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AbstractAn inter-laboratory study of high-pressure gas sorption measurements on two carbonaceous shales has been conducted in order to assess the reproducibility of the sorption isotherms and identify possible sources of error. The measurements were carried out by seven international research laboratories on either in-house or commercial sorption equipment using manometric as well as gravimetric methods. Excess sorption isotherms for methane, carbon dioxide and ethane were measured at 65°C and at pressures up to 25 MPa on two organic-rich shales in the dry state. The samples were taken from the immature Posidonia shale (Germany) and from the over-mature Upper Chokier formation (Belgium). Their total organic carbon (TOC) and vitrinite reflectance (VRr) values were 15.1% and 4.4% and 0.5% and 2.0%, respectively. The objective of the study was to assess the inter-laboratory reproducibility of sorption isotherms as would be expected with each laboratory following its own measurement and data reduction procedures. All labs were asked to follow a predefined sample drying procedure prior to measurement in order to minimize any effects related to moisture. The reproducibility of the methane excess sorption isotherms was better for the high-maturity shale (within 0.02 -0.03 mmol/g) than for the low-maturity sample (up to 0.1 mmol/g), similar to observations in earlier inter-laboratory studies on coals. The reproducibility for CO2 and C2H6 sorption isotherms was satisfactory at pressures below 5 MPa, however,the results deviate considerably at higher pressures. Artefacts in the shape of the excess sorption isotherms were observed for CO2 and C2H6 and these are explained as being due to a high sensitivity of gas density to temperature and pressure close to the critical point as well as from a limited measurement accuracy and possibly uncertainty in the equation of state (EoS).The low sorption capacity of carbonaceous shales (as compared to coals and activated carbons) sets very high demands on the accuracy of pressure and temperature measurement and precise temperature control. Furthermore, the sample treatment, measurement and data reduction procedures must be optimized in order to achieve satisfactory inter-laboratory consistency and accuracy. Unknown systematic errors must be minimized first by calibrating the pressure and temperature measurement sensors to high-quality standards. Blank sorption measurements with a non-sorbing sample (e.g. steel cylinders) can be used to identify and...
Beneficial use of dredged sediments, either in harbours or waterways, is based on their potential as alternative resources. Such sediments can be considered as bulk materials for industrial needs, which is predicated on their current waste status or meeting end-of-waste constraints. They also can be an integral part of beneficial use projects using sediments as a bulk component, including civil engineering and landscaping. This is particularly important for beneficial use projects focusing on climate change effects mitigation, such as flood protection works, coastline defence or littoral urban areas redevelopment. When dredged sediment is used as a bulk material, its acceptability is based on an assumed homogeneity of its properties. On-site analyses allow pre-dredging detailed mapping at a denser scale than laboratory ones; monitoring dredgings during operations and during processing; and continuous control of their properties at the implementation site. This is currently possible only for a selection of inorganic analytes. When dredgings are part of a larger beneficial use project, on-site analyses facilitate first the baseline survey and the sediment source characterisation. Continuous monitoring of the sediment load allows a fast detection of contamination hot spots and their adequate management. Site survey via on-site instruments allow end users and communities to check themselves the contamination level, hence acceptability is better. On-site dredged sediment analyses monitor both building properties and environmental compliance; soil and sediment analyses at receiving sites; surface and groundwater, either for impact assessment or for monitoring works. On-site instruments provide immediate results and allow dynamic or adaptive sampling strategies, as well as allowing operational decisions in real time. Confirmation by laboratory analyses is required for validation, but on-site sample screening for laboratory analyses improves their efficiency. The present paper was developed on the basis of an earlier presentation, which it developed and updated extensively.
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