The 1974 spill of the Bouchard 65 oil barge: petroleum hydrocarbons persist in Winsor Cove salt marsh sediments

Petroleum hydrocarbons persist in salt marsh sediments in Winsor Cove (Buzzards Bay, Massachusetts) impacted from the 1974 spill of No. 2 fuel oil by the barge Bouchard 65. Intertidal sediment cores were collected from 2001 to 2005 and analyzed for total petroleum hydrocarbons (TPHs). TPHs content was greatest (as high as 8.7 mg g(-1) dry weight) in the surface sediments and decreased with distance landward. Select samples were analyzed for polycyclic aromatic hydrocarbons (PAHs) with values as high as 16.7 microg g(-1) for total naphthalenes and phenanthrenes/anthracenes. These remaining PAHs are mainly C(4)-naphthalenes and C(1)-, C(2)-, and C(3)-phenanthrenes/anthracenes revealing preferential loss of almost all of the naphthalenes and the parent compound phenanthrene. Inspection of the data indicates that biodegradation, water-washing and evaporation were major removal processes for many of the petroleum hydrocarbons in the marsh sediments. In addition, historical data and photographs combined with their recent counterparts indicate that erosion has physically removed these contaminants from this site.     

Biomarker responses in pelagic and benthic fish over 1 year following the Hebei Spirit oil spill (Taean, Korea)

After the Hebei Spirit oil spill incident (7th December, 2007) in the west coast of Korea, contamination of biliary PAH metabolite and hepatic biomarkers in a pelagic and a benthic fish was monitored for 1 year. Concentrations of 16 PAHs and alkylated PAHs in fish muscle were highest (22.0 ng/g d.w. for 16 PAHs and 284 ng/g d.w. for alkylated PAHs) at 5 days after the spill and then decreased rapidly to background levels at 11 months after the spill. Fish from the oiled site had elevated biliary PAH metabolite concentrations immediately after the spill; these declined steadily in both species, but were still above reference site concentrations 2 months after the spill. Oiled-site fish showed hepatic CYP 1A induction whose trend closely followed those of biliary PAH metabolite concentrations, implying continuous exposure to PAHs. Brain acetylcholinesterase activity was not related to oil exposure.     

Aliphatic and aromatic hydrocarbons in marine biota and coastal sediments from the Gulf and the Gulf of Oman

The composition and spatial distribution of aliphatic and polycyclic aromatic hydrocarbons (PAHs) were investigated in biota and coastal sediments from four countries surrounding the Gulf (Bahrain, Qatar, United Arab Emirates and Oman). The levels of total petroleum hydrocarbons (TPH), aliphatic unresolved mixture and PAHs in sediments and biota were relatively low compared to world-wide locations reported to be chronically contaminated by oil. Only in the case of the sediments collected near the BAPCO oil refinery in Bahrain, having concentrations of 779 μg g⁻¹ total petroleum hydrocarbon equivalents and 6.6 μg g⁻¹ ∑PAHs, can they be categorized as chronically contaminated. Some evidence of oil contamination was also apparent in sediments and bivalves around Akkah Head and Abu Dhabi in the UAE, and near Mirbat in Oman. Contaminant patterns in sediments and biota indicated that the PAHs were mainly from fossil sources, with the exception of the high PAH concentrations in sediments near the BAPCO refinery that contained substantial concentrations of carcinogenic PAH combustion products.     

Historical polycyclic aromatic and petrogenic hydrocarbon loading in Northern Central Gulf of Mexico shelf sediments

The distribution of selected hydrocarbons within ten dated sediment cores taken from the Mississippi River Bight off coastal Louisiana suggests a chronic contaminant loading from several sources including the river itself, oil and gas exploration in the central Gulf of Mexico (GOM) shelf area, and natural geologic hydrocarbon seeps. Data were grouped as either total polycyclic aromatic hydrocarbons (PAH's), which were indicative of pyrogenic PAH's; or estimated total hopanes (indicative of petrogenic hydrocarbons). The total PAH concentrations and estimated total hopanes begin increasing above background levels (approximately 200 ng g(-1)) after the 1950s. The distribution of these hydrocarbons and hopanes within the dated sediment cores suggests that the Mississippi River is a regional source of pyrogenic PAH's, and that the hopanes are from natural geologic hydrocarbon seeps, oil and gas exploration in the GOM, or both.     

Inputs and sources of hydrocarbons in sediments from Cienfuegos bay, Cuba

The spatial distribution of aliphatic and polycyclic aromatic hydrocarbons (PAHs) was investigated in sediments from the Cienfuegos bay. The highest anthropogenic hydrocarbon inputs were found near the city of Cienfuegos with an unresolved complex mixture (UCM) of aliphatic hydrocarbons and alkylated PAHs, indicative of petrogenic inputs. Parent PAHs, which are typical of high-temperature combustion processes, were evenly distributed in the whole basin and largely prevailing in the southern part of the Cienfuegos city. Biomarker fingerprints assign the sources of pollution to mixes of national and non-national crude oils. The overall levels of anthropogenic hydrocarbons are relatively high compared to relevant areas worldwide and reveal a moderate/high level of hydrocarbon pollution. The Cienfuegos bay sediments received over a period of 5 yr, 50 T/yr of petrogenic unresolved hydrocarbons (UCM) and 2 T/yr of PAHs, being deposited the 80% in the sediments of the north basin.     

Fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp in Hong Kong following an oil spill

The fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp (Yi O) in Hong Kong after an oil spill accident was investigated. The concentrations and profiles of PAHs in surface sediments collected from five quadrats (each of 10 m×10 m) covering different degrees of oil contamination and the most contaminated mangrove leaves were examined in December 2000 (30 days after the accident) and March 2001 (126 days later). The concentrations of total PAHs in surface sediments ranged from 138 to 2135 ng g⁻¹, and PAHs concentrations decreased with time. In the most contaminated sediments, total PAHs dropped from 2135 (30 days) to 1196 ng g⁻¹ (120 days), and the decrease was smaller in less contaminated sediments. The percentage reduction in sediment PAHs over three months (44%) was less significant than that in contaminated leaves (85%), indicating PAH in or on leaves disappeared more rapidly. The PAH profiles were very similar in sediments collected from quadrats Q1 and Q2 with benzo[a]anthracene and pyrene being the most abundant PAH compounds, but were different in the other three quadrats. The proportion of the light molecular weight PAHs to total PAHs increased after three months, especially phenanthrene. Results suggest that physical and photo-chemical weathering (tidal washing and photo-oxidation) of crude oil in surface sediments and on plant leaves were important processes in the first few months after the oil spill. The PAH contamination in Yi O swamp came from both petrogenic and pyrolytic sources. The petrogenic characteristic in the most contaminated sediment was confirmed with high values of phenanthrene to anthracene ratio (>10) and low values of fluoranthene to pyrene ratio (0.3–0.4).     

Comparison of hypoxia among four river-dominated ocean margins: The Changjiang (Yangtze), Mississippi,Pearl, and Rhône rivers

We examined the occurrence of seasonal hypoxia (O₂<2 mg l⁻¹) in the bottom waters of four river-dominated ocean margins (off the Changjiang, Mississippi, Pearl and Rhône Rivers) and compared the processes leading to the depletion of oxygen. Consumption of oxygen in bottom waters is linked to biological oxygen demand fueled by organic matter from primary production in the nutrient-rich river plume and perhaps terrigenous inputs. Hypoxia occurs when this consumption exceeds replenishment by diffusion, turbulent mixing or lateral advection of oxygenated water. The margins off the Mississippi and Changjiang are affected the most by summer hypoxia, while the margins off the Rhône and the Pearl rivers systems are less affected, although nutrient concentrations in the river water are very similar in the four systems. Spring and summer primary production is high overall for the shelves adjacent to the Mississippi, Changjiang and Pearl (1–10 g C m⁻² d⁻¹), and lower off the Rhône River (<1 g C m⁻² d⁻¹), which could be one of the reasons of the absence of hypoxia on the Rhône shelf. The residence time of the bottom water is also related to the occurrence of hypoxia, with the Mississippi margin showing a long residence time and frequent occurrences of hypoxia during summer over very large spatial scales, whereas the East China Sea (ECS)/Changjiang displays hypoxia less regularly due to a shorter residence time of the bottom water. Physical stratification plays an important role with both the Changjiang and Mississippi shelf showing strong thermohaline stratification during summer over extended periods of time, whereas summer stratification is less prominent for the Pearl and Rhône partly due to the wind effect on mixing. The shape of the shelf is the last important factor since hypoxia occurs at intermediate depths (between 5 and 50 m) on broad shelves (Gulf of Mexico and ECS). Shallow estuaries with low residence time such as the Pearl River estuary during the summer wet season when mixing and flushing are dominant features, or deeper shelves, such as the Gulf of Lion off the Rhône show little or no hypoxia.     

Shallow sublittoral meiofauna communities and sediment polycyclic aromatic hydrocarbons (PAHs) content on the Galician coast (NW Spain), six months after the Prestige oil spill

The aim of this work was to detect the impact of Prestige oil spill on meiobenthic community structure at higher levels of taxonomic aggregation. In addition, the relationship between sediment individual polycyclic aromatic hydrocarbon (PAH) concentration and meiofauna community structure was investigated. Six months after the Prestige oil spill, meiobenthos community and sediment PAHs content from seven shallow subtidal localities along the Galician coast were studied. Two sites presented differences in community structure, characterized by high densities of nematodes, gastrotrichs and turbellarians, and low densities of copepods. Chrysene and triphenylene were only found at these two disturbed sites and could be responsible for differences of meiobenthos community structure. However, differences in community structure of sites could be linked with sedimentary parameters, and discrimination between the effect of PAHs and sedimentary parameters was impossible due to the lack of baseline studies on meiobenthos and PAHs contents in this area.     

A retrospective analysis of trace metals, C, N and diatom remnants in sediments from the Mississippi River delta shelf

The development of oil and gas recovery offshore of the Mississippi River delta began in shallow water in the 1950s, expanded into deeper waters, and peaked in the 1990s. This area of the outer continental shelf (OCS) is the historical and present location of >90% of all US OCS oil and gas production and reserves. The juxtaposition of its 4000 producing platforms, recovering $10 billion yr(-1) of oil, gas and produced water in the same area where about 28% of the US fisheries catch (by weight) is made and near 40% of the US coastal wetlands, makes this an area worth monitoring for regional pollutant loading. This loading may come from several sources, including sources related to OCS development, but also from the Mississippi River watershed. In this context, any contaminant loading on this shelf may be neither detectable nor significant against a background of climatic or biological variability. We examined the sedimentary record for indicators of industrial byproducts from OCS oil and gas development and of industrial products entering via the Mississippi River, primarily using vanadium (V) and barium (Ba) concentrations normalized for aluminum (Al). Barium is primarily used in drilling muds in the form of barite, whereas V is an important strengthening component of metal alloys, including steel. The fluctuations in the accumulation of Ba, but not V, were coincidental with the presumed use of barite. The fluctuations in V concentration in the sediments were coincidental with the national consumption of V. Copper (Cu), cadmium (Cd) and zinc (Zn) concentrations in sediments fluctuate coincidentally with V, not Ba, thus indicating that the dominant source of these trace metals in offshore sediments were derived from riverine sources, and were not primarily from in situ industrial processes releasing them on the shelf. This is not to suggest that local site-specific contamination is not a significant management or health concern. The low oxygen (hypoxia; < or = 2 mg l(-1)) zone that consistently covers much of this continental shelf's bottom layer in summer is attributed to nitrate loading from the Mississippi River. Increased nitrogen loading from river to shelf stimulates diatom production whose loading to the bottom layer and subsequent metabolism results in oxygen being depleted faster than it is replaced. In the last two decades there has been an increased accumulation of organic matter in sediments near the mouth of the Mississippi River. This coupling between river water, surface water and bottom water has recently expanded westward of the Atchafalaya River delta towards the Texas coast. The accumulation of biogenic silica (BSi) and carbon in dated sediments is coincidental with variations in riverine nitrate flux, but not with either V or Ba accumulation rates. These analyses indicate that both OCS development and riverine sources exert strong influences on the sediment constituents offshore, and that these influences may be independent of one another.     

Efficient Quantification of Total Petroleum Hydrocarbons and Applications at Two Contaminated Sites

Characterization and remediation of petroleum contamination are complicated issues due to variable product compositions and site conditions. Generic group analytical methods such as total petroleum hydrocarbon (TPH) methods have played important field screening and regulatory functions for site characterization and cleanup. This study evaluated the application of three TPH methods (a GC/MS method, a spectrometric method EPA 418.1, and a rapid field method PetroFLAG). The results showed that quantification of TPH could be attained efficiently by a combination of rapid field methods (i.e., PetroFLAG) and more sophisticated fraction-specific and target-compound methods. TPH distributions suggested different source release information for two sites with different contaminant mixtures and climate conditions. TPH was also found to correlate with reductive redox capacity (RDC), an important parameter for the design of oxidative remediation schemes. The results indicated that good site specific correlations could be established to better estimate costs of the injection of chemical oxidants if necessary. RDC values varied broadly for both background (83 ˜ 569 meq/kg) and contaminated source (523 ˜ 6044 meq/kg) samples collected from actual sites.     

Small Purge Method to Sample Vapor from Groundwater Monitoring Wells Screened Across the Water Table

Groundwater monitoring wells are present at most hydrocarbon release sites that are being assessed for cleanup. If screened across the vadose zone, these wells provide an opportunity to collect vapor samples that can be used in the evaluation of vapor movement and biodegradation processes occurring at such sites. This paper presents a low purge volume method (modified after that developed by the U.S. EPA) for sampling vapor from monitoring wells that is easy to implement and can provide an assessment of the soil gas total petroleum hydrocarbon (TPH) and O₂ concentrations at the base of the vadose zone. As a result, the small purge method allows for sampling of vapor from monitoring wells to support petroleum vapor intrusion (PVI) risk assessment. The small purge volume method was field tested at the Hal's service station site in Green River, Utah. This site is well‐known for numerous soil gas measurements containing high O₂ and high TPH vapor concentrations in the same samples which is inconsistent with well‐accepted biodegradation models for the vapor pathway. Using the low purge volume method, monitoring wells were sampled over, upgradient, and downgradient of the light nonaqueous phase liquid (LNAPL) footprint. Results from our testing at Hal's show that vapor from monitoring wells over LNAPL contained very low O₂ and high TPH concentrations. In contrast, vapor from monitoring wells not over LNAPL contained high O₂ and low TPH concentrations. The results of this study show that a low purge volume method is consistent with biodegradation models especially for sampling at sites where low permeability soils exist in and around a LNAPL source zone.     

Hebei Spirit oil spill monitored on site by fluorometric detection of residual oil in coastal waters off Taean, Korea

The spatiotemporal distributions of dissolved and/or dispersed oil in seawater and pore water were monitored on site by fluorometric detection method after the Hebei Spirit oil spill. The oil concentrations in intertidal seawater, 15 days after the spill, were as high as 16,600 μg/L and appeared to decrease below the Korean marine water quality standard of 10 μg/L at most sites 10 months after the spill. Fluorometric detection of oil in pore water was introduced to eliminate the effects of grain size for the quantification of oil in sediments and to better explain spatial and temporal distribution of oil pollution at sandy beaches. The fluorescence detection method was compared with the conventional laboratory technique of total petroleum hydrocarbon analysis using gas chromatography. The method of fluorescence detection of oil was capable of generating results much faster and more cost-effectively than the traditional GC technique.     

An Assessment of Potential Oil Spill Damage to Salt Marsh Habitats and Fishery Resources in Galveston Bay, Texas

We sampled nekton, benthic infauna, and sediments in salt marshes of upper Galveston Bay, Texas to examine relationships between habitat use and sediment hydrocarbon concentration. Most marsh sediment samples were contaminated with relatively low concentrations of weathered petroleum hydrocarbons. We found few statistically significant negative relationships between animal density and hydrocarbon concentration (6 of 63 taxa examined using simple linear regression). Hydrocarbon concentration did not contribute significantly to Stepwise Multiple Regression models we used to explore potential relationships between animal densities and environmental parameters; in most cases where hydrocarbon concentration was an important variable in the models, the relationship was positive (i.e., animal densities increased with hydrocarbon concentration). Low hydrocarbon concentrations in sediments of upper Galveston Bay marshes could have contributed to our results either because levels were too low to be toxic or levels were toxic but too low to be detected by most organisms.     

2010 oil spill: trajectory projections based on ensemble drifter analyses

An accurate method for long-term (weeks to months) projections of oil spill trajectories based on multi-year ensemble analyses of simulated surface and subsurface (z = −800 m) drifters released at the northern Gulf of Mexico spill site is demonstrated during the 2010 oil spill. The simulation compares well with satellite images of the actual oil spill which show that the surface spread of oil was mainly confined to the northern shelf and slope of the Gulf of Mexico, with some (more limited) spreading over the north/northeastern face of the Loop Current, as well as northwestward toward the Louisiana–Texas shelf. At subsurface, the ensemble projection shows drifters spreading south/southwestward, and this tendency agrees well with ADCP current measurements near the spill site during the months of May–July, which also show southward mean currents. An additional model analysis during the spill period (Apr–Jul/2010) confirms the above ensemble projection. The 2010 analysis confirms that the reason for the surface oil spread to be predominantly confined to the northern Gulf shelf and slope is because the 2010 wind was more southerly compared to climatology and also because a cyclone existed north of the Loop Current which moreover was positioned to the south of the spilled site.     

Sources of sedimentary PAHs in tropical Asian waters: Differentiation between pyrogenic and petrogenic sources by alkyl homolog abundance

We collected surface sediment samples from 174 locations in India, Indonesia, Malaysia, Thailand, Vietnam, Cambodia, Laos, and the Philippines and analyzed them for polycyclic aromatic hydrocarbons (PAHs) and hopanes. PAHs were widely distributed in the sediments, with comparatively higher concentrations in urban areas (∑PAHs: ∼1000 to ∼100 000 ng/g-dry) than in rural areas (∼10 to ∼100 g-dry), indicating large sources of PAHs in urban areas. To distinguish petrogenic and pyrogenic sources of PAHs, we calculated the ratios of alkyl PAHs to parent PAHs: methylphenanthrenes to phenanthrene (MP/P), methylpyrenes + methylfluoranthenes to pyrene + fluoranthene (MPy/Py), and methylchrysenes + methylbenz[a]anthracenes to chrysene + benz[a]anthracene (MC/C). Analysis of source materials (crude oil, automobile exhaust, and coal and wood combustion products) gave thresholds of MP/P = 0.4, MPy/Py = 0.5, and MC/C = 1.0 for exclusive combustion origin. All the combustion product samples had the ratios of alkyl PAHs to parent PAHs below these threshold values. Contributions of petrogenic and pyrogenic sources to the sedimentary PAHs were uneven among the homologs: the phenanthrene series had a greater petrogenic contribution, whereas the chrysene series had a greater pyrogenic contribution. All the Indian sediments showed a strong pyrogenic signature with MP/P ≈ 0.5, MPy/Py ≈ 0.1, and MC/C ≈ 0.2, together with depletion of hopanes indicating intensive inputs of combustion products of coal and/or wood, probably due to the heavy dependence on these fuels as sources of energy. In contrast, sedimentary PAHs from all other tropical Asian cities were abundant in alkylated PAHs with MP/P ≈ 1-4, MPy/Py ≈ 0.3-1, and MC/C ≈ 0.2-1.0, suggesting a ubiquitous input of petrogenic PAHs. Petrogenic contributions to PAH homologs varied among the countries: largest in Malaysia whereas inferior in Laos. The higher abundance of alkylated PAHs together with constant hopane profiles suggests widespread inputs of automobile-derived petrogenic PAHs to Asian waters.     

Spatial and temporal distribution of dissolved/dispersed aromatic hydrocarbons in seawater in the area affected by the Prestige oil spill

Seawater samples collected at three depths from 68 stations along the Northern Spanish coast were analysed for dissolved/dispersed petroleum aromatic hydrocarbons by UV-fluorescence and for 25 individual compounds by GC-MS. Sampling was performed in December 2002, just after the Prestige oil spill, and in February-March and September 2003. Higher concentrations of total aromatic hydrocarbons were found at all depths in the samples collected during December 2002 off the Galicia coast, with levels ranging between 0.19 and 28.8 microg/L eq. oil (0.1-4.8 microg/L chrysene eq.). These values decreased in the following cruises, till <0.05-2.86 microg/L oil eq. (av. 0.23 microg/L chrysene eq.) in September 2003, possibly representing the background levels for the region. However, in the Cantabrian coast they were still high at the surface in the March cruise, probably by the late arrival of the fuel-oil to this area. Some coastal hot spots were also identified, with values up to 29.2 microg/L fuel-oil eq., close to river mouths and urban areas. The individual PAH distributions in the December 2002 sampling off-Galicia were dominated by alkyl-naphthalene derivatives, consistently with the pattern distribution shown by the fuel-oil water accommodated fraction. The higher concentrations were found in the subsurface samples along the Costa da Morte, the area most heavily affected by the spill (av. 0.46 microg/L Sigma16 PAHs). The rest of the samples collected in other areas exhibited lower concentrations and a more even distribution of 2-4 ring PAHs, that ranged from 0.09 to 0.37 microg/L (av. 0.15 microg/L Sigma16 PAHs), with decreasing trends offshore and downward the water column. In September 2003, the values were rather uniform, averaging 0.09 microg/L (Sigma16 PAHs).     

Monitoring of organic micropollutants in Ghana by combination of pellet watch with sediment analysis: E-waste as a source of PCBs

Plastic resin pellets collected at 11 beaches covering the whole Ghanaian coastline were analyzed for polychlorinated biphenyls (PCBs). PCB concentrations (∑13 congeners) were higher in Accra, capital city, and Tema (39–69 ng/g-pellets) than those in rural coastal towns (1–15 ng/g-pellets) which are close to global background, indicating local inputs of PCBs. River sediments were also analyzed for PCBs together with molecular markers. Sedimentary PCBs concentrations were highest at a site (AR02) downstream of an electronic waste (e-waste) scrapyard. At the site (AR02), concentration of linear alkylbenzenes (LABs), a marker of municipal wastewater, was lower than another site (AR03) which is located at the downstream of downtown Accra. This result suggests that PCBs are introduced more to the river from the e-waste site than from activities in downtown Accra. PAHs concentrations were relatively higher in urban areas with strong petrogenic signature. Abundance of triphenylbenzenes suggested plastic combustion near e-waste scrapyard.     

Temporal and spatial trends of total petroleum hydrocarbons in the seawater of Bohai Bay, China from 1996 to 2005

The temporal and spatial distribution of total petroleum hydrocarbons (TPH) in the seawater of Tianjin Bohai Bay during 1996-2005 was investigated for the first time. TPH concentrations in 480 seawater samples collected from 16 stations during a 10-year span were quantified by ultra-violet fluorescence spectroscopy. Petroleum hydrocarbons were ubiquitous in the seawater, and their concentrations were highly variable, ranging from 23.7 to 508 μg L⁻¹. TPH concentrations in the seawater varied with seasons, showing a decreasing order of winter > spring > summer. Over the 10-year period, TPH at all stations steadily decreased. The highest values obtained were at stations near the port areas and Dagu outfall where shipping activities and land-based waste water discharges were the major sources of pollution. Our results provided the background information on the extent of TPH contamination in the seawater and highlighted the need to further control TPH pollution in Tianjin Bohai Bay.     

Tritium hydrology of the Mississippi River basin

In the early 1960s, the US Geological Survey began routinely analysing river water samples for tritium concentrations at locations within the Mississippi River basin. The sites included the main stem of the Mississippi River (at Luling Ferry, Louisiana), and three of its major tributaries, the Ohio River (at Markland Dam, Kentucky), the upper Missouri River (at Nebraska City, Nebraska) and the Arkansas River (near Van Buren, Arkansas). The measurements cover the period during the peak of the bomb‐produced tritium transient when tritium concentrations in precipitation rose above natural levels by two to three orders of magnitude. Using measurements of tritium concentrations in precipitation, a tritium input function was established for the river basins above the Ohio River, Missouri River and Arkansas River sampling locations. Owing to the extent of the basin above the Luling Ferry site, no input function was developed for that location. The input functions for the Ohio and Missouri Rivers were then used in a two‐component mixing model to estimate residence times of water within these two basins. (The Arkansas River was not modelled because of extremely large yearly variations in flow during the peak of the tritium transient.) The two components used were: (i) recent precipitation (prompt outflow) and (ii) waters derived from the long‐term groundwater reservoir of the basin. The tritium concentration of the second component is a function of the atmospheric input and the residence times of the groundwaters within the basin. Using yearly time periods, the parameters of the model were varied until a best fit was obtained between modelled and measured tritium data. The results from the model indicate that about 40% of the flow in the Ohio River was from prompt outflow, as compared with 10% for the Missouri River. Mean residence times of 10 years were calculated for the groundwater component of the Ohio River versus 4 years for the Missouri River. The mass flux of tritium through the Mississippi Basin and its tributaries was calculated during the years that tritium measurements were made. The cumulative fluxes, calculated in grams of ³H were: (i) 160 g for the Ohio (1961–1986), (ii) 98 g for the upper Missouri (1963–1997), (iii) 30 g for the Arkansas (1961–1997) and (iv) 780 g for the Mississippi (1961–1997). Copyright © 2004 John Wiley & Sons, Ltd.     

Distribution and origins of polycyclic aromatic hydrocarbons (PAHs) in riverine, estuarine, and marine sediments in Thailand

To assess the status of polycyclic aromatic hydrocarbon (PAH) contamination in coastal and riverine environments in Thailand, we collected 42 surface sediment samples from canals, a river, an estuary, and coastal areas in Thailand in 2003 and analyzed them for PAHs with 3-7 benzene rings by gas chromatography-mass spectrometry (GC-MS). The total concentration of PAHs ranged from 6 to 8399 ng/g dry weight. The average total PAH concentrations were 2290+/-2556 ng/g dry weight (n=8) in canals, 263+/-174 (n=11) in the river, 179+/-222 (n=9) in the estuary, and 50+/-56 (n=14) in coastal areas. Comparison of the concentration range with a worldwide survey of sedimentary PAH concentrations ranked PAH contamination in Thai sediments as low to moderate. The ratio of the sum of methylphenanthrenes to phenanthrene (MP/P ratio) allows discrimination of PAH sources between petrogenic (>2) and pyrogenic (<0.5) origins. Sediments from urban canals in Bangkok showed the highest PAH concentrations and petrogenic signatures (MP/P=1.84+/-0.98 [n=6] in canal sediments) with abundant alkylated PAHs, indicating major sources of petrogenic PAHs in the city. To identify the sources of the petrogenic inputs in Thailand, we analyzed triterpanes, biomarkers of petroleum pollution, in the sediment samples and in potential source materials. Hopane profiles were remarkably uniform throughout the nation, suggesting a diffuse single source (e.g. automobiles). Molecular profiles of hopanes and PAHs in sediments from the urban canals were similar to those in street dust, indicating that street dust is one of the major sources of petrogenic PAHs in the urban area. On the other hand, low levels of PAHs (approximately 50 ng/g) with a pyrogenic signature (MP/P ratio approximately 0.5) were widely recorded in remote areas of the coast and the Chao Phraya River. These pyrogenic PAHs may be atmospherically transported throughout the nation. Middle and lower reaches of the Chao Phraya River, the river mouth, and the upper Gulf of Thailand showed intermediate concentrations and profiles of PAHs, indicating mixtures of petrogenic and pyrogenic origins. Perylene was abundant in sediments, representing up to approximately 60% of total identified PAHs. High inputs of soil due to frequent heavy rains could contribute to the high perylene abundance in the sediments. Sedimentary PAH concentrations decreased offshore with a half distance of approximately 10 km in the upper Gulf off the mouth of the Chao Phraya River. This is probably due to active deposition of laterally transported riverborne particles.