The role of zooplankton fecal pellets in the sedimentation of polycyclic aromatic hydrocarbons in Dabob Bay,Washington

Polycyclic aromatic hydrocarbon (PAH) compositions were determined in plankton, sediment-trap-collected particulate material and sediment cores from Dabob Bay using a high performance liquid Chromatographie (HPLC)/fluorescence technique. The annual flux of individual PAH measured in a series of sediment traps was compared with the flux of corresponding compounds determined from ²¹⁰Pb dated bottom sediments. Systematic seasonal variations in the fluxes and concentrations of PAH, Al and organic carbon in the trap-collected particulates and seasonally collected plankton were also investigated to determine whether or not PAH are associated with either terrestrial or marine-derived materials.Concentrations of all PAH studied increased tenfold within the last 80–100 yr of sediment deposition, except for perylene which displayed a reasonably constant concentration profile. This suggests at least two sources contribute to the observed sedimentary PAH compositions in Dabob Bay, i.e., anthropogenic combustion and a natural source. Plankton and sediment trap-collected particulates contained PAH mixtures qualitatively similar to underlying surface sediments. Microscopic examination indicated fecal pellets were the major form of particulate material in the sediment traps. The fecal pellets collected in the sediment trap time series quantitatively account for essentially 100% of the PAH fluxes measured in the ²¹⁰Pb dated sediments, implying Zooplankton fecal pellets control the removal of PAH to Dabob Bay sediments. These measurements provide clear evidence that the PAH studied are not produced after sediment deposition. The observed seasonal covariations of PAH and Al in both sediment trap and plankton samples further indicate that PAH originate from terrestrially-based sources, are introduced into the marine environment by runoff and erosion or atmospheric deposition and are not produced by marine plankton.     

Polycyclic aromatic hydrocarbons in Recent lake sediments—I. Compounds having anthropogenic origins

Polycyclic aromatic hydrocarbons (PAH) in sediment cores from Lake Lucerne, Lake Zürich, and Greifensee, Switzerland, and Lake Washington, northwest U.S.A., have been isolated, identified and quantified by glass capillary gas chromatography and gas chromatography/mass spectrometry. Surface sediment layers are greatly enriched in PAH—up to 40 times—compared to deeper layers. In addition, concentration increases in upper sediments generally correspond to increasing industrialization and urbanization in the catchment basins of the lakes. Few PAH could be detected in pre-industrial revolution sediments, indicating that background levels for most PAH in aquatic sediments are extremely low.These results are consistent with an anthropogenic source for most of the aromatic hydrocarbons present in the modern sediments. A comparison of PAH distributions in the sediments and in possible source materials shows that urban runoff of street dust may be the most important PAH input to these lacustrine sediments. There is evidence that a significant contribution to the PAH content of street dust comes from material associated with asphalt.     

Levels and distributions of polycyclic aromatic hydrocarbons (PAHs) in middle reach of Huaihe River,China: anthropogenic influences and ecological risks

Polycyclic aromatic hydrocarbons (PAHs) are a group of aromatic hydrocarbons with high toxicity to human health. PAH emissions from industrial activities have become the primary sources of PAH contamination in Chinese watersheds. Here, we analyzed 10 individual priority PAHs in 120 water samples taken from middle reach of Huaihe River, China. The results show that the PAH levels in studied watershed are significantly lower as compared to other Chinese watersheds, approaching or slightly exceeding the PAH levels in watersheds from selected European and North American countries. We observe rather large variation in spatial and vertical PAH distributions, pointing to PAH inputs from local industrial emissions, and PAH cycle among atmosphere, water and sediment. Individual PAH ratios (i.e., phenanthrene/anthracene and fluorene/pyrene) and principal components analysis suggest a primarily pyrolytic PAH sources (combustion of coal and coke) in water column. Other accompanying PAH sources include emissions from steel industry and gasoline. Total toxic benzo[a]pyrene equivalent of PAHs in studied water column indicates that PAHs in watershed of middle reach of Huaihe River pose limited toxicity to the environment.     

Effects of physical mixing on the attenuation of polycyclic aromatic hydrocarbons in estuarine sediments

To examine the role of physical disturbance on the long-term preservation of polycyclic aromatic hydrocarbons (PAHs) in sediments, cores were collected from two sites removed from point sources of PAHs and representing contrasting seabed mixing regimes. Although ΣPAH concentrations in sediments over the past 50 years were not significantly different between the two sites, several PAH isomer ratios were significantly different (P<0.05) between the two sites. Downcore changes in PAH isomer ratios resulted from preferential losses of the more linear PAH isomers. Thus, episodic, intense seabed mixing contributes to more efficient removal of selected PAHs. However, PAHs are still sufficiently stable relative to mixing events that historical PAH profiles can be used to reconstruct major resuspension events.     

Role of prior exposure on anaerobic degradation of naphthalene and phenanthrene in marine harbor sediments

The anaerobic degradation of the polycyclic aromatic hydrocarbons (PAHs) naphthalene and phenanthrene was investigated in several marine harbor sediments. In sediments from Boston Harbor that were heavily contaminated with petroleum, [¹⁴C]-naphthalene and [¹⁴C]-phenanthrene were oxidized to ¹⁴CO₂ without a lag, suggesting that the microbial community was adapted for anaerobic PAH oxidation in situ. The addition of molybdate, a specific inhibitor of sulfate-reducing microorganisms, inhibited PAH mineralization which suggested that sulfate reducers were involved in the anaerobic oxidation of the PAHs. PAHs were also anaerobically oxidized at another site in Boston Harbor that was less heavily contaminated, but at a slower rate than in the most heavily contaminated sediments. Sediments not contaminated with petroleum did not significantly oxidize the PAHs. A similar correspondence between rates of anaerobic PAH oxidation and the degree of PAH contamination was observed in sediments from Tampa Bay and San Diego Bay. When relatively pristine sediments from San Diego Bay that did not have a significant capacity for anaerobic PAH oxidation were exposed to high concentrations of naphthalene, they developed a potential for naphthalene degradation that was comparable to that in sediments that had a history of PAH contamination. The increase in potential for naphthalene degradation in the sediments exposed to naphthalene was associated with an increase in naphthalene-degrading microorganisms. These results suggest that many marine harbor sediments contain microorganisms capable of anaerobically oxidizing PAHs under sulfate-reducing conditions and that these microorganisms will respond with an increase in their activity when PAHs are introduced into the sediments. Thus, if PAH inputs into harbor sediments from petroleum can be reduced there may be a widespread potential for microorganisms to remove this PAH contamination from the sediments, despite anaerobic conditions.     

Biogenic and abiogenic polynuclear aromatic hydrocarbons in sediments from two remote Adirondack lakes

Sediment cores from Sagamore Lake and Woods Lake in New York State's Adirondack Park, an area remote from industrial activities, were analyzed for polynuclear aromatic hydrocarbons (PAH) by high resolution gas chromatography/mass spectrometry (GC/MS). Their composition and distribution with depth in the sediment indicate that the parental PAH in the surface sediments are primarily produced by anthropogenic combustion of fossil fuels. Perylene in deep sediments is apparently transformed from natural precursors in the reducing environment, however, the exact precursors remain unknown. The rather even sediment distributions of the non-parental PAH differ from the parental, suggesting biogenic origins. Based on their chemical structures, retene and alkylated and partially hydrogenated phenanthrenes are believed to be biogenically converted from abietic acid; hydrochrysenes and hydropicenes, from pentacyclic triterpenes.     

Polycyclic aromatic hydrocarbons in dated sediments from Green Bay and Lake Michigan

Sediment cores from two locations in Green Bay and two in lake Michigan were analyzed for 12 polycyclic aromatic hydrocarbons (PAHs), loss-on-ignition (LOI),²¹⁰Pb,¹³⁷Cs, and⁷Be to study differences in deposition patterns between the freshwater estuary Green Bay, with several local sources, and the open Lake Michigan, dominated by atmospheric inputs. We found that the remote sites receive relatively less high-molecular weight PAHs such as ideno(1,2,3-cd)pyrene and dibenz(ah)anthracene and are more depleted in anthracene and pyrene. This may be related to a low Henry’s law constant for the high molecular compounds and to selective photo-oxidation of anthracene and pyrene during transport. While sedimentation rates are higher in Green Bay than in the open lake, the PAH levels are generally comparable (0.3–8.5 μg g^?1) in the two areas. However, the highest PAH levels are found in a core from Green Bay (GB88G). The two Green Bay cores have total PAH concentration maxima in 1985, which appear to be related to the combustion of petroleum. Also, one Green Bay core (GB88G) and the two from Lake Michigan exhibit PAH maxima in the early 1950s in agreement with observations from other study areas. There is a significant correlation between total PAH and LOI, and thus total organic carbon, for the Green Bay cores, but little or no such correlation for the Lake Michigan cores. This may indicate that PAHs in Green Bay are effectively scavenged by settling detritus.     

The polycyclic aromatic hydrocarbon concentrations in soils in the Region of Valasske Mezirici, the Czech Republic

The polycyclic aromatic hydrocarbon (PAH) contamination of urban, agricultural and forest soil samples was investigated from samples obtained in the surroundings of Valasske Mezirici. Valasske Mezirici is a town located in the north-east mountainous part of the Czech Republic, where a coal tar refinery is situated. 16 PAHs listed in the US EPA were investigated. Organic oxidizable carbon was also observed in the forest soils. The PAH concentrations ranged from 0.86-10.84 (with one anomalous value of 35.14) and 7.66-79.39 mg/kg dm in the urban/agricultural and forest soils, respectively. While the PAH levels in the urban/agricultural soils are within the range typically found in industrialized areas, the forest soils showed elevated PAH concentrations compared to other forest soils in Western and Northern Europe. The PAH concentrations and their molecular distribution ratios were studied as functions of the sample location and the meteorological history. The soils from localities at higher altitudes above sea level have the highest PAH concentrations, and the PAH concentrations decrease with increasing distance from the town.     

Polycyclic aromatic hydrocarbons in an anoxic sediment core from the Pettaquamscutt River (Rhode Island,U.S.A.)

Fifteen sections from an anoxic sediment core were analyzed for polycyclic aromatic hydrocarbons (PAH). Two types of PAH were observed: (a) those from combustion sources such as pyrene and chrysene and (b) those from natural sources such as retene and perylene. The combustion PAH levels in core sections dated between 1900 and 1970 were much higher than in earlier sections; this indicated an anthropogenic origin of these PAH at this location. The perylene and retene core profiles show significant anomalies during the period 1850–1880. Organic carbon does not fluctuate markedly but δC-13 of organic carbon shows several unexplained excursions; one of which correlates with the perylene and retene anomalies.     

Polycyclic aromatic hydrocarbons as evidence of hydrocarbon migration in marine and lagoon sediments of a recent rift zone (Skjálfandi and Öxarfjörður), Iceland

Polycyclic aromatic hydrocarbons (PAHs) content and distribution was studied in the northern part of modern rift zone. All samples analysed represent slightly altered clastic deposits and hot water discharging in springs and from wells. To study PAH in present-day gas emission traps with diatomite absorbent were installed in the Skógalón geothermal field. All samples were analysed by the method of Shpol'sky spectroscopy. Hydrothermally altered deposits show the highest amount of PAH. Data obtained allow to believe that the distribution of PAH is closely associated with the dynamics of the hydrothermal environment. The fissure formation and temperature fluctuation in hydrothermal systems can govern both the processes of PAH synthesis and sorption. The evidences of PAH migration up through the Skjálfandi and Öxarfjörður sedimentary basins show that hydrocarbons associate mainly with hydrothermal minerals and deep ground waters. Studying PAH associations can be used as an indicator of hydrocarbons distribution, ways of migration and possible zones of accumulation in the land and marine sedimentary basins in active and ancient rift zones of Iceland.     

Factors affecting pore water hydrocarbon concentrations in Puget Sound sediments

Polycyclic aromatic hydrocarbon (PAH) and aliphatic hydrocarbon concentrations have been determined for sediments and associated pore waters collected at 2 sites (11 stations) in Puget Sound, Washington (northwest U.S.A.). These sediments have been contaminated to varying degrees by hydrocarbons from a creosote plant and from various combustion sources. PAH were not detected in pore waters of sediments whose PAH were primarily derived from combustion and natural sources, even though pore water concentrations predicted from sediment concentrations and two-phase equilibrium partitioning models were above detection limits from most PAH. Equilibrium partition coefficients calculated from field aqueous and solid phase data from an area contaminated with creosote agreed with laboratory-derived coefficients to within a factor of ± 4. Pore water concentrations of creosote-derived aliphatic hydrocarbons increase with increasing concentration in bulk sediments. However, pore water concentrations of natural and contaminant aliphatic hydrocarbons are much higher than predicted by solubility data, possibly due to association with nonfilterable dissolved organic matter and colloids. Other major factors controlling hydrocarbon pore water concentrations include differential hydrocarbon sources, specific particle associations and solubility.     

Sources and bioavailability of polynuclear aromatic hydrocarbons in Galveston Bay, Texas

Oyster and sediment samples collected from six sites in Galveston Bay from 1986 to 1998 were analyzed for polynuclear aromatic hydrocarbons (PAHs). Total concentrations of parent PAHs in oysters ranged from 20 ng g⁻¹ at one site to 9,242 ng g⁻¹ at another and varied randomly with no clear trend over the 13 year period at any site. Concentrations of alkylated PAHs, which are indications of petroleum contamination, varied from 20 to 80,000 ng g⁻¹ in oysters and were in higher abundance than the parent PAHs, indicating that one source of the PAH contaminants in Galveston Bay was petroleum and petroleum products. Four to six ring parent PAHs, which are indicative of combustion source , were higher than those of 2–3 ring parent PAHs, suggesting incomplete combustion generated PAHs was another source of PAHs into Galveston Bay. Concentrations of parent PAHs in sediments ranged from 57 to 670 ng g⁻¹ and were much lower than those in oysters. Sediments from one site had a high PAH concentration of 5,800 ng g⁻¹. Comparison of the compositions and concentrations of PAHs between sediment and oysters suggests that oysters preferentially bioaccumulate four to six ring PAHs. PAH composition in sediments suggests that the sources of PAH pollution in Galveston Bay were predominantly pyrogenic, while petroleum related PAHs were secondary contributions into the Bay.     

Elevated critical micelle concentration in soil–water system and its implication on PAH removal and surfactant selecting

Triton X-100 (TX100) and Brij 35 (B35) were used to investigate the elevated critical micelle concentration (CMC) induced by surfactant sorption and its influence on PAH removal in soil washing systems. The surface tension technique was applied to determine the CMC and the apparent CMC (CMC_soil) in soil–water systems. Surfactant sorption experiments were conducted by the batch equilibration technique. Surfactants sorbed on the soil at concentrations below the CMC_soil were quantified with data from the surface tension experiments for both an aqueous system and a soil–water system. Due to sorption, the CMC_soil values of the two surfactants are 2.75 and 6.31 times their corresponding CMC values in aqueous solutions, respectively. At concentrations below CMC_soil, the loss of B35 (92–99.7 %) was greater than that of TX100 (63–92 %). The PAH removal efficiencies are greatly dependent on the CMC_soil value. At surfactant concentrations below CMC_soil, the PAH removal is very low and remains almost invariable. Whereas, at concentrations above CMC_soil, the PAH removal increases greatly. B35 inhibited PAH desorption at concentrations below its CMC_soil. For TX100, some degree of PAH desorption enhancement was observed at concentrations below its CMC_soil. CMC_soil is a key parameter while selecting a surfactant for a specific soil washing system, only surfactant concentrations above their CMC_soil should be evaluated.     

Polycyclic aromatic hydrocarbon concentrations in urban soils representing different land use categories in Shanghai

An extensive soil survey was carried out in Shanghai to investigate the spatial distribution and possible sources of polycyclic aromatic hydrocarbons (PAHs) in urban soils. Soil samples were collected from highways, iron-smelting plants, steel-smelting plants, shipbuilding yards, coking plants, power plants, chemical plants, urban parks, university campuses and residential areas and were analyzed for 16 PAHs by gas chromatography with mass detection. High PAH concentrations were found in all locations investigated, with mean values of soil total PAH concentrations in the range 3,279–38,868 μg/kg DM, and the PAH concentrations were significantly influenced by soil organic matter content. Soil PAH profiles in all districts were dominated by PAHs with 4–6 rings. Principal components analysis and diagnostic ratios of PAHs indicate that they were mainly derived from coal combustion and petroleum but in soils from highways the PAHs were derived largely from vehicle exhaust emissions. The high concentrations of PAHs found indicate that many urban soils in Shanghai represent a potential hazard to public health.     

Fluxes of polycyclic aromatic hydrocarbons to marine and lacustrine sediments in the northeastern United States

Polycyclic aromatic hydrocarbons (PAH) were measured in dated sediment cores from several sites in the northeastern United States (Lake Superior, Isle Royale, Somes Sound, Hadlock Lower Pond. Coburn Mountain Pond, and outer Boston Harbor). Fluxes of ten PAH were measured for each site for the periods roughly corresponding to the present, 1950, and 1900. Remote sites consistently demonstrated present-day deliveries of individual PAH near 1 ng cm^?2 yr^?1, probably reflecting the atmospheric fallout of these combustion-derived pollutants. Sites located nearer to urban centers showed much greater current inputs (average of 35 ng cm^?2 yr^?1 for most individual PAH), presumably caused by greater fallout of PAH-laden particles nearer their urban origins, augmented by runoff delivery of PAH-contaminated sediments. Differences in the relative abundances of individual PAH at remote-versus-urban locations support suggestions of different delivery mechanisms. The sedimentary historical records of PAH inputs confirm the previous finding that anthropogenic activities began introducing large quantities of PAH into the environment about 80–100 years ago.     

Source apportionment of elevated PAH concentrations in sediments near deep marine outfalls in Esquimalt and Victoria,BC, Canada: Is coal from an 1891 shipwreck the source?

Previous studies have suggested that coal from the 1891 shipwreck of a collier off Victoria, BC, Canada is responsible for elevated parent (unsubstituted) PAH concentrations in sediments near deep marine outfalls from Esquimalt and Victoria in the Strait of Juan de Fuca. To resolve this question, we analysed a comprehensive suite of resolved and unresolved complex mixture (UCM) alkanes, tricyclic terpane, hopane and sterane biomarkers, and parent and alkyl polycyclic aromatic hydrocarbons (PAHs) in samples of coal, wastewater and sediments. Composition patterns, principal components analysis (PCA) models and PAH and biomarker ratios all indicate that coal from the collier does not make a dominant contribution to any sediment sample. Mass balance calculations based on the n-C₂₄ content and 24/4 tetracyclic terpane to 26/3R tricyclic terpane ratio in coal provide a particularly good match between predicted and observed alkyl PAH concentrations for sediments with high alkyl naphthalenes and phenanthrene/anthracenes and low UCM, but the predicted coal contribution substantially underestimates the measured parent PAHs for all sediment samples. Methylbenz[a]anthracene/chrysene profiles for sediments with a dominance of parent PAHs are very close to coal tar, with a marked predominance of methylbenz[a]anthracenes and the possible 10-methylbenz[a]anthracene as a major constituent, while the methylchrysenes predominate in coal. Hence, coal from the collier could account for most alkyl PAHs in the sediments, but dredged sediment containing pyrolised coal waste from a former coal gas plant in Victoria Harbour is a more likely source for the samples with elevated parent PAHs. PAH ratios indicate that these sources are superimposed on combustion PAHs introduced by a combination of atmospheric deposition and delivery via stormwater and the outfalls. Parent PAH distributions also suggest that PAHs in wastewater that originate from oils and soot in liquid fossil fuel combustion are dispersed and degraded, while the larger wood char particles (containing PAHs more protected from degradation) settle closer to the outfalls. Overall, results suggest that PAHs have predominant sources in wood combustion, coal and possibly coke, with a likelihood of much lower bioavailability than would be expected from wastewater dominated by oils and soot from vehicle combustion.     

Sediment-water column exchange of persistent organic pollutants (PAH<Subscript>s</Subscript> and PCB<Subscript>s</Subscript>) and their transport vector in El Bey watershed,Tunisia

El Bey river, which drains 60% of the pollutant load of several urban cities in the northeast of Tunisia, provides a good example of the transfer of organic and metallic pollutants that result from industrial and urban activity, and can be used to show how these charges are transported and discharged into the Gulf of Tunis. Persistent organic pollutants (PAH and PCB) in dissolved, particulate matter, bed sediments, and three wastewater effluents in El Bey watershed were analyzed. PAH (∑14PAHs) concentration ranged from 0.248 to 9.955 mg L^?1 and from 0.836 to 28.539 mg L^?1 in dissolved and particulate fraction respectively. The particulate/dissolved partition coefficient value (Kd) was less than one which confirmed the affinity of PAH to be adsorbed. In sediment, the high-molecular weight PAHs were found principally with percentage between 50 and 100% witch present 239.99 to 5362.19 μg kg^?1, which is relatively higher in comparison with other estuaries river. Contrary to PAH patterns, PCB were bound to dissolve fraction. Kd _(PCB) value (Kd?>?1) reflected this affinity which is related to environment energy. The spatial distribution and profile of analyzed organic pollutants confirmed the direct impact of wastewater effluent on the organic pollution level in three compartment of El Bey watershed and his profiles suggested different transport patterns.