Ring PAHs Research Articles

Transport of crude oil and associated microbial populations by washover events on coastal headland beaches

Storm-driven transport of MC252 oil, sand and shell aggregates was studied on a low-relief coastal headland beach in Louisiana, USA including measurement of alkylated PAHs and Illumina sequencing of intra-aggregate microbial populations. Weathering ratios, constructed from alkylated PAH data, were used to assess loss of 3-ring phenanthrenes and dibenzothiophenes relative to 4-ring chrysenes. Specific aggregate types showed relatively little weathering of 3-ring PAHs referenced to oil sampled near the Macondo wellhead with the exception of certain SRBs sampled from the supratidal environment and samples from deposition areas north of beach. Aggregates mobilized by these storm-driven washover events contains diverse microbial populations dominated by the class Gammaproteobacteria including PAH-degrading genera such as Halomonas, Marinobacter and Idiomarina. Geochemical assessment of porewater in deposition areas, weathering observations, and microbial data suggest that storm remobilization can contribute to susceptibility of PAHs to biodegradation by moving oil to beach microenvironments with more favorable characteristics. (149).

Influence of composite after-treatment catalyst on particle-bound polycyclic aromatic hydrocarbons–vapor-phase emitted from modern advanced GDI engines

With mutagenic and cacogenic potential polycyclic aromatic hydrocarbons (PAHs) generated from engine source which have contributed to a substantial share of air toxic, so in order to characterize and eliminate the PAHs emissions of commercial engine fuelled, an experimental study has been carried out on a V6 gasoline engine working in spark-ignition (SI) and homogeneous charge compression ignition (HCCI) equipped with smart three-way catalyst converter (TWC). The particle phase and gas phase of PAHS in engine exhaust, downstream and upstream the catalyst were collected by stainless-steel cartridges containing XAD-2 resin to capture PAHs species. The vapour phase and particulate bound PAHs compounds observed with two and three rings to exist almost entirely in the gas phase, on the other hands, five or more fused rings are predominantly adsorbed on soot particles, the intermediate – 4 ring PAHS exist in the two PAHS phases, naphthalene is the most abundant polycyclic aromatic hydrocarbon that was detected in the exhaust vapour-phase on both engine modes. The prototype catalytic converter eliminates most of the polycyclic aromatic hydrocarbons species in both PAHS phases, particle phase and gas phase, except for NAP species. A prototype catalyst showed higher efficient conversion on PAHS particulate-bound phase than vapor phase for both engine modes. However, when hydrogen was added upstream of the catalyst, the catalyst conversion efficiency in reducing naphthalene was increased by approximately 20%.

A field study of bioavailable polycyclic aromatic hydrocarbons (PAHs) in sewage sludge and biochar amended soils

The bioavailable PAHs (freely dissolved concentration, Cfree) were determined in sewage sludge (SL) or sewage sludge and biochar (BC) amended soil. SL or SL with a 2.5, 5 or 10% of BC was applied to the soil. The study was conducted as a long-term field experiment. Addition of BC to SL at a dose of 2.5 and 5% did not affect the content of Cfree PAHs in soils. However a significant difference (by 13%) in Cfree PAHs content was noted in experiment with 10% addition of BC. During the experiment, the concentration of Cfree PAHs in SL- and SL/BC-amended soil decreased. In particular sampling terms the content of Cfree PAHs in SL/BC-amended soil was significantly lower comparing to the Cfree PAHs content in SL-amended soil. After 18 months, Cfree PAH content was significantly lower in SL/BC-amended soil than in the experiment with SL alone, and did not differ significantly from the Σ16 Cfree content in the control soil. The largest decrease relative to the soil with sewage sludge alone was observed for 3-, 5- and 6-ring PAHs. This is the first field-based evidence that biochar soil amendment was effective to reduce of the Cfree of PAHs in sewage sludge-amended soils.

PAH Profiles of Emitted Ashes from Indoor Biomass Burning across the Beijing-Tianjin-Hebei Region and Implications on Source Identification

Sixty-four bottom ash (BA) samples from indoor burning of eight bio-fuels (BFs) including cotton (COT), corn (COR), millet (MIL), soybean (SOY), sorghum (SOR) and sesame (SES), firewood walnut (WAL), and corn cob (COC) were collected across the Beijing-Tianjin-Hebei (BTH) region. Each BA was divided into five differently sized parts for the analysis of eighteen PAHs using the GC/MS system. The Σ18PAHs values for all the BAs varied from 65.0 ± 10.6 to 1310 ± 129 ng g–1. SOR had the highest PAH level, and COC produced the lowest level. The Σ18PAHs for SOY, WAL, COT, COR, COC, and SES were negatively correlated with the BA sizes. The NA, PHE, ACL, AN, FA, PY, FL, and AC dominated in all the BAs except for SES. All the BAs were dominated by 2, 3-ring PAHs. The PAH profiles for differently sized BAs within MIL, SOR, COC, COR, and SES were similar based on lower coefficient of divergence values, while the other three BFs did not exhibit this trend. All the BF pairs except for SOR vs. SES and COC vs. COR had the different PAH profiles. No series of coincident diagnostic ratios (DRs) could represent all BFs based on their significantly varied DRs. AN/(AN + PHE) and BA/BgP might be used in identification of combustion sources of different types of BFs. SOR and SES had higher potential toxicity risk based on higher TEQ, BaPE, and CPAHs values. BgF and BgP were the indicatory PAHs for SOY, MIL, COR, SOR, and COC, while they were AC and FL for the remaining three BFs.

Soot Formation Calculation by Reduced Reaction Model for 4 Ring PAH and Moment Method

Soot Formation Calculation by Reduced Reaction Model for 4 Ring PAH and Moment Method

Enhanced Degradation of Benzo[α]Pyrene in Coal Tar Contaminated Soils Using Biodiesel

The biodegradation of the potent carcinogen, benzo[a]pyrene (BaP), and other priority pollutants was investigated in un-weathered coal tar contaminated soil over a period of 150 days. Results from the laboratory microcosm experiments showed that after 60 days, the concentrations of BaP were significantly reduced by 81%, in the biodiesel amended samples compared to the 26% and 34% depletion in the control and nutrient-only amended microcosms, respectively. The 3-ring PAH anthracene was also almost completely biodegraded in the presence of biodiesel. However, phenanthrene degradation was significantly inhibited in these samples as only 3% reduction occurred as opposed to the 80% depletion observed in the control. A stepwise treatment approach conducted on the coal tar spiked soil also revealed a higher reduction in BaP (98%) in the biodiesel amended microcosms compared to the control (29%) and further enhanced the depletion of phenanthrene by 51% after 60 days of adding biodiesel to soil initially treated with nutrients. Toxicity assays showed that biodiesel amended microcosms stimulated phosphatase enzyme activity and exhibited a lower toxic response to Microtox Vibrio fischeri. Overall, the pattern observed in the removal of the PAHs using biodiesel, suggests the co-metabolic action of ligninolytic fungi, probably via lignin peroxidases, as also evidenced from the visible growth of moulds after 14 days of amendment. The enhanced removal of carcinogenic PAH and the reduced toxicity observed in soil after biodiesel amendment, indicates that this bioremediation technique has potential for full scale field trials.

Modeling and evaluating spatial variation of polycyclic aromatic hydrocarbons in urban lake surface sediments in Shanghai.

To explore the influence of rapid urbanization development on the accumulation of 16 priority PAHs in urban environment, thirty-three surface sediments from city lakes in different urbanized areas of Shanghai were collected to evaluate the occurrence characteristic and source apportionment of PAHs. The concentrations of Σ16PAHs in lake surface sediments ranged from 55.7 to 4928 ng g-1 with a mean value of 1131 ng g-1 (standard deviation, 1228 ng g-1), of which 4-, 5- and 6-ring PAHs were the dominant components. Spatial distribution of PAHs in lake surface sediments showed a significantly declining trend along with a decreasing urbanization gradient (one-way ANOVA, p < .05). Two hotspots of sediment PAHs were mainly distributed at highly urbanized areas with intensive population density and heavy traffic activities and at burgeoning industrial towns in the suburb. Source apportionment of total PAHs identified by a constrained positive matrix factorization model revealed that vehicle emission and combustion of coal, biomass and natural gas were the absolutely predominant sources, respectively accounting for 55.0% and 40.45% of total PAHs burden in lake sediments. Land use regression (LUR) models were successfully developed to evaluate spatial variation of PAHs contamination in urban sediments based on their significant correlations with residential land, commercial land, traffic variables, industrial sources, and population density. All PAH compounds showed strong associations with one or two source indicators (the traffic congestion index and the number of industrial sources), with the fitting R2 varying from 0.529 to 0.984. Our findings suggest that energy consumption related to land use activities obviously promoted PAH accumulations in urban sediment environment during rapid development of urbanization and industrialization in Shanghai.

Polycyclic aromatic hydrocarbons in farmland soils around main reservoirs of Jilin Province, China: occurrence, sources and potential human health risk.

Study on the occurrence, sources and potential human health risk of polycyclic aromatic hydrocarbons in farmland soils around reservoirs is of great significance for the people drinking water security. In the present study, representative farmland soil samples around main reservoirs of Jilin Province, China, were investigated for 16 PAHs. The total concentrations of 16 priority PAHs in 32 farmland soil samples ranged from 602.12 to 1271.87ng/g, with an arithmetic average of 877.23ng/g, and the sum of seven carcinogenic PAH concentrations ranged from 30.07 to 710.02ng/g, with a mean value of 229.04ng/g. The 3-ring and 4-ring PAHs were major exist and account for 45.78 and 32.03%, respectively. Non-cancer andcancer risk of pollutants were calculated, and the results indicate that the complex PAHs in farmland soils were not considered to pose significant health effects. The isomer ratios Fla/(Fla+Pyr) and BaA/(BaA+Chr) show that the PAHs in soils were generally derived from biomass and coal combustion.

Co-application of sewage sludge with biochar increases disappearance of polycyclic aromatic hydrocarbons from fertilized soil in long term field experiment

The application of sewage sludge with biochar as fertilizer may be a new method improves soil properties. Biochar increases of the crops productivity and reduction of bioavailability of contaminants.In the present study the persistence of sum of 16 (Σ16) PAHs (US EPA 16 PAHs) in a sewage sludge-amended soil (11t/h) and in a sewage sludge-amended soil with the addition of biochar (at a rate of 2.5, 5 or 10% of sewage sludge (dry weight basis)) was determined. This study was carried out as a plot experiment over a period of 18months. Samples for analysis were taken at the beginning of the study and after 6, 12 and 18months from the beginning of the experiment.Application of sewage sludge as a soil amendment did not cause a significant change (P≥0.05) in the soil content of Σ16 PAHs. In turn, the addition of biochar with sewage sludge to the soil, regardless of the contribution of biochar in the sewage sludge, resulted in a significant decrease in PAH content already at the beginning of the experiment. Throughout the experiment, in all treatments the PAH content varied, predominantly showing a decreasing trend. Ultimately, after 18months the content of Σ16 PAHs decreased by 19% in the experiment with sewage sludge alone and by 45, 35 and 28% in the experiment with sewage sludge and the 2.5%, 5.0% and 10% biochar rates, respectively. After 18months of the study, the largest losses in the sewage sludge-amended soil were observed for 2- and 3-ring PAHs. In the sewage sludge- and biochar-amended soil, compared to the beginning of the study and the sewage sludge-amended soil, the highest losses were found for 5- and 6-ring PAHs (2.5 and 5.0% rates) as well as for 5- and 2-ring PAHs (10% rate).

The Fate of PAHs Resulting from In-Situ Oil Burns

ABSTRACT PAHs or Polyaromatic Hydrocarbons are ubiquitous in the environment and are found in crude oils. Many environmental PAHs are derived from combustion of many types including forest fires and barbeques. Some PAHs are toxic to biota and man. The concern addressed in this paper is the fate of PAHs found in crude oils when that oil is burned. Crude oil burns result in PAHs downwind of the fire, mostly adsorbed to particulate matter, but the PAH concentration on the particulate matter, both in the plume and the particulate precipitation at ground level, is often an order-of-magnitude less than the concentration of PAHs in the starting oil. This includes the concentration of multi-ringed (5 or 6 rings) PAHs, which are often created in other combustion processes such as low-temperature incinerators and diesel engines. There is a slight increase in the concentration of multi-ringed PAHs in the burn residue. When considering the mass balance of the burn, however, most of the PAHs are destroyed by the fire. Destruction efficiencies are typically 99 % or greater. Diesel fuel contains significant levels of PAHs of smaller molecular size, the 2 to 3-ring PAHs predominating. Burning diesel results in a greater concentration of pyrogenic PAHs of larger molecular sizes. Larger PAHs are either created or concentrated by the fire. Larger PAHs, some of which are not even detectable in the diesel fuel, are found both in the soot and in the residue; however, the concentrations of these larger PAHs are low and often just above detection limits. Overall, more PAHs are destroyed by the fires than are created. As with crude oil burns, the destruction efficiencies for diesel burns are typically 99 % or greater, but often less than those for crude oils. This paper will help to answer the question, are more PAHs destroyed by the fires than are created?

A comprehensive evaluation of the environmental quality of a coastal lagoon (Ravenna, Italy): Integrating chemical and physiological analyses in mussels as a biomonitoring strategy

This study aimed at evaluating the environmental quality of a coastal lagoon (Pialassa Piomboni, NW-Adriatic, Italy) by combining analyses of biomarkers of environmental stress and bioaccumulation of contaminants in marine mussels (Mytilus galloprovincialis) transplanted for 28days to six selected sites. Assessed biomarkers encompassed lysosomal endpoints, oxidative stress and detoxification parameters, specific responses to metals, neuro- and genotoxic substances; chemical analyses focused on PAHs, metals, pesticide and pharmaceuticals. Results showed up to a 67-fold bioaccumulation of 4- to 6-ring PAHs, including pyrene, fluoranthene, chrysene and benzo(ghi)perylene in transplanted mussels compared to reference conditions (T0). A 10-fold increase of Fe, Cr and Mn was observed, while pesticides and pharmaceuticals were not or slightly detected. The onset of a significant (p<0.05) general stress syndrome occurred in exposed mussels, as outlined by a 50–57.7% decrease in haemocytes lysosomal membrane stability and an increased lysosomal volume (22.6–26.9%) and neutral lipid storage (18.9–48.8%) observed in digestive gland. Data also revealed a diffuse lipofuscin accumulation (86.5–139.3%; p<0.05) in digestive gland, occasionally associated to a catalase activity inhibition in gill, indicating an increased vulnerability toward pro-oxidant factors. Higher levels of primary DNA damage (258%; p<0.05) and PAH accumulation were found in mussels exposed along the eastern shoreline, hosting a petrochemical settlement. Bioaccumulated metals showed a positive correlation with increased metallothionein content (85–208%; p<0.05) observed in mussels from most sites. Overall, the use of physiological and chemical analyses detected chronic alterations of the mussel health status induced by specific toxicological pathways, proving a suitable approach in the framework of biomonitoring programs of coastal lagoons.

Assessing human exposure to PM10-bound polycyclic aromatic hydrocarbons during fireworks displays

The “Loy Krathong” festival is a major annual Thai event that includes firework displays. It takes place on the evening of the full moon in the 12th month of the traditional Thai lunar calendar. Since fireworks are widely considered a major source of PAHs, it is considered reasonable to expect a significant increase in PAH levels during this event. The overall PAH profile at the six air quality observatories operated by the Pollution Control Department (PCD), Ministry of Natural Resources and Environment (MNRE), showed that the Kingdom of Thailand's atmosphere was dominated by 5–6-ring PAHs during the firework display period. A significant increase in ΣPAHs (153%) was observed during firework displays. A statistical analysis coupled with the application of diagnostic binary PAH ratios was conducted to determine whether the detected increase in PAH congeners during the festival period was due to firework combustion or whether it was a coincidental effect caused by vehicular exhausts, long-range atmospheric transportation, photolysis and chemical degradation. The average incremental lifetime cancer risk (ILCR) values of adults and children living in Bangkok as estimated by three different TEQs for ingestion, dermal contact, and inhalation exposure pathways were greatly lesser than the US EPA baseline, further highlighting that the cancer risk of bonfire night falls into the ‘‘acceptable level’’ range.

Emissions of Selected Semivolatile Organic Chemicals from Forest and Savannah Fires.

The emission factors (EFs) for a broad range of semivolatile organic chemicals (SVOCs) from subtropical eucalypt forest and tropical savannah fires were determined for the first time from in situ investigations. Significantly higher (t test, P < 0.01) EFs (μg kg-1 dry fuel, gas + particle-associated) for polycyclic aromatic hydrocarbons (∑13 PAHs) were determined from the subtropical forest fire (7,000 ± 170) compared to the tropical savannah fires (1,600 ± 110), due to the approximately 60-fold higher EFs for 3-ring PAHs from the former. EF data for many PAHs from the eucalypt forest fire were comparable with those previously reported from pine and fir forest combustion events. EFs for other SVOCs including polychlorinated biphenyl (PCB), polychlorinated naphthalene (PCN), and polybrominated diphenyl ether (PBDE) congeners as well as some pesticides (e.g., permethrin) were determined from the subtropical eucalypt forest fire. The highest concentrations of total suspended particles, PAHs, PCBs, PCNs, and PBDEs, were typically observed in the flaming phase of combustion. However, concentrations of levoglucosan and some pesticides such as permethrin peaked during the smoldering phase. Along a transect (10-150-350 m) from the forest fire, concentration decrease for PCBs during flaming was faster compared to PAHs, while levoglucosan concentrations increased.

Effective remediation of aged HMW-PAHs polluted agricultural soil by the combination of Fusarium sp. and smooth bromegrass (Bromus inermis Leyss.)

Fusarium sp. strain ZH-H2 is capable to degrade high molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs), smooth bromegrass (Bromus inermis Leyss.) can also degrade 4- to 6-ring PAHs. Pot experiments were conducted to investigate how bromegrass and different inoculum sizes of ZH-H2 clean up HMW-PAHs in agricultural soil derived from a coal mine area. The results showed that, compared with control, different sizes of inocula of ZH-H2 effectively degraded HMW-PAHs, with removal rates of 19.01, 34.25 and 29.26% for 4-, 5- and 6-ring PAHs in the treatment with 1.0 g kg−1 ZH-H2 incubation after 90 d. After 5 mon of cultivation, bromegrass reached degradation rate of these compounds by 12.66, 36.26 and 36.24%, respectively. By adding strain ZH-H2 to bromegrass, HMW-PAHs degradation was further improved up to 4.24 times greater than bromegrass (W), in addition to the degradation rate of Bbf decrease. For removal rates of both 5- and 6-ring PAHs, addition of 0.5 g kg−1Fusarium ZH-H2 to pots with bromegrass performed better than addition of 0.1 g kg−1, while the highest concentration of 1.0 g kg−1Fusarium ZH-H2 did not further improve degradation. Degradation of 4-ring PAHs showed no significant difference among different ZH-H2 incubations with bromegrass treatments. We found that the degradation rates of 4-, 5- and 6-ring PAHs in all treatments are significantly correlated in a positive, linear manner with activity of lignin peroxidase (LiP) (r=0.8065, 0.9350 and 0.9165, respectively), while degradation of 5- and 6-ring PAHs is correlated to polyphenoloxidase (PPO) activity (r=0.7577 and 07806). Our findings suggest that the combination of Fusarium sp. ZH-H2 and bromegrass offers a suitable alternative for phytoremediation of aged PAH-contaminated soil in coal mining areas, with a recommended inoculation size of 0.5 g Fusarium sp. ZH-H2 per kg soil.

Molecular Marker Study of Particulate Organic Matter in Southern Ontario Air.

To study the origins of airborne particulate organic matter in southern Ontario, molecular marker concentrations were studied at Hamilton, Simcoe, and York Gateway Tunnel, representing industrial, rural, and heavy traffic sites, respectively. Airborne particulate matter smaller than 10 μm in aerodynamic diameter was collected on quartz filters, and the collected samples were analyzed for total carbons, 5-6 ring PAHs, hopanes, n-alkanes (C20 to C34), and oxygenated aromatic compounds. Results showed that PAH concentrations at all three sites were highly correlated, indicating vehicular emissions as the major source. Meanwhile, in the scatter plots of α,β-hopane and trisnorhopane, concentrations displayed different trends for Hamilton and Simcoe. The slopes of the linear regressions for Hamilton and the tunnel were statistically the same, while the slope for Simcoe was significantly different from those. Comparison with literature values revealed that the trend observed at Simcoe was explained by the influence from coal combustion. We also found that the majority of oxygenated aromatic compounds at both sites were in the similar level, possibly implying secondary products contained in the southern Ontario air. Regardless of some discrepancies, absolute principal component analysis applied to the datasets could reproduce those findings.

Effects of root exudates on gel-beads/reeds combination remediation of high molecular weight polycyclic aromatic hydrocarbons

Changes in root exudates, including low molecular weight organic acids (LMWOAs), amino acids and sugars, in rhizosphere soils during the gel-beads/reeds combination remediation for high molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs) and the degree of the effects on HMW-PAH biodegradation were evaluated in this study. The results showed that the gel-beads/reeds combination remediation notably increased the removal rates of pyrene, benzo(a)pyrene and indeno(1,2,3-cd)pyrene (65.0–68.9%, 60.0–68.5% and 85.2–85.9%, respectively). During the removal of HMW-PAHs, the LMWOAs, particularly maleic acid, enhanced the biodegradation of HMW-PAHs. Arginine and trehalose monitored in reed root exudates promoted the growth of plants and microorganisms and then improved the removal of HMW-PAHs, especially pyrene. However, the contribution of reed root exudates on degradation of 5- and 6-ring PAHs was minor. These results indicated that the utilization of root exudates was certainly not the only important trait for the removal of HMW-PAHs.

Composition and size distribution of airborne particulate PAHs and oxygenated PAHs in two Chinese megacities

Concentrations and compositions of PAHs and oxygenated PAHs (OPAHs) in four size ranges of ambient particles (<1.1, 1.1–3.3, 3.3–9.0 and >9.0μm) collected in Xi'an and Guangzhou, two megacities of China, during the winter and summer of 2013 were measured and compared with those in 2003. The TSP-equivalent concentrations of Σ14PAHs in Xi'an and Guangzhou are 57±20 and 18±23ngm−3 in winter, 5–10 times higher than those in summer. PAHs in both cities are dominated by 5- and 6-ring congeners in summer. In contrast, they are dominated by 4- and 5-ring congeners in winter, probably due to enhanced gas-to-particle phase partitioning of the semi-volatile PAHs. TSP-equivalent Σ7OPAHs during winter are 54±15 and 23±32ngm−3 in Xi'an and Guangzhou and dominated by 5-ring OPAHs.Size distribution results showed that the fine modes (<3.3μm) of PAHs and OPAHs in both cities are dominated by 4- and 5-ring congeners in winter and 5- and 6-ring congeners in summer. Relative abundances of 3-ring PAHs and OPAHs increased along with an increase in particle sizes, accounting for from about 1% of the total PAHs or OPAHs in the smallest particles (<1.1μm) to >90% of the total in the largest particles (>9.0μm). The toxicity of PAH assessment indicated that atmospheric particles in Xi'an and Guangzhou during winter are much more toxic than those during summer and fine particles are more toxic than coarse particles. Compared to those in 2003, fine particulate PAHs and OPAHs in both cities during winter decreased by 50–90%, most likely due to the replacement of coal by natural gas in the country.

Dispersion, sorption and photodegradation of petroleum hydrocarbons in dispersant-seawater-sediment systems

This work examined effects of model oil dispersants on dispersion, sorption and photodegradation of petroleum hydrocarbons in simulated marine systems. Three dispersants (Corexit 9500A, Corexit 9527A and SPC 1000) were used to prepare dispersed water accommodated oil (DWAO). While higher doses of dispersants dispersed more n-alkanes and PAHs, Corexit 9500A preferentially dispersed C11–C20 n-alkanes, whereas Corexit 9527A was more favorable for smaller alkanes (C10–C16), and SPC 1000 for C12–C28 n-alkanes. Sorption of petroleum hydrocarbons on sediment was proportional to TPH types/fractions in the DWAOs. Addition of 18mg/L of Corexit 9500A increased sediment uptake of 2–3 ring PAHs, while higher dispersant doses reduced the uptake, due to micelle-enhanced solubilization effects. Both dispersed n-alkanes and PAHs were susceptible to photodegradation under simulated sunlight. For PAHs, both photodegradation and photo-facilitated alkylation were concurrently taking place. The information can facilitate sounder assessment of fate and distribution of dispersed oil hydrocarbons in marine systems.

Emission fingerprint of inland navigation vessels compared with road traffic, domestic heating and ocean going vessels

Despite increasing need for cargo shipping, little knowledge exists on emissions from inland navigation. Here we characterized and compared patterns of metals, and parent-, thio- and alkylated PAHs in gaseous and particulate emissions from inland navigation vessels (INVs) with those of road traffic, domestic heating (solid fuels) and ocean going vessels (OGVs) using data from this study and the literature. Diagnostic tools for tracing the environmental impact of inland navigation are proposed. INV and diesel fueled road traffic emissions were differentiated from OGVs and coal combustion via V/Ni values. The PAH inventory of particulate INV emissions also differed significantly from other emitters via a higher proportion of three ring PAHs. The ratio of phenanthrene to dibenzothiophene distinguished diesel fueled road traffic, lignite combustion, OGVs and INVs from gasoline fueled road traffic and wood combustion. The 1,7/(1,7+2,6) and 1,7/(1,7+x4) dimethylphenanthrene ratios (x4=sum of 1,3-, 2,10-, 3,9- and 3,10-dimethylphenanthrene) separated INV, road traffic (diesel), domestic heating and OGV emissions and are recommended for future application in environmental quality studies.

Use of geochemical analysis and vitrinite reflectance to assess different self-heating processes in coal-waste dumps (Upper Silesia, Poland)

Coal-waste dumps are sources of a variety of pollutants, especially when coal-waste material undergoes self-heating. For this research, representative samples were taken from four dumps (Wełnowiec, Czerwionka-Leszczyny, Rymer and Anna) in the Rybnik region. The set of samples collected were divided into three subsets, namely, (1) expelled bitumen precipitated on coal waste, (2) thermally-affected coal waste and (3) highly-thermally affected coal waste from active- and inactive sites. To assess the characteristic features and impacts of self-heating, Rock Eval pyrolysis, measured random vitrinite reflectance (Rr %) and gas chromatography–mass spectrometry (GC–MS) of coal waste extracts were applied. Typical features of the bitumen expelled are elevated parameters of S1, PI, BI, and Py. Generally, the bitumen appeared at lower Tmax values. The self-heating in oxygen deficiency, i.e. under pyrolytic conditions caused thermal cracking of organic matter. Later the generated bitumen expelled from the self-heating zone, migrated and accumulated on colder coal-waste surfaces. This expelled bitumen, observed under fluorescence, shows irregular shapes and coats the organic particles with yellowish–greenish colours. Migrated bitumen is also found in highly-thermally affected, where Tmax values are extremely high due to the oxidation and maturation of organic matter (overmatured). R0 % values based on HI–Tmax comparison and the measured Rr % values generally well correlate in the burning coal waste and in highly-thermally affected samples. The greatest quantities of phenols (mostly C1–C2) occur in the bituminous subset, samples in which 2–3 ring PAHs also dominate. In addition, high relative percentages of phenols (mostly C1–C2) characterize thermally-affected coal waste, together with heavier pyrolytical PAHs; these samples were closer to the heating zone. In totally burned-out porous waste, the presence of adsorbed short-chain n-alkanes and lighter PAHs, and higher CPI, Pr/n-C17 and Pr/Ph values, reflect migration from an active self-heating zone.