Impact of dredged urban river sediment on a Saronikos Gulf dumping site (Eastern Mediterranean): sediment toxicity,contaminant levels,and biomarkers in caged mussels

Impacts of chemical contaminants associated with dumping of dredged urban river sediments at a coastal disposal area in Saronikos Gulf (Eastern Mediterranean) were investigated through a combined approach of sediment toxicity testing and active biomonitoring with caged mussels. Chemical analyses of aliphatic hydrocarbons (AHs), polycyclic aromatic hydrocarbons (PAHs), Cu, and Zn in combination with the solid phase Microtox® test were performed on sediments. Concentrations of PAHs, AHs, Cu, and Zn as well as multiple biomarkers of contaminant exposure and/or effects were measured in caged mussels. Sediments in the disposal and neighboring area showed elevated PAHs and AHs concentrations and were characterized as toxic by the solid-phase Microtox® test during and after dumping operations. Biomarker results in the caged mussels indicated sublethal effects mainly during dumping operations, concomitantly with high concentrations of PAHs and AHs in the caged mussel tissues. Cu and Zn concentrations in sediments and caged mussels were generally not elevated except for sediments at the site in the disposal area that received the major amount of dredges. High PAHs and AHs levels as well as sublethal effects in the caged mussels were not persistent after termination of operations. The combined bioassay–biomarker approach proved useful for detecting toxicological impacts of dredged river sediment disposal in sediments and the water column. Nevertheless, further research is needed to evaluate whether sediment toxicity will have long-term effects on benthic communities of the disposal area.     

Biochemical responses of the marine mussel Mytilus galloprovincialis to petrochemical environmental contamination along the North-western coast of Portugal

Following the development of urban and industrial centres petrochemical products have become a widespread class of contaminants. The aim of this study was to investigate the effects of petrochemical contamination in wild populations of mussels (Mytilus galloprovincialis) along the NW Atlantic coast of Portugal by applying antioxidant and energetic metabolism parameters as biomarkers. For that, mussels were collected at five sampling sites presenting different petrochemical contamination levels. To evaluate the mussels' antioxidant status, enzymatic activities of catalase, superoxide dismutase, glutathione peroxidase, glutathione reductase, glutathione S-transferases, as well as glutathione redox status were evaluated in gills and digestive glands of mussels collected from the selected sites. Lipid peroxidation was determined in the same tissues to quantify cellular oxidative damage. Furthermore, to investigate how energetic processes may respond to these contaminants, the activity of NADP(+)-dependent isocitrate dehydrogenase was determined in mussels' digestive glands, and octopine dehydrogenase was determined in mussels' posterior adductor muscle. Furthermore, the concentrations of aliphatic hydrocarbons, unresolved complex mixture and polycyclic aromatic hydrocarbons (PAHs) were quantified in mussels' tissue, and abiotic parameters were quantified in water samples collected at each site. Several biomarkers showed statistically significant differences among sampling sites. The redundancy analysis (RDA) used to perform the integrated analysis of the data showed a clear separation of the sampling sites in three different assemblages, which are in agreement with the PAHs levels found in mussels tissues. In addition, the RDA indicated that some of the selected biomarkers may be influenced by abiotic parameters (e.g. salinity, pH, nitrates and ammonia). The approach selected for this study seems to be suitable for monitoring petrochemical contamination.     

Polycyclic aromatic hydrocarbons in sewage,mussels and tap water

Polycyclic aromatic hydrocarbons (PAH) have been determined in sewage discharge, mussels and tap water by glass capillary gas chromatography. Up to 30 PAH compounds have been identified. The concentration levels are low, respectively 0.8 – 7.7μg/1, 0.5–1.1 μg/g and 0.002 – 0.2μg/1 of sum PAH have been determined in sewage discharge, mussels and tap water. The accumulation rate in mussels seems to be rather slow at the ambient water concentrations.     

Boiling points of halogenated organic compounds

The normal boiling points of a number of halogenated organic compounds have been compiled from experimental measurements over three decades. Some of these chemicals have not been reported in the literature. The substances listed are halogenated aliphatic hydrocarbons, halogenated aliphatic ethers, halogenated ring (cyclic) hydrocarbons and other related compounds.     

Petroleum Pollutant Degradation by Surface Water Microorganisms (8 pp)

Background, Aims and Scope It is well known that the composition of petroleum or some of its processing products changes in the environment mostly under the influence of microorganisms. A series of experiments was conducted in order to define the optimum conditions for an efficient biodegradation of petroleum pollutant, or bioremediation of different segments of the environment. The aim of these investigations was to show to what extent the hydrocarbons of a petroleum pollutant are degraded by microbial cultures which were isolated as dominant microorganisms from a surface water of a wastewater canal of an oil refinery and a nitrogen plant. Biodegradation experiments were conducted on one paraffinic, and one naphthenic type of petroleum during a three month period under aerobic conditions, varying the following parameters: Inorganic (Kp) or an organic medium (Bh) with or without exposition to light. Methods Microorganisms were analyzed in a surface water sample from a canal (Pančevo, Serbia), into which wastewater from an oil refinery and a nitrogen plant is released. The consortia of microorganisms were isolated from the water sample (most abundant species: Phormidium foveolarum - filamentous Cyanobacteria, blue-green algae and Achanthes minutissima, diatoms, algae). The simulation experiments of biodegradation were conducted with the biomass suspension and crude oils Sirakovo (Sir, paraffinic type) and Velebit (Ve, naphthenic type). After a three month period, organic substance was extracted by means of chloroform. In the extracts, the content of saturated hydrocarbons, aromatic hydrocarbons, alcohols and fatty acids was determined (the group composition). n-Alkanes and isoprenoid aliphatic alkanes, pristane and phytane, in the aliphatic fractions, were analyzed using gas chromatography (GC). Total isoprenoid aliphatic alkanes and polycyclic alkanes of sterane and triterpane types were analyzed by GC-MS. Results and discussion. Paraffinic type petroleums have a significant loss of saturated hydrocarbons. For naphthenic type petroleum, such a trend has not been observed. The most intensive degradation of n-alkanes and isoprenoid aliphatic alkanes (in paraffinic oil) and isoprenoids (in naphthenic oil) was observed using the inorganic medium Kp in the light; the microbial conversion is somewhat lower with Kp in the dark; with organic medium Bh in the light the degradation is of low intensity; with the same medium in the dark the degradation is hardly to be seen. Steranes and triterpanes were not affected by microbial degradation under the conditions used in our experiments. Obviously, the petroleum biodegradation was restricted to the acyclic aliphatics (n-alkanes and isoprenoids). Conclusion Phormidium foveolarum (filamentous Cyanobacteria - blue-green algae) and Achanthes minutissima (diatoms, algae), microbial cultures isolated as dominant algae from a surface water in a wastewater canal of an oil refinery and a nitrogen plant, have degradable effects dominantly involving petroleum hydocarbons. Petroleum microbiological degradation is more intensive when inorganic medium (in the light) is applied. Having in mind that the inorganic pollutants have been released into the canal as well, this medium reflects more the natural environmental conditions. Polycyclic alkanes of sterane and triterpane type, in spite of the fact that these compounds could be degraded, have remained unchanged regarding abundance and distribution. Since this is the case even for naphthenic type petroleum (which is depleted in n-alkanes), it can be concluded that the biodegradation of petroleum type pollutants, under natural conditions, will be restrained to the n-alkane and isoprenoid degradation. Recommendation and Outlook Performed experiments and simulations of petroleum microbiological degradation may serve for the prediction of the fate of petroleum type pollutants, as well as for definition of conditions for bioremediation of some environmental segments.     

GC and GC-MS characterization of crude oil transformation in sediments and microbial mat samples after the 1991 oil spill in the Saudi Arabian Gulf coast

The massive oil discharge in the Saudi Arabian coast at the end of the 1991 Gulf War is used here as a natural experiment to study the ability of microbial mats to transform oil residues after major spills. The degree of oil transformation has been evaluated from the analysis of the aliphatic and aromatic hydrocarbons by gas chromatography (GC) and GC coupled to mass spectrometry (GC-MS). The oil-polluted microbial mat samples from coastal environments exhibited an intermediate degree of transformation between that observed in superficial and deep sediments. Evaporation, photo-oxidation and water-washing seemed to lead to more effective and rapid elimination of hydrocarbons than cyanobacteria and its associated microorganisms. Furthermore, comparison of some compounds (e.g. regular isoprenoid hydrocarbons or alkylnaphthalenes) in the oil collected in the area after the spill or in the mixtures retained by cyanobacterial growth gave rise to an apparent effect of hydrocarbon preservation in the microbial mat ecosystems.     

Oil residues in Baltic sediment,mussel and fish. I. Development of the analysis methods

Sediment, sediment trap, Mytilus, Macoma and flounder samples from Northern Baltic (Finnish archipelago) have been analyzed for their contents of aliphatic and aromatic hydrocarbons. Androstane and hexaethylbenzene were used as internal standards. The analysis procedure consisted of alkaline degradation of fat, column fractionation of the two residue groups and final determination by glass capillary gas chromatography with FID for aliphatic hydrocarbon group and with mass spectrometry for non-polar aromatic residue group. The latter group was also determined by high pressure liquid chromatography. The residues due to oil pollution were distinguished from compounds of pure natural origin on the basis of statistical treatment of the determination results.     

Alkane biodegradation and dynamics of phylogenetic subgroups of sulfate-reducing bacteria in an anoxic coastal marine sediment artificially contaminated with oil

For 503 days, unoiled control and artificially oiled sediments were incubated in situ at 20m water depth in a Mediterranean coastal area. Degradation of the aliphatic fraction of the oil added was followed by GC-MS. At the same time, terminal restriction fragment length polymorphism (T-RFLP) of 16S rRNA encoding genes was used to detect dynamics in the sulfate-reducing bacteria (SRB) community in response to the oil contamination. Specific polymerase chain reaction (PCR) primer sets for five generic or suprageneric groups of SRB were used for PCR amplification of DNA extracted from sediments. During the experiment, hydrocarbons from C(17) to C(30) were significantly degraded even in strictly anoxic sediment layers. Of the five SRB groups, only two groups were detected in the sediments (control and oiled), namely the Desulfococcus-Desulfonema-Desulfosarcina-like group and the Desulfovibrio-Desulfomicrobium-like group. Statistical analysis of community patterns revealed dynamic changes over time within these two groups following the contamination. Significant differences in community patterns were recorded in artificially oiled compared with control sediments. Cloning and sequencing of 16S rRNA encoding genes performed after 503 days showed that many of the most abundant sequences were closely related to hydrocarbonoclastic SRB which could have played an active role in the observed biodegradation of aliphatic hydrocarbons. Results from the present study provide useful information on the dynamics of dominant SRB in heavily oil-contaminated sediments and their potential for anaerobic biodegradation for the treatment of spilled oil in anoxic marine environments.     

A comparison of the efficiency of different surfactants for removal of crude oil from contaminated soils

This paper presents the results from study investigating the efficiency with which different surfactants remove crude oil from contaminated soil using a soil washing process. The surfactants studied were aqueous solutions of rhamnolipid, saponin and sodium dodecyl sulfate (SDS). The efficiency of surfactants' removal was quantified and then GC/MS analysis conducted to investigate the distribution of hydrocarbons remaining on the washed soil samples compared to those on a control. The results showed that SDS removed the most crude oil from soil, followed by rhamnolipid and then saponin. However, the different surfactants showed preferences in terms of which crude oil components they removed from the contaminated soil. SDS removed more of the aliphatics than aromatic hydrocarbons whereas saponin removed the aromatic hydrocarbon preferentially to the aliphatic hydrocarbons. Clearly these results provide important information for the selection of surfactants used to remove crude oil from contaminated soils.     

Biodegradation of aliphatic and aromatic hydrocarbons by natural soil microflora and pure cultures of imperfect and lignolitic fungi

The biodegradation of aliphatic and aromatic hydrocarbons by natural soil microflora and seven fungi species, including imperfect strains and higher level lignolitic species, is compared in a 90-day laboratory experiment using a natural, not-fertilized soil contaminated with 10% crude oil. The natural microbial soil assemblage isolated from an urban forest area was unable to significantly degrade crude oil, whereas pure fungi cultures effectively reduced the residues by 26-35% in 90 days. Normal alkanes were almost completely degraded in the first 15 days, whereas aromatic compounds (phenanthrene and methylphenanthrenes) exhibited slower kinetics. Aspergillus terreus and Fusarium solani, isolated from oil-polluted areas, produced the more efficient attack of aliphatic and aromatic hydrocarbons, respectively. Overall, imperfect fungi isolated from polluted soils showed a somewhat higher efficiency, but the performance of unadapted, indigenous, lignolitic fungi was comparable, and all three species, Pleurotus ostreatus, Trametes villosus and Coriolopsis rigida, effectively degraded aliphatic and aromatic components. The simultaneous, multivariate analysis of 22 parameters allowed the elucidation of a clear reactivity trend of the oil components during biodegradation: lower molecular weight n-alkanes > phenanthrene > 3-2-methylphenanthrenes > intermediate chain length n-alkanes > longer chain length n-alkanes > isoprenoids approximately 9-1-methylphenanthrenes. Irrespective of the individual degrading capacities, all fungi species tested seem to follow this decomposition sequence.     

Organic compounds in the flue gas from a power station with circulating fluid bed combustion of coal

Numerous organic compounds have been analyzed by coupled gas chromatography-mass spectroscopy (GC-MS) in flue gas after fluid bed combustion of four coal species from South Africa, Poland, Spitsbergen and Ruhr area (Germany). Polynuclear aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated, heterocyclic and nitro compounds as well as phthalate esters are detected.     

The integrated use of chemical analysis, cytochrome P450 and stress proteins in mussels to assess pollution along the Galician coast (NW Spain)

Aliphatic and polycyclic aromatic hydrocarbons (PAHs) as well as biochemical markers, such as cytochrome P450, benzo(a)pyrene hydroxylase (BPH) and stress-70 proteins, were determined in mussels (Mytilus galloprovincialis) collected in October 1995 from several locations along the Galician coast (NW Spain). The survey proved the existence of a pollution gradient among sampling sites and a chronic exposure to petrogenic and pyrolitic hydrocarbons. This was reflected in mussel tissue levels of PAHs which ranged from 22 to 562 ng/g wet weight. High levels of total cytochrome P450 were detected in mussels from the most polluted sites, but differences were not statistically significant. BPH activity did not show either differences among sampling sites. Conversely, stress-70 proteins were significantly induced in the most polluted locations, and levels of the 72-kDa band correlated well (r2 = 0.854) with the sum of the PAHs from four to six rings accumulated by mussels.     

Aspects of Hydrocarbon Fingerprinting Using PLS—New Data From Prince William Sound

Partial least squares (PLS) techniques are used in the re-analysis of NOAA hydrocarbon data previously investigated in 4. New data have been provided for coal and oil signatures and these have been investigated further. The effects of zeros (less than the limit of detection) in the dataset can be overcome by addition of small values at approximately half of this limit; this then enables logarithms to be taken of the entire dataset which greatly improved the usefulness of principal component analysis (PCA). Source samples collected close to each other had different signatures, probably due to their environmental histories which was also seen when aliphatic hydrocarbons were included in the signatures. Key compounds describing each could be seen in Coomans' Plots. Signatures developed from formation oils, riperian oils and coals from the eastern Gulf of Alaska (GoA) provided mean fits to subtidal samples within PWS of 22, 19 and 38% respectively. This suggests mixed and variable sources across the sampling area. The overall conclusion must be a question regarding the partitioning between oil and coal source materials as they look very similar in this particular location.     

Aspects of Hydrocarbon Fingerprinting Using PLS-New Data From Prince William Sound

Partial least squares (PLS) techniques are used in the re-analysis of NOAA hydrocarbon data previously investigated in Mudge (2002). New data have been provided for coal and oil signatures and these have been investigated further. The effects of zeros (less than the limit of detection) in the dataset can be overcome by addition of small values at approximately half of this limit; this then enables logarithms to be taken of the entire dataset which greatly improved the usefulness of principal component analysis (PCA). Source samples collected close to each other had different signatures, probably due to their environmental histories which was also seen when aliphatic hydrocarbons were included in the signatures. Key compounds describing each could be seen in Coomans' Plots. Signatures developed from formation oils, riperian oils and coals from the eastern Gulf of Alaska (GoA) provided mean fits to subtidal samples within PWS of 22, 19 and 38% respectively. This suggests mixed and variable sources across the sampling area. The overall conclusion must be a question regarding the partitioning between oil and coal source materials as they look very similar in this particular location.     

Stigmastane and hopanes as conserved biomarkers for estimating oil biodegradation in a former refinery plant-contaminated soil

In the last decade, a refinery plant located in Lido Adriano, East Ravenna (Italy) has been subject to mineral oil contamination. The mineral crude oil, extracted from the offshore in Adriatic sea, consisted of 78% aliphatics, cyclic alkanes and saturated polycyclic hydrocarbons, 9% aromatics, polycyclic aromatic hydrocarbons (PAHs) and alkylated derivatives, and 13% of tars/asphaltenes. Analysis of soil after 10 years of natural attenuation revealed a complete depletion of linear (n-C(9)-C(24)), light aromatics (C1-C3/benzenes) and PAHs (C2/naphthalene, C1/phenanthrene); besides a substantial degradation of isoprenoids prystane and phytane, branched and cyclic alkanes. The remaining contaminants which withstood to natural degradation was saturated polycyclic hydrocarbons (perhydro-PAH derivatives), unsaturated polycyclic hydrocarbons (tetrahydro, dihydro-PAH derivatives), terpanes, steranes and unidentified compounds. Such residues resulted in 80% reduction of its concentration after two months of laboratory treatment. Samples were extracted by organic solvents, separated by silica/alumina gel column chromatography and analyzed by gas chromatography-mass selective detector (GC-MSD). Identification and quantification of aliphatic, cyclic alkanes, typical PAHs, terpanes and steranes were carried out to chromatograms of M/Z=85, 83, individual M/Zs, M/Z=191 and 217, respectively. The present work shows that, among numerous biomarkers present in the source oil, stigmastane and two isomers of hopane showed invariable concentrations after laboratory experiments that mimic natural biodegradation in the field, so they can be used as conserved internal biomarkers. These are very useful tools to assess alterations in less stable classes of saturated compounds contained in petroleum. Marked degradation of perhydro, tetrahydro, dihydro-PAH derivatives in the laboratory treatment has been evidenced.     

Aliphatic Hydrocarbons Distribution in Sediment Cores of Select Creeks in Delta State,Nigeria

The spatial and seasonal changes in the distribution, composition, and concentrations of aliphatic hydrocarbons were investigated in sediment cores of Ubeji, Ifie, and Egbokodo Creeks in the Niger Delta, Nigeria. A total of 222 sediment core samples were collected during the wet season (August 2010) and the dry season (January 2011). The samples were dried, soxhlet extracted, fractionated and analyzed for aliphatic hydrocarbons by using a gas chromatograph with flame ionization detector (GC-FID). The concentrations of aliphatic hydrocarbons ranged from 37 to 286,894 μg/kg (wet season) and from 30 to 11,773 μg/kg (dry season). The concentrations of n-alkanes for a number of stations in this study are comparable to sites with high anthropogenic activities in the Niger Delta. The carbon preference index (CPI) and the pristane/phytane ratios showed that the major source of hydrocarbon pollution in the sediment core was from petrogenic origin.     

Determination of some aliphatic and polycyclic aromatic hydrocarbons in marine sediments of the Baltic Sea

Two representative samples of surficial marine sediments have been studied, one from the northern Baltic Proper and the other from the Gulf of Finland. Aliphatic hydrocarbons were determined by gas chromatography on a fused silica capillary column, and six polyaromatic hydrocarbons were determined by gas chromatography-mass fragmentography. Hydrocarbons were extracted with a benzene-methanol mixture and ultrasonic agitation. The aliphatic hydrocarbons were tentatively identified by their retention times. The polyaromatic hydrocarbons (PAHs) were identified on the basis of their retention times and mass fragmentograms by direct comparison with those of standard compounds. The aliphatic hydrocarbon contents ranged from 0,1 to 2,6 μg/g dry matter. In both samples there was a clear maximum at n-C₁₇ and also a clear odd-carbon predominance. The PAH contents ranged from 4 to 120 ng/g dry matter. The PAH concentration was about 58 per cent higher in the sample from the Gulf of Finland than in the sample from the Baltic Proper.     

利用复合酵母菌系统处理含油污泥

利用筛选得到的10株酵母菌组成复合酵母菌系统，并将该复合菌系统接种到泥浆反应器中对模拟油泥样品进行了处理。在对反应器进行优化的基础上，比较了复合酵母菌体系和经驯化的活性污泥体系对模拟风化油泥的处理效果，发现复合酵母菌在反应速度和油去除率上都优于活性污泥。利用GC—MS对复合酵母菌处理体亲中主要脂肪烃组分的变化进行了分析，结果表明原油组分中脂肪烃部分在处理8d后基本被完全降解。     

利用复合酵母菌系统处理含油污泥

利用筛选得到的10株酵母菌组成复合酵母菌系统,并将该复合菌系统接种到泥浆反应器中对模拟油泥样品进行了处理。在对反应器进行优化的基础上,比较了复合酵母菌体系和经驯化的活性污泥体系对模拟风化油泥的处理效果,发现复合酵母菌在反应速度和油去除率上都优于活性污泥。利用GCMS对复合酵母菌处理体系中主要脂肪烃组分的变化进行了分析,结果表明原油组分中脂肪烃部分在处理8d后基本被完全降解。     

Treatment of hydrocarbon contamination under flow through conditions by using magnetite catalyzed chemical oxidation

Soil pollution by hydrocarbons (aromatic and aliphatic hydrocarbons) is a major environmental issue. Various treatments have been used to remove them from contaminated soils. In our previous studies, the ability of magnetite has been successfully explored to catalyze chemical oxidation for hydrocarbon remediation in batch slurry system. In the present laboratory study, column experiments were performed to evaluate the efficiency of magnetite catalyzed Fenton-like (FL) and activated persulfate (AP) oxidation for hydrocarbon degradation. Flow-through column experiments are intended to provide a better representation of field conditions. Organic extracts isolated from three different soils (an oil-contaminated soil from petrochemical industrial site and two soils polluted by polycyclic aromatic hydrocarbon (PAH) originating from coking plant sites) were spiked on sand. After solvent evaporation, spiked sand was packed in column and was subjected to oxidation using magnetite as catalyst. Oxidant solution was injected at a flow rate of 0.1 mL min^?1 under water-saturated conditions. Organic analyses were performed by GC–mass spectrometry, GC–flame ionization detector, and micro-Fourier transform infrared spectroscopy. Significant abatement of both types of hydrocarbons (60–70 %) was achieved after chemical oxidation (FL and AP) of organic extracts. No significant by-products were formed during oxidation experiment, underscoring the complete degradation of hydrocarbons. No selective degradation was observed for FL with almost similar efficiency towards all hydrocarbons. However, AP showed less reactivity towards higher molecular weight PAHs and aromatic oxygenated compounds. Results of this study demonstrated that magnetite-catalyzed chemical oxidation can effectively degrade both aromatic and aliphatic hydrocarbons (enhanced available contaminants) under flow-through conditions.