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.

Atmospheric movements of lindane (gamma-hexachlorocyclohexane) from canola fields planted with treated seed.

Lindane (gamma-hexachlorocyclohexane [gamma-HCH]) is used as an insecticide in many countries. Concentrations of gamma-HCH have been found in air, water, soil, snow, and tissue samples throughout the world and concerns have been raised for its potential effects on human and ecosystem health. In Canada, gamma-HCH is primarily used as a treatment on canola (Brassica napus L) seed with an estimated 455.3 Mg applied in 1997 and 510.4 Mg in 1998. The purpose of this study was to measure gamma-HCH volatilization from fields planted with treated canola seed. Atmospheric dry and wet deposition and soil samples were collected for two growing seasons (1997 and 1998) from a canola field planted with treated seed. Atmospheric concentrations as high as 16.1 and 7.4 ng m(-3) were measured at 1 m above the canola field compared with maximum concentrations of 2.9 and 2.7 ng m(-3) measured above a grass field located 2 km away (1997 and 1998, respectively). On the basis of measurements made in this study it was estimated that between 12 and 30% of the gamma-HCH applied as canola seed treatment may volatilize and be released to the atmosphere. This would create an atmospheric loading of 66.4 to 188.8 Mg for the 6-wk period following planting, estimated from the quantity of seed sown on the Canadian prairies in 1998. Dry deposition rates and rain concentrations as high as 2,203 ng m(-2) d(-1) and 170 ng L(-1) were measured adjacent to the canola field.

Diffuse geographic distribution of herbicides in northern prairie wetlands.

The concentrations of herbicides in water from wetlands on landscapes where herbicides are not used should be less than on farms with moderate (conventional farms) and intense (minimum-till farms) herbicide use. In general, this hypothesis was not supported for wetlands situated in the Boreal Plains Ecozone of central Saskatchewan, Canada. The overall detection frequency of 10 commonly used herbicides was not significantly different among wildlife habitat with no pesticide use (44.4%), farms with no pesticide use (51.6%), conventional farms (54.9%), and minimum-till farms (56.5%, chi 2 = 5.64, p = 0.13). The herbicides (4-chloro-2-methylphenoxy) acetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D), bromoxynil, dicamba, mecoprop, and diclorprop accounted for 87% of all detections. In general, detection frequencies and concentrations of individual herbicides were similar on all land-use types. For example, the mean concentration of 2,4-D in water on the four land types ranged from 0.12 +/- 0.104 to 0.26 +/- 0.465 microgram/L, and MCPA ranged from 0.08 +/- 0.078 to 0.19 +/- 0.166 microgram/L. However, in the year of application, mean concentrations of MCPA and bromoxynil, but not 2,4-D, were significantly higher by about twofold in wetlands situated in fields where these herbicides were applied compared with all other wetlands. We propose that many agricultural pesticides are rapidly lost to the atmosphere at the time of application by processes such as volatilization from soil and plant evapotranspiration. Then, the herbicides used throughout the region may be directly absorbed to the surface of wetlands from the atmosphere, or they become entrained in local convective clouds, and are redistributed by rainfall in a relatively homogenous mixture over the agricultural landscape. The low levels of individual herbicides we found in most of the wetland waters would not cause chronic effects to aquatic biota.

Atmospheric pentachlorophenol concentrations in relation to air temperature at five Canadian locations.

Pentachlorophenol (PCP), used as a wood preservative and as a disinfectant, has been found in human urine samples from Saskatchewan and in air samples from three Canadian sites. To confirm the presence of atmospheric PCP residues and to explore seasonality, weekly samples were collected at five Canadian sites for three consecutive weeks, in the months of July and October, 1995 and January, April and May, 1996, using a high volume sampler equipped with polyurethane foam (PUF) plugs. PCP was present in all samples collected adjacent to a utility pole storage site with concentrations ranging from 0.7 to 1233.0 ng m-3. There was a very strong correlation between average weekly air temperature, measured over a range of -29.3 to +20.0 degrees C, and the log10 of the average weekly concentration of PCP at this site. PCP was measured in 7 of 11 air samples from each of two small cities (concentrations ranging from 0.2 to 6.8 ng m-3) and the correlation between temperature and PCP concentration, for these two city sites, was similar to that for the utility pole storage site. Concentrations of PCP at two rural sites were lower (0.1-1.5 ng m-3) and detected less frequently. As a consequence, the correlation between air temperature and PCP concentration was more variable.

Gas chromatographic determination of N-nitrosodialkanolamines in herbicide Di- or trialkanolamine formulations.

A modified method is presented to determine trace quantities of N-nitrosodiethanolamine (NDElA) and N-nitrosodiisopropanolamine (NDiPlA) in the triisopropanolamine (TiPlA) formulation of a mixture of picloram and 2,4-D. Aqueous sample is extracted with dichloromethane to remove organic interferences, and then the aqueous layer is passed sequentially through chloride anion exchange column, hydrogen cation exchange column, and Clin-Elut extraction tube. The final eluate, 10% acetone in ethyl acetate, is concentrated. The isolated nitrosamines are converted to the corresponding trimethylsilyl (TMS) derivatives and determined by gas chromatography (GC) on a DB1 column coupled with a thermal energy analyzer (GC-TEA). Eight samples of commercial TiPlA formulations are analyzed. Maximum detected levels of NDElA and NDiPlA were 0.6 and 0.9 ppm, respectively, expressed relative to total weight of active ingredients. Analysis of 13 samples of herbicide DElA formulation using a previously established method and a DB225 column gave NDElA results of 0.7-6.0 ppm. NDiPlA was not detected in those samples. Results are confirmed by GC-mass spectrometry (GC/MS) with oxygen negative chemical ionization (ONCI) detection. Detection limits for both nitrosamines are 0.05 or 0.07 ng (0.1 or 0.17 ppm) for GC-TEA detection, depending on the analytical columns used, and 20 pg (0.04 ppm) for GC/MS detection. Recoveries of NDElA are 87-109% for DElA formulation spiked at 2.6 and 3.9 ppm and 90-115% for TiPlA formulation spiked at 0.2-0.3 ppm. Similarly, recoveries of NDiPlA are 95.7-100% for the DElA formulation spiked at 0.24 and 0.48 ppm, and 82-118% for the TiPlA formulation spiked at 0.2-0.3 ppm.

Determination of N-nitrosodiethanolamine in dinoseb formulations by mass spectrometry and thermal energy analyzer detection.

A new method is described to determine trace quantities of N-nitrosodiethanolamine (NDElA) in aqueous diethanolamine (DElA) formulations and in oil solutions of dinoseb. A formate anion-exchange column is used in series with a cation-exchange column if there is DElA in the formulation. The eluate is then passed through a Clin Elut column. Depending on the concentration of NDElA in the sample, a packed silica-gel column is used to purify the extract further. This extract is analyzed on a liquid chromatograph coupled with a thermal energy analyzer (LC/TEA), using a mixture of methanol-hexane-methylene chloride containing 0.1% acetic acid (8 + 56 + 35) as the mobile phase. This solvent system gives good separation of NDElA from trace quantities of dinoseb remaining in the extract. The NDElA is also converted to the trimethylsilyl derivative and analyzed by gas chromatograph coupled with a mass spectrometer (GC/MS). Analyses of 11 commercial samples of dinoseb diethanolamine salt showed NDElA levels of 116-2409 ppm expressed relative to the weight of dinoseb. In contrast, analyses of 2 samples of organic solutions of technical dinoseb showed NDElA levels to be nondetectable and 0.3 ppm, respectively. Limit of detection by LC/TEA is 6.5 ng (0.5 ppm), and by GC/MS it is 0.02 ng (0.15 ppm). Recoveries from samples spiked at 0.514-1664 ppm range from 92.2 to 105.2%.