Composition and sources of dissolved and particulate PAH in surface waters from the Rhone delta (NW Mediterranean)

PAH were determined in surface waters from the Rhone delta in winter and summer 1987. Both particulate and dissolved phases were analyzed by GC and GC/MS. Concentrations of major unsubstituted compounds associated with particles varied from a few to 20 ng l⁻¹, or from 0.42 to 6.0 μg g⁻¹. The seasonal variations reflected higher inputs in winter resulting from the presence of highly PAH-enriched particles. Tetra- and penta-cyclic PAH with MW 202 and 252 predominated, which reflected a significant origin from pyrolytic processes. A rapid decrease of the level of higher MW PAH was observed seawards in both seasons. Study of the tricyclic compounds and their alkylated homologues demonstrated a mainly fossil origin in winter, whereas in summer a high heterogeneity of particles was observed. PAH in the dissolved phase were found at concentrations up to 31 and 50 ng l⁻¹ in summer and winter, respectively. These levels were much higher than those encountered in the corresponding particulate phases. PAH with MW 178 and 202 predominated, and the alkylated homologues of the tricyclic compounds showed a major fossil orgin in winter and a mixed origin in summer. In winter dissolved PAH were transported through the delta into the marine environment without significant losses.     

Petroleum and PAH contamination of the Black Sea

Concern has been expressed regarding the extent of contamination of the Black Sea. Analyses of coastal sediments taken from throughout the region indicate, however, that levels of petroleum hydrocarbons (2-300 microg g(-1) dry wt total hydrocarbons) are generally comparable to those encountered in the Mediterranean and are lower than concentrations reported for highly contaminated areas such as the Gulf, Hong Kong, Taiwan and New York Bight. Highest concentrations of total hydrocarbons (>100 microg g(-1) dry wt) were associated with discharges from Odessa, Sochi and the River Danube. Chronic/degraded petroleum was the major contributor at these sites. Samples from the Ukrainian coastline were comparatively clean (<10 microg g(-1) dry wt total hydrocarbons). Major contributions of fresh oil (as indicated by sigma n-C14-34) occur through the River Danube. Concerning total PAH, concentrations (7-638 ng g(-1) dry wt) compare to relatively unpolluted locations in the Mediterranean and are much lower than levels reported for polluted UK estuaries (e.g. Mersey, Tyne, Thames). Both pyrolytic and petrogenic PAH are present in most samples, although petroleum derived PAH are dominant at Sochi and pyrolytic sources are prevalent in the Bosphorus region. The absence of a correlation between total hydrocarbons and PAH (R2 = 0.04) indicates different primary sources for the two.     

Occurrence and fate of polycyclic aromatic hydrocarbons in the coastal surface microlayer

Polycyclic aromatic hydrocarbons (PAHs) were measured in the coastal sea surface microlayer (SML), the sub-surface waters (SSW) and the overlying atmosphere in order to investigate the influence of the SML on contaminant enrichment and air-sea exchange. Samples were collected at two contrasting locations of the NW Mediterranean, one urban influenced (off Barcelona, Spain) and another comparatively clean (off Banyuls-sur-Mer, France). Statistical data analysis confirmed the accumulation of PAHs in the SML with respect to the SSW (20.3+/-9.1 vs. 13.1+/-10.0 ng L(-1) in the dissolved phase; 709+/-207 vs. 158+/-111 ng g(-1) in the particulate phase). This accumulation was higher at the contaminated location (Barcelona station) compared with the more pristine one, with PAH enrichments 1.5 and 4.5 times higher for the dissolved and particulate phases, respectively, indicating that the enrichment of PAHs in the SML is dominated by particle transport processes.     

A particle flux study in the Santa Monica-San Pedro Basin off Los Angeles: particle flux,primary production,and transmissometer survey

In May 1983, two short-term (2.5 d) deployments of sediment traps at 100, 300, and 500 m measured the sinking flux of mass (as dry weight), particulate organic carbon and carbonate carbon in the nearshore basins off Los Angeles. The flux of organic carbon at 100 m depth was about 15% of the mass flux and about 5% of the rate of primary production measured in the surface waters. At 500 m the flux of organic carbon had decreased to about half that at 100 m. Characteristics of the trap collections indicated a large biogenic contribution. In the second deployment, much of this appeared to be the fecal material of the pelagic red crab, Pleuroncodes. The biomass carbon of microorganisms determined by microscopy (exclusive of heterotrophic bacteria) in the surface waters was dominated by nano- and picoplankton size categories. In the sediment trap collections, total microorganism carbon comprised <3% of the carbon flux. A six-month (May–November) sediment trap deployment (500 and 824 m) was also made. The higher mass flux to the deeper of these traps indicates near-bottom transport of resuspended sediments. Near-bottom transport of particles may explain the higher mass fluxes (by a factor of two) reported in two 1977 sediment trap studies in the inner basins, and the higher rate of sediment accumulation previously estimated from analysis of sediments. A transmissometer survey indicated that the concentration of suspended particles in the deep waters of the San Pedro Basin was low during the period of the May trap collections.     

Survey of PAH in low density residential stormwater ponds in coastal South Carolina: false dark mussels (Mytilopsis leucophaeata) as potential biomonitors

The distribution of PAHs was studied in sediment and false dark mussels, Mytilopsis leucophaeata, of three brackish stormwater retention ponds on Kiawah Island, a gated residential community and golf resort. Impervious surface in pond watersheds ranged from 5 to 30%. Sediment concentrations were lower than those found in other studies of suburban residential areas, and there were no significant differences among ponds or seasons. Mean summation operatorPAH(16) values for sediments in Ponds 67, 100, and 37 were 184.7+/-101.3ng g(-1), 67.5+/-26.0ng g(-1), and 84.3+/-75.5ng g(-1), respectively. Mussel summation operatorPAH(16) concentrations from Pond 67 in August (mean 734.5+/-148.1ng g(-1)), and from Pond 37 in December (mean 1115.1+/-87.7ng g(-1)), were significantly higher than other ponds. Mean summation operatorPAH(16) values for mussels in Ponds 67, 100, and, 37 were 555.9+/-219.7ng g(-1), 312.5+/-99.1ng g(-1) and 737.8+/-419.8ng g(-1), respectively. The mean biota-to-sediment ratio was 7.6+/-8.1. Isomer ratios generally suggested pyrogenic sources. False dark mussels are a promising indicator species for PAH contamination because they are abundant, easy to sample, bioaccumulate PAH profiles representative of the time-integrated sediment profiles, and their PAH levels are less variable than either stormwater or sediment samples.     

VERTEX: manganese transport through oxygen minima

Manganese transport through a well-developed oxygen minimum was studied off central Mexico (18°N, 108°W) in October–November 1981 as part of the VERTEX (Vertical Transport and Exchange) research program. Refractory, leachable and dissolved Mn fractions associated with particulates caught in traps set at eight depths (120–1950 m) were analyzed. Particles entering the oxygen minimum had relatively large Mn loads; however, as the particulates sank further into the minimum, total Mn fluxes steadily decreased from 190 nmol m^?2 day^?1 at 120 m to 36 nmol m^?2 day^?1 at 400 m. Manganese fluxes then steadily increased in the remaining 800–1950 m, reaching rates of up to 230 nmol m^?2 day^?1 at 1950 m.Manganese concentrations were also measured in the water column. Dissolved Mn levels < 3.0 nmol kg^?1 were consistently observed within the 150–600 m depth interval. In contrast, suspended particulate leachable Mn amounts were especially low at those depths, and never exceeded 0.04 nmol kg^?1.The combined water column and particle trap data clearly indicate that Mn is released from particles as they sink through the oxygen minimum. Rate-of-change estimates based on trap flux data yield regeneration rates of up to 0.44 nmol kg^?1 yr^?1 in the upper oxygen minimum (120–200 m). However, only 30% of the dissolved Mn in the oxygen minimum appears to be from sinking particulate regeneration; the other 70% probably results from continental-slope-release-horizontal-transport processes.Dissolved Mn scavenges back onto particles as oxygen levels begin to increase with depth. Scavenging rates ranging from ?0.03 to ?0.09 nmol kg^?1 yr^?1 were observed at depths from 700 to 1950 m. These scavenging rates result in Mn residence times of 16–19 years, and scavenging rate constants on the order of 0.057 yr^?1. Manganese removal via scavenging on sinking particles below the oxygen minimum is balanced by Mn released along continental boundaries and transported horizontally via advective-diffusive processes.Manganese appears to be very weakly associated with particulates. Nevertheless, the amounts of Mn involved with sinking biogenic particles are large, and the resulting fluxes are on the same order of magnitude as those necessary to explain the excess Mn accumulating on the sea floor. The overall behavior of Mn observed in this, and other, studies strongly suggests some type of equilibrium occurring between dissolved and particulate phases. This equilibrium appears to shift in direct or indirect response to dissolved oxygen levels.     

The extent of hydrocarbon contamination in the marine environment from a research station in the Antarctic

Low level hydrocarbon contamination is measurable in the vicinity of Antarctic stations, N-alkane and polycyclic aromatic hydrocarbon (PAH) concentrations in seawater and sediment at Signy Station, South Orkney Islands indicated contamination was confined to within a few hundred metres of the station. Total n-alkane concentrations in seawater decreased from 7.6 to 2.6 μg l⁻¹ within 500 m of the station. All n-alkane values in seawater were within the limits of variation for oceanic waters proposed by cripps (1992), although the distribution pattern suggested pollution from the station. The total PAH concentration in seawater varied between 110 and 216 ng l⁻¹. These values showed no trend with distance from the station and were all slightly higher than for the open ocean. The n-alkane and PAH concentations in the surface sediment declined to low levels within 375 m of the station. This indicates that a large proportion of the hydrocarbons entering Factory Cove was deposited from the water column. Sediment n-alkane concentrations were similar at all depths of the cores when collected more than 125 m from the station. PAH levels in the sediment appeared to be due to local input, including a small spill in 1965.     

Sedimentary record of polycyclic aromatic hydrocarbons in a sediment core from the Pearl River Estuary, South China

Owing to the hydrodynamic and sedimentation conditions, the western shoal of the Pearl River Estuary (PRE) is known to be an important sink of terrestrial substances including particle-associated pollutants from the Pearl River Delta (PRD) region. In this study, we report the sedimentary record of polycyclic aromatic hydrocarbons (PAHs) during the 20(th) century in a sediment core from the western shoal of the PRE. The summation PAH concentration ranged from 59 ng g(-1) to 330 ng g(-1) in the core with two distinct peaks. An initial increase of summation PAH concentration was found around the 1860s. The amounts of PAHs remained relatively constant for roughly 100 years, followed by the first peak in the 1950s. Then, there was a decrease in PAH concentration and flux in the 1960s and 1970s. A sharp increase of PAH concentration was observed in the early 1980s with a maximum concentration in the 1990s. The PAH diagnostic ratios indicated that the PAHs in the sediment core were mainly of pyrolytic origin, and that atmospheric deposition and land runoff may serve as the important pathways for PAHs input to the sediment. The Gross Domestic Product (GDP) was used as an index of socioeconomic development in the PRD region, which was correlated positively with the changes of PAH concentration and flux in the sediment core. The rapid increase in vehicle numbers and energy consumption in the region in the last two decades may have contributed to the rapid PAH increase since the early 1980s. The results clearly elucidated the impact of regional economic development on the estuarine environment.     

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.     

Comments on some aspects of particulate transport in the oceans

Recent studies of dissolved and particulate concentrations of trace elements and radionuclides amply demonstrate the importance of particulate transport in the case of several elements. A significant in-situ addition (J-flux) or removal (J-efflux) occurs in the case of a number of elements. However, to date it is not clear how the particulate processes occur and how the particles themselves are transported. Some of the problems are outlined briefly.It is shown that whereas a substantial flux in the case of some elements is due to transport by consolidated fecal particles, this transport does not generally lead to any substantial in-situ addition to deep waters. Changes in the dissolved concentrations of elements within the oceans occur due to small particles (1–10 μm) which sink stochastically with a mean speed of ～10^?3 cm/s. The larger particles sinking at higher Stokes' velocities impact and carry along the small particles. The smaller particles, ～1 μm size are thus transported down rapidly by the larger particles by apiggy-back mechanism. Simple theoretical calculations are consistent with the measured vertical transport rates based on studies of radionuclides.     

Polycyclic aromatic hydrocarbons and changes in the trophic structure of polychaete assemblages in sediments of Todos os Santos Bay, Northeastern, Brazil

Polycyclic aromatic hydrocarbons (PAHs) and the trophic structure of polychaete assemblages were studied in sediments at 28 stations in Todos os Santos Bay. Total PAH concentrations varied from 8 to 4163 ng g(-1) dry weight. The indexes used for the determination of PAH origin suggested both pyrolytic and petrogenic sources. A total of 397 individuals of polychaetes was recorded which were classified in three trophic groups. The PCA ordination resulted in the formation of three groups of stations, Group I characterised by sandy sediments, low organic content, low total PAH concentration and percentage of potentially harmful PAH was dominated by subsurface deposit-feeders. The other two groups (IIa and IIb), showed similar percentages of silt and clay, however, Group IIb formed by those stations with high total organic carbon, total nitrogen, sulphur contents, high total PAH concentration and percentage of potentially harmful PAH was dominated by carnivores. Trophic changes could be explained by the level of exposure to PAH effects relative to differences in the life style and feeding strategies between deposit-feeders and carnivores.     

Toxic contaminants and their biological effects in coastal waters of Xiamen,China. I. Organic pollutants in mussel and fish tissues

Organochlorines and organophosphates were measured in four fish species (Lateolabrax japonicus, Pagrasomus major, Miichthys miiuy and Epinephalus awoara) and the mussel Perna viridis collected from aquaculture cages in coastal waters of Xiamen, China. Polycyclic aromatic hydrocarbon (PAH) metabolites were also measured in fish bile. Sites in Xiamen coastal waters (the harbour, Maluan and Tongan) are compared with a "cleaner" reference site at Dongshan Island. DDT was found in livers of all fish sampled (May 1998, 1999 and December 1999) ranging from 0.15 to 2.2 microg/g WW, but levels in muscle tissue (<0.5 ng/g to 0.22 microg/g WW) were at least an order of magnitude lower in the harbour, and were not detectable (<0.5 ng/g) in Tongan samples. All other pesticides examined were not detected in fish or mussels, except for dieldrin in one liver sample (0.07 microg/g WW). Food of the caged fish, small fish and dried pellets, had very low (0.015-0.027 microg/g WW) or non-detectable levels of DDT, indicating significant bioaccumulation of contaminants in caged fish and/or other possible sources of uptake (water and sediments). DDT levels in fish varied with species. DDT contamination in fish livers and whole mussels varied significantly with location. Highest concentrations in fish occurred in the harbour, and less consistently so in Tongan. Dongshan and Maluan had comparatively low levels of DDT. Relatively low residues of DDT in both fish and mussels at Dongshan likely reflect lower levels of pesticide input at this reference site. However, the low levels of DDT contamination in fish tissues from Maluan were unexpected in view of the close proximity of the harbour and possibly reflect the removal of particulate-bound contaminants by the intensive bivalve culture there. Consistently high proportions of DDT in the form of the parent compound (p,p'-DDT: fish 30-45%; mussels 40-65%) from all sites suggest recent releases of this chemical to the environment. Levels of two main groups of PAH metabolites (naphthalene and phenanthrene) in fish bile suggest a different environmental distribution pattern than that of pesticides, in that Dongshan fish appear to be no less exposed to hydrocarbons than those from Xiamen coastal waters.     

Distribution, origin, and potential toxicological significance of polycyclic aromatic hydrocarbons (PAHs) in sediments of Kaohsiung Harbor, Taiwan

Sediment samples were collected from 12 locations of Kaohsiung Harbor, Taiwan and analyzed for polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations varied from 472 to 16,201 ng g(-1) dry weight. The highest PAH concentrations were from the industrial zone docks situated in south Kaohsiung Harbor. Diagnostic ratios showed that the possible source of PAHs in the industrial zone dock could be coal combustion while in the other zones it could be petroleum combustion. The toxic equivalent concentrations (TEQcarc) of PAHs varied from 55 to 1964 ng TEQ g(-1) dry weight. Higher total TEQcarc values were found at industrial zone docks (from 1404 to 1964 ng TEQ g(-1) dry weight). As compared with the US Sediment Quality Guidelines (SQGs), the observed levels of PAHs at industrial zone docks exceeded the effects range low (ERL), and could thus cause acute biological damage. However, the lower levels of PAHs at the other zones would probably not exert adverse biological effects.     

Mercury distribution in Douro estuary (Portugal)

Determinations of dissolved reactive and total dissolved mercury, particulate and sedimentary mercury, dissolved organic carbon (DOC), particulate organic carbon (POC) and suspended particulate matter (SPM) have been made in the estuary of river Douro, in northern Portugal. The estuary was stratified by salinity along most of its length, it had low concentrations of SPM, typically <20 mg dm(-3), and concentrations of DOC in the range <1.0-1.8 mg dm(-3). The surface waters had a maximum dissolved concentration of reactive mercury of about 10 ng dm(-3), whereas for the more saline bottom waters it was about 65 ng dm(-3). The surface waters had maximum concentrations of total suspended particulate mercury of approximately 7 microg g(-1) and the bottom waters were always <1 microg g(-1). Concentrations of mercury in sediments was low and in the range from 0.06 to 0.18 microg g(-1). The transport of mercury in surface waters was mainly associated with organic-rich particulate matter, while in bottom waters the dissolved phase transport of mercury is more important. Lower particulate organic matter, formation of chlorocomplexes in more saline waters and eventually the presence of colloids appear to explain the difference of mercury partitioning in Douro estuarine waters.     

Trace contaminant concentrations in the Kara Sea and its adjacent rivers, Russia.

Trace organic (chlorinated pesticides, PCBs, PAHs and dioxins/furans) and trace metal concentrations were measured in surficial sediment and biological tissues (i.e., worms, crustaceans, bivalve molluscs, and fish livers) collected from the Russian Arctic. Total DDT, chlordane, PCB and PAH concentrations ranged from ND to 1.2, ND to <0.1, ND to 1.5 and <20-810 ng g(-1), respectively, in a suite of 40 surficial sediment samples from the Kara Sea and the adjacent Ob and Yenisey Rivers. High sedimentary concentrations of contaminants were found in the lower part of the Yenisey River below the salt wedge. Total dioxins/furans were analysed in a subset of 20 sediment samples and ranged from 1.4 to 410 pg g(-1). The highest trace organic contaminant concentrations were found in organisms, particularly fish livers. Concentrations as high as 89 ng g(-1) chlordane; 1010 ng g(-1) total DDTs; 460 ng g(-1) total PCBs; and 1110 ng g(-1) total PAH, were detected. A subset of 11 tissue samples was analysed for dioxins and furans with total concentrations ranging from 12 to 61 pg g(-1). Concentrations of many trace organic and metal contaminants in the Kara Sea appear to originate from riverine sources and atmospheric transport from more temperate areas. Most organic contaminant concentrations in sediments were low; however, contaminants are being concentrated in organisms and may pose a health hazard for inhabitants of coastal villages.     

Levels and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in superficial sediment from 15 Italian marine protected areas (MPA)

Surface sediment from 15 Italian marine protected areas (MPA) were analysed for polycyclic aromatic hydrocarbons (PAHs). The organic carbon percentage was also determined. Total PAH concentrations (ng g⁻¹ d.w.) ranged from 0.71 (Penisola del Sinis) to 1550 (Miramare). Individual PAH analysis showed that three and four rings PAHs were the most frequently detected isomers and accounted for 60-70% of the PAH total concentrations. PAH ratio analysis showed a prevalence of pyrolytic PAH origin at most of the MPAs with exception of Porto Cesareo and Ustica where a petrogenic origin was detected. Results for organic carbon percentages ranged from 0.3% (Capo Rizzuto) to 2% (Punta Campanella). These results are comparable to other Mediterranean marine environments. However, our results shows that some MPAs, such as Miramare, Porto Cesareo, Isola Capo Rizzuto and Punta Campanella, are subject to strong pressure from urban and industrial activities where high PAH levels were detected.     

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.     

The use of surface-enhanced Raman scattering (SERS) for detection of PAHs in the Gulf of Gdańsk (Baltic Sea)

A field operable surface enhanced Raman scattering (SERS) sensor system was applied for the first time under real conditions for the detection of polycyclic aromatic hydrocarbons (PAHs) as markers for petroleum hydrocarbons in the Gulf of Gdańsk (Baltic Sea). At six stations, seawater samples were taken, and the sensor system was applied in situ simultaneously. These measurements were compared to the results of conventional GC/MS laboratory analysis of the PAH concentrations in the seawater samples. For a PAH concentration above 150 ng(12PAH)l(-1), there was agreement between the SERS sensor and the GC/MS determinations. A standard addition experiment yielded a PAH concentration of 900 ng l(-1) at the Gdańsk Harbor, which was of the same order as the GC/MS determinations of 12PAHs (200 ng(12PAH)l(-1)). The high SERS detection limit for seawater samples is explained by the competition for PAHs between the sensor membrane and particulate matter surfaces. Thus, the SERS sensor can be applied, e.g., as a non-quantitative alarm sensor for relatively high PAH concentrations in heavily polluted waters. The spectral unmixing procedure applied for Gdańsk Harbor water confirmed the presence of phenanthrene at the highest concentration ([Phe]=140 ngl(-1)) and of Chr (2.7 ng l(-1)), but it did not detect the other PAHs present in the Gdańsk Harbor water, as determined by GC/MS. When compared to the past literature and databases, the SERS spectra indicated the presence of a mixture of molecules consisting of carotenoids, n-alkanes, amines or fatty acids, and benzimidazoles at the coastal station ZN2. The spectra in the offshore direction indicated carboxylic acids. Interpretation of the farthest offshore in situ SERS measurements is difficult, principally due to the limited availability of reference spectra. The detection of the lower PAH concentrations commonly found in Baltic coastal water needs further research and development to obtain better sensitivity of the SERS sensor. However, the high analytical specificity of the SERS sensor also allows the detection of other chemical species that require the development of a SERS/Raman library for specific in situ spectral interpretation.     

Hydrocarbons in sediments of a chronically contaminated bay: the challenge of source assignment

Aliphatic hydrocarbons and 39 PAH (parental and alkylated homologs) determined in ca. 100 sediment samples from the Guanabara Bay, Rio de Janeiro, were evaluated for source discrimination using new approaches. Concentrations of total PAH were in the range of 96-135,000 μg kg(-1) similar to other coastal urbanized embayment. Traditional diagnostic ratios were not as efficient PAH source indicators, e.g. biomass combustion was assigned as the major source of the pyrolytic PAH although the hydrographic basin is highly industrialized and urbanized. It is proved petrogenic imprint cannot be detected if only the 16 USEPA PAH are determined. The high production in the eutrophic system is not apparent in the aliphatic fraction dominated by land derived n-alkanes due to the effectiveness of microbial degradation. The present work demonstrates the complexity of hydrocarbon forensics when applied to chronically contaminated environments.     

Inhomogeneous distribution of polycyclic aromatic hydrocarbons in different size and density fractions of contaminated sediment from Auckland Harbour, New Zealand: an opportunity for mitigation

Polycyclic aromatic hydrocarbons (PAHs) in sediment from Auckland Harbour (New Zealand) are not distributed evenly throughout bulk sediment, but highly concentrated in coarser, low-density fractions. Concentrations of 24 PAHs, measured in sediment that was separated into six size fractions that were furthermore separated into two density sub-fractions by flotation in sodium-polytungstate solution (rho = 2.15 g cm(-3)), varied between 4-103 microg g(-1)dw among grain size fractions and 2-998 microg g(-1)dw for density sub-fractions. Highest PAH concentrations were measured in the low density, 125-250 microm fraction. All sediment fractions had a similar relative PAH composition, dominated by >3-ring PAHs, suggesting a common pyrogenic origin. Low density material had 10-200 times higher PAH concentrations and 10-100 times higher organic carbon (OC) content, yet differences in OC content only partially accounted for variations in PAH concentration. Low density particles contributed more than 75% of the Sigma PAH, while comprising only 3% of bulk sediment dry weight. This may have significant utility for contaminant mitigation efforts in Auckland Harbour.