Sample requirements concentration

Samples that require special handling treatment For example, samples of limited size, samples requiring concentration or prior separation, and radioactive... 

Accuracy The accuracy of a gas chromatographic method varies substantially from sample to sample. For routine samples, accuracies of 1-5% are common. For analytes present at very low concentration levels, for samples with complex matrices, or for samples requiring significant processing before analysis, accuracy may be substantially poorer. In the analysis for trihalomethanes described in Method 12.1, for example, determinate errors as large as +25% are possible. ... 

Requirements of Standards. The general requirements for luminescence standards have been discussed extensively (3,7-9) and include stability, purity, no overlap between excitation and emission spectra, no oxygen quenching, and a high, constant qtiantum yield independent of excitation wavelength. Specific system parameters--such as the broad or narrow excitation and emission spectra, isotropic or anisotropic emission, solubility in a specific solvent, stability (standard relative to sample), and concentration--almost require the standard to be in the same chemical and physical environment as the sample. 

The necessary reference samples are produced by preparing a stock solution of the pure drug substance and diluting it to the required concentrations. On the average, 12 minutes are needed per reference. 

Does the system require all method and sequence data to be defined before a run (For example, can the sample name, concentration, volume, etc. be changed after data are acquired )... 

Initial Pa/ U levels are more difficult to assess, primarily because there is no long-lived or stable isotope of protactinium that can be used as an index isotope. Edwards et al. (1997) analyzed a set of surface coral sub-samples younger than 1000 years by both °Th and Pa techniques. For all samples, Th concentrations were less than 100 p g so that initial °Th/ U values were negligible. Each sub-sample yielded °Th and a ages identical within analytical errors (Fig. 8), indicating that initial Pa/ U was negligible. This suggests that surface corals with typical Th values do not require corrections for initial Pa. Whether or not corals with elevated Th require such corrections is an open question. 

Define the turnaround time for each kind of routine sample analysis and ensure that sample submitters understand requirements for sample size, concentration, and matrix. 

Other kinds of bloassays have been used to detect the presence of specific allelochemical effects (8), effects on N2 fIxatlon (9), the presence of volatile compounds (10) and of Inhibitory substances produced by marine microalgae (11). Putnam and Duke (12) have summarized the extraction techniques and bioassay methods used In allelopathy research. Recent developments In high performance liquid chromatography (HPLC) separation of allelochemlcals from plant extracts dictates the need for bloassays with sensitivity to low concentrations of compounds contained In small volumes of eluent. Einhellig at al. (13) described a bloassay using Lemna minor L. growing In tissue culture cluster dish wells that maximizes sensitivity and minimizes sample requirements. 

The useful life of hplc columns can be extended by proper treatment, in particular by the use of guard and scavenger columns. Pretreatment of samples is often necessary, eg very dilute samples may require concentration, or complex samples may need to be cleaned up. Some of the more important techniques are considered. 

Two-dimensional capillary electrophoresis of complex protein samples requires careful attention to detail. Tissues and cells should be fixed to prevent degradation. Most conventional fixatives are inappropriate because they produce covalent crosslinks, which are difficult to reverse. We find that ethanol produces decent results when the sample is homogenized with high concentrations of SDS. 

The adsorbate gas must be mixed with the carrier gas in the required concentrations for analysis. This can be done prior to analysis and a number of tanks for various concentrations can be kept, or the mixing can be done during the analysis with a gas mixer. The sample holder can allow the gas to flow through the sample (such as a modified U-tube), or a vacuum can be pulled on the sample, which requires a sample holder consisting of a single stem with a bulb at the bottom to hold sample. The most common type of detector is the thermal conductivity... 

Typical instrument set-ups for online sample preparation, for example, solid phase extraction and sample pre-concentration, require the control of a six-port valve with an additional special column and a second pump. Ideally, this system will be fully controlled by the data acquisition software (Figure 3.12 (A)). 

Smaller diameter probes reduce sample volumes from 500 to 600 pi typical with a 5 mm probe down to 120-160 pi with a 3 mm tube. By reducing the sample volume, the relative concentration of the sample can be correspondingly increased for non-solubility limited samples. This dramatically reduces data acquisition times when more abundant samples are available or sample quantity requirements when dealing with scarce samples. At present, the smallest commercially available NMR tubes have a diameter of 1.0 mm and allow the acquisition of heteronuclear shift correlation experiments on samples as small as 1 pg of material, for example in the case of the small drug molecule, ibu-profen [5]. In addition to conventional tube-based NMR probes, there are also a number of other types of small volume NMR probes and flow probes commercially available [6]. Here again, the primary application of these probes is the reduction of sample requirements to facilitate the structural characterization of mass limited samples. Overall, many probe options are available to optimize the NMR hardware configuration for the type and amount of sample, its solubility, the nucleus to be detected as well as the type and number of experiments to be run. 

In the analysis of solid samples (e.g., LA-ICP-MS, SEM), synthetic standards cannot easily be prepared to the required concentrations, and accurate calibration of such techniques is often challenging. In some cases (e.g., SEM) pure element or single mineral standards are used, ideally with an appropriate standard for each element to be quantified. (It is possible in SEM, within limits, to use fewer standards than the number of elements to be determined, with the calibration for other elements being predicted from the response of the nearest element.) More often, however, multielement primary standards are used as the means of calibrating the instrument, e.g., for LA-ICP-MS of glasses, volcanics, and ceramics, two glass standards, NIST 610 and 612 (Pearce et al. 1996), are often used. It is always advisable to use more than one multielement standard in order to cover as wide a range of concentrations as possible, and to use at least one additional independent reference material as an unknown, for quality assurance purposes (see below). 

Sampling Interval To be able to perform valid toxicokinetic analysis, it is not only necessary to properly collect samples of appropriate biological fluids, but also to collect a sufficient number of samples at the current intervals. Both of these variables are determined by the nature of the answers sought. Useful parameters in toxico-kinetic studies are Cmax, which is the peak plasma test compound concentration Tmax, which is the time at which the peak plasma test compound concentration occurs, Cmin, which is the plasma test compound concentration immediately before the next dose is administered AUC, which is the area under the plasma test compound concentration-time curve during a dosage interval, and t which is the half-life for the decline of test compound concentrations in plasma. The samples required to obtain these parameters are shown in Table 18.12. Cmin requires one blood sample immediately before a dose is given and provides information on accumulation. If there is no accumulation in plasma, the test compound may not be detected in this sample. 

Most of the time the unknown sample requires some pretreatment, such as dilution, extraction, or, if it is a solid, dissolving. The analytical concentration of the analyte in the untreated sample must usually be reported, rather than the concentration in the sample solution. Thus, a calculation is usually required to obtain the final answer. 

Applicability of CZE to the Edman phenylthiohydantion derivatives of amino acids (140) is limited because the neutral amino acids cannot be resolved by this method and by the reduced thickness of the sample requiring relatively high concentrations of the fluorescent material for detection. These limitations may be overcome by a micellar technique that confers mobility to neutral 140 species and by application of thermotropic detection that allows one to detect a few tens of fmol of the derivative, obtained after injecting ca 0.5 nL, at a concentration of ca 1 p-M330. 

Most water systems are required to monitor for radioactivity and certain radionuclides, and to meet maximum contaminant levels (MCLs) for these contaminants, to comply with the Safe Drinking Water Act (SDWA). Currently, USEPA requires drinking water to meet MCLs for beta/photon emitters (includes gamma radiation), alpha particles, combined radium 226/228, and uranium. However, this monitoring is required only at entry points into the system. In addition, after the initial sampling requirements, only one sample is required every three to nine years, depending on the contaminant type and the initial concentrations. 

There are two basic approaches used to characterize seawater DOM (Benner, 2002). The first of these is to directly analyze bulk compositions (e.g., elemental or isotopic compositions) or individual compounds in the sample without concentration. This approach requires high-sensitivity methods for either broad biochemical types (e.g., total amino acids or carbohydrates) or individual compounds, often by either spectroscopic or chromatographic methods coupled to electrochemical or mass spectro-metric detectors. The latter type of molecular-level analyses are now feasible for measuring individual amino acids (Lindroth and Mopper, 1979), sugars (Skoog et al., 1999), and amino sugars (Kaiser and Benner,... 

The mass of sample taken for analysis is primarily dependent on four factors (1) the amount of material available, (2) the concentration of the analyte, (3) the heterogeneity of the sample, and (4) the method of analysis. Most conventional solvent extraction techniques currently start with more sample than is required, use more extraction solvent than is necessary, and ultimately only analyze 0.1% of the material prepared, e.g., 1 pi from 1 ml. Micro-extraction techniques [468] can be used in conjunction with on-line LC-GC or LC-MS to utilize the whole extract in the final determinations. This approach can significantly reduce the size of sample required and the volume of solvent used. Many workers have reported the use of solid phase microextraction (SPME) in different environmental matrices for various pollutants [288,342,345,469 - 477]. 

Several strategies have been described for the preconcentration of sample components present at low concentrations. These techniques include zone sharpening,28-29 on-line packed columns,30 and transient capillary isotachophoresis (cITP).31-32 Other standard laboratory techniques are often used, including solid-phase extraction, protein precipitation, ultrafiltration, etc. Two important points to keep in mind when selecting a concentration protocol are the sample requirements of the method and the potential selectivity on relative concentrations of sample components. The latter point applies to purity and concentration analysis. 

Many analyses of organic compounds in liquid samples require selective cleanup and concentration. Direct on-line coupling of sample preparation to the analytical instrumentation minimizes sample handling and thereby the risk for contamination or loss of analyte. Also, on-line coupling makes... 

Traditional macroscale NIR spectroscopy requires a calibration set, made of the same chemical components as the target sample, but with varying concentrations that are chosen to span the range of concentrations possible in the sample. A concentration matrix is made from the known concentrations of each component. The PLS algorithm is used to create a model that best describes the mathematical relationship between the reference sample data and the concentration matrix. The model is applied to the unknown data from the target sample to estimate the concentration of sample components. This is called concentration mode PLS . 

In the separation of biomolecules, sample preparation almost always involves the use of one or more pretreatment techniques. With high-performance liquid chromatography (HPLC), no one sample preparation technique can be appHed to all biological samples. Several techiques may be used to prepare the sample for injection. For example, complex samples require some form of preffactionation before analysis, samples that are too dilute for detection require concentration before analysis, samples in an inappropriate or incompatible solvent require buffer exchange before analysis, and samples that contain particulates require filtration before injection into the analytical instrument. 

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