[a]pyrene and its accumulated metabolites by biodegradation combined with chemical oxidation

A high degradation extent of benzo[a]pyrene (BaP) should not be considered as the sole desirable criterion for the bioremediation of BaP-contaminated soils because some of its accumulated metabolites still have severe health risks to human. Two main metabolites of BaP, benzo[a]pyrene-1,6-quinone (BP1,6-quinone) and 3-hydroxybenzo[a]pyrene (3-OHBP) were identified by high performance liquid chromatography (HPLC) with standards. This study was the first time that degradation of both BaP and the two metabolites was carried out by chemical oxidation and biodegradation. Three main phases during the whole degradation process were proposed. Hydrogen peroxide-zinc (H(2)O(2)-Zn), the fungus - Aspergillus niger and the bacteria - Zoogloea sp. played an important role in the different phases. The degradation parameters of the system were also optimized, and the results showed that the effect of degradation was the best when fungus-bacteria combined with H(2)O(2)-Zn, the concentration range of BaP in the cultures was 30-120mg/l, the initial pH of the cultures was 6.0. However, as co-metabolites, phenanthrene significant inhibited the degradation of BaP. This combined degradation system compared with the conventional method of degradation by domestic fungus only, enhanced the degradation extent of BaP by more than 20% on the 12d. The highest accumulation of BP1,6-quinone and 3-OHBP were reduced by nearly 10% in the degradation experiments, which further proved that the combined degradation system was more effective as far as joint toxicity of BaP and its metabolites are concerned.     

Mutagenic nitrated benzo[a]pyrene derivatives in the reaction product of benzo[a]pyrene in NO2-air in the presence of O3 or under photoirradiation

In order to clarify the contribution of nitrated products to the direct-mutagenic activity of products of the reactions of benzo[a]pyrene in NO2-air under various conditions, heterogeneous reactions of BaP deposited on filter in the air containing 10 ppm of NO2 have been conducted in dark or under photoirradiation. The reaction products have been analyzed by gas chromatography and mutagenicity of the products fractionated by preparative HPLC was assayed for Salmonella typhimurium strains TA98 and YG1024 in the absence of S9 mix. 3,6-dinitrobenzo[a]pyrene and 1,3-dinitrobenzo[a]pyrene, which are strong direct-acting mutagens, largely contributed to the total direct-acting mutagenicity of the dark reaction products in NO2-air. On the other hand, both the dark reaction in the presence of O3 and the photoreaction in NO2-air resulted in the formation of much smaller amounts of nitrobenzo[a]pyrenes than that observed in the dark reaction in the absence of O3. These results show that the contribution of other direct-acting mutagens to the total direct-acting mutagenicity of the products in these reactions should be considered. Benzo[a]pyrene lactones were identified in a highly mutagenic fraction of the products of the dark reaction in the presence of O3 and photoreaction and a nitrobenzo[a]pyrene lactone was also identified in a highly mutagenic fraction of the dark reaction products in the presence of O3. Nitrated oxygenated benzo[a]pyrene derivatives such as nitrobenzo[a]pyrene lactone were considered to largely contribute to direct-acting mutagenicity of the products of the dark reaction in the presence of O3 and photoreaction.     

Effects of anthracene, pyrene and benzo[a]pyrene spiking and sewage sludge compost amendment on soil ecotoxicity during a bioremediation process

The fate of spiked anthracene, pyrene and benzo[a]pyrene in soil with or without sewage sludge compost was assessed during a 6-month bioremediation process simulating landfarming. Bioassays and physico-chemical analyses were employed to monitor toxicity change in soil samples and elutriates through ten sampling campaigns. Pearson product-moment correlation coefficient was determined to measure the strength of relationship between bioassays and physico-chemical analyses. The PAH dissipation in soil was enhanced after the first water addition, and the remaining amounts at the end of the experiment were positively correlated to the number of benzene rings and the presence of sewage sludge compost. Toxicity of soil elutriates to Daphnia magna was evident at early stages, originating exclusively from sewage sludge compost amendment. The lettuce root elongation was continuously inhibited by elutriates for all the treatments including control soil, probably due to high salinity or to unaddressed leachable phytotoxic compounds that were present in the experimental soil. The newly developed direct solid-phase chronic toxicity test using ostracod (Heterocypris incongruens) succeeded in evaluating the soil-bound PAH toxicity, as PAHs could not be detected in elutriates.     

Effects of alfalfa and organic fertilizer on benzo[a]pyrene dissipation in an aged contaminated soil

BACKGROUND: A climate-controlled pot experiment was conducted to investigate the effects of planting alfalfa and applying organic fertilizer on the dissipation of benzo[a]pyrene from an aged contaminated agricultural soil. RESULTS: Short-term planting of alfalfa inhibited the dissipation of benzo[a]pyrene from the soil by 8.9%, and organic fertilizer enhanced benzo[a]pyrene removal from the soil by 11.6% compared with the unplanted and unfertilized treatments, respectively. No significant interaction was observed between alfalfa and organic fertilizer on benzo[a]pyrene dissipation. Sterilization completely inhibited the removal of benzo[a]pyrene from the soil indicating that its degradation by indigenous microorganisms may have been the main mechanism of dissipation. Furthermore, significant positive relationships were observed between benzo[a]pyrene removal and the contents of soil ammonium nitrogen, nitrate nitrogen, and total mineral nitrogen at the end of the experiment, suggesting that competition between plants and microorganisms for nitrogen may have inhibited benzo[a]pyrene dissipation in the rhizosphere of alfalfa and the addition of organic fertilizer may facilitate microbial degradation of benzo[a]pyrene in the soil.     

Dissipation of available benzo[a]pyrene in aging soil co-contaminated with cadmium and pyrene

A microcosm experiment was conducted to investigate the dissipation of available benzo[a]pyrene (BaP) in soils co-contaminated with cadmium (Cd) and pyrene (PYR) during aging process. The available residue of BaP in soil was separated into desorbing and non-desorbing fractions. The desorbing fraction contributed more to the dissipation of available BaP than the non-desorbing fraction did. The concentration of bound-residue fraction of BaP was quite low across all treatments. Within the duration of this study (250 days), transformation of BaP from available fractions to bound-residue fraction was not observed. Microbial degradation was the dominant mechanism of the dissipation of available BaP in the soil. The dissipation of available BaP was significantly inhibited with the increment in Cd level in the soil. The addition of PYR (250 mg kg^?1) remarkably promoted the dissipation of available BaP without reducing Cd availability in the soil. The calculated half-life of available BaP in the soil prolonged with the increment in Cd level; however, the addition of PYR shortened the half-life of available BaP by 13.1, 12.7, and 32.8 % in 0.44, 2.56, and 22 mg Cd kg^?1 soils, respectively. These results demonstrated that the inhibiting effect of Cd and the promoting effect of PYR on the dissipation of available BaP were competitive. Therefore, this study shows that the bioremediation process of BaP can be more complicated in co-contaminated soils.     

Bioavailability of atrazine, pyrene and benzo[a]pyrene in European river waters.

Thirteen river waters and one humic lake water were characterized. The effects of dissolved organic matter (DOM) on the bioavailability of atrazine, pyrene and benzo[a]pyrene (B[a]P) was evaluated. Binding of the chemicals by DOM was analyzed with the equilibrium dialysis technique. For each of the water samples, 24 h bioconcentration factors (BCFs) of the chemicals were measured in Daphnia magna. The relationship between DOM and other water characteristics (including conductivity, water hardness and pH), and bioavailability of the chemicals was studied by performing several statistical analyses, including multiple regression analyses, to determine how much of the variation of BCF values could be explained by the quantity and quality of DOM. The bioavailability of atrazine was not affected by DOM or any other water characteristics. Although equilibrium dialysis showed binding of pyrene to DOM, the bioavailability of pyrene was not significantly affected by DOM. The bioavailability of B[a]P was significantly affected by both the quality and quantity of DOM. Multiple regression analyses, using the quality (ABS270 and HbA%) and quantity of DOM as variables, explained up to 70% of the variation in BCF of B[a]P in the waters studied.     

Uncertainty analysis of parameters for modeling the transfer and fate of benzo(a)pyrene in Tianjin wastewater irrigated areas

A Monte Carlo simulation for uncertainty analysis of three key parameters (local coal consumption rate Q(1L), dry deposition velocity of aerosol particulate Kp and biodegradation rate of benzo(a)pyrene in soil and sediment K(R3)) was conducted in this study. Results of the simulation indicate that the three parameters were influenced by uncertainty and that all equilibrium concentrations in the four bulk compartments and various sub-compartments were log-normally distributed. However, the results also indicated that among the six primary transfer fluxes, erosion associated with solids in soil and deposition associated with solids in water, along with output from sewers were also log-normally distributed, while deposition from air to soil and biodegradation in soil and sediment followed normal distributions. The effect of uncertainty on the model results of the three key parameters was derived using a comparison of upper and lower of confidence interval boundaries at the 95% level of confidence. The results reveal that uncertainty in the key parameters had a more significant influence on equilibrium concentrations of the chemical in the bulk compartments of soil and sediment than on concentrations in the other two bulk compartments, various sub-compartments and the six predominant transfer fluxes.     

Biomarker responses at different levels of biological organisation in crabs (Carcinus aestuarii) experimentally exposed to benzo(alpha)pyrene

The aim of this study was to validate a multi-trial biomarker approach for the evaluation of toxicological risk due to benzo(alpha)pyrene. Carcinus aestuarii, exposed to increasing concentrations of B(alpha)P in the water, was used as the bioindicator organism. A set of biomarkers were tested in order to: identify biological materials for biomarker and residue analysis; determine a group of sensitive techniques for the assessment of PAH contamination; investigate correlation between responses at different levels of biological organisation. The results underlined that BPMO activities in hepatopancreas and gills were a good biomarker of exposure to PAH-type compounds. B esterases activities in hemolymph and porphyrin patterns in excreta could be proposed as a non-destructive approach for evaluating chemical exposure in this species.     

Protective effect of silymarin on erythrocyte haemolysate against benzo(a)pyrene and exogenous reactive oxygen species (H2O2) induced oxidative stress

The present study was carried out to evaluate the in vitro antioxidant properties and protective effects of silymarin (milk thistle) in human erythrocyte haemolysates against benzo(a)pyrene [B(a)P], a potent carcinogenic chemical. Protective effect of silymarin was assessed in vitro by monitoring the antioxidant enzymes and malondialdehyde in three groups of haemolysates-(I) vehicle control (II) B(a)P incubated group and (III) B(a)P co incubated with silymarin. The effects of silymarin on lipid peroxidation (LPO) and antioxidant enzymes [superoxide dismutase; SOD, catalase; CAT, glutathione peroxidase; GPx, glutathione reductase; GR and glutathione-S-transferases; GST] were assessed on haemolysates. It was observed that specific activity of antioxidant enzymes were significantly decreased and the malondialdehyde levels were elevated when haemolysates were incubated with B(a)P. The protective effect of silymarin is elucidated by the significant reversal of the antioxidant enzymes and reduction in the levels of malondialdehyde. In addition, haemolysates were incubated with B(a)P for 45 min and the B(a)P metabolite, 3-hydroxy benzo(a)pyrene (3-OH-B(a)P) was detected using HPLC. An increased level of the metabolite was detected in group II. Whereas, when haemolysates were co-incubated with silymarin, the reactive metabolite 3-OH-B(a)P was not detectable which further confirms the protective role of silymarin. Generation of 3-OH-B(a)P in group II implicates the possibility of reactive oxygen species (O2- and H2O2) production in haemolysates during cytochrome P4501A1 (CYP1A1) mediated Phase-I-metabolism. Hence, we incubated the haemolysates with exogenous reactive oxygen species H2O2 and assessed the protective role of silymarin against H2O2. From the results of our study, it was suggested that silymarin possess substantial protective effect and free radical scavenging mechanism against environmental contaminants induced oxidative stress damages.     

Association of benzo(a)pyrene with dissolved organic matter: Prediction of Kdom from structural and chemical properties of the organic matter

The affinity of dissolved organic matter (DOM) for binding a polycyclic aromatic hydrocarbon, benzo(a)pyrene (BaP), was measured for 11 surface and ground waters and a commercial humic acid. The hydrophobic-acid (HbA) and hydrophobic-neutral (HbN) compositions of the DOM, solution absorptivity at 270nm (ABS₂₇₀), and DOM molar volumes were determined. Waters enriched in HbA material had a larger molar volume and higher aromatic content (as indicated by the ABS₂₇₀). There was a good correlation between the size and HbA content of the DOM from the different sources and the K_dom for binding BaP. An excellent predictive relationship (r² = 0.9) was demonstrated between the ABS₂₇₀ of a water and the K_dom for binding BaP. Based on these results, it is suggested that binding of BaP to DOM depends not only on the hydrophobicity of DOM, but also on the existence of an open structure within the DOM to provide access of the aqueous solute to hydrophobic domains within the DOM.