High Molecular Weight Polyaromatic Hydrocarbons Research Articles

Insights into seasonal-variability of SVOCs, morpho-elemental and spectral characteristics of PM2.5 collected at a dense industrial site: Faridabad, Haryana, India

The development-oriented anthropogenic activities have led to intensive increase in emission of various organic pollutants, which contribute considerably to human health risk. In the present study, chemical, physical and spectral characterisation of fine particulate matter (PM2.5), collected at Faridabad city, in northern India, were examined. Seasonal variation of organic compounds [n-alkanes, polyaromatic hydrocarbons (PAHs) and phthalic acid esters (PAEs)], and potential health risk of Polyaromatic hydrocarbons (PAHs) exposure using toxic equivalency potential (TEQ) approach had been assessed. These showed seasonal average values ranging from 156.4 ± 57.0 ng/m3 to 217.6 ± 72.9 ng/m3, 98.0 ± 21.4 ng/m3 to 177.8 ± 72.8 ng/m3, and 30.9 ± 11.9 ng/m3 to 82.5 ± 29.2 ng/m3, respectively, with the highest value for winter. It is noteworthy that unlike, n-alkanes and PAEs, PAHs were least during spring. The high molecular weight PAHs (BaP, BkF, DahA and IcdP) were found to exhibit higher TEQ values (ranging from 0.7 to 9.7) despite of their lower concentrations. The PAH diagnostic ratio, carbon preference index and total index revealed the enhanced impact of biogenic sources of emissions in comparison to diesel emission sources during winter.

Bacterial communities of the Black Sea exhibit activity against persistent organic pollutants in the water column and sediments

The ability of bacteria to degrade organic pollutants influences their fate in the environment, impact on the other biota and accumulation in the food web. The aim of this study was to evaluate abundance and expression activity of the catabolic genes targeting widespread pollutants, such as polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and hexachloro-cyclohexane (HCH) in the Black Sea water column and sediments. Concentrations of PAHs, PCBs and HCH were determined by gas chromatography (GC) coupled to mass spectrometry (MS) and electron capture (ECD) detectors. bphA1, PAH-RHDα, nahAc, linA and linB that encode biphenyl 2,3 dioxygenase, α-subunits of ring hydroxylating dioxygenases, naphthalene dioxygenase, dehydrochlorinase and halidohydrolase correspondently were quantified by quantitative PCR. More recalcitrant PAHs, PCBs and HCH tended to accumulate in the Black Sea environments. In water samples, 3- and 4-ringed PAHs outnumbered naphthalene, while PAHs with > 4 rings prevailed in the sediments. Congeners with 4–8 chlorines with ortho-position of the substituents were the most abundant among the PCBs. β-HCH was determined at highest concentration in water samples, and total amount of HCH exceeded its legacy Environmental Quality Standard value. bphA1, was the most numerous gene in water layers (105 copies/mL) and sediments (105 copies/mg), followed by linB and PAH-RHDα genes (103 copies/mL; 105 copies/mg). The least abundant genes were linA (103 copies/mL; 104 copies/mg) and nahAc (102 copies/mL; 104 copies/mg). The most widely distributed gene bphА1 was one of the least expressed (10−3-10−2 copies/mL; 10−1 copies/mg). The most actively expressed genes were linB (101-102 copies/mL; 103 copies/mg), PAH-RHDα (101 copies/mL; 102 copies/mg) and linA (10−1-100 copies/mL; 100 copies/mg). Interaction of bacteria with PAHs, PCBs and HCH is evidenced by high copy numbers of the catabolic genes that initiate their degradation. More persistent compounds, such as high-molecular weight PAHs or β-HCH are accumulating in the Black Sea water and sediments, albeit microbial activity is directed against them.

Unravelling the genetic and functional diversity of dominant bacterial communities involved in manure co-composting bioremediation of complex crude oil waste sludge

The present study aimed to characterize the bacterial community and functional diversity in co-composting microcosms of crude oil waste sludge amended with different animal manures, and to evaluate the scope for biostimulation based in situ bioremediation. Gas chromatography–mass spectrometry (GC–MS) analyses revealed enhanced attenuation (>90%) of the total polyaromatic hydrocarbons (PAHs); the manure amendments significantly enhancing (up to 30%) the degradation of high molecular weight (HMW) PAHs. Microbial community analysis showed the dominance (>99% of total sequences) of sequences affiliated to phyla Proteobacteria, Firmicutes, Actinobacteria and Bacteroidetes. The core genera enriched were related to hydrocarbon metabolism (Pseudomonas, Delftia, Methylobacterium, Dietzia, Bacillus, Propionibacterium, Bradyrhizobium, Streptomyces, Achromobacter, Microbacterium and Sphingomonas). However, manure-treated samples exhibited high number and heterogeneity of unique operational taxonomic units (OTUs) with enrichment of additional hydrocarbon-degrading bacterial taxa (Proteiniphilum, unclassified Micrococcales, unclassified Lachnospiraceae, Sphingobium and Stenotrophomonas). Thirty-three culturable hydrocarbon-degrading microbes were isolated from the co-composting microcosms and mainly classified into Burkholderia, Sanguibacter, Pseudomonas, Bacillus, Rhodococcus, Lysinibacillus, Microbacterium, Brevibacterium, Geobacillus, Micrococcus, Arthrobacter, Cellulimicrobacterium, Streptomyces Dietzia,etc,. that was additionally affirmed with the presence of catechol 2,3-dioxygenase gene. Finally, enhanced in situ degradation of total (49%), LMW (>75%) and HMW PAHs (>35%) was achieved with an enriched bacterial consortium of these microbes. Overall, these findings suggests that co-composting treatment of crude oil sludge with animal manures selects for intrinsically diverse bacterial community, that could be a driving force behind accelerated bioremediation, and can be exploited for engineered remediation processes.

Mapping carcinogen exposure across urban fire incident response arenas using passive silicone-based samplers

Carcinogens are emitted in significant quantities at fire scenes and are a major contributor in the increased cancer risk observed in firefighters when compared to the general population. A knowledge gap exists in the current understanding of the distribution of these toxic compounds within a localized fire incident response arena. Here, we employ stationary silicone-based passive samplers at controlled live fire trainings to evaluate the deposition behavior of polyaromatic hydrocarbons (PAHs) emitted by fires. Our findings indicate significantly greater total PAH exposure in fires fueled by biomass and wood compared to fires burning cleaner fuels, such as propane. A 22% increase in total PAH deposition and a 68% increase in high molecular weight PAH deposition was recorded for biomass fueled fires compared to propane fueled fires. Furthermore, we observe that heavier molecular weight PAHs exhibit a pronounced deposition front within a certain radius of the hot zone, whereas low molecular weight PAHs are more uniformly distributed throughout the area. These findings highlight that the warm zones and cold zones of fire situations yield elevated levels of carcinogen exposure to first responders within them. We anticipate that these findings will help inform decisions made by emergency personnel when evaluating risk for the hot zone, warm zone, and cold zone of urban fires helping ease the carcinogenic risk experienced.

Distribution and fate of PAHs contaminants deposited in the sediments of North-Western Creeks adjoining the Arabian sea of Mumbai, India: Implications for monitoring

Assessment of 17 polyaromatic hydrocarbons (PAHs) was made to understand the sources, toxicity risk and biological impact in surface sediments of Malad and Versova creek of Mumbai. The concentration of ΣPAHs was found to vary in the range of 2915–4204 ng/g dw (mean 3367 ± 948 ng/gdw). The concentration of high molecular weight PAHs (HMW PAHs) in the range of 2378–3394 ng/g dw (mean 2723 ± 755 ng/g dw) was higher than that of low molecular PAHs (LMW PAHs) which was in the range of 528–810 ng/g dw (mean 644 ± 202 ng/g dw). The contribution of HMW PAHs to the ∑PAHs was 80.86% while that of LMW PAHs was 19.14%. The concentration of carcinogenic PAHs was 1452–1996 ng/g dw (mean 1631 ± 447 ng/g dw) having contribution of 48.43% to the ∑PAHs. The assessment of biological risk and toxicity was made based on toxic equivalent quantity (TEQ) and sediment quality guideline quotient (SQGQ). The PAH levels are feared to increase in coming times thereby creating probable threat to the biological life and health hazard to the nearby human population.

Accumulation pattern of polycyclic aromatic hydrocarbons using Plantago lanceolata L. as passive biomonitor

Biomonitors are considered a cheap alternative of active air samplers, especially where spatial pattern of air quality is to be monitored, requiring numerous parallel measurements. Of higher plants, Plantago lanceolata L. has been proven a good monitor species with proper accumulation capacity. While biomonitoring studies are difficult to compare due to inherent errors such as the diverse plant material used in different studies, the No. 227 OECD GUIDELINE FOR THE TESTING OF CHEMICALS: Terrestrial Plant Test: Vegetative Vigour Test provides a tool to test extract of aerosol samples under controlled laboratory conditions. In our study, this guideline was followed to experimentally treat Plantago with the aqueous extract of a diesel exhaust sample. Accumulation pattern of polyaromatic hydrocarbons (PAHs) was assessed and compared to samples collected in the field. Unlike most studies reported in the literature, both in the experimentally treated and field Plantago samples, high ratio of high molecular weight PAHs was experienced. Distribution pattern of accumulated PAHs showed strong correlation between the experimentally treated sample and most of the field plantain samples, underlying the usefulness of laboratory treatments for bioaccumulation studies.

Treatment of heavy oil wastewater by UASB–BAFs using the combination of yeast and bacteria

A novel system integrating an upflow anaerobic sludge blanket (UASB) reactor and a two-stage biological aerated filter (BAF) system was investigated as advanced treatment of heavy oil wastewater with large amounts of dissolved recalcitrant organic substances and low levels of nitrogen and phosphorus nutrients. #1 BAF, inoculated with two yeast strains (Candida tropicalis and Rhodotorula dairenensis), was installed in the upper reaches of #2 BAF inoculated with activated sludge. During the 180-day study period, the chemical oxygen demand (COD), ammonia nitrogen (NH3-N), oil and polyaromatic hydrocarbons (PAHs) in the wastewater were removed by 90.2%, 90.8%, 86.5% and 89.4%, respectively. Although the wastewater qualities fluctuated and the hydraulic retention time continuously decreased, the effluent quality index met the national discharge standard steadily. The UASB process greatly improved the biodegradability of the wastewater, while #1 BAF played an important role not only in degrading COD but also in removing oil and high molecular weight PAHs. This work demonstrates that the hybrid UASB–BAFs system containing yeast–bacteria consortium has the potential to be used in bioremediation of high-strength oily wastewater.

Monitoring polycyclic aromatic hydrocarbons in the Northeast Aegean Sea using Posidonia oceanica seagrass and synthetic passive samplers

The concentrations of 22 polyaromatic hydrocarbons (PAH) in Posidonia oceanica seagrass, sediments, and seawater from the Alexandroupolis Gulf in the Aegean Sea, were investigated from 2007 to 2011. Temporal trends of total PAH contents in P. oceanica and sediments were similar. PAH levels in seawater, sediments, and seagrasses generally decreased with increasing distance from Alexandroupolis Port. Leaves and sheaths of P. oceanica had higher PAH levels than roots and rhizomes. P. oceanica accumulates PAHs and has good potential as a bioindicator of spatiotemporal pollution trends. PAH concentrations were also examined using in situ passive seawater sampling and were compared to results of passive sampling in the laboratory using local sediments and seawater. Levels of high molecular weight PAHs assessed using passive samplers confirmed the decreasing gradient of pollution away from Alexandroupolis Port. Passive sampling also proved useful for investigating sources of PAHs in P. oceanica meadows.

Structure of hydrocarbonoclastic nitrate-reducing bacterial communities in bioturbated coastal marine sediments.

The organisation of denitrifying microorganisms in oil-polluted bioturbated sediments was investigated in mesocosms under conditions as closer as possible to that observed in the environment. Molecular and culture-dependent approaches revealed that denitrifying Gammaproteobacteria were abundant in oil-polluted and bioturbated sediments suggesting that they may play a key role in hydrocarbon degradation in the environment. T-RFLP and gene libraries analyses targeting nirS gene showed that denitrifying microbial communities structure was slightly affected by either the addition of Hediste diversicolor or crude oil revealing the metabolic versatility of denitrifying microorganisms. From oil-polluted sediments, distinct denitrifying hydrocarbonoclastic bacterial consortia were obtained by enrichment cultures on high molecular weight polyaromatic hydrocarbons (PAHs) (dibenzothiophene, fluoranthene, pyrene and chrysene) under nitrate-reducing conditions. Interestingly, molecular characterisation of the consortia showed that the denitrifying communities obtained from oiled microcosms with addition of H.diversicolor were different to that observed without H.diversicolor addition, especially with fluoranthene and chrysene revealing the bacterial diversity involved in the degradation of these PAHs.

Bioremediation of PAH-contaminated soil with fungi – From laboratory to field scale

The purpose of this study was to develop a fungal bioremediation method that could be used for soils heavily contaminated with persistent organic compounds, such as polyaromatic hydrocarbons (PAHs). Sawmill soil, contaminated with PAHs, was mixed with composted green waste (1:1) and incubated with or without fungal inoculum. The treatments were performed at the laboratory and field scales. In the laboratory scale treatment (starting concentration 3500 mg kg−1, sum of 16 PAH) the high molecular weight PAHs were degraded significantly more in the fungal-inoculated microcosms than in the uninoculated ones. In the microcosms inoculated with Phanerochaete velutina, 96% of 4-ring PAHs and 39% of 5- and 6-ring PAHs were removed in three months. In the uninoculated microcosms, 55% of 4-ring PAHs and only 7% of 5- and 6-ring PAHs were degraded. However, during the field scale (2 t) experiment at lower starting concentration (1400 mg kg−1, sum of 16 PAH) the % degradation was similar in both the P. velutina-inoculated and the uninoculated treatments: 94% of the 16 PAHs were degraded in three months. In the field scale experiment the copy number of gram-positive bacteria PAH-ring hydroxylating dioxygenase genes was found to increase 1000 fold, indicating that bacterial PAH degradation also played an important role.

Magnetism of outdoor and indoor settled dust and its utilization as a tool for revealing the effect of elevated particulate air pollution on cardiovascular mortality

Settled indoor and outdoor dusts in urban environment represent an important source of secondary pollution. Magnetic characteristics of the settled dust from six cities in Bulgaria are explored, allowing comparison on a national (country) scale. Monthly variations of the mass‐specific magnetic susceptibilities (χindoor) and (χoutdoor) and calculated dust loading rates for a period of 17 months do not show seasonal variability, probably due to the dominant role of traffic‐related emissions and soil‐derived particles in the settled dust. The main magnetic mineral is magnetite, present as spherules and irregular particles of pseudo‐single‐domain grain sizes. Systematically lower remanence coercivities are obtained for outdoor dusts when compared with the corresponding indoor samples, implying that penetration of smaller particles of ambient origin indoors is the main source of the indoor dust. Mean yearly values of the ratio (χindoor/χoutdoor) for each city show statistically significant correlation with mortality due to cardiovascular diseases. This ratio reveals the source‐ and site‐specific importance of the anthropogenically derived toxicogenic fraction. Heavy metal content of the settled dust is related to the contribution from several pollution sources (soil‐derived, combustion and industrial), discriminated through analysis of principal components. SEM/EDX analyses reveal abundant presence of anthopogenic Fe‐containing spherules, irregular particles and diesel exhaust conglomerates. High molecular weight polyaromatic hydrocarbons (PAH) dominate the total PAH content of the outdoor dust samples. The observed linear correlation between total PAH content, coercivity of remanence and the ratio Mrs/χ suggest either adsorption of PAHs on iron oxide particles and especially magnetite, or emission related increase in total PAH concentration along with a decrease of effective magnetic grain size of the accompanying magnetic fraction.

Bioremediation of high molecular weight polyaromatic hydrocarbons co-contaminated with metals in liquid and soil slurries by metal tolerant PAHs degrading bacterial consortium

Bioremediation of polyaromatic hydrocarbons (PAH) contaminated soils in the presence of heavy metals have proved to be difficult and often challenging due to the ability of toxic metals to inhibit PAH degradation by bacteria. In this study, a mixed bacterial culture designated as consortium-5 was isolated from a former manufactured gas plant (MGP) site. The ability of this consortium to utilise HMW PAHs such as pyrene and BaP as a sole carbon source in the presence of toxic metal Cd was demonstrated. Furthermore, this consortium has proven to be effective in degradation of HMW PAHs even from the real long term contaminated MGP soil. Thus, the results of this study demonstrate the great potential of this consortium for field scale bioremediation of PAHs in long term mix contaminated soils such as MGP sites. To our knowledge this is the first study to isolate and characterize metal tolerant HMW PAH degrading bacterial consortium which shows great potential in bioremediation of mixed contaminated soils such as MGP.

Biodegradation of high molecular weight PAHs using isolated yeast mixtures: application of meta-genomic methods for community structure analyses

Bioaugmentation for the removal of polyaromatic hydrocarbons (PAHs) from wastewater using bacteria and yeasts is considered environment-friendly and a cost-effective technique. The effectiveness of this biodegradation system depends on the stability of inoculated microorganisms and the availability of nutrients. This study is aimed to investigate the removal of high molecular weight (HMW)-PAHs from biologically treated produced water using different biological systems. Three systems, inoculated with activated sludge (AS), the mixture of five yeast strains (MY), and the mixture of AS and the five yeast strains (SY), respectively, were constructed, and their performance for the removal of HMW-PAHs was compared over 10 weeks. The effluent of the biologically treated produced water from an oilfield was used as the influent after chrysene and benzo(a)pyrene were spiked as HMW-PAHs. Polymerase chain reaction-based denaturing gradient gel electrophoresis (PCR-DGGE) and fluorescent in situ hybridization (FISH) techniques were used to examine the changes in the structures and abundances of the bacterial and yeast communities in these three systems. Only SY and MY systems were capable to remove chrysene (90.7 % and 98.5 %, respectively) and benzo(a)pyrene (80.7 % and 95.2 %, respectively). PCR-DGGE analysis confirmed that all of the five yeast strains inoculated remained in the SY and MY systems, while FISH results showed that the relative abundance of yeast in the SY and MY systems (10.6 % to 21.9 %, respectively) were significantly higher than AS system (2.3 % to 7.8 %, respectively). The relative abundances of the catechol 2,3-dioxygenase (C23O) indicated that the copy number ratios of benzene ring cleavage gene C23O in the yeast amended systems were much higher than that in the AS system. In this study, all of the three systems were effective in removing the low molecular weight (LMW)-PAHs, while HMW-PAHs including chrysene and benzo(a)pyrene were efficiently removed by MY and SY systems, not by AS system. The high HMW-PAHs removal in the MY and SY bioaugmentation systems possibly attributed to the inoculation of the mixed yeast culture. By combining the PCR-DGGE results with the FISH analyses, it was found that yeast probably consisting mainly of the five inoculated strains inhabited in the two bioaugmentation systems as a dominant population. The relatively higher performance of the SY system might be attributed to the suspended growth type which permitted a more efficient contact between microbial cells and contaminants. The bioaugmentation systems (SY and MY) were successfully established by inoculating with five nonindigenous yeast strains and demonstrated high performance in removal of HMW-PAHs.

Polycyclic Aromatic Hydrocarbon Emissions and Mutagenicity Assessment of Exhaust from a Diesel Generator

Diesel fuel and diesel exhaust are known to be highly mutagenic partly because of the presence of polyaromatic hydrocarbons (PAHs) and their derivatives. The present study investigated the PAHs content in the diesel fuel fed to a diesel generator and also in the gas and particulate phase of generator emissions. Mutagenicity of the exhaust was also determined. Exhaust emissions were collected by a stack sampler: gas phase on XAD-2 resin while particulate phase on glass fibre thimble. PAHs were characterized by a gas chromatograph by using a flame ionization detector. The low molecular weight PAHs dominated in the fuel, whereas the high molecular weight PAHs dominated in the exhaust with a greater emission factor in the particulate phase. The results reveal the pyrosynthesis of high molecular weight PAHs during the combustion process. Emissions also increased with increase in load. Extract of exhaust emissions were positive in both Salmonella typhimurium tester strains TA 98 and TA 100 without metabolic activation, suggesting the presence of direct mutagens that can cause both frame-shift and base-pair mutation. The mutagenic response was greater for TA 100 than TA 98, suggesting greater activity for base-pair mutagenicity than frame-shift mutagenicity. Mutagenic activity increased with the increase in load.

Hydropyrolysis: A new technique for the analysis of macromolecular material in meteorites

The carbonaceous chondrite meteorites are fragments of asteroids that have remained relatively unprocessed since the formation of the Solar System 4.56 billion years ago. The major organic component in these meteorites is a macromolecular phase that is resistant to solvent extraction. The information contained within macromolecular material can be accessed by degradative techniques such as pyrolysis. Hydropyrolysis refers to pyrolysis assisted by high hydrogen gas pressures and a dispersed sulphided molybdenum catalyst. Hydropyrolysis of the Murchison macromolecular material successfully releases much greater quantities of hydrocarbons than traditional pyrolysis techniques (twofold greater than hydrous pyrolysis) including significant amounts of high molecular weight polyaromatic hydrocarbons (PAH) such as phenanthrene, carbazole, fluoranthene, pyrene, chrysene, perylene, benzoperylene and coronene units with varying degrees of alkylation. When hydropyrolysis products are collected using a silica trap immersed in liquid nitrogen, the technique enables the solubilisation and retention of compounds with a wide range of volatilities (i.e. benzene to coronene). This report describes the hydropyrolysis method and the information it can provide about meteorite macromolecular material constitution.

PAHs contamination and PAH-degrading bacteria in Xiamen Western Sea

Six stations were established in Xiamen Western Sea (24°29’ N, 118°04’ E) on summer and autumn cruises in July and October 2001 to investigate the level of polyaromatic hydrocarbons (PAHs) and PAHs-degrading bacteria in surface water and sediments. PAHs in the surface water were mainly dominated by low molecular weight PAH compounds (2–3 rings PAH) in July and by high molecular weight PAH compounds (4–6 rings PAH) in October. PAHs in sediments were mainly dominated by high molecular weight PAH compounds (4–6). The percentage of 4–6 rings PAH to total PAHs ranged from 80.4 to 94.9% in July and 78.3 to 88.7% in October. No correlation was found between Fluoranthene-degrading bacteria numbers and Fluoranthene concentration among different stations in the surface water on the two cruises, and the same situation occurred between Pyrene-degrading bacteria numbers and pyrene concentration. But the numbers of fluorene- and phenanthrenedegrading bacteria were positively related to the fluorene and phenanthrene concentrations respectively. In the sediments, a significant positive relationship was found between PAH-degrading bacteria and PAHs concentration, except at station 6 on the two cruises.

00/00510 Bench-scale optimization of bioaugmentation strategies for treatment of soils contaminated with high molecular weight polyaromatic hydrocarbons

00/00510 Bench-scale optimization of bioaugmentation strategies for treatment of soils contaminated with high molecular weight polyaromatic hydrocarbons

Bench-scale optimization of bioaugmentation strategies for treatment of soils contaminated with high molecular weight polyaromatic hydrocarbons

The chemical composition of crude oil and even of refined petroleum includes hundreds of different alkanes and aromatic hydrocarbons. Among these are the polycyclic aromatic hydrocarbons (PAHs), which are known carcinogens and widespread environmental contaminants. Some compounds present in hydrocarbon-contaminated soils are rapidly removed by the activities of autochthonous bacterial populations while other PAHs, especially those with four or more fused aromatic rings, are refractory to biodegradation. The persistence of high molecular weight polyaromatic hydrocarbons (hPAHs) in soils implies either that their low solubility renders them poorly available to bacteria, or that autochthonous bacteria do not contain the metabolic or co-metabolic pathways required for their degradation or both. The rate and extent of PAH degradation in contaminated soil is not always predictable for standard biological treatment strategies. This study examines a matrix of treatments suitable for land farming in order to identify those that maximize the removal of hPAHs. The treatments include those intended to increase the bioavailability of hPAH, such as additions of biosurfactant-producing bacteria (i.e. Pseudomonas aeruginosa #64) and addition of light oils, as well as treatments intended to increase the metabolic potential of the bacterial community. The latter includes the addition of inorganic nutrients and bacterial strains capable of degrading hPAHs co-metabolically (i.e. Sphingomonas paucimobilis EPA 505). The efficacy of immobilizing PAH-degrading bacteria on vermiculite is also considered, as will be the monitoring of leachate for biodegradation of PAHs in a simulated land farming operation.