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.     

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.     

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.     

苯并(a)芘的环境多介质迁移和归宿模拟

利用Level Ⅲ逸度模型,模拟分析了苯并(a)芘在天津地区气、水、土和沉积物多介质相间的浓度分布、迁移通量和累积趋势,结果表明:气、水相的平流输入是该区域苯并(a)芘的主要来源,土壤和沉积物是其最大的储库,占总残留量的99.38%;在气、水、土和沉积相中的浓度分别为1.96×10-10 mol/m3、3.26×10-6 mol/m3、1.34×10-3 mol/m3和7.74×10-3 mol/m3时,模型估测结果与同期实测浓度吻合较好,验证了模型的可靠性,并通过灵敏度分析,确定了模型的关键参数.     

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.     

Fluorescence-based evidence for adsorptive binding of pyrene to effluent dissolved organic matter

Using fluorescence intensity measurements, pyrene interactions with different types of effluent dissolved organic matter (EDOM) originated from treated municipal wastewater are examined. Multiple observations show that fluorescence intensity of pyrene–EDOM solutions is non-linearly related to pyrene concentration, with distinct concave-up dependence. Testing the effect of pyrene concentration on fluorescence intensity of pyrene–EDOM solutions provides a tool to examine whether binding of an organic compound to EDOM follows linear or non-linear isotherm. Possible coupling between static and dynamic quenching effects was addressed while analyzing fluorescence data. Limited number of EDOM binding sites results in a non-linear binding isotherm such that the concept of pyrene “partitioning” between aqueous phase and “bulky” EDOM organic phase is hardly relevant. Maximal EDOM capacity for pyrene binding is estimated approximately as 0.1% w w⁻¹. Examination of the differences between the total fluorescence intensity of pyrene–EDOM solution and the fluorescence intensities of separated constituents (pyrene and EDOM) was used to illustrate the accumulation of pyrene–EDOM complexes and saturation of some EDOM binding sites. Strong interactions between pyrene and EDOM binding sites may result in pyrene distribution coefficients differing at least by a factor 3.5–7 at varying pyrene concentrations.     

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.     

Exploring micromycetes biodiversity for screening benzo[a]pyrene degrading potential

Twenty-five strains of filamentous fungi, encompassing 14 different species and belonging mainly to Ascomycetes, were tested for their ability to degrade benzo[a]pyrene (BaP) in mineral liquid medium. The most performing isolates for BaP degradation (200 mg?l^?1) in mineral medium were Cladosporium sphaerospermum with 29 % BaP degradation, i.e., 82.8 μg BaP degraded per day (day^?1), Paecilomyces lilacinus with 20.5 % BaP degradation, i.e., 58.5 μg BaP day^?1, and Verticillium insectorum with 22.3 % BaP degradation, i.e., 64.3 μg BaP day^?1, after only 7 days of incubation. Four variables, e.g., biomass growth on hexadecane and glucose, BaP solubilization, activities of extracellular- and mycelium-associated peroxidase, and polyethylene glycol degradation, were also studied as selective criteria presumed to be involved in BaP degradation. Among these variables, the tests based on polyethylene glycol degradation and on fungal growth on hexadecane and glucose seemed to be the both pertinent criteria for setting apart isolates competent in BaP degradation, suggesting the occurrence of different mechanisms presumed to be involved in pollutant degradation among the studied micromycetes.     

Distribution of benzo[a]pyrene and coronene with respect to particle size in pasadena aerosols in the submicron range

Two polycyclic aromatic hydrocarbons (PAHs), benzo[a]pyrene (BaP) and coronene (COR) were studied. Although reported equilibrium vapor concentrations of BaP are much higher than atmospheric concentrations, detectable amounts of BaP were not found in the gas phase. Coronene vapor pressures are too low for this species to appear in the gas phase.Aerosols were size fractionated by an eight stage low pressure impactor capable of size fractionation down to 0.05 μm dia. After ultrasonic extraction with benzene, each stage of the impactor was analyzed for BaP and COR by thin layer Chromatographie and spectrophotofluorometric (TLC-SPF) analysis.About 75% of the BaP and 85% of the COR are associated with particles of aerodynamic diameter less than 0.26 μn. Almost one half of the total mass of both PAHs is associated with aerosols in a very narrow size range (0.075–0.12 μm). Total concentrations ranged between 0.39 and 1.06 ng m⁻³ for BaP and between 1.81 and 6.66 ng m⁻³ for COR. The distributions of both PAHs with respect to particle size were unimodal.     

芘和苯并[a]芘复合污染土壤中的环糊精-微生物连续修复

人为制作芘（Pyr）和苯并[a]芘（BaP）浓度分别为200 mg·kg-1、100 mg·kg-1的污染土样,通过羟丙基-β-环糊精（HPCD）和芘的降解菌,研究土壤中Pyr和BaP的修复效果及对微生物群落结构的变化。通过添加10%（w/w）HPCD和5%（v/w）降解菌修复人为污染的土壤,研究发现添加HPCD和降解菌对两种多环芳烃的降解均有促进作用,且同时添加的效果依次强于单独添加HPCD、单独添加降解菌。培养14周后,和对照相比,所有处理的土样中3种酶（脱氢酶、多酚氧化酶以及荧光素二乙酸酯酶）活性均增强,且HPCD+降解菌处理效果使酶活性增强最为显著,与样品的降解效果趋势相似。通过对土壤中2种多环芳烃进行Tenax TA 6 h提取来表征生物有效性,得出土壤中Pyr的生物有效性依次为HPCD处理（M）>> 对照处理（CK）>（HPCD+降解菌）处理（MB）>> 降解菌处理（CKB）;即HPCD可以显著增强土壤中Pyr的生物有效性,MB和CKB对土壤中Pyr的生物有效性具有减弱作用,且CKB处理的减弱效果最明显;BaP的生物有效性依次为HPCD处理（M）>>（HPCD+降解菌）处理（MB）> 对照处理（CK）>> 降解菌处理（CKB）;即不仅HPCD对土壤中BaP的生物有效性增强作用,MB对BaP的生物有效性也具有增强作用,而且CKB对土壤中BaP的生物有效性同样具有减弱作用。高通量测序表明,培养10周后,M、MB、CK和CKB 4种样品的土壤细菌组成相似。外接种菌液会提高土壤中的细菌多样性,环糊精的添加会降低土样的细菌多样性,两者都会改变土壤的细菌群落结构。     

Bioaccumulation of cyclopenta[cd]pyrene and benzo[ghi]fluoranthene by mussels transplanted in a coastal lagoon

The bioaccumulation of two isomeric non-alternant non-priority polycyclic aromatic hydrocarbons (PAHs), namely cyclopenta[cd]pyrene and benzo[ghi]fluoranthene, was investigated in caged mussels (Mytilus galloprovincialis) exposed for 30 days in three sites of a coastal lagoon (Pialassa Baiona, Ravenna, Italy) contaminated by pyrogenic PAHs. The concentration of cyclopenta[cd]pyrene and benzo[ghi]fluoranthene increased from undetectable levels in reference mussels withdrawn from the Adriatic sea to 10-30 ng g(-1) dry weight in transplanted mussels. Other contaminants bioaccumulated by caged mussels included pyrene, fluoranthene and mercury. Whilst the isomer concentration ratio pyrene/fluoranthene in biota was comparable to that observed in sediments, the cyclopenta[cd]pyrene/benzo[ghi]fluoranthene ratio was much lower in mussels than in sediments. The lower sediment biota accumulation factor of cyclopenta[cd]pyrene with respect to that of benzo[ghi]fluoranthene was tentatively attributed to the greater biological activity of the former compound, which contains a reactive olefinic bond in the cyclopenta fused ring moiety. Given the higher mutagenic activity of cyclopenta[cd]pyrene with respect to other priority PAHs, its bioaccumulation from contaminated sediments may rise considerably the overall toxicity of PAH residues in exposed biota.     

Comparison of microbial pyrene and benzo[a]pyrene mineralization in liquid medium, soil slurry, and soil

The microbial degradation of 14C-pyrene and 14C-benzo[a]pyrene by a bacterial mixed culture was studied within a mixture of the PAHs phenanthrene, anthracene, pyrene, fluoranthene, and benzo[a]pyrene as sole carbon source in the different culture systems: (i) liquid medium, (ii) soil slurry (surface and grinding influence), and (iii) soil. The fate of these two labeled compounds was followed in these systems with an emphasis on mineralization to carbon dioxide, extractability, and adsorption to humic materials and formation of unextractable residual. Mineralization showed the most obvious differences: soil slurries achieved the best results both concerning the extent of mineralization and the time required. The highest extent of pyrene mineralization (54% within 21 days) was observed in soil slurries; in liquid media, pyrene mineralization was slower, but reached approximately the same extent (54% in 150 days); in soils, mineralization reached only 36% of added pyrene after 160 days. Benzo[a]pyrene was mineralized in a mixture of PAHs in soil slurries to an extent of 34% within 70 days, whereas mineralization in liquid medium and soil occurred in the range of 5% (70 days). Mineralization of benzo[a]pyrene in sand slurries was lower compared to soil slurries (19% in sand slurries vs. 32% in soil slurries within 50 days).     

Molecular evidence for benzo[a]pyrene and naphthalene genotoxicity in Trifolium repens L

Polycyclic aromatic hydrocarbons (PAHs) are among the most dangerous environmental contaminants due to their toxic, carcinogenic and mutagenic effects. Although there are many data in literature that detail the effects of PAHs on animals, little is known about their action on higher plants which are often used as bioindicators. The aim of the present study was to evaluate the genotoxicity of two different PAHs, benzo[a]pyrene (BaP) and naphthalene (Naph), on Trifolium repens L. Clover plants were exposed to soil which had been artificially contaminated with three concentrations of BaP (5, 10 and 20 microg g-1) or Naph (25, 50 and 100 microg g-1). After 15 days, changes in the DNA content and sequence of roots and shoots were evaluated by flow cytometry (FCM) and amplified fragment length polymorphism (AFLP). Root and shoot dry weight were also determined to assess plant growth. Results showed that BaP and Naph were both genotoxic for white clover, inducing significant changes in root and shoot DNA sequence. Damage was more severe in the root than in the shoot suggesting that the translocation of these compounds and their genotoxic metabolites was limited. Ploidy alterations were not detected and the extent of damage caused by all the tested PAH concentrations was not sufficient to affect plant development.     

水体溶解性有机物的化学分级表征：原理与方法

综述了水体溶解性有机物（DOM）的化学分级表征法即树脂吸附分级法（RA）的研究与进展，同时基于该方法存在的一些问题结合我国典型水质体系，从树脂的选择、净化、分级的定义、水样过柱流速、水样树脂体积比的确定等方面进行了研究探讨，给出了完整的实验参数和操作方法。     

水体溶解性有机物的化学分级表征:原理与方法

综述了水体溶解性有机物(DOM)的化学分级表征法即树脂吸附分级法(RA)的研究与进展,同时基于该方法存在的一些问题结合我国典型水质体系,从树脂的选择、净化、分级的定义、水样过柱流速、水样树脂体积比的确定等方面进行了研究探讨,给出了完整的实验参数和操作方法.     

Relationships between colored dissolved organic matter and dissolved organic carbon in different coastal gradients of the Baltic Sea

Due to high terrestrial runoff, the Baltic Sea is rich in dissolved organic carbon (DOC), the light-absorbing fraction of which is referred to as colored dissolved organic matter (CDOM). Inputs of DOC and CDOM are predicted to increase with climate change, affecting coastal ecosystems. We found that the relationships between DOC, CDOM, salinity, and Secchi depth all differed between the two coastal areas studied; the W Gulf of Bothnia with high terrestrial input and the NW Baltic Proper with relatively little terrestrial input. The CDOM:DOC ratio was higher in the Gulf of Bothnia, where CDOM had a greater influence on the Secchi depth, which is used as an indicator of eutrophication and hence important for Baltic Sea management. Based on the results of this study, we recommend regular CDOM measurements in monitoring programmes, to increase the value of concurrent Secchi depth measurements.     

Effects of benzo[a]pyrene as an environmental pollutant and two natural antioxidants on biomarkers of reproductive dysfunction in male rats

Benzo[a]pyrene (B[a]P) is an environmental toxicant and endocrine disruptor. Therefore, the aim of the present study was to investigate the toxicity of B[a]P in testis of rats and also to study the role of silymarin and thymoquinone (TQ) as natural antioxidants in the alleviation of such toxicity. Data of the present study showed that levels of testosterone, estrogen and progesterone were significantly decreased after treatment of rats with B[a]P. In addition, B[a]P caused downregulation of the expressions of steroidogenic enzymes including CYP17A1 and CP19A1, and decreased the activity of 17-β hydroxysteroid dehydrogenase (17β-HSD). Moreover, B[a]P decreased the activities of antioxidant enzymes including catalase (CAT), glutathione peroxidase (GP_X) and superoxide dismutase (SOD), and significantly increased free radicals levels in testis of male rats. However, pretreatment of rats with silymarin prior to administration of B[a]P was found to restore the level of free radicals, antioxidant status, and activities of steroidogenic enzymes to their normal levels in testicular tissues. Moreover, histopathological finding showed that silymarin recovered the abnormalities occurred in tubules caused by B[a] P in testis of rats. On the other hand, TQ showed pro-oxidant effects and did not ameliorate the toxic effects of B[a] P on the testicular tissue since it decreased antioxidant enzymes activities and inhibited the protein expression of CYP11A1 and CYP21A2 compared to control rats. Moreover, TQ decreased the levels of testosterone, estrogen, and progesterone either in the presence or absence of B[a]P. It is concluded that B[a]P decreased testosterone levels, inhibited antioxidant enzymes activities, caused downregulation of CYP isozymes involved in steroidogenesis, and increased free radical levels in testis. Moreover, silymarin was more effective than TQ in restoring organism health and alleviating the deleterious effects caused by B[a]P in the testis of rats. Due to its negative impact, it is highly recommended to limit the use of TQ as a dietary supplement since millions of people in the Middle East are using it to improve their health.