Imma Tolosa

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.

Aliphatic and aromatic hydrocarbons in coastal Caspian Sea sediments

This investigation represents the first extensive study of the spatial distribution and sources of aliphatic (n-alkanes and unresolved complex mixture of fossil hydrocarbons) and polycyclic aromatic hydrocarbons (PAHs) in coastal sediments from the Caspian Sea. PAH concentrations, n-alkanes and biomarker profiles all suggested that there was limited petrogenic contamination in the shallow North Caspian Sea sediments, which are coarse with a low total organic carbon content. In contrast, moderate to high petrogenic contamination was found in the South Caspian Sea, in particular in the offshore oil fields near Baku, Azerbaijan. Contaminant patterns indicated that the PAHs were mainly from fossil sources, with higher contributions of pyrolytic only near industrialized and urban areas. A high contribution of perylene, a geochemically derived PAH, to the total PAHs was found in the west and south at sites influenced by the Kura, Safid Rud, Terek, Sulak and Samur Rivers.

Persistent organochlorine residues in sediments from the Black Sea

The extent of contamination of the Black Sea by selected organochlorine compounds has been assessed through the analysis of surficial sediments taken from throughout the region. Concentrations of HCHs at sites influenced by the Danube delta are among the highest recorded on a global basis (up to 40 ng g(-1) dry wt). The ratio between the alpha- and gamma-isomers was relatively low indicating contamination through the use of lindane. Concentrations of DDTs (0.06-72 ng g(-1) dry wt) and PCBs (0.06-72 ng g(-1) dry wt) were not especially high in comparison to levels reported from throughout the world. The DDE/DDT ratio was, however, low indicating fresh inputs and hence current usage of DDT within the Black Sea region.

Comparison of the performance of solid-phase extraction techniques in recovering organophosphorus and organochlorine compounds from water

Solid-phase extraction (SPE) of 11 organochlorine and 24 organophosphorus compounds from aqueous solution was evaluated using different Amberlite (XAD-2 and XAD-7) resin mixtures, reversed-phase C18 bonded-silica disks, and poly(styrene-divinylbenzene) (SDB) co-polymer disks. Macroreticular resins provided low recoveries and unacceptable reproducibility for some compounds including malathion, methylparathion, ethylparathion, chlorthion and endosulfan compounds. This is probably due to irreversible adsorption or chemical degradation. No relationship was observed between the recoveries and the log Kow of the compounds. Octadecyl-bonded silica and styrene-divinylbenzene disks provided comparable results for the selected compounds with recovery efficiencies depending on the polarity of the compounds. Good recoveries were achieved for compounds with water solubilities below 300 mg/l or with log Kow greater than 2. Poor recoveries were obtained for dichlorvos, monocrotophos and dimethoate.

PCBs in the western Mediterranean. Temporal trends and mass balance assessment

Comparison of data reported for polychlorinated biphenyl (PCB) concentrations in different environmental compartments of the western Mediterranean (dissolved and particulate phases of water, sediment and biota) over the last two decades shows a substantial decline in PCB concentrations, which coincides with legislated restrictions in the use of these compounds. Nevertheless, localised chronic (“hotspot”) contamination continues, which underscores the importance of these compounds as environmental contaminants in certain specific areas of the region. Data on depositional fluxes are used to estimate and model transport processes to investigate the fate of these chemicals in the study area. A tentative mass balance of the compounds suggests that dry and wet deposition (12 t year−1) account for most of the input. This comparess with approximately 1 t year−1 discharged from rivers and sewage outfalls into coastal environments. Sedimentation is estimated to remove 5 t year−1 from the water column. Losses through volatilization are difficult to model owing to the critical dependance within calculations on atmospheric and dissolved seawater concentrations, for which very few data exist.

Recovery of the coastal marine environment in the Gulf following the 1991 war-related oil spills

Results from a 1991 rapid assessment survey to investigate the extent of hydrocarbon contamination resulting from the massive spillage of petroleum and the burning of oil wells revealed that war-related pollution in the Gulf was restricted to approximately 400 km from the sources. Subsequent surveys of the impacted zone were organized during 1992 and 1993 to investigate temporal changes in petroleum hydrocarbon contamination and recovery. Sub-tidal surface sediments from the coastlines of Kuwait and Saudi Arabia were sampled and analysed for petroleum hydrocarbons and polycyclic aromatic hydrocarbons (PAHs). At most locations by 1992, degradation had resulted in a composition (as determined by gas chromatography) dominated by an unresolved complex mixture, with only the most resistant resolved compounds surviving. Levels of contamination at impacted sites were generally shown to have decreased by approximately 50% between 1991 and 1992. A much lesser reduction in contamination was recorded for the period 1992 to 1993, and an increase in hydrocarbon concentrations was noted for stations in Kuwait and northern Saudi Arabia, possibly as a result of increased tanker activity and associated deballasting. PAH concentrations are shown to remain comparatively low, with oil rather than combustion being the major source.

Distribution of petroleum hydrocarbons and organochlorinated contaminants in marine biota and coastal sediments from the ROPME Sea Area during 2005.

The composition and spatial distribution of various petroleum hydrocarbons (PHs), comprising both aliphatic and polycyclic aromatic hydrocarbons (PAHs), and selected chlorinated pesticides and PCBs were measured in biota and coastal sediments from seven countries in the Persian Gulf and the Gulf of Oman (Bahrain, Iran, Kuwait, Oman, Qatar, Saudi Arabia and the United Arab Emirates). Evidence of extensive marine contamination with respect to organochlorinated compounds and PHs was not observed. Only one site, namely the BAPCO oil refinery in Bahrain, was considered to be chronically contaminated. Comparison of the results from this survey for Σ DDTs and Σ PCBs in rock oysters from the Gulf of Oman with similar measurements made at the same locations over the past two decades indicates a temporal trend of overall decreasing Σ PCB concentrations in oysters, whereas Σ DDTs levels have little changed during that period.

Assessment of organotin contamination in marine sediments and biota from the Gulf and adjacent region

Butyltin species were measured in sediments from coastal locations in the Gulf and Gulf of Oman. Both butyltin and phenyltin species were measured in biota samples from four countries in this region. With tributyltin (TBT) concentrations up to 60 ngSng(-1), some sediments could be classified as contaminated (i.e. TBT>1.3 ngSng(-1)), namely Dukhan (Qatar), the BAPCO industrial complex and Askar (Bahrain), and Hilf and the Raysut Port Area (Oman). Higher concentrations of total butyltins were found in oysters relative to fish, but ranging from 6.5 to 488 ngSng(-1) dry weight they are nonetheless relatively low. Diphenyltin and triphenyltin were found in some fish and bivalves from the Gulf, but not in biota from the Gulf of Oman. The environmental levels of organotin species are comparatively low by global standards and pose no immediate public health problems.

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.

Organochlorine contamination (PCBs, DDTs, HCB, HCHs) in sediments from Cienfuegos bay, Cuba

The spatial distribution of various organochlorinated compounds, e.g. PCBs, DDTs, HCB and HCHs, were investigated in sediments from Cienfuegos bay, Cuba. Their concentrations appeared to be relatively low by global standards and only sediments receiving the impact from the residual waters of the city and thermoelectrical power approached the sediment quality guidelines for PCBs and DDTs. Relatively higher SigmaDDT concentrations and high DDT/DDE+DDD ratios in two sites near the outfalls of the city indicated a current DDT usage, probably linked to public health emergencies. These results contribute to the sparse regional database for organochlorinated compounds in the Caribbean marine environment.