Detection of naphthenic acids in fish exposed to commercial naphthenic acids and oil sands process-affected water

Naphthenic acids are a complex mixture of carboxylic acids that occur naturally in petroleum. During the extraction of bitumen from the oil sands in northeastern Alberta, Canada, naphthenic acids are released into the aqueous phase and these acids become the most toxic components in the process-affected water. Although previous studies have exposed fish to naphthenic acids or oil sands process-affected waters, there has been no analytical method to specifically detect naphthenic acids in fish. Here, we describe a qualitative method to specifically detect these acids. In 96-h static renewal tests, rainbow trout (Oncorhynchus mykiss) fingerlings were exposed to three different treatments: (1) fed pellets that contained commercial naphthenic acids (1.5mg g(-1) of food), (2) kept in tap water that contained commercial naphthenic acids (3mg l(-1)) and (3) kept in an oil sands process-affected water that contained 15mg naphthenic acids l(-1). Five-gram samples of fish were homogenized and extracted, then the mixture of free fatty acids and naphthenic acids was isolated from the extract using strong anion exchange chromatography. The mixture was derivatized and analyzed by gas chromatography-mass spectrometry. Reconstructed ion chromatograms (m/z=267) selectively detected naphthenic acids. These acids were present in each fish that was exposed to naphthenic acids, but absent in fish that were not exposed to naphthenic acids. The minimum detectable concentration was about 1microg naphthenic acids g(-1) of fish.     

In vivo endocrine effects of naphthenic acids in fish

Oil pollution from various sources, including exploration, production and transportation, is a growing global concern. The highest toxicity of hydrocarbon pollutants is associated with the water-soluble phase compounds, including naphthenic acids, a known component found in all hydrocarbon deposits. Recently, naphthenic acids (NAs) have shown estrogenic and anti-androgenic effects in vitro. For this reason we investigated the potential effects of two commercial mixtures of naphthenic acids on fish in vivo, using the three-spined stickleback (Gasterosteus aculeatus) as a model species.     

Isolation and characterization of naphthenic acids from Athabasca oil sands tailings pond water

A laboratory bench procedure was developed to efficiently extract naphthenic acids from bulk volumes of Athabasca oil sands tailings pond water (TPW) for use in mammalian oral toxicity testing. This solvent-based procedure involved low solvent losses and a good extraction yield with low levels of impurities. Importantly, labour-intensive centrifugation of source water to remove solids was avoided, allowing processing of much larger volumes of water compared with previous protocols. Naphthenic acids, present at an estimated concentration of 81 mg/l, were procured from 515.5 l of TPW at an overall extraction efficiency of approximately 85%. By using distillation to recover and recycle solvent, a high solvent:water ratio was maintained while actual solvent consumption was limited to 70 ml per liter of water processed. Electrospray ionization mass spectrometry suggested a highly heterogeneous naphthenic acid mixture that exhibited nearly identical proportions of monocyclic, polycyclic, and acyclic acids with molecular weights primarily between 220 and 360. Biphenyls, naphthalenes, and phenanthrene/anthracene were the most prominent impurities detected, but their levels were low (< or = 13 microg/l) even in a concentrated solution of the naphthenic acids (8549 mg/l). Naphthenic acids stored at 4 degrees C at this concentration were stable, exhibiting no significant change in concentration over a 10-month period. This bulk isolation procedure should be useful to others needing to process large volumes of tailings or other source water for the purpose of procuring moderate amounts of naphthenic acids.     

Estimating chemical biotransformation rates from food web concentrations

Biotransformation is widely recognized as the most important and most uncertain determinant of bioaccumulation. A step-wise method for estimating organism-specific biotransformation half-lives from field observations and using established food web modeling is developed. As a proof of concept, the method is applied to the case of nine polycyclic aromatic hydrocarbons (PAHs) in a well-studied food web in Bohai Bay, China. The estimated half-lives are in good agreement with the existing literature. The proposed biotransformation estimation method, through data mining, for sufficiently defined ecosystems, may greatly reduce the necessary animal testing involved in chemical assessments by providing useful guidance to experimentalists and regulators.     

Electrochemical mineralization and detoxification of naphthenic acids on boron-doped diamond anodes

Electrochemical oxidation (ELOX) with boron-doped diamond (BDD) anodes was successfully applied to degrade a model aqueous solution of a mixture of commercial naphthenic acids (NAs). The model mixture was prepared resembling the NA and salt composition of oil sands process-affected water (OSPW) as described in the literature. The initial concentration of NAs between 70 and 120 mg/L did not influence the electrooxidation kinetics. However, increasing the applied current density from 20 to 100 A/m² and the initial chloride concentration from 15 to 70 and 150 mg/L accelerated the rate of NA degradation. At higher chloride concentration, the formation of indirect oxidative species could contribute to the faster oxidation of NAs. Complete chemical oxygen demand removal at an initial NA concentration of 120 mg/L, 70 mg/L of chloride and applied 50 A/m² of current density was achieved, and 85% mineralization, defined as the decrease of the total organic carbon (TOC) content, was attained. Moreover, after 6 h of treatment and independently on the experimental conditions, the formation of more toxic species, i.e. perchlorate and organochlorinated compounds, was not detected. Finally, the use of ELOX with BDD anodes produced a 7 to 11-fold reduction of toxicity (IC₅₀ towards Vibrio fischeri) after 2 h of treatment.     

Ozonation of oil sands process water removes naphthenic acids and toxicity

Naphthenic acids are naturally-occurring, aliphatic or alicyclic carboxylic acids found in petroleum. Water used to extract bitumen from the Athabasca oil sands becomes toxic to various organisms due to the presence of naphthenic acids released from the bitumen. Natural biodegradation was expected to be the most cost-effective method for reducing the toxicity of the oil sands process water (OSPW). However, naphthenic acids are poorly biodegraded in the holding ponds located on properties leased by the oil sands companies. In the present study, chemical oxidation using ozone was investigated as an option for mitigation of this toxicity. Ozonation of sediment-free OSPW was conducted using proprietary technology manufactured by Seair Diffusion Systems Inc. Ozonation for 50min generated a non-toxic effluent (based on the Microtox bioassay) and decreased the naphthenic acids concentration by approximately 70%. After 130min of ozonation, the residual naphthenic acids concentration was 2mgl(-1): <5% of the initial concentration in the filtered OSPW. Total organic carbon did not change with 130min of ozonation, whereas chemical oxygen demand decreased by approximately 50% and 5-d biochemical oxygen demand increased from an initial value of 2mgl(-1) to a final value of 15mgl(-1). GC-MS analysis showed that ozonation resulted in an overall decrease in the proportion of high molecular weight naphthenic acids (n> or = 22).     

Comparison of GC-MS and FTIR methods for quantifying naphthenic acids in water samples

The extraction of bitumen from the oil sands in Canada releases toxic naphthenic acids into the process-affected waters. The development of an ideal analytical method for quantifying naphthenic acids (general formula C(n)H(2n+Z)O(2)) has been impeded by the complexity of these mixtures and the challenges of differentiating naphthenic acids from other naturally-occurring organic acids. The oil sands industry standard FTIR method was compared with a newly-developed GC-MS method. Naphthenic acids concentrations were measured in extracts of surface and ground waters from locations within the vicinity of and away from the oil sands deposits and in extracts of process-affected waters. In all but one case, FTIR measurements of naphthenic acids concentrations were greater than those determined by GC-MS. The detection limit of the GC-MS method was 0.01 mg L(-1) compared to 1 mg L(-1) for the FTIR method. The results indicated that the GC-MS method is more selective for naphthenic acids, and that the FTIR method overestimates their concentrations.     

A review of the occurrence, analyses, toxicity, and biodegradation of naphthenic acids

Naphthenic acids occur naturally in crude oils and in oil sands bitumens. They are toxic components in refinery wastewaters and in oil sands extraction waters. In addition, there are many industrial uses for naphthenic acids, so there is a potential for their release to the environment from a variety of activities. Studies have shown that naphthenic acids are susceptible to biodegradation, which decreases their concentration and reduces toxicity. This is a complex group of carboxylic acids with the general formula CnH(2n+Z)O2, where n indicates the carbon number and Z specifies the hydrogen deficiency resulting from ring formation. Measuring the concentrations of naphthenic acids in environmental samples and determining the chemical composition of a naphthenic acids mixture are huge analytical challenges. However, new analytical methods are being applied to these problems and progress is being made to better understand this mixture of chemically similar compounds. This paper reviews a variety of analytical methods and their application to assessing biodegradation of naphthenic acids.     

Arsenic speciation in field-collected and laboratory-exposed earthworms Lumbricus terrestris

Mature Lumbricus terrestris were host soils and leaf litter were collected from a former arsenic mine in Devon, UK (Devon Great Consols), a former gold mine in Ontario, Canada (Deloro), and an uncontaminated residential garden in Nottingham, UK. Arsenic concentrations determined by inductively coupled plasma-mass spectrometry (ICP-MS) in soils were 16-348 mg kg⁻¹, 6.0-239 mg kg⁻¹ in the earthworms and 8.6 mg kg⁻¹ in leaf litter sampled at Deloro (all dry weight). High performance liquid chromatography (HPLC-ICP-MS) analysis revealed arsenite (As^III), arsenate (As^V) and five organoarsenic species; arsenobetaine (AB), methylarsonate (MA^V), dimethylarsinate (DMA^V), arsenosugar 1 (glycerol sugar), arsenosugar 2 (phosphate sugar), and trimethylarsineoxide (TMAO) in field-collected L. terrestris. Differences were observed in the variety of organoarsenic species present between field sites. Several organoarsenic species were observed in the leaf litter (DMA^V, arsenosugar 2 and TMAO) but not AB. Depuration resulted in higher concentrations of inorganic As being detected in the earthworm whereas the concentration or variety of organoarsenic species was unchanged. Commercially sourced L. terrestris were exposed to As contaminated soil in laboratory mesocosms (1.0, 98, 183, 236, 324 and 436 mg kg⁻¹) without leaf litter and were additionally analyzed using X-ray absorption near edge structure (XANES). Only inorganic As^III and As^V was observed. It is proposed that ingestion of leaf litter and symbiotic processes in the natural soil environment are likely sources of organoarsenic compounds in field-collected L. terrestris.     

Bioaccumulation of PAHs from creosote-contaminated sediment in a laboratory-exposed freshwater oligochaete, Lumbriculus variegatus

The oligochaete, Lumbriculus variegatus, was used for a bioaccumulation assay in the creosote-contaminated sediment of Lake J?ms?nvesi in a 28-day experiment. The PAH concentrations of the whole body tissue of worms, sediments and water samples were determinated by GC-MS. Chemical analyses showed that benzo(k)fluoranthene, anthracene and fluorene were the main PAH compounds present in the tissue of oligochaetes, just as in the sediment. The biota-sediment accumulation factors (BSAFs) of the individual PAHs varied from 1.2 to 5.7. It is concluded that oligochaetes have a marked ability to accumulate and retain PAHs from creosote-contaminated sediment.     

Acute toxicity of aromatic and non-aromatic fractions of naphthenic acids extracted from oil sands process-affected water to larval zebrafish

The toxicity of oil sands process-affected water (OSPW) has regularly been attributed to naphthenic acids, which exist in complex mixtures. If on remediation treatment (e.g., ozonation) or on entering the environment, the mixtures of these acids all behave in the same way, then they can be studied as a whole. If, however, some acids are resistant to change, whilst others are not, or are less resistant, it is important to establish which sub-classes of acids are the most toxic.     

The effect of oil sands process-affected water and naphthenic acids on the germination and development of Arabidopsis

Oil sands mining in the Athabasca region of northern Alberta results in the production of large volumes of oil sands process-affected water (OSPW). We have evaluated the effects of OSPW, the acid extractable organic (AEO) fraction of OSPW, and individual naphthenic acids (NAs) on the germination and development of the model plant, Arabidopsis thaliana (Arabidopsis). The surrogate NAs that were selected for this study were petroleum NAs that have been used in previous toxicology studies and may not represent OSPW NAs. A tricyclic diamondoid NA that was recently identified as a component of OSPW served as a model NA in this study. Germination of Arabidopsis seeds was not inhibited when grown on medium containing up to 75% OSPW or by 50 mg L⁻¹ AEO. However, simultaneous exposure to three simple, single-ringed surrogate NAs or a double-ringed surrogate NA had an inhibitory effect on germination at a concentration of 10 mg L⁻¹, whereas inhibition of germination by the diamondoid model NA was observed only at 50 mg L⁻¹. Seedling root growth was impaired by treatment with low concentrations of OSPW, and exposure to higher concentrations of OSPW resulted in increased growth inhibition of roots and primary leaves, and caused bleaching of cotyledons. Treatment with single- or double-ringed surrogate NAs at 10 mg L⁻¹ severely impaired seedling growth. AEO or diamondoid NA treatment was less toxic, but resulted in severely impaired growth at 50 mg L⁻¹. At low NA concentrations there was occasionally a stimulatory effect on root and shoot growth, possibly owing to the broad structural similarity of some NAs to known plant growth regulators such as auxins. This report provides a foundation for future studies aimed at using Arabidopsis as a biosensor for toxicity and to identify genes with possible roles in NA phytoremediation.     

Estimating PM10 air concentrations from dust storms in Iraq,Kuwait and Saudi Arabia

A model for the emission of PM₁₀ dust has been constructed using the concept of a threshold friction velocity which is dependent on surface roughness. Surface roughness in turn was correlated with geomorphology or soil properties for Kuwait, Iraq, part of Syria, Saudi Arabia, the United Arab Emirates and Oman. The PM₁₀ emission algorithm was incorporated into a Lagrangian transport and dispersion model. PM₁₀ air concentrations were computed from August 1990 through August 1991. The model predicted about the right number of dust events over Kuwait (events occur 18% of the time). The model results agreed quantitatively with measurements at four locations in Saudi Arabia and one in Kuwait for one major dust event (>1000 μg/m³). However, for smaller scale dust events (200–1000 μg/m³), especially at the coastal sampling locations, the model substantially over-predicted the air concentrations. Part of the over-prediction was attributed to the entrainment of dust-free air by the sea breeze, a flow feature not represented by the large-scale gridded meteorological data fields used in the model computation. Another part of the over-prediction was the model's strong sensitivity to threshold friction velocity and the surface soil texture coefficient (the soil emission factor), and the difficulty in accurately representing these parameters in the model. A comparison of the model predicted PM₁₀ spatial pattern with the TOMS satellite aerosol index (AI) yielded a spatial pattern covering a major portion of Saudi Arabia that was quite similar to the observed AI pattern.     

Nationwide monitoring of mercury in wild and farmed fish from fresh and coastal waters of Korea

Mercury (Hg) concentrations were monitored in wild and cultured fish collected from fresh and coastal waters in the Korean peninsula from April 2006 to August 2008 nationwide. Total Hg concentrations were reported for 5043 fish samples, including 78 species from 133 locations. Significant interspecies variation was noted in the Hg levels. The average Hg concentration in each fish species ranged from 6.31 μg kg⁻¹ for mullet (Mugil cephalus) to 200 μg kg⁻¹ for mandarin fish (Siniperca scherzeri). Among the species collected, the maximum concentration of Hg, 1720 μg kg⁻¹, was measured in an Amur catfish (Silurus asotus). Only wild freshwater fish exceeded the WHO ingestion standard. Wild freshwater piscivorous fish samples from a large artificial upstream lake contained the highest Hg levels. Hg concentrations were compared between fish groups categorized as wild and farmed fish from freshwater and coastal waters. Although the wild freshwater fish had similar size ranges, their Hg concentrations were higher than those of the other groups. Compared to the feed of farmed marine and freshwater fishes, the prey of wild freshwater fish had a higher Hg concentration, and the total Hg concentrations in freshwater and associated sediment samples were higher than those in coastal water and associated sediment samples. In the freshwater environment, piscivorous fish bioaccumulated two times more Hg than carnivorous and omnivorous fish and four times more than planktivorous fish. The difference in Hg concentrations among trophic groups might have been due to differences in the size of fish, in addition to the variations among different trophic groups. These data will be useful for developing the fish consumption advisory as a management measure to reduce Hg exposure.     

Fluorinated alkyl compounds including long chain carboxylic acids in wild bird livers from Japan

A wide range of fluorinated alkyl compounds (FACs) has been reported in wildlife in various locations in the world. However, such information regarding Japanese wildlife is rarely found. In the present study, we investigated the occurrence of 21 FACs, including perfluorinated alkyl sulfonates (PFASs), perfluorinated carboxylates (PFCAs), and fluorotelomer acids, in the livers of 10 wild bird species from two regions in northern Japan. To avoid interferences, FACs were quantified by a recently developed method using acetonitrile and solid-phase extraction followed by an ion exchange HPLC column separation. Apart from perfluorooctane sulfonate (PFOS), which was found at the highest levels of all the compounds detected, several long chain perfluorinated carboxylates (PFCAs) from C8 to C16, particularly perfluorotetradecanoic acid (PFTeDA) and perfluorohexadecanoic acid (PFHxDA), were detected for the first time. Additionally, 7:3 FTCA, a fluorotelomer acid, was also detected in most swan livers from Miyagi prefecture and all the birds from Tochigi prefecture. However, none of the sulfonamides and unsaturated telomer acids were detected in any species. Swans seem to be the least exposed wild birds to FACs among the investigated birds, signifying that feeding habits may reflect FAC accumulation in wild birds. The highest total concentration of detected FACs was 405 ng g⁻¹ wet wt., which was found in a Japanese sparrowhawk, indicating that the top predatory wild birds can accumulate several long chain carboxylic acids. However, the current FAC concentrations found in livers may suggest that these compounds alone would not cause a severe toxic effect in these species.     

Estimating changes in urban ozone concentrations due to life cycle emissions from hydrogen transportation systems

Hydrogen has been proposed as a low polluting alternative transportation fuel that could help improve urban air quality. This paper examines the potential impact of introducing a hydrogen-based transportation system on urban ambient ozone concentrations. This paper considers two scenarios, where significant numbers of new hydrogen vehicles are added to a constant number of gasoline vehicles. In our scenarios hydrogen fuel cell vehicles (HFCVs) are introduced in Sacramento, California at market penetrations of 9% and 20%. From a life cycle analysis (LCA) perspective, considering all the emissions involved in producing, transporting, and using hydrogen, this research compares three hypothetical natural gas to hydrogen pathways: (1) on-site hydrogen production; (2) central hydrogen production with pipeline delivery; and (3) central hydrogen production with liquid hydrogen truck delivery. Using a regression model, this research shows that the daily maximum temperature correlates well with atmospheric ozone formation. However, increases in initial VOC and NO_x concentrations do not necessarily increase the peak ozone concentration, and may even cause it to decrease. It is found that ozone formation is generally limited by NO_x in the summer and is mostly limited by VOC in the fall in Sacramento. Of the three hydrogen pathways, the truck delivery pathway contributes the most to ozone precursor emissions. Ozone precursor emissions from the truck pathway at 9% market penetration can cause additional 3-h average VOC (or NO_x) concentrations up to approximately 0.05% (or 1%) of current pollution levels, and at 20% market penetration up to approximately 0.1% (or 2%) of current pollution levels. However, all of the hydrogen pathways would result in very small (either negative or positive) changes in ozone air quality. In some cases they will result in worse ozone air quality (mostly in July, August, and September), and in some cases they will result in better ozone air quality (mostly in October). The truck pathway tends to cause a much wider fluctuation in degradation or improvement of ozone air quality: percentage changes in peak ozone concentrations are approximately −0.01% to 0.04% for the assumed 9% market penetration, and approximately −0.03% to 0.1% for the 20% market penetration. Moreover, the 20% on-site pathway occasionally results in a decrease of about −0.1% of baseline ozone pollution. Compared to the current ambient pollution level, all three hydrogen pathways are unlikely to cause a serious ozone problem for market penetration levels of HFCVs in the 9–20% range.     

Hg concentrations and related risk assessment in coral reef crustaceans, molluscs and fish from New Caledonia

There is a dramatic lack of data on Hg levels in marine organisms from tropical areas, and in particular from New Caledonia. For the first time, this study reports the total Hg concentrations in the tissues of several marine taxa from the New Caledonian lagoon. Seafood from both wild and farmed populations was considered. Hg concentrations varied over three orders of magnitudes according to factors including species, age (size/weight), trophic level, lifestyle and geographical origin. Taking into account the edible tissues, estimations of the amount of flesh that should be consumed by a 60-kg person to reach the Hg Provisional Tolerable Weekly Intake (PTWI) reveal acceptable risk for Human health in general. However, a risk was clearly identified in one site of the lagoon (i.e. Grande Rade) where high Hg concentrations were measured. These concentrations were higher than values reported in the current literature.     

Distribution and bioaccumulation of steroidal and phenolic endocrine disrupting chemicals in wild fish species from Dianchi Lake, China

The distribution and bioaccumulation of steroidal and phenolic endocrine disrupting chemicals (EDCs) were studied in various tissues of wild fish species from Dianchi Lake, China. In muscle tissue, 4-tert-octylphenol, 4-cumylphenol, 4-nonlyphenol and bisphenol A were detected in fish from each sampling site, with maximal concentrations of 4.6, 4.4, 18.9 and 83.5 ng/g dry weight (dw), respectively. Steroids (estrone, 17β-estradiol 17α-ethynylestradiol and estriol) were found at lower levels (<11.3 ng/g dw) and less frequently in muscle samples. The highest concentrations of steroids and phenols were found in liver, followed by those in gill and the lowest concentration was found in muscle. The field bioconcentration factors (BCFs) of phenols were calculated in fish species ranged from 18 to 97. Moreover, the measured tissue concentrations were utilized in order to estimate water concentration of steroids (4.4-18.0 ng/L). These results showed that steroidal and phenolic EDCs were likely ubiquitous contaminants in wild fish.     

Malondialdehyde and heavy metal concentrations in tissues of wild boar (Sus scrofa L.) from central Croatia

The aim of this research was to assess the degree of heavy metal (cadmium, lead and mercury) contamination of wild boars from central Croatia and thereby conduct further tests to connect the contamination to oxidative stress occurrence. The highest cadmium concentration was noticed in the kidneys of older boars, the lead concentration was approximately the same in the liver and kidneys, but it was much higher than the concentration in the muscles, while the highest mercury concentration was measured in the kidneys of all wild boars. The correlation between the malondialdehyde (MDA) and the heavy metal concentrations was higher in tissue samples taken from younger animals (1 to 3 years of age) than in the tissue samples taken from older animals (5 to 6 years of age). In the kidneys of all wild boars there was a statistically significant connection between the MDA and cadmium concentration; in the kidneys of younger wild boars there was a statistically significant connection between the MDA and lead concentration. Further research on this topic should focus on MDA potential to find its use, not only as a contamination biomarker in the area of ecotoxicology, but also in the evaluation of the hygienic acceptability of animal products.