The chemical and biogenotoxic characterization of organic xenobiotics in aquatic sediment materials 1. The application and comparison of chemically non-specific and biogenotoxic methods

The aim of this work was to evaluate the Ames assay and mixed function oxidase (MFO)-Induct Test used in parallel with chemical group tests (ECD fingerprint and PAH estimation) for the characterization of the organic pollution of water sediment materials. Sediment materials were collected from “clean” and relatively heavily polluted locations in the Middle Adriatic Sea, and from some locations in continental Croatia polluted with wastewaters from different enterprises. Characterization of the organic extracts of the sediment materials investigated was performed chemically using UV spectrofluorometry for the determination polyaromatic hydrocarbons (PAH) and gas chromatography for the determination of volatile EC detector sensitive materials. Genotoxic analysis of the extracts was performed using the MFO-Induct Test and mutagenicity testing using the Standard Plate Incorporation Test as described by Maron and Ames with Salmonella typhimurium TA 98. Measurement of the BaPMO enzyme activity in the livers of carp treated i.p. with total extracts of the sediment investigated confirmed that the methanol extracts generally contained more inducing matter than the petroleum ether extracts. Ames assay showed that for all the samples following the elimination of the sulfur, there was an increase in the number of revertants in comparison to the control number, which indicates that the samples contained mutagenic substances. The larger doses of extracts generally demonstrated cytotoxicity, as evidenced by a reduced number of spontaneous revertants in the Salmonella/Microsome Test. Investigation of the correlation of the chemical parameters with the biological parameter showed that the induction of BaPMO exhibited a statistically significant correlation with the level of the ECD fingerprint of the petroleum ether sediment extract.     

Factors affecting the distribution of hydrocarbon contaminants and hydrogeochemical parameters in a shallow sand aquifer

The distributions of hydrocarbon contaminants and hydrogeochemical parameters were investigated in a shallow sand aquifer highly contaminated with petroleum hydrocarbons leaked from solvent storage tanks. For these purposes, a variety of field investigations and studies were performed, which included installation of over 100 groundwater monitoring wells and piezometers at various depths, soil logging and analyses during well and piezometer installation, chemical analysis of groundwater, pump tests, and slug tests. Continuous water level monitoring at three selected wells using automatic data-logger and manual measuring at other wells were also conducted. Based on analyses of the various investigations and tests, a number of factors were identified to explain the distribution of the hydrocarbon contaminants and hydrogeochemical parameters. These factors include indigenous biodegradation, hydrostratigraphy, preliminary pump-and-treat remedy, recharge by rainfall, and subsequent water level fluctuation. The permeable sandy layer, in which the mean water table elevation is maintained, provided a dominant pathway for contaminant transport. The preliminary pump-and-treat action accelerated the movement of the hydrocarbon contaminants and affected the redox evolution pattern. Seasonal recharge by rain, together with indigenous biodegradation, played an important role in the natural attenuation of the petroleum hydrocarbons via mixing/dilution and biodegradation. The water level fluctuations redistributed the hydrocarbon contaminants by partitioning them into the soil and groundwater. The identified factors are not independent but closely inter-correlated.     

Interpretation of analytical data on n-alkanes and polynuclear aromatic hydrocarbons in Arbacia lixula from the coasts of Tenerife (Canary Islands, Spain) by multivariate data analysis

The hydrocarbons contents (n-alkanes, polycyclic aromatic hydrocarbons) were determined in the sea urchin Arbacia lixula. Multivariate data analysis as principal component analysis, factor analysis and, cluster analysis were applied to elucidate sources of pollution. PCA and FA were performed to establish the relationships between variables (hydrocarbons), samples (sea urchin) and sources of pollution.     

加油站场地油品渗漏探测及土壤污染评估

用洛阳铲采集某地区10座地下贮罐罐龄接近或超过10年的典型加油站场地不同深度土样,并分别用吹脱/捕集/热脱附/气相色谱法和快速溶剂萃取/硅酸镁净化/气相色谱法分析样品中的挥发性和萃取性石油烃,发现2座加油站疑似油品渗漏,其中1座为柴油渗漏,地下贮罐附近1.2 ～3.0 m深度土壤总石油烃含量16.1 ～24.6 g/kg,均超过荷兰土壤清除标准,另1座为汽油和柴油混合渗漏,其地下贮罐附近2.4m深度土壤总石油烃含量较高,但未超标.个别加油站场地较高的土壤天然有机物背景值可能计入EPH的分析结果,但其色谱指纹明显不同于石油烃.     

Bioremediation and reclamation of soil contaminated with petroleum oil hydrocarbons by exogenously seeded bacterial consortium: a pilot-scale study

Purpose  

Spillage of petroleum hydrocarbons causes significant environmental pollution. Bioremediation is an effective process to remediate petroleum oil contaminant from the ecosystem. The aim of the present study was to reclaim a petroleum oil-contaminated soil which was unsuitable for the cultivation of crop plants by using petroleum oil hydrocarbon-degrading microbial consortium.     

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) distributions in the Bay of Marmara sea: Izmit Bay

In 1999, the concentrations of 16 polycyclic aromatic hydrocarbons (PAHs), the total PAH and polychlorinated biphenyls (PCBs) were measured in sea water, sediment and mussels collected along the coast of Izmit Bay, the most important bay of the Marmara Sea. The total-PAH concentrations, measured by Spectrofluorometry were in the range of 1.16-13.68 microg/l in sea water, in the range of 30.0 1670.0 microg/g dry weight in sediments and in the range from 5.67 to 14.81 microg/g wet weight in edible part of mussel. HPLC revealed Phenanthrene (three rings), chrysene (four rings) and benz[a]antracene (five rings) to be the dominant PAHs in sea water, while 16 different PAHs compounds were observed and measured in mussel samples. The most pollution occured at Dogu Kanali and Dil Deresi where were the main rivers containing wastes fall into the the Izmit Bay. Although the maximum mono-ortho PCB concentrations in sea water were measured in the Dil Deresi River (26.33 ng/l) and the Solventa? (22.19 ng/l) stations, maximum PCB concentrations in mussels were measured in the SEKA (28.11 microg/kg) and the Dil Deresi River (25.68 microg/kg). The dominant congeners of PCBs were from tetra to hexachlorobiphenyls. The toxicity equivalent values were very low in sea water and mussels.     

Brazilian Oil Spills Chemical Characterization--Case Studies

In the last decade, PETROBRAS has experienced some significant oil spills cases and the PETROBRAS Research Center has played an important role in the company emergency response program by characterizing the spilled oil, monitoring the affected ecosystem, determining the fate of the oil in the environment, and, subsequently, helping the company in assessing the environmental damage. This paper presents the use of advanced chemical analytical techniques (GC/FID, P&T/GC/PID and GC/MS) in some Brazilian oil spill studies in order to determine fractions and individual petroleum hydrocarbons in different matrices such as water, groundwater, sediment, sand, fish and the spilled oil itself. The spill studies encompassed crude and fuel oil releases on land and coastal ecosystems, related to the incidents in Guanabara Bay (Rio de Janeiro), Barigui and Iguassu Rivers (Parana) and Sao Sebastiao Channel (Sao Paulo). Total petroleum hydrocarbons (TPH), n -alkanes, isoprenoids, unresolved complex mixtures (UCM), volatile monoaromatic compounds--benzene, toluene, ethylbenzene and xylenes (BTEX), parent and alkylated homologues polycyclic aromatic hydrocarbons (PAH), and terpanes and steranes were characterized for determining correlation to the spilled oil and other known oil sources and environmental assessment. Some of the acute ecotoxicity data for water and sediment samples is also presented.     

Fingerprinting and Groundwater Model Application to Evaluate Hydraulic Barrier Efficiency (Italy)

Remediation actions at contaminated sites are based on multiple numerical model scenarios considering different parameter distributions, source positions and contaminant transport paths. In some cases the excess of scenarios is due to uncertainties in the conceptual model as a result of the spread of contamination through heterogeneities in the physical system. Reduction of project hypotheses and conceptual model uncertainty is therefore needed. This result can be achieved by coupling hydrogeological investigations with environmental forensic techniques, better localization of the source and understanding of contamination history. In this respect, in the present study, compositional fingerprinting and groundwater flow modeling were applied to a former oil storage facility where, even though a hydraulic barrier had been built to stop the hydrocarbon plume, the presence of some hydrocarbons was still found in downgradient monitoring wells. The final aim was to evaluate the efficacy of the hydraulic barrier and identify of the source of pollution. Fingerprinting results indicated pollution with a gasoline-diesel mixture much altered by water washing and/or biodegradation. Comparison of seven groundwater samples collected in wells and monitoring wells was performed by analyzing the volatile fraction (BTEX) and the total ion chromatogram (TIC), focusing attention on: n-alkanes (m/z 85), alkylcyclohexanes (m/z 83), isoprenoids (m/z 113), C4-alkylbenzenes (m/z 134), C3-C6 alkylbenzenes and polycyclic aromatic hydrocarbons (PAHs). The most probable scenario was then identified by combining the results of fingerprinting with different contaminant paths obtained using the numerical model.     

Brazilian Oil Spills Chemical Characterization—Case Studies

In the last decade, PETROBRAS has experienced some significant oil spills cases and the PETROBRAS Research Center has played an important role in the company emergency response program by characterizing the spilled oil, monitoring the affected ecosystem, determining the fate of the oil in the environment, and, subsequently, helping the company in assessing the environmental damage. This paper presents the use of advanced chemical analytical techniques (GC/FID, P&T/GC/PID and GC/MS) in some Brazilian oil spill studies in order to determine fractions and individual petroleum hydrocarbons in different matrices such as water, groundwater, sediment, sand, fish and the spilled oil itself. The spill studies encompassed crude and fuel oil releases on land and coastal ecosystems, related to the incidents in Guanabara Bay (Rio de Janeiro), Barigui and Iguassu Rivers (Parana) and Sao Sebastiao Channel (Sao Paulo). Total petroleum hydrocarbons (TPH), n -alkanes, isoprenoids, unresolved complex mixtures (UCM), volatile monoaromatic compounds—benzene, toluene, ethylbenzene and xylenes (BTEX), parent and alkylated homologues polycyclic aromatic hydrocarbons (PAH), and terpanes and steranes were characterized for determining correlation to the spilled oil and other known oil sources and environmental assessment. Some of the acute ecotoxicity data for water and sediment samples is also presented.     

The effects of perennial ryegrass and alfalfa on microbial abundance and diversity in petroleum contaminated soil

Enhanced rhizosphere degradation uses plants to stimulate the rhizosphere microbial community to degrade organic contaminants. We measured changes in microbial communities caused by the addition of two species of plants in a soil contaminated with 31,000 ppm of total petroleum hydrocarbons. Perennial ryegrass and/or alfalfa increased the number of rhizosphere bacteria in the hydrocarbon-contaminated soil. These plants also increased the number of bacteria capable of petroleum degradation as estimated by the most probable number (MPN) method. Eco-Biolog plates did not detect changes in metabolic diversity between bulk and rhizosphere samples but denaturing gradient gel electrophoresis (DGGE) analysis of PCR-amplified partial 16S rDNA sequences indicated a shift in the bacterial community in the rhizosphere samples. Dice coefficient matrices derived from DGGE profiles showed similarities between the rhizospheres of alfalfa and perennial ryegrass/alfalfa mixture in the contaminated soil at week seven. Perennial ryegrass and perennial ryegrass/alfalfa mixture caused the greatest change in the rhizosphere bacterial community as determined by DGGE analysis. We concluded that plants altered the microbial population; these changes were plant-specific and could contribute to degradation of petroleum hydrocarbons in contaminated soil.     

Petroleum hydrocarbon in surficial sediment from rivers and canals in Tianjin, China

Surficial sediment samples were collected from three rivers and six canals in Tianjin, China and analyzed for petroleum hydrocarbons. Chemical compositions and distribution patterns, as well as possible sources, of the petroleum hydrocarbons in the sediments were discussed. A series of petroleum hydrocarbons, including n-alkanes, isoprenoid alkanes, anteiso-alkanes, alkyl hexamethylene, hopanes and steranes were detected in the samples. The concentration of petroleum hydrocarbons varied in a wide range of 0.072-3.000 mg g(-1) in the surficial sediment of the rivers and canals in Tianjin. In the samples studied, the total concentrations of petroleum hydrocarbons in the sediment samples from North Canal, South Canal, and G3 segment of South Sewage Canal were higher than those from Hai River, South Sewage Canal and North Sewage Canal. Accumulation of pollutants in the sediments from reaches close to urban area was also observed. The PHC spatial variability is mostly affected by many local inputs. The main sources of petroleum hydrocarbons in the sediment in Tianjin were considered to be petroleum importation and biochemical degradation of organisms, including cuticular of aquatic vegetation and algae.     

Seasonal and spatial variation of solvent extractable organic compounds in fine suspended particulate matter in Hong Kong

The results of a 12-month study of more than 100 solvent extractable organic compounds (SEOC) in particulate matter (PM) less than or equal to 2.5 microm (PM2.5) collected at three air monitoring stations located at roadside, urban, and rural sites in Hong Kong are reported. The total yield of SEOC that accounts for approximately 8-18% of organic carbon (OC) determined by a thermal optical transmittance method was 125-2060 ng/m3, which included 14.6-128 ng/m3 resolved aliphatic hydrocarbons, 39.4-1380 ng/m3 unresolved complex mixtures, 0.6-17.2 ng/m3 polycyclic aromatic hydrocarbons, 41.6-520 ng/m3 fatty acids, and < 0.1-12.1 ng/m3 alkanols. Distinct seasonal variations (summer/winter differences) were observed with higher concentrations of the total and each class of SEOC in the winter and lower concentrations in the summer. Spatial variations are also obvious, with the roadside samples having the highest concentrations of SEOC and the rural samples having the lowest concentrations in all seasons. Characteristic ratios of petroleum hydrocarbons, such as carbon preference index, unresolved to resolved components, and carbon number with maximum concentration, suggest that PM2.5 carbon in Hong Kong originates from both biogenic and anthropogenic sources. The proportion of SEOC in PM2.5 from anthropogenic sources is estimated.     

Advanced multivariate analysis to assess remediation of hydrocarbons in soils

Accurate monitoring of degradation levels in soils is essential in order to understand and achieve complete degradation of petroleum hydrocarbons in contaminated soils. We aimed to develop the use of multivariate methods for the monitoring of biodegradation of diesel in soils and to determine if diesel contaminated soils could be remediated to a chemical composition similar to that of an uncontaminated soil. An incubation experiment was set up with three contrasting soil types. Each soil was exposed to diesel at varying stages of degradation and then analysed for key hydrocarbons throughout 161 days of incubation. Hydrocarbon distributions were analysed by Principal Coordinate Analysis and similar samples grouped by cluster analysis. Variation and differences between samples were determined using permutational multivariate analysis of variance. It was found that all soils followed trajectories approaching the chemical composition of the unpolluted soil. Some contaminated soils were no longer significantly different to that of uncontaminated soil after 161 days of incubation. The use of cluster analysis allows the assignment of a percentage chemical similarity of a diesel contaminated soil to an uncontaminated soil sample. This will aid in the monitoring of hydrocarbon contaminated sites and the establishment of potential endpoints for successful remediation.     

Influence of soil and hydrocarbon properties on the solvent extraction of high-concentration weathered petroleum from contaminated soils

Petroleum ether was used to extract petroleum hydrocarbons from soils collected from six oil fields with different history of exploratory and contamination. It was capable of fast removing 76–94 % of the total petroleum hydrocarbons including 25 alkanes (C₁₁–C₃₅) and 16 US EPA priority polycyclic aromatic hydrocarbons from soils at room temperature. The partial least squares analysis indicated that the solvent extraction efficiencies were positively correlated with soil organic matter, cation exchange capacity, moisture, pH, and sand content of soils, while negative effects were observed in the properties reflecting the molecular size (e.g., molecular weight and number of carbon atoms) and hydrophobicity (e.g., water solubility, octanol–water partition coefficient, soil organic carbon partition coefficient) of hydrocarbons. The high concentration of weathered crude oil at the order of 10⁵ mg kg^?1 in this study was demonstrated adverse for solvent extraction by providing an obvious nonaqueous phase liquid phase for hydrocarbon sinking and increasing the sequestration of soluble hydrocarbons in the insoluble oil fractions during weathering. A full picture of the mass distribution and transport mechanism of petroleum contaminants in soils will ultimately require a variety of studies to gain insights into the dynamic interactions between environmental indicator hydrocarbons and their host oil matrix.     

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.     

Effect of long term exposure to petroleum on mixed function oxygenases in fish: Further support for use of the enzyme system in biological monitoring

A number of long term, low level petroleum hydrocarbon exposures were carried out from 1978 to 1981 in order to further evaluate use of the mixed function oxygenase (MFO) system in biological monitoring. The studies involved exposure, at ambient temperatures, of fish from three separate families including (a) spawning codfish ($\text{Gadus morhua}$), (b) post-spawned sculpins ($\text{Myoxocephalus octodecemspinosus}$), and (c) gonadally maturing flounder ($\text{Pseudopleuronectes americanus}$). MFO activity remained elevated approximately four-fold in the liver, and three-fold in the gills of codfish exposed for four months to water concentrations of 0.30–0.60 ppm petroleum, at ?1-1°C. Similarly, liver enzyme activity remained elevated approximately three-fold in sculpins exposed to very low levels (0.15–0.20 ppm) of petroleum for three months, at 4–12°C. Results indicate that several years may be required before hydrocarbon concentrations are reduced in petroleum contaminated sediments, such as those heavily impacted by oil spills, to non-inducing threshold levels. Oil contaminated sediment was, even after a year of weathering, quite effective in inducing a high level of MFO activity (seven-fold) in flounder, at 11-6°C. A number of factors that might detract from use of the mixed function oxygenase system in biological monitoring were not realized in these long term studies with petroleum hydrocarbons.     

Prioritisation of organic contaminants in a river basin using chemical analyses and bioassays

Region-specific contaminant prioritisation is an important prerequisite for sustainable and cost-effective monitoring due to the high number of different contaminants that may be present. Surface water and sediment samples from the Sava River, Croatia, were collected at four locations covering a 150-km-long river section characterised by well-defined pollution gradients. Analysis of contaminant profiles along the pollution gradients was performed by combining toxicity screening using a battery of small-scale or in vitro bioassays, which covered different modes of action, with detailed chemical characterisation based on gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). A large number of contaminants, belonging to different toxicant classes, were identified in both analysed matrices. Analyses of water samples showed that contaminants having polar character occurred in the highest concentrations, while in sediments, contributions from both non-polar and amphiphilic contaminants should be taken into account. Estimated contributions of individual contaminant classes to the overall toxicity indicated that, besides the classical pollutants, a number of emerging contaminants, including surfactants, pharmaceuticals, personal care products and plasticizers, should be taken into consideration in future monitoring activities. This work demonstrates the importance of the integrated chemical and bioanalytical approach for a systematic region-specific pollutant prioritisation. Finally, the results presented in this study confirm that hazard assessment in complex environmental matrices should be directed towards identification of key pollutants, rather than focusing on a priori selected contaminants alone.     

Sediment-associated aliphatic and aromatic hydrocarbons in coastal British Columbia, Canada: concentrations, composition, and associated risks to protected sea otters

Sediment-associated hydrocarbons can pose a risk to wildlife that rely on benthic marine food webs. We measured hydrocarbons in sediments from the habitat of protected sea otters in coastal British Columbia, Canada. Alkane concentrations were dominated by higher odd-chain n-alkanes at all sites, indicating terrestrial plant inputs. While remote sites were dominated by petrogenic polycyclic aromatic hydrocarbons (PAHs), small harbour sites within sea otter habitat and sites from an urban reference area reflected weathered petroleum and biomass and fossil fuel combustion. The partitioning of hydrocarbons between sediments and adjacent food webs provides an important exposure route for sea otters, as they consume ∼25% of their body weight per day in benthic invertebrates. Thus, exceedences of PAH sediment quality guidelines designed to protect aquatic biota at 20% of the sites in sea otter habitat suggest that sea otters are vulnerable to hydrocarbon contamination even in the absence of catastrophic oil spills.     

Polycyclic aromatic hydrocarbons in suspended particulate matter and sediments from the Pearl River Estuary and adjacent coastal areas, China

The spatial distribution, composition, and sources of polycyclic aromatic hydrocarbons (PAHs) in sediments and suspended particulate matter (SPM) from the Pearl River Estuary and adjacent coastal areas were examined. Total PAH concentrations varied from 189 to 637 ng/g in sediments and 422 to 1,850 ng/g in SPM. PAHs were dominated by 5,6-ring compounds in sediments and by 2,3-ring compounds in SPM samples. Assessment of PAH sources suggested that biomass and coal combustion is the major PAH source to the outer part of the estuary sediments and that petroleum combustion is the major PAH source to the inner part of estuary sediments. As for SPM samples, PAH isomer pair ratios indicated multiple (petroleum, petroleum combustion, and biomass and coal combustion) PAH sources, and significant temporal variations could exist for the sources of water column PAHs in the study area. The distribution of perylene in SPM samples indicated that the river was the dominant source of perylene in SPM and that perylene could be taken as an index to assess the contribution of river inflow to the total PAHs in SPM samples. The high concentration of perylene in the sediment was indicative of an in situ biogenic origin.     

Trace organic and heavy metal pollutants in the Mississippi River

A study was conducted to characterize and measure organic and heavy metal pollutants in the Mississippi River. Water samples were collected along the entire length of the river, and were screened for semivolatile organics by capillary GC and for heavy metals by atomic absorption spectrophotometry. Four water samples were further examined for semivolatile organics by capillary GC/MS. Eight heavy metals and more than sixty distinct organic chemicals were identified including alkylbenzenes, various halogenated organics, five herbicides or derivatives, plasticizers, polynuclear aromatic hydrocarbons (PAHs), saturated hydrocarbons, and three miscellaneous organics. All organic compounds were detected at the parts-per-trillion (pptr) level. In spite of the limited nature of the sampling effort, the large number of data derived from this study suggests the need for a more rigorous monitoring of the river for a wide spectrum of chemical pollutants.