Vertical distribution and anaerobic biodegradation of polycyclic aromatic hydrocarbons in mangrove sediments in Hong Kong, South China

The vertical distribution of polycyclic aromatic hydrocarbons (PAHs) at different sediment depths, namely 0-2 cm, 2-4 cm, 4-6 cm, 6-10 cm, 10-15 cm and 15-20 cm, in one of the most contaminated mangrove swamps, Ma Wan, Hong Kong was investigated. It was the first time to study the intrinsic potential of deep sediment to biodegrade PAHs under anaerobic conditions and the abundance of electron acceptors in sediment for anaerobic degradation. Results showed that the total PAHs concentrations (summation of 16 US EPA priority PAHs) increased with sediment depth. The lowest concentration (about 1300 ng g^− 1 freeze-dried sediment) and the highest value (around 5000 ng g^− 1 freeze-dried sediment) were found in the surface layer (0-2 cm) and deeper layer (10-15 cm), respectively. The percentage of high molecular weight (HMW) PAHs (4 to 6 rings) to total PAHs was more than 89% at all sediment depths. The ratio of phenanthrene to anthracene was less than 10 while fluoranthene to pyrene was around 1. Negative redox potentials (Eh) were recorded in all of the sediment samples, ranging from − 170 to − 200 mv, with a sharp decrease at a depth of 6 cm then declined slowly to 20 cm. The results suggested that HMW PAHs originated from diesel-powered fishing vessels and were mainly accumulated in deep anaerobic sediments. Among the electron acceptors commonly used by anaerobic bacteria, sulfate was the most dominant, followed by iron(III), nitrate and manganese(IV) was the least. Their concentrations also decreased with sediment depth. The population size of total anaerobic heterotrophic bacteria increased with sediment depth, reaching the peak number in the middle layer (4-6 cm). In contrast, the aerobic heterotrophic bacterial count decreased with sediment depth. It was the first time to apply a modified electron transport system (ETS) method to evaluate the bacterial activities in the fresh sediment under PAH stress. The vertical drop of the ETS activity suggested that the indigenous bacteria were still active in the anaerobic sediment layer contaminated with PAHs. The biodegradation experiment further proved that the sediment collected at a depth of 10-15 cm harbored anaerobic PAH-degrading bacterial strains (two Sphingomonas, one Microbacterium, one Rhodococcus and two unknown species) with some intrinsic potential to degrade mixed PAHs consisting of fluorene, phenanthrene, fluoranthene and pyrene under low oxygen (2% O₂) and non-oxygen (0% O₂) conditions. This is the first paper to report the anaerobic PAH-degrading bacteria isolated from subsurface mangrove sediment.     

Distribution of polycyclic aromatic hydrocarbons in snow of Mount Nanshan,Xinjiang

Polycyclic aromatic hydrocarbon (PAH) in snow samples collected from Mount Nanshan (Xinjiang, China) was investigated for eight stations. Fourteen PAHs were detected in these samples. The total PAH concentration ranged from 70.15 ng/L to 155.67 ng/L, with an average of 113.02 ng/L. Human carcinogens, such as fluoranthene, chrysene, benzo(a)pyrene, dibenzo(a,h)anthracene, indeno(1,2,3‐cd)pyrene and benzo(ghi)perylene in snow were assessed based on risk quotient. Preliminary assessment showed that these PAHs posed a moderate risk. Component analysis showed that the PAHs found in the snow samples were mainly three‐ring PAHs, which comprised 34.51–90.81% of the total PAHs. Phenanthrene, fluorene and anthracene accounted for 35.08, 11.90 and 11.13% of the total PAHs, respectively. The ΣPAH content increased with the increasing altitude, and the highest concentration of 155.67 ng/L was observed in snow samples from the N7 station, which was located near the top of the mountain. This high PAH concentration in N7 was possibly due to more frequent human activities in the area and long‐distance transportation of PAHs. Isomer ratios were used to determine the possible sources of PAHs in the samples. The results indicate that coal and biomass combustion made a larger contribution than emissions from petroleum consumption. It is therefore of utmost importance to develop new fuels taking the place of coal and to achieve as complete as possible for the burning of carbon‐containing materials.     

The spatio-temporal variations and fluxes of polycyclic aromatic hydrocarbons in the sediments of the Saguenay Fjord, Québec, Canada

The temporal variations of polycyclic aromatic hydrocarbon (PAH) concentrations demonstrate that the inputs to the sediments have increased considerably in the Saguenay Fjord, Québec, especially since 1930. However, a decrease in the concentrations in the Fjord sediments was noted for the last decade, but it was not observed in the sediments of Baie des Ha! Ha! The data indicate that the Saguenay River is a main route of entry of PAH to the Fjord system. The calculated PAH fluxes reveal that a great portion of the PAH, released in the Saguenay hydrographic basin, is not incorporated in the Fjord sediments. The spatio-temporal behavior of PAH in the sediments suggests that the major source of PAH in the Saguenay area originates from two aluminum reduction plants located upstream of the Saguenay Fjord.     

Modelling of runoff behaviour of particle-bound polycyclic aromatic hydrocarbons (PAHs) from roads and roofs

Road and roof dust was collected and samples of runoff were taken at an urban storm sewer system in a residential area in Japan. Suspended solids (SS) in the runoff samples were classified into two fractions: fine (smaller than 45 μm) and coarse (larger than 45 μm). Runoff monitoring and chemical analysis data were also used to validate a runoff model for particle-bound polycyclic aromatic hydrocarbons (PAHs) that was originally developed to explain the behaviour of SS in the same area. The model, in which roads and roofs were considered separately as impervious surfaces, expressed the SS and particle-bound PAHs runoff behaviour for fine and coarse particles very well, except during and after heavy rainfalls (more than 10 mm/h). However, the model could not explain the PAH profiles of runoff particles; the profiles of 12 PAH compounds tracked in this study were almost constant and more similar to those of road dust than roof dust throughout the event. An improved model is developed which explains the runoff behaviour by considering two types of road dust with different mobility.     

Seasonal changes and temperature-dependent accumulation of polycyclic aromatic hydrocarbons in high-altitude soils

Polycyclic Aromatic Hydrocarbons (PAHs) are a major group of pollutants whose occurrence in the environment is mainly of anthropogenic origin. In this paper, we examine the effect of topographical slope exposure on PAH contamination and seasonal change in PAH concentrations in soils. We collected soil samples on three dates in 2007 (early May, end of July and beginning of November) from south- and north-facing aspects at 1900 m a.s.l. in the central Italian Alps. We found greater PAH contamination in soils from a north-facing slope than in those from a south-facing slope at all seasons. We calculated North-South Enrichment Factors as the ratio between the concentrations measured in soils from northern and southern aspects. These ratios ranged from 1.4 to 1.9 for lighter PAHs (from 2 to 4 rings). These values are consistent with theoretical calculations based on temperature-specific octanol-air partition coefficients (predicted North-South Enrichment Factors range from 1.6 to 2.0). For heavier PAHs (from 5 to 6 rings), smaller differences were observed between soils from northern and southern aspects, due to the gas/particle distribution of these compounds. We also found consistent differences in normalised PAH concentrations across the three sampling periods. The majority of compounds showed a significant decreasing trend from the beginning of May to the end of July, due to the annual cycles of physical processes (deposition vs. volatilisation) and biological processes (uptake and/or biotransformation). Only a few compounds showed different trends, presumably due to season-specific local emission sources.     

Leaching of heavy metals and polycyclic aromatic hydrocarbons from reclaimed asphalt pavement

The work presented herein displays the results of a study addressing environmental concerns related to the possible leaching of pollutants from reclaimed asphalt pavement. Samples from an experimental site were tested in both static batch tests and column leaching tests. Selected heavy metals and polycyclic aromatic hydrocarbons (PAHs) were analysed in leachates. The results have allowed us to consider the leaching of pollutants to be rather weak for most of the parameters studied. Concentrations in solutions from batch leaching tests were generally below the EC limit values for drinking water. Pollutant concentrations from column experiments were higher in solutions as of the initial leaching stages, but then decreased rapidly and wound up at values below the detection limits. The factors influencing results proved to be the material grain size and the percolation water flow rate. Results from leaching experiments performed on core samples taken on two rebuilt road section pavements, containing 10% and 20% of reclaimed asphalt pavement, respectively, confirmed the results obtained from the batch and column experiments.     

Ozonation of polycyclic aromatic hydrocarbons in oil/water-emulsions: mass transfer and reaction kinetics

The ozonation of highly condensed polycyclic aromatic hydrocarbons (PAH) was studied in oil/water-emulsions, which are comparable to poorly water-soluble PAH in industrial wastewaters and at contaminated sites. As there was a lack of knowledge about the ozonation in oil/water-emulsions, first the ozone mass transfer was studied and optimized from the gas to the water phase and from the water to the oil phase. The ratio of mass transfer and oxidation reaction was determined by the Hatta-number and revealed a slow, quasi homogeneous reaction of ozone with PAH inside the oil droplets. Because the ozone gas concentration had no influence under the optimized conditions, the selective PAH-ozonation could be described microkinetically by a direct ozone reaction of pseudo-first order regarding PAH-concentrations. The determined PAH mean reaction rate constants of 1.02 min(-1) in oil/water-emulsions are in the upper range as found for PAH dissolved in water. These results give a new insight into the ozonation in the three-phase systems and into the treatment of highly condensed, hardly biodegradable PAH.     

Particulate-bound polycyclic aromatic hydrocarbons in naturally ventilated multi-storey residential buildings of Singapore: Vertical distribution and potential health risks

The main objective of the study is to quantify the polycyclic aromatic hydrocarbons (PAHs) concentration levels (US EPA priority components) in fine traffic-generated particles (PM_2.5) at various heights of typical multi-storey public housing buildings located in close proximity, i.e. within 30 m and along a busy major expressway in Singapore. The secondary objective is to estimate the potential health risks associated with inhalation exposure, based on the toxic equivalency factors (TEFs) at the various floors of these buildings. Two typical public housing buildings, both naturally ventilated residential apartment blocks, of point block configuration (22-storey) and slab block configuration (16-storey) were selected for the study. Particulate samples were collected for chemical analysis at three representative floors: the lower, the mid, and the upper floors of the buildings. Key meteorological parameters such as wind speed, wind direction, ambient temperature, and relative humidity were also measured at the representative floors. All samples were analyzed for the 16 PAH priority pollutants listed by US EPA. The vertical PAH distribution profile varies with height of building depending on the type of block configuration. The total mean concentrations of particulate PAHs for point and slab blocks are 3.32±1.76 ng/m³ (0.56–7.2 ng/m³) and 6.0±1.88 ng/m³ (3.19–10.26 ng/m³), respectively. For the point block, the highest mean total PAH concentration occurred at the mid floor followed by the upper floor. The lower floor had the least mean total PAH concentration. For the slab block, the highest mean total PAH concentration occurred at the lower floor and remained almost constant up to the mid floor and thereafter gradually decreased from mid floor to upper floor of the building. These results suggest that the building configuration influences the vertical distribution of particulate PAHs. The dominant particulate PAHs measured at the point block are naphthalene, acenaphthylene, benzo(b)fluoranthene, and benzo(g,h,i)perylene while those for the slab block, the main particulate PAHs are naphthalene, phenanthrene, fluoranthene, and benzo(g,h,i)perylene. The Bpe/Ind ratio for both blocks ranged from 0.92±0.2 to 1.63±0.6 indicating particulate PAHs are contributed by a mixture of both diesel and petrol engine type of vehicles, with diesel engine vehicles contributing a higher percentage of particulate PAHs to the different floor levels of both buildings. The total BaP_eq concentrations for point and slab blocks are 1.06±0.64 ng/m³ (0.14–2.45 ng/m³) and 0.94±1.22 ng/m³ (0.10–4.59 ng/m³), respectively. The total BaP equivalency results showed the potential health risk to cancer due to inhalation exposure is of concern for residents living in both blocks since the total BaP_eq concentrations for both blocks were very close to, or slightly exceeded the maximum permissible risk level of 1 ng/m³ of benzo(a)pyrene.     

Spatial and temporal distribution of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere of Xiamen, China

An intensive sampling program was conducted from October 2008 to September 2009 at the five different environmental sites in Xiamen, Fujian Province, to study the spatial and temporal characteristics of Polycyclic Aromatic Hydrocarbons (PAHs) in the gaseous and particulate phase, respectively. The PAHs concentrations at different sites were quite distinct during four seasons. The average concentrations of PAHs in winter were about 8.4 times higher than those in spring, and the concentrations of background were 0.56 times lower than those of industrial area. In addition, the higher temperature in summer affected the particle/gas partitioning of PAHs and led to the higher concentrations of gaseous PAHs. Diagnostic ratios of PAHs, which were employed to indicate the primary sources of PAHs in Xiamen, showed that the traffic vehicle exhaust was the largest contributor and the primary source for PAHs in Xiamen, especially in urban area; while the stationary combustion processes, such as petrochemical factories and power plants, were mainly responsible for PAHs sources in the industrial areas. The health risk of PAHs in the particulate phase was higher than those of the gaseous phase at the five sampling sites. The average toxic equivalent (BaP_eq) of the benzo[a]pyrene values for PAHs were 0.14, 0.32, 1.38 and 3.59 ng m^− 3 in spring, summer, autumn and winter, respectively. Furthermore, the results of average BaP_eq in all four seasons indicated that the health risks of particulate PAHs were higher than those of the gaseous PAHs at different sampling sites.     

Native polycyclic aromatic hydrocarbons (PAH) in coals - A hardly recognized source of environmental contamination

Numerous environmental polycyclic aromatic hydrocarbon (PAH) sources have been reported in literature, however, unburnt hard coal/ bituminous coal is considered only rarely. It can carry native PAH concentrations up to hundreds, in some cases, thousands of mg/kg. The molecular structures of extractable compounds from hard coals consist mostly of 2-6 polyaromatic condensed rings, linked by ether or methylene bridges carrying methyl and phenol side chains. The extractable phase may be released to the aquatic environment, be available to organisms, and thus be an important PAH source. PAH concentrations and patterns in coals depend on the original organic matter type, as well as temperature and pressure conditions during coalification. The environmental impact of native unburnt coal-bound PAH in soils and sediments is not well studied, and an exact source apportionment is hardly possible. In this paper, we review the current state of the art.     

Source apportionment of polycyclic aromatic hydrocarbons in New York/New Jersey Harbour sediment

Data on polycyclic aromatic hydrocarbons (PAHs) measured in surface sediment and cores in the New York/New Jersey Harbour under the Contamination Assessment and Reduction Project (CARP) was examined via Positive Matrix Factorization (PMF), which revealed six sources. Two represented the higher and lower molecular weight (MW) fractions of coal tar and/or creosote (pyrogenic) sources and explained 49% of PAH mass in the sediment samples. Two sources were related to uncombusted petroleum (petrogenic) sources, such as heavy fuel oil and crude oil, and explained 30% of PAH mass. The final two sources were related to combustion (pyrogenic) sources such as gasoline- and diesel-fuelled vehicles and explained 21% of the PAH mass. Sediment cores revealed that Σ₂₂PAH increased from the pre-industrial period until about 1980 and then decreased because of efforts to control water pollution via mechanisms such as the Clean Water Act.     

Inferences over the sources and processes affecting polycyclic aromatic hydrocarbons in the atmosphere derived from measured data

Data concerning atmospheric lifetime and relative source contributions of polycyclic aromatic hydrocarbons (PAH) are fragmentary and contradictory. In this study, two datasets of measurements of atmospheric PAH (sum of particulate and gaseous phases), one from a national network, the other from a more local three-site study, were analysed and used to infer processes affecting PAH in the atmosphere, and their sources. PAH congener profiles measured at urban and rural locations were remarkably similar suggesting that atmospheric decay processes are relatively slow. This allows the use of such profiles to elucidate sources. A spatial analysis of two PAH datasets showed a clear influence of industry and road traffic upon local PAH concentrations. When Principal Component Analysis (PCA) was applied to UK national network data, it showed a clear influence of steel industry emissions and of home heating emissions from coal and oil in Northern Ireland. These sites also showed different winter/summer concentration ratios to the main group of sites. In the data from Birmingham (UK), PCA identified separate factors relating to gasoline and diesel vehicles, as well as the influence of wood combustion on “Bonfire night”, and a factor related to home heating emissions which shows up only in the cold season.     

Photolysis of polycyclic aromatic hydrocarbons in water

The decomposition of benzo[a]pyrene (BAP), chrysene (CHR) and fluorene (FLU) in an aqueous solution by means of photolysis has been studied. The influence of initial polycyclic aromatic hydrocarbons' (PAHs) concentration, pH of the reaction mixture, temperature, presence of oxygen and tert-butyl alcohol (t-BuOH) on the degradation rate has been observed. BAP and CHR are decomposed by a mechanism different than FLU. Quantum yields of the photolytic decomposition of BAP, CHR and FLU were determined and equal 0.014, 0.0031 and 0.0038, respectively.     

Distributions of polycyclic aromatic hydrocarbons in surface waters, sediments and soils of Hangzhou City, China

Ten polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in 17 surface water samples and 11 sediments of four water bodies, and 3 soils near the water-body bank in Hangzhou, China in December 2002. It was observed that the sum of PAHs concentrations ranged from 0.989 to 9.663 microg/L in surface waters, from 132.7 to 7343 ng/g dry weight in sediments, and from 59.71 to 615.8 ng/g dry weight in soils. The composition pattern of PAHs by ring size in water, sediment and soil were surveyed. Three-ring PAHs were dominated in surface waters and soils, meanwhile sediments were mostly dominated by four-ring PAHs. Furthermore, PAHs apparent distribution coefficients (K(d)) and solid f(oc)-normalized K(d) (e.g. K(oc)= K(d) / f(oc)) were calculated. The relationship between logK(oc) and logK(ow) of PAHs for field data on sediments and predicted values were compared. The sources of PAHs in different water bodies were evaluated by comparison of K (oc) values in sediments of the river downstream with that in soils. Hangzhou section of the Great Canal was heavily polluted by PAHs released from industrial wastewater in the past and now PAHs in sediment may serve as sources of PAHs in surface water. PAHs in Qiantang River were contributed from soil runoff. Municipal road runoff was mostly contributed to West Lake PAHs.     

Levels and patterns of polycyclic aromatic hydrocarbons in incineration ashes

Polycyclic aromatic hydrocarbons were analysed in weathered bottom ash from municipal solid waste incineration, fly ash from a mixed heating plant and an ash mixture from different kinds of biofuels. Although of different origin and age, all three ashes are evaluated in different small-scale fill applications. The ultimate goal is the usage of these ashes on a larger scale. The samples were Soxhlet extracted and analysed using GC/MS in the full scan mode. The sum of the 16 US EPA PAHs was found to vary from 140 microg/kg up to more than 77000 microg/kg. Total amounts of PAHs were similar in bottom ash and in fly ash. The concentration in the mixed biofuel ash was more than 10 times higher, and exceeded the generic guidelines for PAHs in soil set by the Swedish Environmental Protection Agency. The patterns of the individual PAHs normalised to the total concentration of PAHs were found to be very similar for all the three ashes. Naphthalene and phenanthrene were the dominating PAHs for all ash samples, but the mixed biofuel ash also contained high levels of fluoranthene and pyrene.     

Wet deposition of polycyclic aromatic hydrocarbons in The Netherlands

The concentrations of 11 polycyclic aromatic hydrocarbons (PAH) in rainwater at four locations in the Netherlands in 1983 are reported. From literature data for these PAH in air, scavenging ratios were calculated. For PAH predominantly adsorbed on aerosols these scavenging ratios are in the range 3-13 X 10(4). For phenanthrene the scavenging ratios are in the range 0.35-2.5 X 10(4). The data for the aerosol-associated PAH at the various locations are discussed in terms of aerosol in-cloud scavenging, and are compared with reported data from Belgium and Germany. The scavenging ratios for phenanthrene are compared with those predicted on the basis of Henry's law constant and were found to be less than one order of magnitude higher than expected, possibly because of enhanced aqueous solubility.     

The environmental load and cycle of polycyclic aromatic hydrocarbons

Many polycyclic aromatic hydrocarbons (PAH) are known to be carcinogenic to animals and probably to man. Therefore, a better understanding of their formation, behavior and fate in the environment is necessary. Of the PAH carcinogens, 3,4-benzpyrene (BaP), which constitutes only about 1 % – 20 % of the group, is one of the most potent and ubiquitous, and therefore the most widely studied. Although the risk from carcinogenic PAH cannot yet be estimated, synergistic effects with other substances have also to be considered.The formation of PAH in the environment is due to an endogenic synthesis by microorganisms, phytoplankton, algae and highly developed plants, which provide the natural background, and to a second process which is connected with man-controlled high temperature pyrolitic reactions, open burning, and natural volcanic activities. Photooxidation is the major decomposition process by which PAH are reduced, biodegradation by microorganisms being a secondary reduction mechanism.The worldwide production of PAH by biosynthesis cannot be estimated on the basis of the limited data available at present. However, the global emission of BaP derived from exogenous sources has been estimated at about 5000 tons per year, a quantity which appears to exceed that formed endogenically. It may be assumed, that until the beginning of this century there still existed a natural balance between the production and degradation of PAH, which kept the natural background concentration low and fixed. However, with the ever-increasing industrial development in many parts of the world the natural balance is being disturbed and the production rate of PAH is constantly rising, while their rate of decomposition remains more or less constant. In view of the carcinogenic characteristics of many PAH compounds, their concentration in the environment should be considered alarming and efforts should be made to reduce or even eliminate them wherever possible. At the same time, an environmental programme should be developed for monitoring the PAH compounds and the various parameters affecting their formation, retention and destruction.     

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in sediments from the Mersey Estuary, U.K

Sediments from the Mersey Estuary were analysed for polycylic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Total PAH concentrations ranged from 626 to 3766 microg/kg and total PCB concentrations ranged from 36 to 1409 microg/kg. These concentrations are intermediate in comparison to other U.K estuaries with similar histories of industrialisation and urbanisation. The distribution of individual PAHs were consistent throughout the Mersey Estuary, this together with molecular indices suggests mainly pyrolitic inputs, augmented by a variety of industrial petrogenic sources. Comparison of tri-to-hepta PCB congeners revealed multiple sources and inputs throughout the estuary. A sediment core collected in close proximity to Garston Docks revealed the take-off, peak pollutant input and recent decline of PCB pollution. However, a second depth profile of sediments at Ellesmere Port showed little change in total or individual PCB concentrations due to extensive sediment reworking and mixing.     

Summer fluxes of atmospheric greenhouse gases N2O, CH4 and CO2 from mangrove soil in South China

The atmospheric fluxes of N₂O, CH₄ and CO₂ from the soil in four mangrove swamps in Shenzhen and Hong Kong, South China were investigated in the summer of 2008. The fluxes ranged from 0.14 to 23.83 μmol m⁻² h⁻¹, 11.9 to 5168.6 μmol m⁻² h⁻¹ and 0.69 to 20.56 mmol m⁻² h⁻¹ for N₂O, CH₄ and CO₂, respectively. Futian mangrove swamp in Shenzhen had the highest greenhouse gas fluxes, followed by Mai Po mangrove in Hong Kong. Sha Kong Tsuen and Yung Shue O mangroves in Hong Kong had similar, low fluxes. The differences in both N₂O and CH₄ fluxes among different tidal positions, the landward, seaward and bare mudflat, in each swamp were insignificant. The N₂O and CO₂ fluxes were positively correlated with the soil organic carbon, total nitrogen, total phosphate, total iron and NH₄⁺-N contents, as well as the soil porosity. However, only soil NH₄⁺-N concentration had significant effects on CH₄ fluxes.     

Concentrations, sources, and spatial distribution of individual polycyclic aromatic hydrocarbons (PAHs) in agricultural soils in the Eastern part of the EU: Poland as a case study

Soils from agricultural areas receive unsatisfactory attention as regards the contamination with organic pollutants. To answer those needs the contents of the sixteen individual PAH compounds were determined (GC/MS technique) in agricultural soils in Poland. The samples (n = 216) were collected from the upper layer of arable land in the year 2005. Half of the samples represented typical rural areas, while the rest derived from the territories potentially subjected to the urban/industrial pressure of various intensity. The mean (geometric) content of individual compounds varied from 1 μg kg^− 1 for acenaphtylene to 55 μg kg^− 1 for fluoranthene with the highest contributions (11.6%-12.9%) of phenanthrene, fluoranthene and pyrene. Higher molecular weight PAHs (4 rings) were strongly linked mutually and with the ∑16PAHs. They contributed substantially (73%) to the overall content of PAHs, which implies domination of anthropogenic sources. The calculated molecular indexes suggest that most of those PAHs derive from the combustion of coal, the main energy source in Poland. Simultaneously, the concentrations of lower molecular weight compounds seem to reflect the background, “natural” PAH compounds, which represent mainly atmospherically distributed emission. The division of the samples into groups describing geographical regions and landscape type enabled evaluation of the spatial trends in contamination of soils with PAH compounds. The most pronounced effect of spatial parameters corresponded to PAHs > 4 rings, while lower molecular weight compounds showed more homogeneous concentration through the country.