Distribution of organochlorine pesticides in the northern South China Sea: implications for land outflow and air-sea exchange

The South China Sea (SCS) is surrounded by developing countries in Southeast Asia, where persistent organic pollutants (POPs), such as organochlorine pesticides (OCPs), are still used legally or illegally, and are of concern. Yet little is known about the distribution of OCPs in the water and atmosphere over SCS, as well as their air-sea equilibrium status and time trends. In this study, ship-board air samples and surface seawater collected in the northern SCS between September 6 and 22, 2005 were analyzed for selected OCPs. The measured OCP concentrations in the atmosphere over the northern SCS were influenced by proximity to source regions and air mass origins. The highest atmospheric OCP concentrations were found at sampling sites adjacent to continental South China. OCPs in surface seawater showed significant spatial variations, with the highest concentration observed in a water sample from off Vietnam. The coastal currents were suggested to play a key role in the delivery of waterborne OCPs in the northern SCS. Time trend, land outflow, and air-sea exchange of selected OCPs in the SCS were investigated, by comparison of this dataset with historical data.     

Time trends of polybrominated diphenyl ethers in sediment cores from the Pearl River Estuary, South China

The present study provides information on the time trend of PBDEs in three sediment cores from the Pearl River Estuary (PRE), South China, using 210Pb dating technique. The sigmaPBDEs (except for BDE 209) concentrations in all sediment cores increased gradually from the bottom (mid-1970s) to the middle layer (later 1980s and early 1990s) followed by different temporal trends in different locations to the surface sediments, reflecting the variations in the consumption of commercial penta-BDEs mixture in different regions of the Pearl River Delta. The BDE 209 concentrations remained constant until 1990 and thereafter increased exponentially to the present, with doubling times of 2.6 +/- 0.5-6.4 +/- 1.6 years, suggesting the increasing market demands for deca-BDE mixture after 1990 in China. The inventories of sigmaPBDEs and BDE 209 in sediments of the PRE were 56.0 and 368.2 ng cm(-2), respectively, and the total burden of PBDEs in the PRE were estimated at 8.6 metric tons. The current sigmaPBDEs and BDE 209 fluxes to the PRE were 2.1 and 29.7 ng cm(-2) yr(-1), respectively. The concurrent increase of BDE 209 fluxes and the annual gross industrial output values of electronics manufacturing revealed that the rapid growth of electronics manufacturing in this region since the early 1990s was responsible for the sharp rise of BDE 209 fluxes in the past decade. The PBDE congener compositions of the cores indicated the various input pathways for PBDEs transport to different locations of the estuary.     

Distributed sequestration and release of PAHs in weathered sediment: the role of sediment structure and organic carbon properties

Polycyclic aromatic hydrocarbon (PAH) contaminated sediments from Piles Creek (PC) and Newtown Creek (NC) in the NY/NJ Harbor estuary were separated into size fractions and further separated into low (<1.7 g cm(-3)) and high (>1.7 g cm(-3)) density fractions. The fractionated sediments were characterized for carbon content pore structure, surface area, and PAH concentration. Most PAHs (50-80%) in both sediments were associated with the low-density fraction, which represents only 3-15% of total sediment mass, at levels greater than expected based on equilibrium partitioning. PC low-density sediment had 10 times greater organic carbon-normalized equilibrium partitioning coefficients (Koc) than the other size fractions and whole sediment. Characterization of the sediment organic matter suggested that the preferential sequestration observed in PC sediment was not correlated with soot carbon but was likely due to the presence of detrital plant debris, an important food source for benthic animals. Fractional PAH desorption from whole PC sediment was significantly higher than from NC sediment after 3 months. For both sediments, a smaller percentage of the total PAHs was desorbed from the low-density fraction. However, because PAH concentrations were greatly elevated in these fractions, more PAH mass was desorbed than from the corresponding bulk and high-density fractions. These results demonstrate that PAHs are preferentially sequestered in a separable, low-density fraction at levels not predictable by equilibrium partitioning theory. Further, the low-density fraction apparently controls whole-sediment PAH release. Although plant debris appears to be an important sorbent for PAHs, this material may readily release PAHs into the aqueous phase.     

Atmospheric outflow of anthropogenic semivolatile organic compounds from East Asia in spring 2004

To estimate the emissions of anthropogenic semivolatile organic compounds (SOCs) from East Asia and to identify unique SOC molecular markers in Asian air masses, high-volume air samples were collected on the island of Okinawa, Japan between 22 March and 2 May 2004. Contributions from different source regions (China, Japan, the Koreas, Russia, and ocean/local) were estimated by use of source region impact factors (SRIFs). Elevated concentrations of hexachlorobenzene (HCB), hexachlorcyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs), and particulate-phase polycyclic aromatic hydrocarbons (PAHs) were attributed to air masses from China. A large proportion of the variation in the current-use pesticides, gas-phase PAHs, and polychlorinated biphenyl (PCB) concentrations was explained by meteorology. Chlordanes showed a technical mixture profile and similar concentrations regardless of source region. alpha/gamma HCH and trans/cis chlordane ratios did not vary significantly with different source regions and had regional averages of 2.5 +/- 1.0 and 1.2 +/- 0.3, respectively. Particulate-phase PAH concentrations were significantly correlated (p value < 0.05) with other incomplete combustion byproduct concentrations, including elemental mercury (Hg0), CO, NOx, black carbon, submicrometer aerosols, and SO2. By use of measured PAH, CO, and black carbon concentrations and estimated CO and black carbon emission inventories, the emission of six carcinogenic particulate-phase PAHs was estimated to be 1518-4179 metric tons/year for Asia and 778-1728 metric tons/year for China, respectively. These results confirm that East Asian outflow contains significant emissions of carcinogenic particulate-phase PAHs.     

Characterization and FATE of PAH-contaminated sediments at the Wyckoff/Eagle Harbor Superfund Site

Eagle Harbor, a shallow marine embayment of Bainbridge Island, WA approximately 10 miles west of Seattle, WA), was formerly the site of the Wyckoff wood-treatment facility. The facility used large quantities of creosote in its wood-treating processes from the early 1900s to 1988. Historical creosote seepage into the harbor resulted in substantial accumulation of polycyclic aromatic hydrocarbon (PAH) contamination in the harbor sediments over time. This investigation focused on the distribution and fate of the PAH-contaminated harbor sediments. Analyses of 10 sediment cores using total petroleum hydrocarbon (TPH) fingerprinting, the distribution of 50 PAH analytes, and sediment age dating revealed the contributions of three distinct sources of PAHs to sediment contamination in the harbor during various periods over the past 100 years; namely, creosote, urban runoff, and natural background. Surface sediments (upper 20-30 cm) in the cores closestto the Wyckoff wood-treatment facility and southeast of an existing cap were dominated by urban runoff and weathered creosote; the deeper sediments (> 30 cm) were heavily contaminated with relatively unweathered creosote and some pure-phase creosote. Cores located the furthest from the area of contamination, in the center of the harbor, were dominated by urban runoff, showed no signs of creosote contamination, and had much lower PAH and TPH concentrations than those adjacent to the facility. In the four cores in the center of the Harbor, farthest from the former Wyckoff facility, PAH concentrations increased significantly (p < 0.01) with proximity to the northern shore of the harbor, which is more heavily developed than the southern shore and is where all automobile traffic enters and exits the island through the Bainbridge Island ferry terminal. Deeper portions of these cores were contaminated primarily with natural background PAHs, likely representing preurbanization sediments. Sedimentation rates ranged from 0.54 to 1.10 gm/ cm2 in the four cores located in the middle of the harbor, and for the single nearshore core that could be used to calculate sedimentation rates. Recognition that urban runoff has been a fairly consistent and ongoing source of PAHs to the harbor's sediments for the past 50-70 years may influence future sediment management decisions for this site with respect to long-term monitoring of surface sediments to assess cap performance. The results provided information on the ability of Eagle Harbor sediments to recover under natural conditions, identified the occurrence of creosote-derived PAH weathering in off-cap surface sediments, and distinguished between these distinct PAH sources in the harbor (creosote, urban runoff, and natural background).     

Polycyclic aromatic hydrocarbons in riverine runoff of the Pearl River Delta (China): concentrations, fluxes, and fate

On the basis of a monthly sampling effort from March 2005 to February 2006, the total concentrations of the sums of 27 and 15 polycyclic aromatic hydrocarbons (defined as sigma27PAHs and sigma15PAHs, respectively) in riverine runoff of the Pearl River Delta (PRD), China, and associated fluxes were determined. No clear temporal and spatial trends of PAH concentrations were found at all eight riverine runoff outlets where the samples were collected. The annual fluxes of sigma27PAHs and sigma15PAHs from the PRD to the coastal ocean were 60.2 and 33.9 metric tons, respectively. Assuming that riverine flux was positively related to the regional emission of PAHs, the annual riverine fluxes from five major rivers in China to the global oceans were estimated, which are quite significant relative to other major rivers of the world. On the basis of mass balance considerations, approximately 87% of sigma15PAHs inputting to the Pearl River Estuary and northern South China Sea was derived from riverine runoff from the PRD. In addition, approcimately 22.3 metric tons of sigma15PAHs annually outflow to open seas, which is equivalent to a concentration of 0.34 pg/L in the global oceans if the PAHs are evenly distributed in the upper 200 m of the water column. A comparison with the global background level of PAHs indicated that approximately 0.4% of PAHs in the open oceans may have been contributed by 1-year discharge from the PRD.     

Distribution of polycyclic aromatic hydrocarbons (PAHs) in rivers and estuaries in Malaysia: a widespread input of petrogenic PAHs

This is the first publication on the distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in riverine and coastal sediments in South East Asia where the rapid transfer of land-based pollutants into aquatic environments by heavy rainfall and runoff waters is of great concern. Twenty-nine Malaysian riverine and coastal sediments were analyzed for PAHs (3-7 rings) by gas chromatography mass spectrometry. Total PAHs concentrations in the sediment ranged from 4 to 924 ng/g. Alkylated homologues were abundant for all sediment samples. The ratio of the sum of methylphenanthrenes to phenanthrene (MP/P), an index of petrogenic PAHs contribution, was more than unity for 26 sediment samples and more than 3 for seven samples for urban rivers covering a broad range of locations. The MP/P ratio showed a strong correlation with the total PAHs concentrations, with an r2 value of 0.74. This ratio and all other compositional features indicated that Malaysian urban sediments are heavily impacted by petrogenic PAHs. This finding is in contrast to other studies reported in many industrialized countries where PAHs are mostly of pyrogenic origin. The MP/P ratio was also significantly correlated with higher molecular weight PAHs such as benzo[a]pyrene, suggesting unique PAHs source in Malaysia which contains both petrogenic PAHs and pyrogenic PAHs. PAHs and hopanes fingerprints indicated that used crankcase oil is one of the major contributors of the sedimentary PAHs. Two major routes of inputs to aquatic environments have been identified: (1) spillage and dumping of waste crankcase oil and (2) leakage of crankcase oils from vehicles onto road surfaces, with the subsequent washout by street runoff. N-Cyclohexyl-2-benzothiazolamine (NCBA), a molecular marker of street dust, was detected in the polluted sediments. NCBA and other biomarker profiles confirmed our hypothesis of the input from street dust contained the leaked crankcase oil. The fingerprints excluded crude oil, fresh lubricating oil, asphalt, and tire-particles as major contributors.     

Distribution of polybrominated diphenyl ethers in sediments of the Pearl River Delta and adjacent South China Sea

Spatial and temporal distributions of polybrominated diphenyl ethers (PBDEs) in sediments of the Pearl River Delta (PRD) and adjacent South China Sea (SCS) of southern China were examined. A total of 66 surface sediment samples were collected and analyzed to determine the concentrations of 10 PBDE congeners (BDE-28, -47, -66, -100, -99, -154, -153, -138, -183, and -209). The concentrations of BDE-209 and SigmaPBDEs (defined as the sum of all targeted PBDE congeners except for BDE-209) ranged from 0.4 to 7340 and from 0.04 to 94.7 ng/g, respectively. The SigmaPBDEs concentrations were mostly < 50 ng/g, within the range for riverine and coastal sediments around the world, whereas the BDE-209 concentrations at the most contaminated sites were at the high end of the worldwide figures. Congener compositions were dominated by BDE-209 (72.6 - 99.7%), with minor contributions from penta- and octa-BDEs. Slightly different PBDE compositions were observed among samples collected from different locations, attributable to possible decomposition of highly brominated congeners and/or redistribution between particles of various sizes during atmospheric or fluvial transportation. The PBDE patterns in the SCS and Pearl River Estuary sediments were similar to those in sediments of the Zhujiang and Dongjiang Rivers, reflecting the widespread influence from local inputs. Analyses of two short sediment cores collected from the Pearl River Estuary showed that concentrations of BDE-209 rapidly increased in the upper layers of both cores, coincident with the growth of the electronics manufacturing capacities in the PRD region. The major sources of PBDEs were probably waste discharges from the cities of Guangzhou, Dongguan, and Shenzhen, the three fastest growing urban centers in the PRD.     

Distribution of polycyclic aromatic hydrocarbons in the coastal region off Macao, China: assessment of input sources and transport pathways using compositional analysis

The coastal region off Macao is a known depositional zone for persistent organic pollutants (POPs) in the Pearl River Delta and Estuary of southern China and an important gateway for the regional contributions of contamination to the globe. This paper presents a comprehensive assessment of the input sources and transport pathways of polycyclic aromatic hydrocarbons (PAHs) found in the coastal sediments of Macao, based on measurements of 48 2-7 ring PAHs and 7 sulfur/oxygenated (S/O) PAH derivatives in 45 sediment, 13 street dust, and 68 aerosol samples. Total sediment PAHs concentrations ranged from 294 to 12741 ng/g, categorized as moderate contamination compared to other regions of Asia and the world. In addition, the PAH compounds appeared to be bound more strongly to aromatics-rich soot particles than to natural organic matter, implying a prevailing atmospheric transport route for PAHs to Macao's coast. Compositional analysis and principal component analysis (PCA) suggested that different classes of PAHs in the coastal sediments of Macao may have been derived from different input sources via various transport pathways. For example, alkylated and S/O PAHs were likely derived from fossil fuel leakage and transported to sediments by both aerosols particles and street runoff. High-molecular-weight parent PAHs were predominantly originated from automobile exhausts and distributed by direct and indirect atmospheric deposition. Low-molecular-weight parent PAHs, on the other hand, may have stemmed from lower temperature combustion and fossil fuel (such as diesel) spillage from ships and boats and were transported to sediments by river runoff or direct discharge as well as by air-water exchange.     

Atmospheric deposition and marine sedimentation fluxes of polycyclic aromatic hydrocarbons in the Eastern Mediterranean Basin

Atmospheric input was studied and found to be the major source of PAHs in the eastern Mediterranean open marine ecosystem. Dry and wet atmospheric deposition, air-sea exchange, and sediment trap fluxes of polycyclic aromatic hydrocarbons (PAHs) in the eastern Mediterranean basin were estimated from November 2000 to July 2002. Seven dry and four wet deposition samples were analyzed in total and PAH concentrations were determined. Airsea exchange fluxes based on air-water concentration gradientwere drawn from five air and water samples collected concurrently from a coastal area in the eastern Mediterranean. Total annual average deposition fluxes of dry, wet, and air-sea exchange sigma35PAHs were 58.0, 165.7, and -706.4 microg m(-2) y(-1), respectively. Only 1.1 and 0.7% of the total atmospheric deposition flux of PAHs was measured in the sediment traps at 280 and 1440 m depth, respectively.     

Polybrominated diphenyl ethers in the sediments of the Great Lakes. 1. Lake Superior

Sediment cores were taken in 2001 and 2002 in Lake Superior at six locations away from lakeshores and segmented at 0.5-5 cm intervals. The year of sediment deposition was estimated for each segment of four cores using the 210Pb dating technique. Samples were Soxhlet-extracted and cleaned up by silica gel fractionation, and the concentrations of 10 polybrominated diphenyl ethers (PBDEs) and 19 polychlorinated biphenyls (PCBs) were measured by GC-MS in SIM mode. In contrast to recent declining or level-off trends in PCB fluxes, the sedimentary records of PBDEs generally show a significant increase in recent years. The load of total PBDEs to Lake Superior was estimated to be 2-6 metric tons, and the current loading rate was about 80-160 kg yr(-1). With the exclusion of decabromodiphenyl ether (BDE209), the surficial concentration of sumPBDE (sum of 9 congeners) ranged from 0.5 to 3 ng g(-1), and the current sumPBDEs flux was 8-31 pg cm(-2) yr(-1). The concentrations of BDE209 were about an order of magnitude higher than the sum of other congeners, comprising 83-94% of the total PBDE inventory in the sediments. Among the other nine PBDEs detected, congeners 47 and 99 were the most abundant, and congeners 100, 153, 154, and 183 were also detected in all the cores. Congener analysis demonstrated that the pattern of PBDEs in Lake Superior sediments differs from those in air and fish.     

Advection dominated transport of polycyclic aromatic hydrocarbons in amended sediment caps

Typical sand caps used for sediment remediation have little sorption capacity to retard the migration of hydrophobic contaminants such as PAHs that can be mobilized by significant groundwater flow. Laboratory column experiments were performed using contaminated sediments and capping materials from a creosote contaminated USEPA Superfund site. Azoic laboratory column experiments demonstrated rapid breakthrough of lower molecular weight PAHs when groundwater seepage was simulated through a column packed with coarse sand capping material. After eight pore volumes of flow, most PAHs measured showed at least 50% of initial source pore water concentrations at the surface of 65 cm capping material. PAH concentration in the cap solids was low and comparable to background levels typically seen in urban depositional sediment, but the pore water concentrations were high. Column experiments with a peat amendment delayed PAH breakthrough. The most dramatic result was observed for caps amended with activated carbon at a dose of 2% by dry weight. PAH concentrations in the pore water of the activated carbon amended caps were 3-4 orders of magnitude lower (0.04 ± 0.02 μg/L for pyrene) than concentrations in the pore water of the source sediments (26.2 ± 5.6 μg/L for pyrene) even after several hundred pore volumes of flow. Enhancing the sorption capacity of caps with activated carbon amendment even at a lower dose of 0.2% demonstrated a significant impact on contaminant retardation suggesting consideration of active capping for field sites prone to groundwater upwelling or where thin caps are desired to minimize change in bathymetry and impacts to aquatic habitats.     

Dechlorane plus and other flame retardants in a sediment core from Lake Ontario

Our previous research on atmospheric samples suggested that Lake Ontario might receive significant amounts of Dechlorane Plus (DP), a highly chlorinated flame retardant, from the atmosphere and from inputs from DP's manufacturing facility in Niagara Falls, New York. To confirm this suspicion, a sediment core from the central basin of Lake Ontario was analyzed for the two isomers of DP, for polybrominated diphenyl ethers (PBDEs), and for 1,2-bis-(2,4,6-tribromophenoxy)ethane (TBE). The results showed that the concentration of DP in sediment increased rapidly starting in the mid-1970s and reached its peak concentration (310 ng g(-1) dry weight) in the mid-1990s. The peak flux and total inventory of DP were estimated to be 9.3 ng cm(-2) yr(-1) and 120 ng cm(-2), respectively. These values suggest that the total burden of DP in Lake Ontario is approximately 20 tons and that the maximum load rate was approximately 2 tons per year. The highest concentrations of PBDEs and TBE were found in the surficial sediment, with average concentrations of 2.8, 14, and 6.7 ng g(-1) d.w. for PBDE(3-7) (tri-through hepta-BDEs), BDE-209, and TBE, respectively. The surface fluxes were 0.08, 0.43, and 0.20 ng cm(-2) yr(-1), and the inventories were 0.87, 3.9, and 1.8 ng cm(-2) for PBDE3-7, BDE-209, and TBE, respectively. The concentration of DP in Lake Ontario sediment exceeds that of the brominated flame retardants combined.     

Solid-phase microextraction measurement of parent and alkyl polycyclic aromatic hydrocarbons in milliliter sediment pore water samples and determination of K(DOC) values

The U.S. Environmental Protection Agency (EPA) narcosis model for benthic organisms in polycyclic aromatic hydrocarbon (PAH) contaminated sediments requires the measurement of 18 parent PAHs and 16 groups of alkyl PAHs ("34" PAHs) in pore water with desired detection limits as low as nanograms per liter. Solid-phase microextraction (SPME) with gas chromatographic/mass spectrometric (GC/ MS) analysis can achieve such detection limits in small water samples, which greatly reduces the quantity of sediment pore water that has to be collected, shipped, stored, and prepared for analysis. Four sediments that ranged from urban background levels (50 mg/kg total "34" PAHs) to highly contaminated (10 000 mg/kg total PAHs) were used to develop SPME methodology for the "34" PAH determinations with only 1.5 mL of pore water per analysis. Pore water was obtained by centrifuging the wet sediment, and alum flocculation was used to remove colloids. Quantitative calibration was simplified by adding 15 two- to six-ring perdeuterated PAHs as internal standards to the water calibration standards and the pore water samples. Response factors for SPME followed by GC/MS were measured for 22 alkyl PAHs compared to their parent PAHs and used to calibrate for the 18 groups of alkyl PAHs. Dissolved organic carbon (DOC) ranging from 4 to 27 mg/L had no measurable effect on the freely dissolved concentrations of two- and three-ring PAHs. In contrast, 5-80% of the total dissolved four- to six-ring PAHs were associated with the DOC rather than being freely dissolved, corresponding to DOC/water partitioning coefficients (K(DOC)) with log K(DOC) values ranging from 4.1 (for fluoranthene) to 5.6 (for benzo[ghi]perylene). However, DOC-associated versus freely dissolved PAHs had no significant effect on the total "34" PAH concentrations or the sum of the "toxic units" (calculated bythe EPA protocol), since virtually all (86-99%) of the dissolved PAH concentrations and toxic units were contributed by two- and three-ring PAHs.     

Dissolved PCBs, PAHs, and HCB in pore waters and overlying waters of contaminated harbor sediments

Aqueous concentrations of polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs), pentachlorobenzene, and hexachlorobenzene (HCB) were determined by exposing low-density polyethylene (LDPE) strips to the pore waters and the overlying water in two contaminated harbors. LDPE strips were also exposed in the laboratory to sediment slurries and to stagnant sediments collected at the same locations. Surprisingly short equilibration time scales (1-60 days for log K(ow) < 7) were observed for the exposures to sediment slurries. This was a result of a profound decrease in transport resistance, due to the presence of particles in the aqueous boundary layer. Concentrations in the pore water were calculated from the initial uptake rates and the dissipation rates of performance reference compounds. Good correspondence existed with concentrations estimated from the equilibrium amounts in the strips and LDPE-water partition coefficients. Sediment-water partition coefficients for PAHs were higher than for PCBs and chlorobenzenes by approximately 1 order of magnitude. A one-dimensional diffusion model was used to describe contaminant uptake by LDPE strips from stagnant sediments. The results indicated that 95% of the PAHs and 50% of the PCBs were immobile on a time scale of two months. A comparison of concentrations in pore waters and water columns indicated that a fair degree of equilibrium existed for PCBs and that one sediment was a potential source of PAHs. Concentrations of HCB near a former discharge site were higher by a factor of 6 compared to reference locations.     

Demonstration of a method for the direct determination of polycyclic aromatic hydrocarbons in submerged sediments

We describe the development of a novel method for real-time in situ characterization of polycyclic aromatic hydrocarbons (PAHs) in submerged freshwater sediments. Laser-induced fluorescence (LIF) spectroscopy, a mature technique for PAH characterization in terrestrial sediments, was adapted for shipboard use. A cone penetrometer-type apparatus was designed for probe penetration at a constant rate (1 cm/s) to a depth of 3 m. A field-portable LIF system was used for in situ measurements in which the output of a pulsed excimer laser was transmitted by optical fiber to a sapphire window (6.4-mm o.d.) in the probe wall; fluorescent emission was collected by a separate optical fiber for transmission to the spectrometer on deck. Four wavelengths (340, 390, 440, 490 nm) were selected via optical delay lines, and multiple-wavelength waveforms were created. These multiple-wavelength waveforms contain information on the fluorescence frequency, intensity, and emission decay rate. Field testing was conducted at 10 sites in Milwaukee Harbor (total PAH concentrations ranged from approximately 10 to 650 microg/g); conventional sediment core samples were collected concurrently. The core samples were analyzed by EPA methods 3545 (pressurized fluid extraction, PFE) and 8270C (gas chromatography-mass spectrometry, GC-MS) for PAHs. A partial least-squares regression (PLSR) model wasthen created based on laboratory LIF measurements and PFE-GC-MS of the core samples. The PLSR model was applied to the in situ field test data, and 13 of the 16 EPA-regulated PAHs were quantified with a relative error of <30% overall (the remaining three PAHs were found at levels insufficient to quantify). We additionally describe preliminary source apportionment relationships that were revealed by the PLSR model for the in situ LIF measurements.     

Brominated flame retardants in sediment cores from Lakes Michigan and Erie

The history of polybrominated diphenyl ethers (PBDEs) and the major polybrominated biphenyl congener (BB-153) was studied in dated sediment cores taken from Lakes Michigan and Erie. The surficial concentration of total PBDE (65 [corrected] ng/g dry weight) in Lake Michigan was about 1.6 [corrected] times higher than that in Lake Erie (40 ng/g) and about 5 times higher than that [corrected] in Lake Superior (approximately 12 ng/g). The concentrations of total PBDEs in these sediments have increased rapidly, with doubling times of 5-10 years, reflecting the increasing market demand for these flame retardants over the last 30 years. BDE-209 was found to be the predominant congener in both sediment cores, making up approximately 95% [corrected] of the total PBDE load. The inventories of total PBDEs in Lakes Michigan and Erie were both [corrected] 40 ng/cm2 [corrected] The total burdens of these compounds in the sediment of Lakes Michigan and Erie were 23 [corrected] and 10 metric tons, respectively. We estimate [corrected] the total burden of these compounds in all of the Great Lakes is on the order of 100 [corrected] tons. In both lakes, BB-153 was found to increase rapidly during the 1970s and to peak around 1980.     

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.     

Lead concentrations and isotopic ratios in the sediments of the Sea of Galilee

The isotopic composition and concentrations of Pb in the sediments of the Sea of Galilee (Lake Kinneret) were measured. The studied sediments have been deposited in the lake since the early 1900s (ca. 1920), hence Pb data record the transition from a period when the lake vicinity was sparsely populated to the present (approximately 100,000 people living in the area around the lake). In general, there is either a constant or a relatively slow increase in Pb concentrations from 40 cm depth (3.5-4.4 microg/g; ca. 1920) to 17 +/- 2 cm below the sediment-water interface (3.7-7.2 microg/g;), which was deposited in the mid-1960s. From 17 +/- 2 cm below the surface, there is a much faster increase up to 7 +/- 2 cm below the surface (from 6.5 to 11.5 microg/g; 1982-1983), and from 7 +/- 2 cm there is a gradual decrease in Pb concentrations toward the sediment-water interface. At station G, near the outlet of the Jordan River, Pb concentrations drop between 29 and 25 cm below the surface, probably reflecting changes in the particulate load of the Jordan River due to the drying out of the Hula Swamp in the early 1950s. 206Pb/207Pb values in all the stations record most of the shifts displayed by Pb concentrations in the sediment. The estimated value of total Pb deposited annually in the lake sediment in the early 1990s is very close to the value obtained from measurements of Pb fluxes to the lake from eolian and fluvial sources. On the basis of the linear relationship between 206Pb/207Pb (or 208Pb/207Pb) and 1/[Pb], we argue that two end-members contribute most of the Pb to the lake sediments. Sources of Pb to the lake include (i) the weathering of basalt from the eastern Galilee and the Golan Heights contributing 2.6 +/- 0.5 microg/g Pb to the sediment and (ii) anthropogenic Pb that is affecting both surface and deep (from 30 to 40 cm) lake sediments. At station S, a third source, Pb released from soils developed on carbonates, should be considered as well.     

Polycyclic aromatic hydrocarbons in the indoor and outdoor air of three cities in the U.S

The indoor and outdoor concentrations of 30 polycyclic aromatic hydrocarbons (PAHs) were measured in 55 nonsmoking residences in three urban areas during June 1999-May 2000. The data represent the subset of samples collected within the Relationship of Indoor, Outdoor, and Personal Air study (RIOPA). The study collected samples from homes in Los Angeles, CA, Houston, TX, and Elizabeth, NJ. In the outdoor samples, the total PAH concentrations (sigmaPAH) were 4.2-64 ng m(-3) in Los Angeles, 10-160 ng m(-3) in Houston, and 12-110 ng m(-3) in Elizabeth. In the indoor samples, the concentrations of sigmaPAH were 16-220 ng m(-3) in Los Angeles, 21-310 ng m(-3) in Houston, and 22-350 ng m(-3) in Elizabeth. The PAH profiles of low molecular weight PAHs (3-4 rings) in the outdoor samples from the three cities were not significantly different. In contrast, the profiles of 5-7-ring PAHs in thesethree citieswere significantlydifferent, which suggested different dominant PAH sources. The signatures of 5-7-ring PAHs in the indoor samples in each city were similar to the outdoor profiles, which suggested that indoor concentrations of 5-7-ring PAHs were dominated by outdoor sources. Indoor-to-outdoor ratios of the PAH concentrations showed that indoor sources had a significant effect on indoor concentrations of 3-ring PAHs and a smaller effect on 4-ring PAHs and that outdoor sources dominated the indoor concentrations of 5-7-ring PAHs.