Sampling techniques samples

This chapter presents a rationale for the use of atomic absorption spectrometry (AAS) for trace element analysis of air samples, and a comparison with other analytical methods currently in use. Sampling techniques, sample preparation and analytical methods, and applications to workplace and ambient atmospheres are also discussed. Step-by-step procedures will be given which can be used to analyze air-filter samples for a broad spectrum of possible analytes. 

X-ray fluorescence A method of analysis used to identify and measure heavy elements in the presence of each other in any matrix. The sample is irradiated with a beam of primary X-rays of greater energy than the characteristic X-radiation of the elements in the sample. This results in the excitation of the heavy elements present and the emission of characteristic X-ray energies, which can be separated into individual wavelengths and measured. The technique is not suitable for use with elements of lower atomic number than calcium. 

The most common technique for estimating thermal stability is called the Jet Fuel Thermal Oxidation Test (JFTOT). It shows the tendency of the fuel to form deposits on a metallic surface brought to high temperature. The sample passes under a pressure of 34.5 bar through a heated aluminum tube (260°C for Jet Al). After two and one-half hours, the pressure drop across a 17-micron filter placed at the outlet of the heater is measured (ASTM D 3241). 

Fluid samples may be collected downhole at near-reservoir conditions, or at surface. Subsurface samples are more expensive to collect, since they require downhole sampling tools, but are more likely to capture a representative sample, since they are targeted at collecting a single phase fluid. A surface sample is inevitably a two phase sample which requires recombining to recreate the reservoir fluid. Both sampling techniques face the same problem of trying to capture a representative sample (i.e. the correct proportion of gas to oil) when the pressure falls below the bubble point. 

Sampling saturated reservoirs with this technique requires special care to attempt to obtain a representative sample, and in any case when the flowing bottom hole pressure is lower than the bubble point, the validity of the sample remains doubtful. Multiple subsurface samples are usually taken by running sample bombs in tandem or performing repeat runs. The samples are checked for consistency by measuring their bubble point pressure at surface temperature. Samples whose bubble point lie within 2% of each other may be sent to the laboratory for PVT analysis. 

The oil and gas samples are taken from the appropriate flowlines of the same separator, whose pressure, temperature and flowrate must be carefully recorded to allow the recombination ratios to be calculated. In addition the pressure and temperature of the stock tank must be recorded to be able to later calculate the shrinkage of oil from the point at which it is sampled and the stock tank. The oil and gas samples are sent separately to the laboratory where they are recombined before PVT analysis is performed. A quality check on the sampling technique is that the bubble point of the recombined sample at the temperature of the separator from which the samples were taken should be equal to the separator pressure. 

SWS are useful to obtain direct indications of hydrocarbons (under UV light) and to differentiate between oil and gas. The technique is applied extensively to sample microfossils and pollen for stratigraphic analysis (age dating, correlation, depositional environment). Qualitative inspection of porosity is possible, but very often the sampling process results in a severe crushing of the sample thus obscuring the true porosity and permeability. 

A novel approach for suppression of grain noise in ultrasonic signals, based on noncoherent detector statistics and signal entropy, is presented. The performance of the technique is demonstrated using ultrasonic B-scans from samples with coarse material structure. 

The technique presented above has been extensively evaluated experimentally using ultrasonic data acquired from a test block made of cast stainless steel with cotirse material structure. Here we briefly present selected results obtained using two pressure wave transducers, with refraction angles of 45° and 0°. The -lOdB frequency ranges of the transducers were 1.4-2.8 MHz and 0.7-1.4 MHz, respectively. The ultrasonic response signals were sampled at a rate of 40 MHz, with a resolution of 8 bits, prior to computer processing. 

The comparison between the detection cartography (fig. 12) and the signal cartography given by the sensors (figure 7) for the same tube sample, shows the efficiency of our detection technique. Indeed, in the detection cartography, every inner notch present in the tube sample, even the 10% deep notch, is detected... 

The method of volume rendering uses the whole sample volume for visualization. Therefor semitransparent representations of the samples inner structure are possible and the detection of small cracks or faults is much easier compared to the surfaces based techniques (Fig. 4 b). From its principle volume rendering is more time consuming compared to surface representation. 

The scattering techniques, dynamic light scattering or photon correlation spectroscopy involve measurement of the fluctuations in light intensity due to density fluctuations in the sample, in this case from the capillary wave motion. The light scattered from thermal capillary waves contains two observables. The Doppler-shifted peak propagates at a rate such that its frequency follows Eq. IV-28 and... 

Surface defects (Section VII-4C) are also influenced by the history of the sample. Such imperfections may to some extent be reversibly affected by processes such as adsorption so that it is not safe to regard even a refractory solid as having fixed surface actions. Finally, solid surfaces are very easily contaminated detection of contamination is aided by ultra-high-vacuum techniques and associated cleaning protocols [24]. 

Transmission electron microscopy (TEM) can resolve features down to about 1 nm and allows the use of electron diffraction to characterize the structure. Since electrons must pass through the sample however, the technique is limited to thin films. One cryoelectron microscopic study of fatty-acid Langmuir films on vitrified water [13] showed faceted crystals. The application of TEM to Langmuir-Blodgett films is discussed in Chapter XV. 

A novel modification of the STM supplements images with those due to the thermopower signal across the tip-sample temperature gradient [49]. Images of guanine on graphite illustrate the potential of this technique. 

A tremendous amount of work has been done to delineate the detailed reaction mechanisms for many catalytic reactions on well characterized surfaces [1, 45]. Many of tiiese studies involved impinging molecules onto surfaces at relatively low pressures, and then interrogating the surfaces in vacuum with surface science teclmiques. For example, a usefiil technique for catalytic studies is TPD, as the reactants can be adsorbed onto the sample in one step, and the products fonned in a second step when the sample is heated. Note that catalytic surface studies have also been perfonned by reacting samples in a high-pressure cell, and then returning them to vacuum for measurement. 

Electrons are extremely usefiil as surface probes because the distances that they travel within a solid before scattering are rather short. This implies that any electrons that are created deep within a sample do not escape into vacuum. Any technique that relies on measurements of low-energy electrons emitted from a solid therefore provides infonuation from just the outenuost few atomic layers. Because of this inlierent surface sensitivity, the various electron spectroscopies are probably the most usefid and popular teclmiques in surface science. 

The implementation of high-pressure reaction cells in conjunction with UFIV surface science techniques allowed the first tme in situ postmortem studies of a heterogeneous catalytic reaction. These cells penult exposure of a sample to ambient pressures without any significant contamination of the UFIV enviromnent. The first such cell was internal to the main vacuum chamber and consisted of a metal bellows attached to a reactor cup [34]- The cup could be translated using a hydraulic piston to envelop the sample, sealing it from... 

Another example of a teclmique for detecting absorption of laser radiation in gaseous samples is to use multiphoton ionization with mtense pulses of light. Once a molecule has been electronically excited, the excited state may absorb one or more additional photons until it is ionized. The electrons can be measured as a current generated across the cell, or can be counted individually by an electron multiplier this can be a very sensitive technique for detecting a small number of molecules excited. 

At still shorter time scales other techniques can be used to detenuiue excited-state lifetimes, but perhaps not as precisely. Streak cameras can be used to measure faster changes in light intensity. Probably the most iisellil teclmiques are pump-probe methods where one intense laser pulse is used to excite a sample and a weaker pulse, delayed by a known amount of time, is used to probe changes in absorption or other properties caused by the excitation. At short time scales the delay is readily adjusted by varying the path length travelled by the beams, letting the speed of light set the delay. 

It should be noted that this technique is not without some disadvantages. The blackbody emission background in the near IR limits the upper temperature of the sample to about 200°C [43]. Then there is the dependence of the Raman cross-section ( equation (B 1.3.16) and equation ( B1.3.20)-equation ( B 1.3.21)) which calls for an order of magnitude greater excitation intensity when exciting in the near-IR rather than in the visible to produce the same signal intensity [39]. 

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