Chemical fingerprinting of naphthenic acids and oil sands process waters-A review of analytical methods for environmental samples.

This article provides a review of the routine methods currently utilized for total naphthenic acid analyses. There is a growing need to develop chemical methods that can selectively distinguish compounds found within industrially derived oil sands process affected waters (OSPW) from those derived from the natural weathering of oil sands deposits. Attention is thus given to the characterization of other OSPW components such as oil sands polar organic compounds, PAHs, and heavy metals along with characterization of chemical additives such as polyacrylamide polymers and trace levels of boron species. Environmental samples discussed cover the following matrices: OSPW containments, on-lease interceptor well systems, on- and off-lease groundwater, and river and lake surface waters. There are diverse ranges of methods available for analyses of total naphthenic acids. However, there is a need for inter-laboratory studies to compare their accuracy and precision for routine analyses. Recent advances in high- and medium-resolution mass spectrometry, concomitant with comprehensive mass spectrometry techniques following multi-dimensional chromatography or ion-mobility separations, have allowed for the speciation of monocarboxylic naphthenic acids along with a wide range of other species including humics. The distributions of oil sands polar organic compounds, particularly the sulphur containing species (i.e., OxS and OxS2) may allow for distinguishing sources of OSPW. The ratios of oxygen- (i.e., Ox) and nitrogen-containing species (i.e., NOx, and N2Ox) are useful for differentiating organic components derived from OSPW from natural components found within receiving waters. Synchronous fluorescence spectroscopy also provides a powerful screening technique capable of quickly detecting the presence of aromatic organic acids contained within oil sands naphthenic acid mixtures. Synchronous fluorescence spectroscopy provides diagnostic profiles for OSPW and potentially impacted groundwater that can be compared against reference groundwater and surface water samples. Novel applications of X-ray absorption near edge spectroscopy (XANES) are emerging for speciation of sulphur-containing species (both organic and inorganic components) as well as industrially derived boron-containing species. There is strong potential for an environmental forensics application of XANES for chemical fingerprinting of weathered sulphur-containing species and industrial additives in OSPW.

Environmental monitoring of bleached kraft pulp mill chlorophenolic compounds in a northern Canadian river system.

The environmental transport of pulp mill effluent compounds and the exposure of two fish species has been monitored by parallel analyses of effluent, water column and suspended sediment samples, and fish bile and muscle. Compounds analyzed included over 20 chlorophenolic compounds and 12 fatty and resin acids. The concentration of chlorophenols varied with seasonal river flows and mill process changes such as the substitution of chlorine dioxide (ClO2) for chlorine gas (Cl2) in the bleach plant. At 100% (ClO2) substitution, the effluent and the water column concentrations of most chlorophenolics approached the analytical detection limits of 0.1-1 parts per billion. Chlorophenolic and fatty/resin acid compounds were detected in the bile of both mountain whitefish (Prosopium williamsoni) and longnose sucker (Catostomus catostomus), but were rarely detected in fillets. Fish bile concentrations were observed in an apparent spatial gradient as far as 230 km downstream of the mill. A depuration experiment with fish held in uncontaminated water for eight days indicated a rapid decrease in chlorophenol levels. These observations corroborate previous investigations that chlorophenolic compounds are rapidly excreted and can be used as sensitive markers for recent exposure to mill effluents.

Uptake and biotransformation of 6,7-dimethylquinoline and 6,8-dimethylquinoline by rainbow trout (Salmo gairdneri).

1. 6,7-Dimethylquinoline (6,7-DMQ) is readily taken up by rainbow trout and bioconcentrated in tissue after exposure to ca 1 mg/l for 7.5 h. Mean bioconcentration factors (from water) were 21, 18, 6 and 14 for bile, liver, muscle and carcass respectively. Mean tissue concentrations after 69-96 h depuration were ND, ND, 0.54 and 0.48 micrograms/g for bile, liver, muscle and carcass respectively. 2. Major metabolites, following exposure to 6,7-DMQ, were conjugates (glucuronide or sulphate) of 7-hydroxymethyl-6-methylquinoline and 6-hydroxymethyl-7-methylquinoline. Mean concentration of metabolites in the bile were 500 micrograms/g after 7.5 h exposure to ca 1 mg/l and 1367 micrograms/g after 9.5 h exposure to ca 1 mg/l and 69 h depuration. 3. 6,8-Dimethylquinoline (6,8-DMQ) is also readily bioconcentrated in fish tissue after exposure to ca 1 mg/l. Mean bioconcentration factors (from water) were 23, 20, 13 and 25 for bile, liver, muscle and carcass respectively. Mean tissue concentrations after 7 h exposure to ca 1 mg/l and 63 h depuration were 4.0, 0.67, 0.49, and 3.2 micrograms/g respectively for bile, liver, muscle and carcass. 4. Major metabolites, following exposure to 6,8-DMQ were conjugates (glucuronide or sulphate) of 6,8-dimethyl-5-hydroxyquinoline, 6,8-dimethyl-7-hydroxyquinoline, 6,8-dimethyl-3-hydroxyquinoline and 6-hydroxymethyl-8-methylquinoline. Mean concentration of metabolites in the bile were 1278 micrograms/g after exposure to ca 1 mg/l for 8 h and 1031 micrograms/g after exposure to ca 1 mg/l for 7 h and 63 h depuration.

Determination of polycyclic aromatic compounds in fish tissue.

A method is presented for the analysis of polycyclic aromatic hydrocarbons (PAHs), polycyclic aromatic sulfur heterocycles (PASHs), and basic polycyclic aromatic nitrogen heterocycles (PANHs) in fish. The analytical procedure includes Soxhlet extraction of prepared fish tissue with methylene chloride followed by gel permeation chromatography (GPC) using Bio-beads SX-3. For PAHs/PASHs, further cleanup is performed using adsorption chromatography on Florisil (5% water deactivated) and elution with hexane. For basic PANHs further cleanup of the fish extracts after GPC is achieved using liquid-liquid partitioning with 6 M hydrochloric acid and chloroform and then basifying the aqueous phase and extracting it with chloroform. Analysis of fortified fish samples was performed using capillary gas chromatography with flame ionization detection and capillary gas chromatography-mass spectrometry. Good agreement was observed for both methods of analysis when applied to fish samples fortified with PAHs, PASHs and basic PANHs at 0.1 to 1 microgram/g, suggesting that the method is effective at removing interfering biogenic compounds prior to analysis. Average recovery of PAHs/PASHs from fortified fish tissue was 87% and 70% for fish tissue fortified at 0.24-1.1 and 0.024-0.11 microgram/g, respectively. Average recovery for basic PANHs was 97% for fish fortified at 1.2-1.4 micrograms/g.