Molecular tracers of saturated and polycyclic aromatic hydrocarbon inputs into Central Park Lake, New York City

Saturated hydrocarbons (SH) and polycyclic aromatic hydrocarbons (PAHs) have been quantified in a sediment core obtained from Central Park Lake, New York City. Radionuclides 210Pb and 137Cs were used to assign approximate dates to each individual section in the core. The dating profile based on 210Pb matches very well with the time constraints provided by 137Cs. Radionuclide-derived depositional dates are consistent with temporal information from the petroleum-indicator ratio U/R [the ratio of unresolved complex mixture (UCM)to saturated hydrocarbons in the aliphatic fraction] and the history of fuel use in the NYC area. Ratios of 1,7-dimethylphenanthrane (DMP) to 1,7-DMP plus 2,6-DMP [1,7/(1,7 + 2,6)-DMP], retene to retene plus chrysene [Ret/(Ret + Chy)], and fluoranthene to fluoranthene plus pyrene [FI/(FI + Py)] provide additional source discrimination throughoutthe core. Results show that the ratio U/R is sensitive to petroleum inputs and Ret/(Ret + Chy) is responsive to contributions from softwood combustion, whereas both FI/(FI + Py) and 1,7/ (1,7 + 2,6)-DMP can be used to discriminate among wood, coal, and petroleum combustion sources. Combined use of these ratios suggests that in New York City, wood combustion dominated 100 years ago, with a shift to coal combustion occurring from the 1900s to the 1950s. Petroleum use began around the 1920s and has dominated since the 1940s.     

Sediment records of polycyclic aromatic hydrocarbons (PAHs) in the continental shelf of China: implications for evolving anthropogenic impacts

Sources, compositions, and historical records of polycyclic aromatic hydrocarbons (PAHs) in sediment cores collected from the Yellow Sea and the South China Sea were analyzed to investigate the influence of anthropogenic activities. The occurrence of PAHs was mainly derived from various combustion sources, especially the combustion of biomass and domestic coal. Uniform composition of sedimentary PAHs (52-62% of phenanthrene, benzo[b]fluoranthene, indeno[1,2,3-cd]pyrene, and benzo[g,h,i]perylene) suggested air-borne mixtures intractable to degradation. The concentrations of the sum of 15 PAHs (16 priority pollutants designed by the United States Environmental Protection Agency minus naphthalene; designed as Σ(15)PAH) in Yellow Sea sediment cores were generally higher than those in the South China Sea. The profiles of Σ(15)PAH concentrations recorded in the sediment cores closely followed historical socioeconomic development in China. In general, Σ(15)PAH concentrations started to increase from the background pollution level posed by agricultural economy at the turn of 20th century. In addition, a Σ(15)PAH concentration reduction was observed during the Chinese Civil War (1946-1949) and Great Cultural Revolution (1966-1976), suggesting them as setbacks for economic development in Chinese history. Increasing PAH emissions as a result of increasing coal combustion associated with the rapid urbanization and industrialization since the implementation of the Reform and Open Policy (since 1978) accounted for the fast growth of Σ(15)PAH concentrations in sediment cores. The decline of Σ(15)PAH concentrations from subsurface maximum until sampling time was inconsistent with current-day economic development in China, and may possibly suggest emission reductions due to decreasing proportional use of domestic coal and increasing consumption of cleaner energies (natural gas and liquefied petroleum gas).     

Fossil fuel and wood combustion as recorded by carbon particles in Lake Erie sediments 1850-1998

Carbon particle analysis was performed on a dated sediment core from Lake Erie in order to explore the inputs of pollution from incomplete combustion of coal, oil, and wood. Carbon particles were isolated from the sediment by chemical digestion, and elemental carbon content was determined by CHN analysis. The type of carbon particle (from burning coal, oil, and wood) and particle size and relative abundance were determined using scanning electron microscopy on 100 particles from each core section. The elemental carbon content in the Lake Erie core ranges from 2.5 to 7.4 mg of carbon/g of sediment (1850-1998), and the maximum carbon content in the sediment occurs in the late 1960s to early 1970s. It is shown that particle mass is a better predictor than particle number of historical energy consumption records. This is especially clear for wood where variable particle volumes play a significant role in determining the record of elemental carbon mass from wood burning. Lake Erie core's content of total carbon and carbon particle type is in agreement with U.S. energy consumption records, except that a wood maximum occurs during 1905-1917, about 36 yr after the U.S. consumption maximum from 1870 to 1880.     

Pyrogenic inputs of anthropogenic Pb and Hg to sediments of the Hood Canal, Washington, in the 20th century: source evidence from stable Pb isotopes and PAH signatures

Combustion-derived PAHs and stable Pb isotopic signatures ((206)Pb/(207)Pb) in sedimentary records assisted in reconstructing the sources of atmospheric inputs of anthropogenic Pb and Hg to the Hood Canal, Washington. The sediment-focusing corrected peak fluxes of total Pb and Hg (1960-70s) demonstrate that the watershed of Hood Canal has received greater atmospheric inputs of these metals than its mostly rural land use would predict. The tight relationships between the Pb, Hg, and organic markers in the cores indicate that these metals are derived from industrial combustion emissions. Multiple lines of evidence point to the Asarco smelter, located in the Main Basin of Puget Sound, as the major emission source of these metals to the watershed of the Hood Canal. The evidence includes (1) similar PAH isomer ratios in sediment cores from the two basins, (2) the correlations between Pb, Hg, and Cu in sediments and previously studied environmental samples including particulate matter emitted from the Asarco smelter's main stack at the peak of production, and (3) Pb isotope ratios. The natural rate of recovery in Hood Canal since the 1970s, back to preindustrial metal concentrations, was linear and contrasts with recovery rates reported for the Main Basin which slowed post late 1980s.     

Transport of gas-phase polycyclic aromatic hydrocarbons to the Venice lagoon

Concentrations of gas-phase polycyclic aromatic hydrocarbons (PAHs) were studied over one year at two sites of the Venice lagoon (designated Marine and Industrial) and at a mainland station (designated Rural) in Italy. Average sigmaPAH concentrations, calculated as sum of 16 PAHs, at Marine are about three and five times lower than those at Industrial and Rural, respectively. The seasonal trends, the temperature-PAH relationship, and principal component analysis indicate that at Industrial and Marine sites several local sources (vehicle and industrial emissions, etc.) could be the PAH sources in the warmer months, whereas in the colder months the main PAH sources could alternate between vehicle emissions and residential heating. At Rural the main PAH sources are: vehicle emissions in the spring and autumn; vehicle emissions, field burning, and wood combustion in the summer; and vehicle emissions and fuel consumption for residential heating in the winter. To evaluate the contribution from different sources to the Venice Lagoon air, horizontal fluxes of PAHs have been obtained. The estimated annual flux of PAHs is about 9 times greater at Industrial (193.5 mg m(-2) y(-1)) than at Marine (20.6 mg m(-2) y(-1)). These results show that study of the chemical contamination of the Venice atmosphere must take into account the PAH flux derived from marine sources as well as the continental input.     

Sources, vertical fluxes, and equivalent toxicity of aromatic hydrocarbons in coastal sediments of the Río de la Plata Estuary, Argentina

Settling particles and bottom sediments collected at 1, 2.5, and 4 km off the metropolitan Buenos Aires coast in the Río de la Plata were analyzed to evaluate the sources and toxicity of resolved (PAHs) and unresolved (AROUCM) aromatic hydrocarbons. PAHs (0003-2.1 microg g(-1)) and AROUCM (0.01-78 microg g(-1)) presented the highest concentrations nearthe Buenos Aires port and sewer and decreasing values up- and downstream and along on- and offshore gradients. Sediment traps deployed in the Central area revealed large aromatic fluxes (1.3 +/- 1.5 and 31 +/- 47 mg m(-2) day(-1) for PAHs and AROUCM). The composition of sedimentary PAHs was dominated by uniformly distributed high molecular weight pyrogenic PAHs (53 +/- 11% fluoranthene, pyrene, and heavier PAHs), followed by diagenetically derived perylene more abundant in less polluted sites (29 +/- 15%) and lower molecular weight petrogenic PAHs (18 +/- 7.1% phenanthrene, anthracene, and methylated compounds), which covaried inversely with perylene. PAH diagnostic ratios indicated a stronger influence of petrogenic discharges close to the shore and the prevalence of combustion of fossil fuels and vehicle emissions over wood in offshore sediments. Sediment cores showed sustained hydrocarbon levels with decreasing proportion of petrogenic PAHs and relative enrichment of pyrogenic components and perylene down to 20-cm depth. PAH toxicity assessment by sediment quality guidelines (SQG) and dioxin-equivalent factors (PAH TEQ: 0.08-395 pg g(-1) dw) identified 1-2.5 km sediments close to the port and sewer as the most affected area. According to SQG, dibenz[a,h]anthracene and pyrene were the most critical PAHs, followed by benzo[a]pyrene, benz[a]anthracene, and chrysene. In contrast, PAH TEQs were dominated by indeno[1,2,3-cd]pyrene, benzo[k]fluoranthene, benzo[a]pyrene, perylene, and benz[a]anthracene which accounted for an average 86 +/- 5.7% of total TEQs.     

Retene emission from residential solid fuels in China and evaluation of retene as a unique marker for soft wood combustion

Retene (1-methyl-7-isopropylphenanthrene) is often used as a marker for softwood combustion and for polycyclic aromatic hydrocarbon (PAH) source apportionment. The emission factors of retene (EF(RET)s) from 11 crop residues, 27 firewood fuels, and 5 coals were measured using traditional rural Chinese stoves. Retene was measured in combustion emissions from all of the residential fuels tested and EF(RET)s varied significantly among the fuels due to the differences in fuel properties and combustion conditions. EF(RET)s for pine (0.34 ± 0.08 mg/kg) and larch (0.29 ± 0.22 mg/kg) were significantly higher than those of other wood types, including fir and cypress (0.081 ± 0.058 mg/kg). However, EF(RET)s for crop residues varied from 0.048 ± 0.008 to 0.37 ± 0.14 mg/kg and were not significantly lower than those for softwood (0.074 ± 0.026 to 0.34 ± 0.08 mg/kg). The EF(RET)s for coal were very high and ranged from 2.2 ± 1.5 (anthracite briquette) to 187 ± 113 mg/kg (raw bituminous chunk). EF(RET) was positively correlated with EFs of coemitted particulate matter (EF(PM)) and phenanthrene (EF(PHE)) for crop residue and coal, but not for wood. In addition, the ratios of EF(PHE)/EF(RET) and EF(PM)/EF(RET) for coals were much lower than those for crop residues and wood. These data suggest that retene is not a unique PAH marker for softwood combustion and that coal combustion, in particular, should be taken into account when retene is used for PAH source apportionment.     

Black carbon emissions in China from 1949 to 2050

Black carbon (BC) emissions from China are of global concern. A new BC emission inventory (PKU-BC(China)) has been developed with the following improvements: (1) The emission factor database was updated; (2) a 0.1° × 0.1° gridded map was produced for 2007 based on county-level proxies; (3) time trends were derived for 1949-2007 and predicted for 2008-2050; and (4) the uncertainties associated with the inventory were quantified. It was estimated that 1957 Gg of BC were emitted in China in 2007, which is greater than previously reported. Residential coal combustion was the largest source, followed by residential biofuel burning, coke production, diesel vehicles, and brick kilns. By using a county-level disaggregation method, spatial bias in province-level disaggregation, mainly due to uneven per capita emissions within provinces, was reduced by 42.5%. Emissions increased steadily since 1949 until leveling off in the mid-1990s, due to a series of technological advances and to socioeconomic progress. BC emissions in China in 2050 are predicted to be 920-2183 Gg/yr under various scenarios; and the industrial and transportation sectors stand to benefit the most from technological improvements.     

Sorption characteristics of polycyclic aromatic hydrocarbons in aluminum smelter residues

High temperature carbon oxidation in primary aluminum smelters results in the release of polycyclic aromatic hydrocarbons (PAH) into the environment. The main source of PAH are the anodes, which are composed of petroleum coke (black carbon, BC) and coal tar pitch. To elucidate the dominant carbonaceous phase controlling the environmental fate of PAH in aluminum smelter residues (coke BC and/or coal tar), the sorptive behavior of PAHs has been determined, using passive samplers and infinitesink desorption methods. Samples directly from the wet scrubber were studied as well as ones from an adjacent 20-year old storage lagoon and roof dust from the smelter. Carbon-normalized distribution coefficients of native PAHs were 2 orders of magnitude higher than expected based on amorphous organic carbon (AOC)/water partitioning, which is in the same order of magnitude as reported literature values for soots and charcoals. Sorption isotherms of laboratory-spiked deuterated phenanthrene showed strong (-100 times stronger than AOC) but nonetheless linear sorption in both fresh and aged aluminum smelter residues. The absence of nonlinear behavior typical for adsorption to BC indicates that PAH sorption in aluminum smelter residues is dominated by absorption into the semi-solid coal tar pitch matrix. Desorption experiments using Tenax showed that fresh smelter residues had a relatively large rapidly desorbing fraction of PAH (35-50%), whereas this fraction was strongly reduced (11-16%) in the lagoon and roof dust material. Weathering of the coal tar residue and/or redistribution of PAH between coal tar and BC phases could explain the reduced availability in aged samples.     

Polycyclic aromatic hydrocarbon emissions from the combustion of alternative fuels in a gas turbine engine

We report on the particulate-bound polycyclic aromatic hydrocarbons (PAH) in the exhaust of a test-bed gas turbine engine when powered by Jet A-1 aviation fuel and a number of alternative fuels: Sasol fully synthetic jet fuel (FSJF), Shell gas-to-liquid (GTL) kerosene, and Jet A-1/GTL 50:50 blended kerosene. The concentration of PAH compounds in the exhaust emissions vary greatly between fuels. Combustion of FSJF produces the greatest total concentration of PAH compounds while combustion of GTL produces the least. However, when PAHs in the exhaust sample are measured in terms of the regulatory marker compound benzo[a]pyrene, then all of the alternative fuels emit a lower concentration of PAH in comparison to Jet A-1. Emissions from the combustion of Jet A-1/GTL blended kerosene were found to have a disproportionately low concentration of PAHs and appear to inherit a greater proportion of the GTL emission characteristics than would be expected from volume fraction alone. The data imply the presence of a nonlinear relation between fuel blend composition and the emission of PAH compounds. For each of the fuels, the speciation of PAH compounds present in the exhaust emissions were found to be remarkably similar (R(2) = 0.94-0.62), and the results do provide evidence to support the premise that PAH speciation is to some extent indicative of the emission source. In contrast, no correlation was found between the PAH species present in the fuel with those subsequently emitted in the exhaust. The results strongly suggests that local air quality measured in terms of the particulate-bound PAH burden could be significantly improved by the use of GTL kerosene either blended with or in place of Jet A-1 kerosene.     

Measurement of emissions from air pollution sources. 3. C1-C29 organic compounds from fireplace combustion of wood

Organic compound emission rates for volatile organic compounds (VOC), gas-phase semivolatile organic compounds, and particle-phase organic compounds are measured from residential fireplace combustion of wood. Firewood from a conifer tree (pine) and from two deciduous trees (oak and eucalyptus) is burned to determine organic compound emissions profiles for each wood type including the distribution of the alkanes, alkenes, aromatics, polycyclic aromatic hydrocarbons (PAH), phenol and substituted phenols, guaiacol and substituted guaiacol, syringol and substituted syringols, carbonyls, alkanoic acids, resin acids, and levoglucosan. Levoglucosan is the major constituent in the fine particulate emissions from all three wood types, contributing 18-30% of the fine particulate organic compound emissions. Guaiacol (2-methoxyphenol), and guaiacols with additional substituents at position 4 on the molecule, and resin acids are emitted in significant quantities from pine wood combustion. Syringol (2,6-dimethoxyphenol) and syringols with additional substituents at position 4 on the molecule are emitted in large amounts from oak and eucalyptus firewood combustion, but these compounds are not detected in the emissions from pine wood combustion. Syringol and most of the substituted syringols are found to be semivolatile compounds that are present in both the gas and particle phases, but two substituted syringols that have not been previously quantified in wood smoke emissions, propionylsyringol and butyrylsyringol, are found exclusively in the particle phase and can be used to help trace hardwood smoke particles in the atmosphere. Benzene, ethene, and acetylene are often used as tracers for motor vehicle exhaust in the urban atmosphere. The contribution of wood smoke to the ambient concentrations of benzene, ethene, and acetylene could lead to an overestimate of the contribution of motor vehicle tailpipe exhaust to atmospheric VOC concentrations.     

Contribution of biomass burning to atmospheric polycyclic aromatic hydrocarbons at three European background sites

Radiocarbon analysis of atmospheric polycyclic aromatic hydrocarbons (PAHs) from three background areas in Sweden, Croatia, and Greece was performed to apportion their origin between fossil and biomass combustion. Diagnostic ratios of PAHs implied that wood and coal combustion was relatively more important in the northern European site, while combustion of fossil fuels was the dominant source of PAHs to the two central-southern European background sites. The radiocarbon content (delta14C) of atmospheric PAHs in Sweden ranged between -388 per thousand and -381 per thousand, while more depleted values were observed for Greece (-914 per thousand) and Croatia (-888 per thousand). Using a 14C isotopic mass balance model it was calculated that biomass burning contributes nearly 10% of the total PAH burden in the studied southern European atmosphere with fossil fuel combustion making up the 90% balance. In contrast, biomass burning contributes about 50% of total PAHs in the atmosphere at the Swedish site. Our results suggest that the relative contributions of biomass burning and fossil fuels to atmospheric PAHs may differ considerably between countries, and therefore, different national control strategies might be needed if a further reduction of these pollutants is to be achieved on a continental-global scale.     

Long-term change of polycyclic aromatic hydrocarbon deposition to peatlands of eastern Canada

To date, studies about historic PAH (polycyclic aromatic hydrocarbons) deposition at a regional scale have rarely been published. To address this research gap, we sampled 17 ombrotrophic peatlands across eastern Canada. The peat cores from hollows were dated with 210Pb for the period of about 1850-2000 and analyzed fortheir PAH concentration, so PAH deposition could be reconstructed. Peat samples were extracted by accelerated solvent extraction (ASE). The extracts were purified by column chromatography with aluminum oxide and silica gel. PAH were measured by gas chromatography-tandem mass spectrometry (GC-MS/MS). Overall reconstructed deposition rates of sigma-11 PAH ranged from 4 to 1432 microg m(-2) year(-1). Three different long-term trends in PAH deposition could be distinguished: sites with two separated periods of maximum PAH deposition, sites with one period of maximum PAH deposition, and sites with no clearly separated period of maximum PAH deposition. Increasing PAH depositions were caused by rapid industrialization accompanied by extensive use of fossil fuels; decreasing PAH depositions were caused by substitution of these fuels and movements of PAH emitting industry to different regions. At all sites either phenanthrene (20-60%) or benzo[b+k]fluoranthene (10-40%) was the predominant PAH. Detailed analysis of three bogs suggested that combustion of coal and vehicle exhausts mainly contributed to the peat PAH burden. The temporal trends of PAH deposition indicated that increases in the PAH deposition rates followed the industrial development in Canada, particularly in the periods 1880-1910 and 1940-1960. Recent abatement efforts were reflected in decreased PAH deposition rates to about 15% of the maximum.     

Three-ring PAH removal from waste hot gas by sorbents: influence of the sorbent characteristics

Three-ring polycyclic aromatic hydrocarbons (PAH) are one of the most abundant PAH groups emitted during coal combustion. Four of them-acenaphthene (Ac), phenanthrene (Phe), fluorene (Fu), and anthracene (An)-have been listed by the U.S. EPA as priority pollutants. The aim in this paper is to study the abatement of this particular group of three-ring PAH from hot gas emissions during energy generation in coal combustion. The three-ring PAH adsorption capacities are related to the morphological and chemical properties of the 16 sorbents used in this work. Single and multiple linear regressions-principal component regression (PCR)-were applied in this study. The main conclusions reached are, first, that the micropore volume is the most determinant parameter for removal of these PAHs and, second, that the adsorption of three-ring PAH by sorbents from waste hot gas emissions is inversely proportional to their volatility: the lower the PAH volatility, the higher the adsorbent adsorption capacity. The adsorption isotherms show that Phe and An, both examples of PAH with three aromatic rings, behave similarly. However, their behavior differs from that of Ac and Fu, compounds in which only two of their three rings exhibit an aromatic nature.     

Semi volatile organic compounds in ambient PM2.5. Seasonal trends and daily resolved source contributions

Concentrations of ambient semivolatile organic compounds (SVOC) in the PM2.5 fraction of Augsburg, Germany, have been monitored on a daily basis from January 2003 through December 2004. Samples were taken in a large garden in the city center. Quantitative analysis of n-alkanes, alkanones, alkanoic acid methylesters, long chain linear alkyl benzenes and toluenes, hopanes, polycyclic aromatic hydrocarbons (PAH) and oxidized PAH, and some abietan type diterpenes was done. All compounds showed distinct seasonal variations in concentration. Most compounds showed highest concentrations during the cold seasons, but some n-alkanones and 6,10,14-trimethylpentadecanone showed maximum concentration during summer. Changes in patterns between and within compound classes were obvious, e.g., the hopane pattern exhibited a strong seasonal variation. The main source related contributions to changes observed were discussed. Using positive matrix factorization (PMF) for the statistical investigation of the data set, five factors have been separated. These factors are dominated by the pattern of single sources or groups of similar sources: factor 1, lubricating oil; factor 2, emissions of unburned diesel and heating oil consumption; factor 3, wood combustion; factor 4, brown coal combustion; and factor 5, biogenic emissions and transport components. Like the SVOC, the factors showed strong seasonality with highest values in winter for factors 1-4 and in summer for factor 5.     

Speciation of gas-phase and fine particle emissions from burning of foliar fuels

Fine particle matter with aerodynamic diameter <2.5 microm (PM2.5) and gas-phase emissions from open burning of six fine (foliar) fuels common to fire-prone U.S. ecosystems are investigated. PM2.5 distribution is unimodal within the 10-450 nm range, indicative of an accumulation mode. Smoldering relative to flaming combustion shows smaller particle number density per unit time and median size. Over 100 individual organic compounds in the primarily carbonaceous (>70% by mass) PM2.5 are chemically speciated by gas chromatography/mass spectrometry. Expressed as a percent of PM2.5 mass, emission ranges by organic compound class are as follows: n-alkane (0.1-2%), polycyclic aromatic hydrocarbon (PAH) (0.02-0.2%), n-alkanoic acid (1-3%), n-alkanedioic acid (0.06-0.3%), n-alkenoic acid (0.3-3%), resin acid (0.5-6%), triterpenoid (0.2-0.5%), methoxyphenol (0.5-3%), and phytosterol (0.2-0.6%). A molecular tracer of biomass combustion, the sugar levoglucosan is abundant and constitutes a remarkably narrow PM2.5 mass range (2.8-3.6%). Organic chemical signatures in PM2.5 from open combustion of fine fuels differ with those of residential wood combustion and other related sources, making them functional for source-receptor modeling of PM. Inorganic matter [PM2.5 - (organic compounds + elemental carbon)] on average is estimated to make up 8% of the PM2.5. Wavelength dispersive X-ray fluorescence spectroscopy and ion chromatography identify 3% of PM2.5 as elements and water-soluble ions, respectively. Compared with residential wood burning, the PM2.5 of fine fuel combustion is nitrate enriched but shows lower potassium levels. Gas-phase C2-C13 hydrocarbon and C2-C9 carbonyl emissions are speciated by respective EPA Methods T0-15 and T0-11A. They comprise mainly low molecular weight C2-C3 compounds and hazardous air pollutants (48 wt % of total quantified volatile organic carbon).     

Historical perspective of industrial lead emissions to the atmosphere from a Canadian smelter

Dated sediment cores from four remote Canadian Shield headwater lakes, where atmospheric deposition has been the only input of anthropogenic Pb, situated along a transect extending 300 km from a nonferrous metal smelter, were analyzed for both lead concentrations and isotopic composition; porewater samples collected at the same sites were analyzed for Pb and other geochemical variables. The depth distributions of stable Pb isotope ratios show the presence of several isotopically distinct Pb types since the preindustrial period. Lead from the smelter emissions had an isotopic signature (e.g., 206Pb/207Pb approximately 0.993) that was clearly distinct from those of Pb in aerosols collected at sites remotefrom point sources in Eastern Canada (e.g., 206Pb/207Pb usually approximately 1.15-1.20) and the United States (e.g., 206Pb/207Pb usually approximately 1.15-1.22), allowing the geographical area impacted by the smelter Pb emissions to be traced. On the basis of the sediment Pb isotopic composition, it is estimated that lead from the smelter accounts for 89%, 88%, and 5-34% of the total inventory of anthropogenic Pb deposited in the sediments of lakes located 10, 25, and 150 km from the smelter, respectively; but lead from this point source was not detected in sediments of a fourth lake that is 300 km from the smelter. We also estimate that the amount of smelter-derived Pb deposited within a distance of 150 km is equivalent to 5-10% of the amount released by leaded gasoline combustion in all of Canada. Sharp decreases in the recent Pb fluxes to lake sediments indicate that the measures taken to mitigate metal emissions from the smelter were effective.     

A 3500-year record of Hg and Pb contamination in a mediterranean sedimentary archive (the Pierre Blanche Lagoon, France)

A sediment core encompassing 3500 years of continuous sedimentation has been collected from a coastal lagoon located on the southwestern French Mediterranean coast. Lead concentrations and stable isotopes show that the sediments have recorded the three major periods of Pb pollution: the Etruscan-Greek-Roman period (650 BC to AD 50), the medieval period (AD 650 to AD 1450), and the modern period (from around AD 1850 to the present). These periods were separated by low pollution periods during the Dark Ages (between AD 50 and 650) and during the 16th century. From the end of the 19th century to the 1960s, Pb pollution increased exponentially. Coal combustion was the major source of Pb in the lagoon in the second half of the 20th century. Both the decrease in coal consumption and the ban on leaded gasoline resulted in a decrease in Pb pollution by a factor of 1.5 between 1973 and 1995. From 1991, sewage treatment plants and incinerators could be the major source of Pb. The average baseline Hg concentration from 1525 BC to AD 900 was 0.017 ± 0.003 μg g?1 (n = 54). The Hg concentrations profile shows three major peaks: in AD 1150, AD 1660, and AD 1969, with the concentrations being respectively 8, 5, and 34 times higher than the baseline levels. The medieval peak (AD 1150) is attributed the medical use of Hg in the town of Montpellier and/or the burning of soil and vegetation. Noticeable Hg pollution was also detected during the 17th century in relation to gold and silver amalgamation in Europe. From the end of the 19th century, Hg concentrations increased exponentially until 1969. This modern pollution is attributed to the burning of coal.     

PCB and PAH speciation among particle types in contaminated harbor sediments and effects on PAH bioavailability

This research provides particle-scale understanding of PCB and PAH distribution in sediments obtained from three urban locations in the United States: Hunters Point, CA; Milwaukee Harbor, WI; and Harbor Point, NY. The sediments comprised mineral grains (primarily sand, silt, and clays) and carbonaceous particles (primarily coal, coke, charcoal, pitch, cenospheres, and wood). The carbonaceous sediment fractions were separated from the mineral fractions based on their lower density and were identified by petrographic analysis. In all three sediments, carbonaceous particles contributed 5-7% of the total mass and 60-90% of the PCBs and PAHs. The production of carbonaceous particles is not known to be associated with PCB contamination, and it is very unlikely that these particles can be the source of PCBs in the environment Thus, it appears that carbonaceous particles preferentially accumulate PCBs acting as sorbents in the aqueous environment if PCBs are released directly to the sediment or if deposited as airborne soot particles. Aerobic bioslurry treatment resulted in negligible PAH loss from the carbonaceous coal-derived material in Milwaukee Harbor sediment but resulted in 80% of the PAHs being removed from carbonaceous particles in Harbor Point sediment. Microscale PAH extraction and analysis revealed that PAHs in Harbor Point sediment were associated mainly with coal tar pitch residue. PAHs present in semisolid coal tar pitch are more bioavailable than PAHs sorbed on carbonaceous particles such as coal, coke, charcoal, and cenosphere. Results of this study illustrate the importance of understanding particle-scale association of hydrophobic organic contaminants for explaining bioavailability differences among sediments.     

Onset of industrial pollution recorded in Mumbai mudflat sediments, using integrated magnetic, chemical, 210Pb dating, and microscopic methods

The onset and rise of urban and industrial pollution in the Mumbai region was reconstructed from an anthropogenically contaminated mudflat sediment profile from the adjacent Thane creek using magnetic parameters, polycyclic aromatic hydrocarbon (PAH) data, metal contents, and the (210)Pb dating technique. The 1.8 m vertical section at Airoli (Navi Mumbai) reveals an increase of magnetic susceptibility (χ) from background values of (20-50) to (75-100) × 10(-8) [m(3) kg(-1)] in the anthropogenically affected zone above ～93 cm. A sharp rise of χ from (75-100) to (130-215) × 10(-8) [m(3) kg(-1)] subdivides the anthropogenically affected zone at a depth of ～63 cm. Characterization with rock magnetic parameters (SIRM, Soft IRM, and S-ratio) reveals a significant contribution of ferri(o)magnetic phases in the upper zone. Based on the magnetic classification sampling intervals for cost-intensive PAH and metal analyses were determined. Steadily increasing contents of PAH and metals of anthropogenic origin are observed above the boundary depth at ～93 cm. A sediment accumulation rate of 1.2 ± 0.3 cm/yr provided by (210)Pb dating dates the ～63 cm boundary to 1951. Increasing industrial activity, including the establishment of a coal-fired power plant in 1956, and refineries between 1955 and 1960, correlates well with the substantial increase of χ, PAH, and metal contents. Scanning electron microscopy (SEM) investigation on magnetic extracts from the contaminated zone reveals the presence of magnetic spherules derived from industrial high-temperature processes.