Tommy Noernberg

Airborne Petcoke Dust is a Major Source of Polycyclic Aromatic Hydrocarbons in the Athabasca Oil Sands Region

Oil sands mining has been linked to increasing atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) in the Athabasca oil sands region (AOSR), but known sources cannot explain the quantity of PAHs in environmental samples. PAHs were measured in living Sphagnum moss (24 sites, n = 68), in sectioned peat cores (4 sites, n = 161), and snow (7 sites, n = 19) from ombrotrophic bogs in the AOSR. Prospective source samples were also analyzed, including petroleum coke (petcoke, from both delayed and fluid coking), fine tailings, oil sands ore, and naturally exposed bitumen. Average PAH concentrations in near-field moss (199 ng/g, n = 11) were significantly higher (p = 0.035) than in far-field moss (118 ng/g, n = 13), and increasing temporal trends were detected in three peat cores collected closest to industrial activity. A chemical mass-balance model estimated that delayed petcoke was the major source of PAHs to living moss, and among three peat core the contribution to PAHs from delayed petcoke increased over time, accounting for 45-95% of PAHs in contemporary layers. Petcoke was also estimated to be a major source of vanadium, nickel, and molybdenum. Scanning electron microscopy with energy-dispersive X-ray spectroscopy confirmed large petcoke particles (>10 μm) in snow at near-field sites. Petcoke dust has not previously been considered in environmental impact assessments of oil sands upgrading, and improved dust control from growing stockpiles may mitigate future risks.

Suggested protocol for collecting, handling and preparing peat cores and peat samples for physical, chemical, mineralogical and isotopic analysesPresented as part of the Archives of Environmental Contamination at the 6th International Symposium on Environmental Geochemistry, Edinburgh, Scotland, 7?11 September 2003.

For detailed reconstructions of atmospheric metal deposition using peat cores from bogs, a comprehensive protocol for working with peat cores is proposed. The first step is to locate and determine suitable sampling sites in accordance with the principal goal of the study, the period of time of interest and the precision required. Using the state of the art procedures and field equipment, peat cores are collected in such a way as to provide high quality records for paleoenvironmental study. Pertinent field observations gathered during the fieldwork are recorded in a field report. Cores are kept frozen at -18 degree C until they can be prepared in the laboratory. Frozen peat cores are precisely cut into 1 cm slices using a stainless steel band saw with stainless steel blades. The outside edges of each slice are removed using a titanium knife to avoid any possible contamination which might have occurred during the sampling and handling stage. Each slice is split, with one-half kept frozen for future studies (archived), and the other half further subdivided for physical, chemical, and mineralogical analyses. Physical parameters such as ash and water contents, the bulk density and the degree of decomposition of the peat are determined using established methods. A subsample is dried overnight at 105 degree C in a drying oven and milled in a centrifugal mill with titanium sieve. Prior to any expensive and time consuming chemical procedures and analyses, the resulting powdered samples, after manual homogenisation, are measured for more than twenty-two major and trace elements using non-destructive X-Ray fluorescence (XRF) methods. This approach provides lots of valuable geochemical data which documents the natural geochemical processes which occur in the peat profiles and their possible effect on the trace metal profiles. The development, evaluation and use of peat cores from bogs as archives of high-resolution records of atmospheric deposition of mineral dust and trace elements have led to the development of many analytical procedures which now permit the measurement of a wide range of elements in peat samples such as lead and lead isotope ratios, mercury, arsenic, antimony, silver, molybdenum, thorium, uranium, rare earth elements. Radiometric methods (the carbon bomb pulse of (14)C, (210)Pb and conventional (14)C dating) are combined to allow reliable age-depth models to be reconstructed for each peat profile.

Dust is the dominant source of "heavy metals" to peat moss (Sphagnum fuscum) in the bogs of the Athabasca Bituminous Sands region of northern Alberta.

Sphagnum fuscum was collected from twenty-five ombrotrophic (rain-fed) peat bogs surrounding open pit mines and upgrading facilities of Athabasca Bituminous Sands (ABS) in northern Alberta (AB) in order to assess the extent of atmospheric contamination by trace elements. As a control, this moss species was also collected at a bog near Utikuma (UTK) in an undeveloped part of AB and 264km SW of the ABS region. For comparison, this moss was also collected in central AB, in the vicinity of the City of Edmonton which is approximately 500km to the south of the ABS region, from the Wagner Wetland which is 22km W of the City, from Seba Beach (ca. 90km W) and from Elk Island National Park (ca. 45km E). All of the moss samples were digested and trace elements concentrations determined using ICP-SMS at a commercial laboratory, with selected samples also analyzed using instrumental neutron activation analysis at the University of Alberta. The mosses from the ABS region yielded lower concentrations of Ag, As, Bi, Cd, Cu, Pb, Sb, Tl, and Zn compared to the moss from the Edmonton area. Concentrations of Ni and Mo in the mosses were comparable in these two regions, but V was more abundant in the ABS samples. Compared with the surface vegetation of eight peat cores collected in recent years from British Columbia, Ontario, Quebec and New Brunswick, the mean concentrations of Ag, As, Bi, Cd, Cu, Mo, Ni, Pb, Sb, Tl and Zn in the mosses from the ABS region are generally much lower. In fact, the concentrations of these trace elements in the samples from the ABS region are comparable to the corresponding values in forest moss from remote regions of central and northern Norway. Lithophile element concentrations (Ba, Be, Ga, Ge, Li, Sc, Th, Ti, Zr) explain most of the variation in trace metal concentrations in the moss samples. The mean concentrations of Th and Zr are greatest in the moss samples from the ABS region, reflecting dust inputs to the bogs from open pit mines, aggregate quarries, and gravel roads. Linear regressions of V, Ni, and Mo (elements enriched in bitumen) versus Sc (a conservative, lithophile element) show excellent correlations in the mosses from the ABS region, but this is true also of Ag, Pb, Sb and Tl: thus, most of the variation in the trace metal concentrations can be explained simply by the abundance of dust particles on the plants of this region. Unlike the moss samples from the ABS region and from UTK where Pb/Sc ratios resemble those of crustal rocks, the moss samples from the other regions studied yielded much greater Pb/Sc ratios implying significant anthropogenic Pb contributions at these other sites.

Peat bogs in northern Alberta, Canada reveal decades of declining atmospheric Pb contamination

Peat cores were collected from six bogs in northern Alberta to reconstruct changes in the atmospheric deposition of Pb, a valuable tracer of human activities. In each profile, the maximum Pb enrichment is found well below the surface. Radiometric age dating using three independent approaches (14C measurements of plant macrofossils combined with the atmospheric bomb pulse curve, plus 210Pb confirmed using the fallout radionuclides 137Cs and 241Am) showed that Pb contamination has been in decline for decades. Today, the surface layers of these bogs are comparable in composition to the “cleanest” peat samples ever found in the Northern Hemisphere, from a Swiss bog ~ 6000 to 9000 years old. The lack of contemporary Pb contamination in the Alberta bogs is testimony to successful international efforts of the past decades to reduce anthropogenic emissions of this potentially toxic metal to the atmosphere.

Characterization of Naphthenic Acids and Other Dissolved Organics in Natural Water from the Athabasca Oil Sands Region, Canada

With growth of the Canadian oil sands industry, concerns have been raised about possible seepage of toxic oil sands process-affected water (OSPW) into the Athabasca River (AR). A sampling campaign in fall 2015 was undertaken to monitor for anthropogenic seepage while also considering natural sources. Naphthenic acids (NAs) and thousands of bitumen-derived organics were characterized in surface water, groundwater, and OSPW using a highly sensitive online solid phase extraction-HPLC-Orbitrap method. Elevated NA concentrations and bitumen-derived organics were detected in McLean Creek (30.1 μg/L) and Beaver Creek (190 μg/L), two tributaries that are physically impacted by tailings structures. This was suggestive of OSPW seepage, but conclusive differentiation of anthropogenic and natural sources remained difficult. High NA concentrations and bitumen-derived organics were also observed in natural water located far north of the industry, including exceedingly high concentrations in AR groundwater (A5w-GW, 2000 μg/L) and elevated concentration in a tributary river (Pierre River, 34.7 μg/L). Despite these evidence for both natural and anthropogenic seepage, no evidence of any bitumen-derived organics was detected at any location in AR mainstem surface water. The chemical significance of any bitumen-derived seepage to the AR was therefore minimal, and focused monitoring in tributaries will be valuable in the future.

Peat Bogs Document Decades of Declining Atmospheric Contamination by Trace Metals in the Athabasca Bituminous Sands Region

Peat cores were collected from five bogs in the vicinity of open pit mines and upgraders of the Athabasca Bituminous Sands, the largest reservoir of bitumen in the world. Frozen cores were sectioned into 1 cm slices, and trace metals determined in the ultraclean SWAMP lab using ICP-QMS. The uppermost sections of the cores were age-dated with 210Pb using ultralow background gamma spectrometry, and selected plant macrofossils dated using 14C. At each site, trace metal concentrations as well as enrichment factors (calculated relative to the corresponding element/Th ratio of the Upper Continental Crust) reveal maximum values 10 to 40 cm below the surface which shows that the zenith of atmospheric contamination occurred in the past. The age-depth relationships show that atmospheric contamination by trace metals (Ag, Cd, Sb, Tl, but also V, Ni, and Mo which are enriched in bitumen) has been declining in northern Alberta for decades. In fact, the greatest contemporary enrichments of Ag, Cd, Sb, and Tl (in the top layers of the peat cores) are found at the control site (Utikuma) which is 264 km SW, suggesting that long-range atmospheric transport from other sources must be duly considered in any source assessment.

Sphagnum Moss as an Indicator of Contemporary Rates of Atmospheric Dust Deposition in the Athabasca Bituminous Sands Region

Sphagnum moss was collected from ombrotrophic (rain-fed) peat bogs to quantify dust emissions from the open-pit mining and upgrading of Athabasca bituminous sands (ABS). A total of 30 bogs were sampled in the ABS region, and 5 were sampled in central Alberta. Ash was separated into the acid-insoluble ash (AIA) and acid-soluble ash (ASA) fractions using HCl. The AIA concentrations increase toward industry from 0.4 ± 0.5% to 4.7 ± 2.0% over a distance of 30 km; the control site at the Utikuma Region Study Area (URSA) yielded 0.29 ± 0.07% (n = 30). Mass accumulations rates showed similar spatial variation. The morphology and mineralogy of the AIA particles were studied using scanning electron microscopy and energy-dispersive X-ray analysis and the particle size distributions using optical methods. Particle size was more variable in moss closer to industry. Major ions in the ASA fraction showed elevated accumulation rates of Ca, K, Fe, Mg, P, and S, with P being up to 5 times greater in samples nearest industry compared to those in distal locations. Given that P has been regarded as the growth-limiting nutrient in bogs, fertilization of nutrient-poor ecosystems, such as these from fugitive emissions of dusts from open-pit mining, may have long-term ecological ramifications.

Response to Comment on "Sphagnum mosses from 21 ombrotrophic bogs in the Athabasca bituminous sands region show no significant atmospheric contamination of 'heavy metals'".

Ombrotrophic Bogs in the Athabasca Bituminous Sands Region Show No Significant Atmospheric Contamination of ‘Heavy Metals’” L concentrations had been measured in three samples collected from each of 21 peat bogs, and the values averaged. These values are now shown for individual moss samples as a function of distance from the midpoint between the two upgraders (Figure 1a). Note that seven sites, representing 21 moss samples, are within 20 km of the midpoint between the two upgraders, not five sites (and 15 samples) as claimed by Blais and Donahue. As a point of reference, the horizontal dashed line indicates the natural “background” Pb concentration for ancient, preanthropogenic peat samples from Etang de la Grueŕe (EGR), an ombrotrophic bog in the Jura Mountains of Switzerland. Peat formation at the EGR bog began nearly 15 000 years ago, and it represents the longest record of continuous peat accumulation in the northern hemisphere. These peat samples, dating from the mid-Holocene (∼6000− 9000 years old), represent the lowest Pb concentrations found in this profile since peat formation began during the Late Glacial, and contain 0.28 ± 0.05 mg/kg Pb; n = 17. Notice that some of the contemporary moss samples collected from the ABS region approach the background concentrations for ombrotrophic (i.e., rain-fed) peat dating from the mid-Holocene. Except for one site (site 12, which is adjacent to an open pit mine, as shown in Figure 1 of Shotyk et al.), all of the ABS region moss samples are within a factor of 5 of the background Pb concentration for peat from EGR. In contemporary moss samples, comparable Pb concentrations have been reported for specimens from southernmost South America and Antarctica. However the moss data from the ABS region is viewed, the Pb concentrations are low. Thorium concentrations, taken to reflect the abundance of mineral dust particles in the moss, are plotted in the same way (Figure 1b). Again, as a point of reference, peat samples from the EGR bog and dating from the mid-Holocene, contain 0.07 ± 0.02 mg/kg Th; n = 18. All of the moss samples from the ABS region are within a factor of 8 of the “background” value for Th in ombrotrophic peat. It is clear from these illustrations that Pb (Figure 1a) and Th (Figure 1b) exhibit similar spatial distributions, with greater concentrations closest to the midpoint between the two upgraders. A plot of Pb/Th against distance (Figure 1c) shows the ratio ranges from 2.2 to 3.9 in every sample <45 km from the midpoint between the two upgraders. As a point of reference, the Pb/Th ratio is also shown for the ancient, pre-anthropogenic peat samples from EGR (Pb/Th = 4). Clearly, the Pb/Th ratio of all of the moss samples <45 km from the midpoint between the two upgraders is below the “natural background” ratio and is independent of distance (r = 0.06, n.s.). Lead in any given moss sample is deposited exclusively from the atmosphere, from either natural or anthropogenic sources, or both. We have reconstructed atmospheric Pb deposition for

Bioaccumulation of Tl in otoliths of Trout-perch (Percopsis omiscomaycus) from the Athabasca River, upstream and downstream of bitumen mining and upgrading

It has been suggested that open pit mining and upgrading of bitumen in northern Alberta releases Tl and other potentially toxic elements to the Athabasca River and its watershed. We examined Tl and other trace elements in otoliths of Trout-perch (Percopsis omiscomaycus), a non-migratory fish species, collected along the Athabasca River. Otoliths were analyzed using ICP-QMS, following acid digestion, in the metal-free, ultraclean SWAMP laboratory. Compared to their average abundance in the dissolved (<0.45 μm) fraction of Athabasca River, Tl showed the greatest enrichment in otoliths of any of the trace elements, with enrichments decreasing in the order Tl, Sr, Mn, Zn, Ba, Th, Ni, Rb, Fe, Al, Cr, Ni, Cu, Pb, Co, Li, Y, V, and Mo. Normalizing Tl in the otoliths to the concentrations of lithophile elements such as Li, Rb, Al or Y in the same tissue reveals average enrichments of 177, 22, 19 and 190 times, respectively, relative to the corresponding ratios in the water. None of the element concentrations (Tl, Li, Rb, Al, Y) or ratios were significantly greater downstream of industry compared to upstream. This natural bioaccumulation of Tl most likely reflects the similarity in geochemical and biological properties of Tl+ and K+. SUMMARY OF MAIN FINDINGS: Thallium is enriched in fish otoliths, relative to the chemical composition of the river, to the same degree both upstream and downstream of industry.