Brian Fowler

Natural and anthropogenic inputs of hydrocarbons to the Strait of Georgia

Sediment cores from the Fraser estuary, Vancouver Harbour and Strait of Georgia, suspended sediment samples from the Fraser River and sediment grabs from Vancouver Harbour have been analyzed for alkanes and parent and alkyl PAHs (polycyclic aromatic hydrocarbons). Principal components analysis (PCA) clearly distinguishes mixed sources by separating parent PAHs according to molecular size, and separating alkyl substituted PAHs from higher plant PAHs. We find the Fraser River to be the predominant source for natural and anthropogenic hydrocarbons to the Strait of Georgia. The natural hydrocarbon burden from the Fraser River is augmented principally by petroleum hydrocarbons and combustion PAHs from Vancouver. Contaminated sediments from Vancouver Harbour very likely have also been transported to a major ocean disposal site off the Fraser estuary. Petroleum alkanes, which dominate Fraser River suspended sediment samples, are lost by processes such as dissolution or microbial degradation during transport and sedimentation, while PAHs from the river are delivered essentially unchanged to sediments in the strait. Hydrocarbon composition undergoes little change with depth at a reference location in the Strait of Georgia, indicating that PAH inputs have changed very little since the early part of this century. In Vancouver Harbour the low rate of sediment accumulation coupled with surface mixing has led to the retention of contaminant PAHs within the surface mixed layer, while the rapid delivery of sediments from the Fraser River has buried contaminant PAHs from historical ocean disposal in the Strait of Georgia.

Alkane, terpene and polycyclic aromatic hydrocarbon geochemistry of the Mackenzie River and Mackenzie shelf: Riverine contributions to Beaufort Sea coastal sediment

Abstract To study the largest source of river sediment to the Arctic Ocean, we have collected suspended particulates from the Mackenzie River in all seasons and sediments from the Mackenzie shelf between the river mouth and the shelf edge. These samples have been analyzed for alkanes, triterpenes and polycyclic aromatic hydrocarbons (PAHs). We found that naturally occurring hydrocarbons predominate in the river and on the shelf. These hydrocarbons include biogenic alkanes and triterpenes with a higher plant/peat origin, diagenetic PAHs from peat and plant detritus, petrogenic alkanes, triterpenes and PAHs from oil seeps and/or bitumens and combustion PAHs that are likely relict in peat deposits. Because these components vary independently, the season is found to strongly influence the concentration and composition of hydrocarbons in the Mackenzie River. While essentially the same pattern of alkanes, diagenetic hopanes and alkyl PAHs is observed in all river and most shelf sediment samples, alkane and triterpene concentration variations are strongly linked to the relative amount of higher plant/peat material. Polycyclic aromatic hydrocarbon molecular-mass profiles also appear to be tied primarily to varying proportions of peat, with an additional petrogenic component which is most likely associated with lithic material mobilized by the Mackenzie River at freshet. Consistent with the general lack of alkyl PAHs in peat, the higher PAHs found in the river are probably derived from forest and tundra fires. A few anthropogenic/pyrogenic compounds are manifest only at the shelf edge, probably due to a weakening of the river influence. We take this observation of pyrogenic PAHs and the pronounced source differences between two sediment samples collected at the shelf edge as evidence of a transition from dominance by the Mackenzie River to the geochemistry prevalent in Arctic regions far removed from major rivers.

Concentrations of dioxin-like PCB congeners in unweathered Aroclors by HRGC/HRMS using EPA Method 1668A

We have determined the congener compositions of nine commercial Aroclor products of polychlorinated biphenyls (PCBs) to the sub-part-per-million level using high-resolution gas chromatography combined with high-resolution mass spectrometry according to US Environmental Protection Agency (EPA) Method 1668A. These Aroclor composition data should allow improved characterization and risk assessment of PCB contamination at hazardous waste sites, particularly for dioxin-like PCB congeners. By combining the data on the concentrations of each dioxin-like congener with its World Health Organization toxicity equivalency factor, we have established dioxin toxic equivalent concentrations for each pure Aroclor product.

Geochemistry and fluxes of hydrocarbons to the Beaufort Sea shelf: A multivariate comparison of fluvial inputs and coastal erosion of peat using principal components analysis

Abstract The allochthonous inputs of hydrocarbon to the Canadian Beaufort Shelf were studied by applying principal components analysis (PCA) to well-validated and rigorously blank-corrected samples. Incorporation of a wide range of perdeuterated n-alkanes and PAH into the analysis scheme ensured that only reliably quantified variables were used to interpret the hydrocarbon geochemistry. Application of PCA to Mackenzie River samples demonstrated a homogeneous system, from which we infer coupling or equilibrium between the river particulate hydrocarbons and the dissolved fraction. Particulate (particle size > 0.7 μm) hydrocarbon flux from the Mackenzie River is by far the most important terrestrially derived source of hydrocarbons to the Beaufort Sea. The Mackenzie River particulates have a distinct n-alkane signature which can be used to identify the riverine influence on the hydrocarbon geochemistry of the Beaufort Sea shelf. Based on one years data, the flux of total alkanes is 440 ± 94 tonne/a, and PAH is 49 ± 8 tonne/a (uncertainties are one standard deviation of the sampling and analytical variation). The particulate flux exceeds the accompanying dissolved hydrocarbon flux by two orders of magnitude and has a strong seasonal cycle: winter contributes less than an estimated 0.6% of total annual flux. Deltaic silt from the western Mackenzie delta and the smaller amounts of detritus from coastal erosion of peat are minor hydrocarbon sources and contribute, in total, less than 10% to the budget for most alkanes. An important exception, with regard to shelf geochemistry, is the significant quantity of peat-derived higher plant n-alkanes.

Characteristics of PAHs, PCDD/Fs and PCBs in sediment following forest fires in northern Alberta

Extensive forest fires occurred in northern Alberta, Canada, in 1998. Polynuclear aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were studied following these forest fires in order to explore natural and anthropogenic influences on the affected forest fire area. Specifically, concentrations and profiles of these compounds were determined in sediment samples. A predominance of alkylated PAH derivatives over parent PAHs were observed at the burned and reference sites. Naturally dervied PAHs were abundant at all sites. A high proportion and concentration of retene was observed at the totally burned site and indicates some inputs from forest fires. Very low concentrations of PCDD/Fs and PCBs were observed at all sites, and the profiles were very similar. This likely reflects common atmospheric contributing sources to the study area.

Biota – Sediment partitioning of aluminium smelter related PAHs and pulp mill related diterpenes by intertidal clams at Kitimat, British Columbia

The question of polycyclic aromatic hydrocarbon (PAH) bioavailability and its relationship to specific PAH sources with different PAH binding characteristics is an important one, because bioavailability drives PAH accumulation in biota and ultimately the biochemical responses to the PAH contaminants. The industrial harbour at Kitimat (British Columbia, Canada) provides an ideal location to study the bioavailability and bioaccumulation of sediment hydrocarbons to low trophic level biota. Samples of soft shell clams (Mya arenaria) and intertidal sediment collected from multiple sites over six years at various distances from an aluminium smelter and a pulp and paper mill were analysed for 106 PAHs, plant diterpenes and other aromatic fraction hydrocarbons. Interpretation using PAH source ratios and multivariate data analysis reveals six principal hydrocarbon sources: PAHs in coke, pitch and emissions from anode combustion from the aluminium smelter, vascular plant terpenes and aromatised terpenes from the pulp and paper mill, petroleum PAHs from shipping and other anthropogenic activities and PAHs from natural plant detritus. Harbour sediments predominantly contain either pitch or pyrogenic PAHs from the smelter, while clams predominantly contain plant derived PAHs and diterpenes from the adjacent pulp mill. PAHs from the smelter have low bioavailability to clams (Biota-Sediment Accumulation Factors; BSAFs <1 for pitch and coke; <10 for anode combustion, decreasing to ∼0.1 for the mass 300 and 302 PAHs), possibly due to binding to pitch or soot carbon matrices. Decreases in PAH isomer ratios between sediments and clams likely reflect a combination of variation in uptake kinetics of petroleum PAHs and compound specific metabolism, with the importance of petroleum PAHs decreasing with increasing molecular weight. Plant derived compounds exhibit little natural bioaccumulation at reference sites, but unsaturated and aromatised diterpenes released from resins by industrial pulping processes are readily accumulated by the clams (BSAFs >500). Thus while most of the smelter associated PAHs in sediments may not be bioavailable to benthic organisms, the plant terpenes (including retene, totarol, ferruginol, manool, dehydroabietane and other plant terpenes that form the chemical defence mechanism of conifers) released by pulp mills are bioavailable and possess demonstrated toxic properties. The large scale release of plant terpenes by some of the many pulp mills located in British Columbia and elsewhere represents a largely undocumented risk to aquatic biota.

PCB, PCDD and PCDF congener profiles in two types of Aroclor 1254.

Monsanto produced two distinct variants of Aroclor 1254. The late-production variant resulted from a change in Monsantos manufacturing process in the early 1970s. Previous literature had reported that the late-production variant was produced from 1974 to 1976, but subsequent work has identified a sample known to be obtained in 1972. In this paper, we present congener-specific PCB and PCDD/F data for this 1972 late-production sample, and a brief historical record of late-production Aroclor 1254.

On the distribution of dissolved hydrocarbons in natural water

Abstract The identity and form of dissolved organic matter in rivers and oceans are fundamental to the biogeochemical cycle of carbon. In particular, understanding the phase distribution of hydrocarbon compounds is a prerequisite to predicting the transfer between phases and the impact of anthropogenic inputs of fossil fuels to the aquatic environment. After rigorous blank-correction of each individual hydrocarbon component of dissolved and particulate hydrocarbon samples from the Mackenzie River, we obtained dissolved hydrocarbon measurements that were unquestionably above the mean blank. Equivalence of the dissolved and particulate hydrocarbon compositions indicates that the two fractions are coupled or at equilibrium in natural waters. Changes in individual hydrocarbon concentrations with sample volume suggest that the dissolved hydrocarbons may be distributed fractally in water.

The quantification of toxaphene in environmental samples

Abstract A simplified analytical method is described for the determination of toxaphene in environmental samples by electron capture negative ion GC/MS using internal standards. The method allows toxaphene to be determined at the low ppb level in the presence of PCBs for a variety of sample matrices including sediment and biological tissue. Toxaphene is quantified from the total peak area response for 21 prominent components using mass chromatograms of the characteristic polychlorobornane [M-Cl] − ions. The quantitation method shows minimal interference from PCB congeners, or from compounds in the chlordane group. Performance was evaluated using a cod liver oil NIST 1588 standard reference material. The effect of oxygen pressure on PCB interference and toxaphene quantitation is discussed.

The determination of toxaphene in environmental samples by negative ion electron capture high resolution mass spectrometry.

A method is described for the analysis of toxaphene in environmental samples by high resolution gas chromatography high resolution mass spectrometry in selected ion electron capture negative ion mode. Toxaphene is detected by monitoring [M-Cl]- fragments ions of chlorobornanes (Cl6-Cl10) and chlorobornenes (Cl6-Cl7) using formal ion ratio criteria. The method shows high sensitivity and excellent specificity for the detection of chlorobornanes with negligible interference from of a wide range of common environmental organochlorines including chlordanes, PCBs and PCB-oxygen adducts. The analytical scheme is applicable to sediment and biological tissue samples and typically provide sample detection limits of less than 0.2 ng/g technical toxaphene for a 10 g sample.