The spectral dependencies of absorption and fluorescence emission (emission maxima (lamdamax), quantum yields (phi), and mean lifetimes (taum)) were acquired for a commercial lignin, Suwannee River humic (SRHA) and fulvic (SRFA) acids, and a series solid phase extracts (C18) from the Middle Atlantic Bight (MAB extracts). These parameters were compared with the relative average size and total lignin phenol content (TLP). TLP was strongly correlated with absorption at 280 and 355 nm for the MAB extracts, SRHA, and SRFA. The spectral dependence of lamdamax, phi), and taum was very similar for all samples, suggesting a common photophysical and thus structural basis. A strong decrease of phi and taum with increasing average size indicates that intramolecular interactions must be important. When combined with previous work, the results lead us to conclude that the optical properties commonly associated with terrestrial humic substances and chromophoric dissolved organic matter arise primarily from an ensemble of partially oxidized lignins derived from vascular plant sources. Theyfurther provide additional support for an electronic interaction model in which intramolecular energy transfer, excited-state electron transfer, as well as charge transfer likely play important roles in producing the observed optical and photochemical properties of these materials.

No abstract

Mud-gas technologies for continuous PVT-like analysis of reservoir fluids in the drilling mud require a calibration procedure to determine the efficiency of the gas extraction process. This procedure is required because the efficiency of the hydrocarbons extraction process is strongly affected by the drilling mud type and properties, and so it must be performed any time the mud significantly changes. The calibration procedure requires a sample of drilling mud that contains significant amounts of alkanes. Currently, this sample is collected while drilling during a gas peak and stored until the end of the phase, when the calibration can be performed. Thus, the gas extraction efficiency can only be determined at the end of each drilled section, and the quantitative analysis of the reservoir fluid in the mud is made available only at the end of each section. This paper presents a new procedure, in which a Calibration Mud sample is built by injecting and emulsifying several alkanes into the mud. The calibration can then be performed at any time before drilling commences. It is extremely difficult to inject and dissolve gaseous light hydrocarbons into a mud sample at the rigsite. For this reason, we inject a sample of six liquid alkanes into the mud and emulsify it to build a mud sample suitable for the calibration procedure. The extraction efficiencies for the lighter gas alkanes are then extrapolated from those of the injected alkanes using a model of the extraction process. The new calibration process has been tested in several wells around the world. In each test, the new calibration process and standard calibration (performed at the end of the phase using mud collected while drilling) were performed. Validation of the new technique comes from ensuring the extraction efficiency coefficients using our new calibration mud match those coming from the standard calibration. The results were conclusive with similar coefficients obtained in each test. The uncertainty intervals overlap, and the calibration coefficients are statistically equivalent. The new calibration procedure represents an innovative methodology enabling real-time, continuous quantification of the light hydrocarbons content (C1-C6) of the reservoir fluid, comparable to the PVT monophasic composition, while drilling, at surface. This is the first time that such data can be delivered in real-time while drilling. The resulting measurements have multiple applications such as enhanced geosteering and well placement, real-time identification of gas-oil contacts, and real-time selection of sampling points and can be integrated with downhole tool measurements to provide a true real-time understanding of the subsurface fluids.