Whitby formation

Historically, shale oil was produced in Ontario from a plant near Craigleigh, on Lake Huron. In 1859, rock of the Ordovician Whitby Formation was retorted to produce fuel and lubricants. In... 

In 1981, the Ontario Geological Survey began a program to assess the resource potential of the Whitby Formation and the other black shales of Ontario. Prior to this study, information on Ontario s black shales has been very sparse due to poor or non-existent exposure and limited subsurface information. Existing data suggested three units were sufficiently organic-rich to warrant further study—the Ordovician Whitby and the Devonian Kettle Point and Marcellus Formation (JL). ... 

The initial phase of the project involved shallow sampling of the Whitby Formation by diamond drilling at 20 locations. 

The Middle Devonian Marcellus Formation consists of black bituminous shale and minor argillaceous limestone lying conformably on the Dundee Formation limestones. Its depositional setting resembles that of the Whitby Formation and the Marcellus... 

The Upper Ordovician Whitby Formation overlies the Lindsay Formation of the Middle Ordovician Simcoe Group. The Lindsay Formation is a limestone with interbedded shaley units. The character of the contact with the overlying Whitby Formation is variable and may be an important control over the organic content of the lower part of the Whitby Formation. The Whitby Formation is overlain by interbedded limestone and shale of the Upper Ordovician Georgian Bay Formation. 

Total Organic Carbon (TOC) analyses of core of the Whitby Formation indicate that the Upper and Middle members rarely contain more than 2.5% TOC. In contrast, the Collingwood member often includes considerable intervals with more than 3% TOC although the maximum thickness where TOC exceeds 5% is always... 

In the Whitby Formation, the available FA oil yields (59 samples) are less than 60 litres/tonne (14 U.S. gallons/ton). This oil has a specific gravity in the range 0.893 to 0.942. Twenty FA determinations on Kettle Point samples revealed oil yields up to 72 1/t (17 gal/ton) with specific gravity in the range 0.896 to 0.956. Few FA analyses of Marcellus shales are available the highest oil yield to date is 64 1/t (15.4 gal/ton). 

Table I summarizes the indicated maturation levels of organic matter from the Kettle Point, Marcellus and Whitby Formations and equivalents in various areas. Using Figure 4, these may be related to thermal maturation. Only a few samples have been ex-...

None of the indicators alone provide a definitive indication of thermal maturation, but, when considered together, they provide a reasonably consistent picture. It seems that the Billings equivalent of the Whitby Formation in the Ottawa area is mature to overmature, while the Whitby Formation along its subcrop is marginally mature to mature. The Marcellus is marginally mature and the Kettle Point is immature to perhaps marginally mature. 

The relative proportions of amorphous, exinous and vitrinous plus fusinous kerogen material in the few samples examined to date are shown in Figure 7. Whitby Formation kerogens from the Collingwood area are highest in amorphous material and so one... 

Infrared absorption (I.R.) spectra provide a qualitative indication of the organic structures present in the kerogen and their variation between samples. In general, the I.R. spectra of Whitby and Kettle Point kerogens are dominated by aromatic and aliphatic absorption bands with a minor OH band. Many samples from the Whitby Formation of the Toronto area show stronger OH absorption, and perhaps a more aromatic than aliphatic nature compared to samples from other locales. 

Figure 8. A typical gas chromatogram of pyrolysate of Whitby Formation kerogen. Identifications are...

Significant variation in organic geochemistry has been observed within the Whitby Formation and between the Whitby and Kettle Point Formations. Research is in progress to define the geological controls and to relate the resource potential as measured by TOC analyses and FA oil yields to observed variations in organic matter type and maturation level. 

The Upper Ordovician Whitby Formation represents a transition from carbonate to shale deposition on a broad, shallow shelf. The Lower member—the Collingwood member—has the most potential for shale oil production. This member is an organic-rich marl or carbonate with considerable lateral variation along its subcrop trend from Manitoulin Island to the Toronto area. TOC values up... 

Although the Whitby Formation was a viable oil shale in 1860, it does not appear to constitute a major, world-scale oil shale resource today. However, additional research has been undertaken to identify the richest and thickest shales which may be suitable for smaller-scale production as was practiced near Collingwood around 1860. The studies of the Marcellus Formation are very preliminary, but they point towards a resource of similarly limited value. 

In 1997, Whitby reported that treatment of 2,5-dihydrofuran with Et3Al in the presence of 5 mol% 31 leads to the enantioselective formation of 39 (Scheme 6.13), rather than the product obtained from catalytic carbomagnesations (40) [34]. This outcome can be rationalized on the basis of Dzhemilev s pioneering report that with Et3Al, in contrast to the mechanism that ensues with EtMgCl (see Scheme 6.2), the intermediate alumina-cyclopentane (i) is converted to the corresponding aluminaoxacyclopentane ii. To ensure the predominant formation of 39, catalytic alkylations must be carried out in absence of solvent. 

Busfield A, Gilmour JD, Whitby JA, Turner G (2004) Iodine-xenon analysis of ordinary chondrite halide implications for early solar system water. Geochim Cosmochim Acta 68 195-202 Busso M, Gallino R, Wasserburg GJ (1999) Nucleosynthesis in asymptotic giant branch stars relevance for galactic enrichment and solar system formation. Annu Rev Astronom Astrophys 37 239-309 Cameron AGW (1969) Physical conditions in the primitive solar nebula. In Meteorite Research. Millman PM (ed) Reidel, Dordrecht, p 7-12... 

In 1978, Whitby suggested the use of a combination of three lognormal distributions to characterize an urban aerosol (Horvath, 2000). This so-called multimodal size distribution, from which the current nomenclature for aerosol particles has been developed, reflects the diversity of formation mechanisms and the randomness of both particle transformation and removal processes (Seinfeld and Pandis, 1998 Horvath, 2000 Raes et al., 2000). Accordingly, atmospheric particles are classified into three distinct modes ... 

Clark and Whitby (1967) used Friedlander s self-preserving spectrum theory to explain the general shape of the observed size distribution of atmospheric aerosols. Although the formation of the distribution is so slow that there is little likelihood of finding this form in most cases, it is possible that for some global aerosols the quasi selfpreserving spectrum of Friedlander is actually developed. 

This method is most practical for complexes where methane elimination is facile and occurs below room temperature. Zirconaaziridines such as those in Fig. 1 (with N-aryl and N-silyl [19] substituents) have been readily prepared in this manner [20-22]. Buchwald noted that methane elimination from 1 is facile when the availability of the lone pairs on nitrogen is reduced [20] Whitby suggests that such reduced availability... [is] due to conjugation with the aromatic n system, or overlap with the Si d orbitals (or Si-C o orbitals) [23]. The rate of zirconaaziridine formation from le, for example, is faster by a factor of 1,000 than the rate of the formation from If (Fig. 2). 

Saelen G., Tyson R. V., Talbot M. R., and Telnaes N. (1998) Evidence of recycling of isotopically light C02(aq) in stratified black shale basins contrasts between the Whitby Mudstone and Kimmeridge Clay formations, United Kingdom. Geology 26, 747-750. 

Figure 2. The relationship between Fischer Assay oil yield and total organic carbon (TOC) content for shale samples from the Whitby (left) and Kettle Point (right) Formations.

Figure 7. The relative proportions of amorphous (am), exinous (ex), and vitrinous plus fusinous (vit. + fus.) kerogen macerals. Key to formations , Kettle Point a, Marcellus , Manitoulin, Whitby A, Collingwood, Whitby and o, Toronto, Whitby.

Experiments on simultaneous coagulation and growth were made by Husar and Whitby (1973). A 90-m polyethylene bag was filled with laboratory air from which paniculate matter had been removed by filtration. Solar radiation penetrating the bag induced photochemical reactions among gaseous pollutants, probably SO2 and organics, but the chemical composition was not determined. The reactions led to the formation of condensable species and photochemical aerosols. Size distributions were measured in 20-min intervals using an electrical mobility analyzer. The results of one set of experiments for three different time,s are shown in Fig. 11.3. 

Figure 11.4 Evolution of the moments of the size distribution function for the aerosols shown in Fig. 11.3, The peak in the number distribution probably results when formation by homogeneous nudeaiiun is balanced by coagulation. Total aerosol volume increases with time as gas-tO partide conversion takes place. Total. surface area, A, increases at first and then approaches an approximately constant value, due probably toa balance between growth and coagulation (Husarand Whitby, 1973). The results should be compared with Pig. 11.2.

With regard to their formation process and size, aerosol particles can be divided into two distinct groups fine and coarse particles (Whitby, 1978). Fine particles with radius smaller than 0.5-1.0 /im are formed by condensation and coagulation (see Subsection 4.2.2), while coarse particles arise mostly from surface disintegration (see Subsection 4.2.1). Since this classification provides an explanation of the form of the particle size distribution, we will discuss Whitby s ideas in more detail in Subsection 4.3.2. 

The formation of aerosol particles from gaseous components is appropriately investigated under laboratory conditions. In so-called aerosol chambers an artificial atmosphere is created to which small quantities of appropriate trace gases (e.g. SO, NO, H,0, NH, and organics) is added. It is also possible to use ambient air purified from particulate matter. The chamber may be illuminated to initiate photochemical processes, and the behaviour of particles formed is studied by the methods outlined in Subsection 4.1.2, e.g. by electrical mobility analyzers (Whitby et aL 1972). 

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