This study investigates the effect of water pressure on hydrocarbon generation and maturation of coals. Using a 25 ml Hastalloy pressure vessel, two high-volatile coals (Longannet, UK 0.75% Ro, and perhydrous Svalbard (Spitsbergen), Norway 0.68% Ro) were pyrolysed under non-hydrous, hydrous at 175 bar pressure, and high water pressure hydrous (500 bar and 900 bar) conditions at 350 °C for 24 h. The bitumen yield obtained during pyrolysis, together with the Rock-Eval S2, hydrogen index (HI) and vitrinite reflectance (VR) results from the pyrolysed coal residues indicated that water under relatively low pressure (175 bar) hydrous conditions promoted hydrocarbon generation and coal maturation in relation to non-hydrous conditions, consistent with previous work. However, under high water pressure (500 and 900 bar) conditions, a combination of the hydrocarbon gas (C1-C4) and bitumen yields, RockEval S2, HI, VR and solid state 13C NMR results demonstrated that the changes in reaction pathways occurring with increasing pressure resulted in both hydrocarbon generation and maturation being retarded. The observed effect of pressure implies that for Type III source rocks, hydrocarbon generation will be retarded in high pressure geological basins, with gas yields being proportionally reduced more than bitumen yields. Source rock maturation (or coalification) is also retarded, with the decreases in vitrinite reflectance and carbon aromaticity being relatively small but significant in terms of explaining retardation in geological basins.
Exploration for shale gas occurs in onshore basins, with two approaches used to predict the maximum gas in place (GIP) in the absence of production data. The first estimates adsorbed plus free gas held within pore space, and the second measures gas yields from laboratory pyrolysis experiments on core samples. Here we show the use of sequential high-pressure water pyrolysis (HPWP) to replicate petroleum generation and expulsion in uplifted onshore basins. Compared to anhydrous pyrolysis where oil expulsion is limited, gas yields are much lower, and the gas at high maturity is dry, consistent with actual shales. Gas yields from HPWP of UK Bowland Shales are comparable with those from degassed cores, with the ca. 1% porosity sufficient to accommodate the gas generated. Extrapolating our findings to the whole Bowland Shale, the maximum GIP equate to potentially economically recoverable reserves of less than 10 years of current UK gas consumption.
The chemical evidence
that IQOS emissions fit the definition of
both an aerosol and smoke, and that IQOS and potentially other heated
tobacco products (HTPs) pose some harmful health threats from the
range of compounds released even at somewhat lower concentrations
is reviewed. Further, we address the yields of harmful and potentially
harmful compounds (HPHCs), including polycyclic aromatic hydrocarbons
(PAHs), and the constituents of IQOS emission that are diagnostic
of pyrolysis to provide information on the temperatures reached in
IQOS tobacco sticks. The HPHCs present in IQOS emissions are the same
as in conventional cigarette smoke (CCs), analogous to emissions from
earlier generation of HTPs classed as smoke. However, Philip Morris
International (PMI) studies have to some degree underestimated IQOS
aerosol HPHC yields, which are a factor of between 3.2 and 3.6 higher
when expressed on a tobacco rather than an IQOS stick basis compared
to the reference 3R4F cigarette. Further, IQOS emissions contain carbon
particles, which fit definition of both aerosol and smoke. Continual
reheating of deposited tar in the IQOS device will occur with real-life
use, likely leading to generation of even higher concentrations of
HPHCs and particulate matter. Despite IQOS not exceeding 350 °C,
local hot spots could exist, causing formation of species (phenol/cresols,
PAHs). It is recommended that the impact of repeated use to determine
the levels of black carbon (insoluble organic matter) in the particulate
matter, and the extent to which compounds in IQOS emissions are formed
by pyrolysis need to be assessed rigorously. To address whether uneven
temperature profiles in heat sticks can lead to potential hot spots
that could, for example, lead to PAH formation, it is recommended
that pyrolysis studies on tobacco and other constituents of HTPs are
required in conjunction with more effort on heating tobacco blends
under controlled temperature/time conditions.
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