Historical residues of organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs) in a flood sediment profile from the Longwang Cave in Yichang, China.

Historical residual of persistent organic pollutants (POPs) in flood sediment from a karst cave were investigated. Fifteen vertical sediment samples were collected from a 6 m-deep flood sediment profile in the Longwang Cave, and the concentrations of organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) and particle size distribution in the sediments were analysed. The concentrations of OCPs and PAHs varied from 0.85 ng g-1 to 63.1 ng g-1 (mean 8.11 ng g-1) and 5.05 ng g-1 to 82.6 ng g-1 (mean 13.9 ng g-1), respectively; major PAHs in the profile were 2- and 3-ringed PAHs and a few were 5- or 6- ringed PAHs, which indicated less influence from industry but a high impact from the local combustion of coal and biomass; HCHs and DDTs in the profile were historically residual in this region, and HCHs mainly originated from the application of Lindane, while DDTs originated from the application of dicofol and technical DDTs; no significant correlation between the concentrations of OCPs and PAHs and the sedimental particle size in the sediments was found.

Sedimentary record of polycyclic aromatic hydrocarbons in mud deposits along the southeastern coast of Liaodong Peninsula and its relation to the anthropogenic and natural activities in the Northeast China.

The concentrations of polycyclic aromatic hydrocarbons (PAHs) in two 210Pb-dated sediment cores collected from mud deposits along the southeastern coast of the Liaodong Peninsula were investigated to reconstruct the sedimentary records of PAHs and their relationship with anthropogenic and natural activities. The concentrations of 16 PAHs (∑PAHs) were low and remained stable before the year 1820, reflecting an autarkic agricultural civilization. From 1820 to 1900, with the gradual lifting of prohibition, people migrated into Northeast China, resulting in the release of large amounts of ∑PAHs into the environment. At the beginning of the 1900s, the ∑PAH levels in the two cores displayed increasing trends with significant fluctuations, linked to a period of social turbulence with continuous wars in Northeast China. After 1949, vertical ∑PAH trends in the cores predominantly reflected trends in economic development. Based on the different PAH composition trends (2-3-ring and 4-6-ring PAHs), we consider that historical energy usage in Northeast China can be divided into three stages: biomass fuel use dominated before 1920, biomass and fossil fuels co-existed from 1920 to 1980, and fossil fuels dominated after 1980. In addition, this study also demonstrates that the PAH concentrations (2-3-ring PAHs) in these two sediment cores can be used, to a certain extent, to identify anthropogenic fire events.

Ancient water bottle use and polycyclic aromatic hydrocarbon (PAH) exposure among California Indians: a prehistoric health risk assessment.

BACKGROUND: Polycyclic aromatic hydrocarbons (PAHs) are the main toxic compounds in natural bitumen, a fossil material used by modern and ancient societies around the world. The adverse health effects of PAHs on modern humans are well established, but their health impacts on past populations are unclear. It has previously been suggested that a prehistoric health decline among the native people living on the California Channel Islands may have been related to PAH exposure. Here, we assess the potential health risks of PAH exposure from the use and manufacture of bitumen-coated water bottles by ancient California Indian societies. METHODS: We replicated prehistoric bitumen-coated water bottles with traditional materials and techniques of California Indians, based on ethnographic and archaeological evidence. In order to estimate PAH exposure related to water bottle manufacture and use, we conducted controlled experiments to measure PAH contamination 1) in air during the manufacturing process and 2) in water and olive oil stored in a completed bottle for varying periods of time. Samples were analyzed with gas chromatography/mass spectrometry (GC/MS) for concentrations of the 16 PAHs identified by the US Environmental Protection Agency (EPA) as priority pollutants. RESULTS: Eight PAHs were detected in concentrations of 1-10 µg/m3 in air during bottle production and 50-900 ng/L in water after 2 months of storage, ranging from two-ring (naphthalene and methylnaphthalene) to four-ring (fluoranthene) molecules. All 16 PAHs analyzed were detected in olive oil after 2 days (2 to 35 µg/kg), 2 weeks (3 to 66 µg/kg), and 2 months (5 to 140 µg/kg) of storage. CONCLUSIONS: For ancient California Indians, water stored in bitumen-coated water bottles was not a significant source of PAH exposure, but production of such bottles could have resulted in harmful airborne PAH exposure.

Sedimentary organic biomarkers suggest detrimental effects of PAHs on estuarine microbial biomass during the 20th century in San Francisco Bay, CA, USA.

Hydrocarbon contaminants are ubiquitous in urban aquatic ecosystems, and the ability of some microbial strains to degrade certain polycyclic aromatic hydrocarbons (PAHs) is well established. However, detrimental effects of petroleum hydrocarbon contamination on nondegrader microbial populations and photosynthetic organisms have not often been considered. In the current study, fatty acid methyl ester (FAME) biomarkers in the sediment record were used to assess historical impacts of petroleum contamination on microbial and/or algal biomass in South San Francisco Bay, CA, USA. Profiles of saturated, branched, and monounsaturated fatty acids had similar concentrations and patterns downcore. Total PAHs in a sediment core were on average greater than 20× higher above ∼200 cm than below, which corresponds roughly to the year 1900. Isomer ratios were consistent with a predominant petroleum combustion source for PAHs. Several individual PAHs exceeded sediment quality screening values. Negative correlations between petroleum contaminants and microbial and algal biomarkers - along with high trans/cis ratios of unsaturated FA, and principle component analysis of the PAH and fatty acid records - suggest a negative impacts of petroleum contamination, appearing early in the 20th century, on microbial and/or algal ecology at the site.

Polycyclic aromatic hydrocarbons in sediments from the Old Yellow River Estuary, China: occurrence, sources, characterization and correlation with the relocation history of the Yellow River.

The levels of 16 USEPA priority PAHs were determined in surface sediments and one dated sediment core from the abandoned Old Yellow River Estuary, China. Total PAH concentrations in the surface sediments ranged from 100.4 to 197.3 ng g(-1) dry weight and the total toxic equivalent quantity (TEQ(carc)) values of the carcinogenic PAHs were very low. An evaluation of PAH sources based on diagnostic ratios and principal component analysis suggested that PAHs in the surface sediments mainly derived from combustion sources. The total PAH concentrations altered significantly with year of deposition and showed quite different patterns of change compared with other studies: it is hypothesized that the principal cause of these changes is the relocation of the course of the Yellow River to the sea in 1976 and 1996.

Source apportionment of polycyclic aromatic hydrocarbons (PAHs) into Central Park Lake, New York City, over a century of deposition.

Relative contributions of polycyclic aromatic hydrocarbons (PAHs) from combustion sources of wood, petroleum, and coal were computed in sediments from Central Park Lake in New York City (NY, USA) by chemical mass balance based on several reliable source indicators. These indicators are the ratio of retene to the sum of retene and chrysene, the ratio of 1,7-dimethylphenanthrene (DMP) to 1,7-DMP and 2,6-DMP, and the ratio of fluroanthene to fluroanthene and pyrene. The authors found that petroleum combustion-derived PAH fluxes generally followed the historical consumption data of New York State. Coal combustion-derived PAH flux peaked approximately in the late 1910s, remained at a relatively high level over the next 3 decades, then rapidly declined from the 1950s to the 1960s; according to historical New York State coal consumption data, however, there was a 2-peak trend, with peaks around the early 1920s and the mid-1940s. The 1940s peak was not observed in Central Park Lake, most likely because of the well-documented shift from coal to oil as the major residential heating fuel in New York City during the late 1930s. It was widely believed that the decreased PAH concentrations and fluxes in global sediments during the last century resulted from a major energy shift from coal to petroleum. The data, however, show that this shift occurred from 1945 through the 1960s and did not result in an obvious decline. The sharpest decrease, which occurred in the 1970s was not predominantly related to coal usage but rather was the result of multiple factors, including a decline in petroleum usage largely, the introduction of low sulfur-content fuel in New York City, and the introduction of emission-control technologies.

Historical records of mercury, lead, and polycyclic aromatic hydrocarbons depositions in a dated sediment core from the Eastern Mediterranean.

Depth profiles of mercury, lead and its stable isotopes, and polycyclic aromatic hydrocarbons were determined in a dated sediment core from the Levantine basin. Sedimentary records show that preindustrial fluxes and levels of Hg, Pb, and PAHs remained generally constant in the region before 1850. An almost concurrent uniform increase of both metals and PAHs deposition occurring at the beginning of the Industrial Revolution suggests coal combustion as a main source of these contaminants in the Levantine basin after the 1850s. However, none of the contaminant profiles indicates a decline after 1950-60, the characteristic period of coal use reduction. The modern fluxes of Hg and Pb reveal a 3- to 5-fold increase over preindustrial loads, while the contemporaneous flux of PAHs rises by 4-7 times. On the whole, records in the Eastern Mediterranean suggest atmospheric inputs from relatively distant sources, likely from Central and Eastern Europe.

How suitable are peat cores to study historical deposition of PAHs?

Ombrotrophic peat bogs are natural archives of atmospheric pollution, their depth profiles can be used to study the deposition chronology of harmful contaminants. Prerequisites for deriving historical deposition rates from the peat archive are that contaminants are persistent and immobile in the peat and that the applied dating technique is accurate. To examine these requirements and the accuracy of peat archives for polycyclic aromatic hydrocarbons (PAHs) 12 peat profiles were sampled in 4 bogs in Ontario, Canada, as well as surface peat in one bog. Additionally we carried out laboratory incubations; no degradation occurred over a 3-year period in these experiments. The standard deviations of PAH concentrations in surface samples and of PAH inventories in whole cores was approximately 30%, and concentrations in surface peat were on average 50% higher in hollows than in hummocks. No indications for mobility of PAHs were observed in peat. Temporal deposition trends inferred from peat cores were generally in agreement with trends derived from a sediment core sampled close by but deposition rates to the sediment were substantially higher. A major source of uncertainty was the rather coarse vertical sampling resolution of 5 cm which introduced substantial uncertainty in the dating of the individual segments. This caused variations of the deposition rates up to 70% per PAH between three replicate cores, and it also impedes the identification of deposition peaks. Overall, we conclude that peat cores are suitable archives for inferring atmospheric deposition trends, but due to their relatively low temporal resolution short-term events may not be identified and the development of sampling methods that allow a higher vertical resolution would greatly improve the performance of the method. The analysis of more than one core per site is suggested to provide a realistic estimate of the historic deposition and total inventories.

Sedimentary records of PAHs in a sediment core from tidal flat of Haizhou Bay, China.

The concentrations and depositional fluxes of polycyclic aromatic hydrocarbons (PAHs) were investigated in a dated sediment core collected from a tidal flat in Haizhou Bay, China. The USEPA's 16 priority PAH concentrations ranged from 72.51 ng g(-1) dw in 1969 to 805.21 ng g(-1) dw in 2010, while the deposition fluxes were in the range of 102.36-861.02 ng cm(-2) yr(-1). The PAH concentrations and fluxes changed dramatically with depth, suggesting changes in energy usage and corresponding closely with the historical economic development of eastern China. The levels of PAHs slightly increased from the late 1970s, following China's "Reform and Open" policy of 1978; however, a drastic increase in the concentration of PAHs observed in 1990 was indicative of the rapid growth in coal and petroleum incomplete combustion byproducts, which was associated with the increase in economic development in this area. Furthermore, isomer ratio analysis and principle component analysis revealed the main anthropogenic pyrolytic source that causes PAH contamination in the coastal sediment.

Sedimentary record of polycyclic aromatic hydrocarbons and DDTs in Dianchi Lake, an urban lake in Southwest China.

Unique time trends of polycyclic aromatic hydrocarbons (PAHs) and dichlorodiphenyltrichloroethanes (DDTs) were found in a dated sediment core from Dianchi Lake (DC), an urban lake in Southwest China. The temporal trend of PAHs in DC was not only different from those in China's coastline and remote lakes of China, but also different from those in more developed countries. Identification of sources suggested that PAHs in DC originated primarily from domestic combustion of coal and biomass. However, a change of source from low- and moderate-temperature combustion to high-temperature combustion processes was observed. Different from those in China's coastline and some developed countries, the temporal trend of DDTs in DC mirrored the historical usage of DDTs in China, with erosion of soils and surface runoff from its drainage area the most likely routes of DDT introduction to the lake. Rapid urbanization and industrialization in its catchment, effective interception of point-source pollution, and changes in sources of energy during the last few decades have significantly influenced the vertical profiles of PAHs in DC.

Sedimentary record of PAHs in the Liangtan River and its relation to socioeconomic development of Chongqing, Southwest China.

Concentrations of polycyclic aromatic hydrocarbons (PAHs) were detected in sediment cores and surface sediment samples from the Liangtan River of Chongqing, Southwest China. The total concentration of 16 PAHs ranged from 69 to 6251 ng g(-1). The spatial distribution of the PAHs reflects the intensity and scope of human activity in the catchment. A historical record of PAH contamination was reconstructed using a sediment core from a background segment of the river. The characteristic changes of concentrations, fluxes and patterns of 16 PAHs over the past ~90years were captured in detail. An obvious peak of PAH concentration and flux was found in the 1940s, i.e., during war time, and then a sharp increase was observed from the early 1980s to the present. The maximum concentration and flux reached 1260 ng g(-1) and 470 ng cm(-2)year(-1), respectively. The sharp increase was attributed to the contribution of pyrogenic sources of PAHs. The population, length of highways and energy consumption of Chongqing, as indexes of socioeconomic development, were positively correlated with PAH input in the sediment core from the 1950s to the present. The results clearly show that the local socioeconomic development in the last decades remarkably aggravated the environmental load of sedimentary PAHs.

Pre-industrial accumulation of anthropogenic polycyclic aromatic hydrocarbons found in a blanket bog of the Iberian Peninsula.

Studies on the temporal deposition of polycyclic aromatic hydrocarbons (PAHs) in peatlands are scarce, and none have been carried out in the Iberian Peninsula. To address this gap, ten PAHs were determined in a short peat core (spanning the last 1000 years) sampled in NW Iberian Peninsula, by HPLC-fluorescence. Fluoranthene, pyrene, benzo[b]fluoranthene and indeno[1,2,3-cd]pyrene predominated in the upper layers (10 cm), whereas fluoranthene and pyrene were the most abundant in the lower layers (40 cm), which showed an absence of high molecular weight PAHs (benzo[ghi]perylene and Indeno[1,2,3-cd]pyrene). Although increased PAH contents have been detected since 1700 A.D., coinciding with the beginning of the Metallurgical and Industrial Revolution, high levels of fluoranthene and pyrene were present in peat samples dating back to the 12th century A.D. The results suggest that changes in sources, type of emission (global or local) and transport could be responsible for the different PAH content and composition of the peat core. These changes are consistent with the history of the use of natural resources in the NW of the Iberian Peninsula.

Paleolimnological evidence of variations in deposition of atmosphere-borne Polycyclic Aromatic Hydrocarbons (PAHs) in Ireland.

Polycyclic Aromatic Hydrocarbons (PAHs) are ubiquitous in the environment and are produced by both natural and anthropogenic processes, principally from the incomplete combustion of organic matter. Levels of emissions of PAHs from the combustion of fossil fuels have increased rapidly over the last ca. 200 years. As PAHs have detrimental environmental and human health impacts, assessing spatial and temporal variations in environmental loadings has become a pressing issue in many industrialised and industrializing countries. The current paper reports spatial and temporal variations in levels of atmospheric deposition of PAHs recorded in sediment cores from three lakes in Ireland, the locations of which were selected on the basis of known geographic differences in the deposition of atmospheric pollutants. Thirteen PAH compounds were analysed for in samples of lake sediment that were assumed to represent contemporary/recent and historical (possibly reference) levels of deposition. A third sample was selected from each core on the basis of measured levels of spheroidal carbonaceous particles, which are regarded as a direct indicator of depositions from the industrial-level combustion of fossil fuels. Chronological control was provided by the (210)Pb dating technique which also allowed for the calculation of PAH flux. For the most part, and when compared with the limited published data, measured levels of PAH depositions were relatively low. However, levels of deposition of PAHs in the west of Ireland are higher now than previously, which is in contrast to a general trend of decreasing levels in Europe.

Historical changes in the concentrations of polycyclic aromatic hydrocarbons (PAHs) in Lake Peipsi sediments.

The distribution of 11 individual polycyclic aromatic hydrocarbons (PAHs) was analysed in a (210)Pb dated sediment core from the deepest area of Lake Peipsi and in four surface sediment samples taken from littoral areas. According to the concentrations in the core three groups of PAHs may be distinguished: (1) relatively stable concentrations of PAHs within the whole studied time interval; (2) very low concentrations in sediments accumulated before intensive anthropogenic impact (from 19th century up to the 1920s) following a slight increase and (3) an overall increase in PAH concentrations since the 1920s up to the present. Comprehensive analysis of PAHs in the core and monitoring data obtained in the 1980s together with the lithology of sediments show that an increase of anthropogenically induced PAHs correlates well with the history of fuel consumption in Estonia and speaks about atmospheric long-distance transport of PAHs. The continuous increase of PAH concentrations since the 1920s do not support the earlier hypothesis about the dominating impact of the oil shale fired power plants near the lake, because their emissions decreased significantly in the 1990s. The concentration of PAHs in the deep lake core sample correlates well with the content of organic matter, indicating absorption and co-precipitation with plankton in the sediment.

Slightly weathered Exxon Valdez oil persists in Gulf of Alaska beach sediments after 16 years.

Oil stranded by the 1989 Exxon Valdez spill has persisted in subsurface sediments of exposed shores for 16 years. With annualized loss rates declining from approximately 68% yr(-1) prior to 1992 to approximately 4% yr(-1) after 2001, weathering processes are retarded in both sediments and residual emulsified oil ("oil mousse"), and retention of toxic polycyclic aromatic hydrocarbons is prolonged. The n-alkanes, typically very readily oxidized by microbes, instead remain abundant in many stranded emulsified oil samplesfrom the Gulf of Alaska. They are less abundant in Prince William Sound samples, where stranded oil was less viscous. Our results indicate that, at some locations, remaining subsurface oil may persist for decades with little change.

Historical records of airborne polycyclic aromatic hydrocarbons by analyzing dated corks of the bark pocket in a Longpetiole Beech tree.

Historical monitoring of airborne polycyclic aromatic hydrocarbons (PAHs) pollution levels was novelly demonstrated by analyzing the dated corks of a bark pocket formed from 1873 to 2003 in a Longpetiole Beech (Fagus longipetiolata) tree trunk sampled from southeastern China. The fundamental studies indicated that the PAHs of log K(oa) < 8.5 are primarily accumulated through interactions with lipid substances in cork and log K(oa) dependent, while the PAHs of log K(oa) > 8.5 existing as particle-phase dependent on log Vp are accumulated through stochastic entrapment by the lenticels on the surface of the cork. The translocation of PAHs by xylem flow and phloem stream as well as radial diffusion from the cork to the inner tissues was not significant, and the cork is most effective for accumulating airborne PAHs. The total concentrations of 16 EPA PAHs (sumPAHs) in the dated corks progressively increased from 43.5 ng/g recorded in the earliest available cork in 1873-1875 to the maximum 345.7 ng/g in 1956-1961, and then gradually decreased to 267.0 ng/g in 2003, while the concentration of perylene (PER) was slightly fluctuating at 0.178 +/- 0.033 ng/g. Moreover, the concentration ratio of sumPAHs to PER increased from 193 to 2431 from 1873 to 2003, indicating a progressive increase in PAH pollution in southeastern China.

Source apportionment of PAHs in dated sediments from the Black River, Ohio.

Black River, OH, is contaminated with polycyclic aromatic hydrocarbons (PAHs) from coke ovens of a US Steel Corp. Plant. Closing of a coking plant in 1983 and environmental dredging of the sediments during 1989 and 1990 has reduced the PAH levels significantly. This study quantifies the decrease, and consider source apportionment of PAHs in Black River sediments using chemical mass balance modeling. Five vibra cores collected in 1998 and dated using 210Pb and 137Cs, were analyzed for 18 PAHs. The cores had total PAH concentrations between 250 and 0.10 ppm. PAH maxima occur in 1949, 1969, in accordance with regional historical inputs (core BR4), and in 1991 due to remediation (BR6). Coke oven emissions (CO), highway dust (HWY), and wood burning (WB) are likely sources. The CO source (6-92% of total PAHs) is maximal in 1954, and again in 1992-1994 due to the exposure and redistribution of older contaminated sediments during dredging, and decreases thereafter. There is minimal CO content in 1985 (BR4), 2 yr after closure of the coking plant. The HWY contribution (2-86%) is high during 1969-1988, and increases again after 1993. The WB source is less than 23%, and exhibits a minimum (2%) around 1979 (BR4). There is evidence of aerobic biodegradation or photolysis in the sediment of phenanthrene (PhA) at PhA concentrations >500 ppb.

High-resolution record of pyrogenic polycyclic aromatic hydrocarbon deposition during the 20th century.

A high-resolution record of polycyclic aromatic hydrocarbon (PAH) deposition in Rhode Island over the past approximately 180 years was constructed using a sediment core from the anoxic Pettaquamscutt River basin. The record showed significantly more structure than has hitherto been reported and revealed four distinct maxima in PAH flux. The characteristic increase in PAH flux at the turn of the 20th century was captured in detail, leading to an initial maximum prior to the Great Depression. The overall peak in PAH flux in the 1950s was followed by a maximum that immediately preceded the 1973 Organization of Petroleum Exporting Countries (OPEC) oil embargo. During the most recent portion of the record, an abrupt increase in PAH flux between 1996 and 1999 has been found to follow a period of near constant fluxes. Because source-diagnostic ratios indicate that petrogenic inputs are minor throughout the record, these trends are interpreted in terms of past variations in the magnitude and type of combustion processes. For the most recent PAH maximum, energy consumption data suggest that diesel fuel combustion, and hence traffic of heavier vehicles, is the most probable cause for the increase in PAH flux. Systematic variations in the relative abundance of individual PAHs in conjunction with the above changes in flux are interpreted in relation to the evolution of combustion processes. Coronene, retene, and perylene are notable exceptions, exhibiting unique down-core profiles.