Minimum detection limits

High power pulsed lasers are used to produce plasmas and thus to sample and excite the surfaces of soHds. Improvements in minimum detectable limits and decreases in background radiation and in interelement interference effects result from the use of two lasers (99) (see Surface and interface analysis). 

Environment. Detection of environmental degradation products of nerve agents directly from the surface of plant leaves using static secondary ion mass spectrometry (sims) has been demonstrated (97). Pinacolylmethylphosphonic acid (PMPA), isopropylmethylphosphonic acid (IMPA), and ethylmethylphosphonic acid (EMPA) were spiked from aqueous samples onto philodendron leaves prior to analysis by static sims. The minimum detection limits on philodendron leaves were estimated to be between 40 and 0.4 ng/mm for PMPA and IMPA and between 40 and 4 ng/mm for EMPA. Sims analyses of IMPA adsorbed on 10 different crop leaves were also performed in order to investigate general apphcabiflty of static sims for... 

The minimum detectable limit has been determined to be 3.4 mg of SO9 per cubic meter of gas (2.1 X 10" lb of SO9 per cubic foot of gas). Although no upper hmit has been established, the theoretical upper concentration umit in a 20-liter sample is about 93,300 mg/m. ... 

The minimum detectable limit depends on the analytical range, span, and signal-to-noise ratio of the measurement system. For a well-designed system, the minimum detectable limit should be less than 2 percent of the span. 

With modern detectors and electronics most Enei -Dispersive X-Ray Spectroscopy (EDS) systems can detect X rays from all the elements in the periodic table above beryllium, Z= 4, if present in sufficient quantity. The minimum detection limit (MDL) for elements with atomic numbers greater than Z = 11 is as low as 0.02% wt., if the peaks are isolated and the spectrum has a total of at least 2.5 X 10 counts. In practice, however, with EDS on an electron microscope, the MDL is about 0.1% wt. because of a high background count and broad peaks. Under conditions in which the peaks are severely overlapped, the MDL may be only 1—2% wt. For elements with Z < 10, the MDL is usually around 1—2% wt. under the best conditions, especially in electron-beam instruments. 

The minimum detection limit, MDL, of an isolated peak on a uniform background is proportional to the square root of the FWHM. So a 20% reduction in spectrometer resolution will produce about a 10% improvement in MDL. If there is peak overlap, however, then it can be shown that a 20% improvement in resolution can reduce the interference between overlapping peaks by a factor of 3, which gives about a 50% improvement in MDL. 

Principles and Characteristics As mentioned already (Section 3.5.2) solid-phase microextraction involves the use of a micro-fibre which is exposed to the analyte(s) for a prespecified time. GC-MS is an ideal detector after SPME extraction/injection for both qualitative and quantitative analysis. For SPME-GC analysis, the fibre is forced into the chromatography capillary injector, where the entire extraction is desorbed. A high linear flow-rate of the carrier gas along the fibre is essential to ensure complete desorption of the analytes. Because no solvent is injected, and the analytes are rapidly desorbed on to the column, minimum detection limits are improved and resolution is maintained. Online coupling of conventional fibre-based SPME coupled with GC is now becoming routine. Automated SPME takes the sample directly from bottle to gas chromatograph. Split/splitless, on-column and PTV injection are compatible with SPME. SPME can also be used very effectively for sample introduction to fast GC systems, provided that a dedicated injector is used for this purpose [69,70],... 

Table 8.25 Principal spectral emission lines, minimum detectable limits, and linear dynamic range of some commonly monitored elements in GC-AED...

Dynamic range Minimum detection limit Precision Accuracy... 

Polymer Additive Functionality" Solvent Matrix modification Minimum detection limit ... 

It is apparent that PIXE exhibits its maximum sensitivity or minimum detection limit (MDL) in the two atomic number regions 20 < Z < 35 and 75 < Z < 85. These are attained at relatively low proton energies, which implies that small accelerators are most suitable for PIXE with the corresponding benefits in reliability and economics. Analysis times are typically a few minutes in duration. The MDL is very strongly influenced by the nature of the sample, especially if there are strong X-rays from the matrix visible in the spectrum or if the sample is strongly insulating. 

Williams et al. (2002) have reviewed the current state of AEM X-ray microanalysis, and they suggest ways in which the highest resolution of X-ray mapping may be achieved in the STEM with an EDS spectrometer. Because of their small collection angles and thin specimens, very small numbers of X-ray counts are generated, so the minimum detection limit is typically at best 0.1 wt%. This value is an order of magnitude worse than the 0.01 wt% figure for bulk-specimen in an SEM/EPMA. 

The pollutants characteristic of the industry wastewaters are summarized in Table 5.4 through Table 5.11, for both classical and toxic pollutants. The toxic pollutant data have been developed using a verification protocol established by U.S. EPA, with the exception of the following selenium, silver, thallium, and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCCD). Table 5.12 presents the minimum detection limit for the toxic pollutants. Any value below the minimum limit is listed in the summary tables as below detection limit (BDL). 

Wastewaters generated from manufacturing plants that produce or use inorganic chemicals vary considerably, depending on raw materials, type of process, and the end product, among others. A screening program is often conducted to determine the presence, concentration, and toxicity of metal ions in such wastewaters. The minimum detection limits for the toxic metals are presented in Table 22.1. 

Minimum Detection Limits for Some Toxic Metals... 

The limitations of ELISA methods include the specificity of antibodies, the concentrations of primary antibody and antigen, and the type of reaction solution. Nonspecific binding of either of the antibodies to related antigens, unrelated proteins of other bacteria, or even the microtiter plate may lead to false positive reactions.49,52 57 Use of a monoclonal antibody may decrease crossreactivity with other antigens. For detection of low numbers of bacteria, as in drinking water, the sample may be filtered to concentrate the cells or cultured in a selective broth until it reaches the minimum detection limit for ELISA.49,58 Commercial test kits using dipsticks, immunoblots, and sandwich ELISA methods have been developed for the identification of pathogenic bacteria.58,59... 

Systematic error is also known as bias. The bias is the constant value difference between a measured value (or set of values) and a consensus value (or true value if known). Specificity is the analytical property of a method or technique to be insensitive to interferences and to yield a signal relative to the analyte of interest only. Limit of reliable measurement predates the use of minimum detection limit (MDL). The MDL... 

Luther et al. [92] have described a procedure for the direct determination of iodide in seawater. By use of a cathodic stripping square-wave voltammetry, it is possible to determine low and sub-nanomolar levels of iodide in seawater, freshwater, and brackish water. Precision is typically 5% (la). The minimum detection limit is 0.1 - 0.2 nM (12 parts per trillion) at 180 sec deposition time. Data obtained on Atlantic Ocean samples show similar trends to previously reported iodine speciation data. This method is more sensitive than previous methods by 1-2 orders of magnitude. Triton X-100 added to the sample enhances the mercury electrode s sensitivity to iodine. 

The calibration curves for fructose were compared between PP/FDH/Pt and PP/FCN/FDH/Pt electrodes (prepared by the two-step method) [Fig.23]. In both cases, the response current was directly proportional to fructose concentration up to 10 mM and with a detection range of up to 30mM fructose. The minimum detection limit was 10 //M and 5 mM in the case of PP/FDH/Pt and PP/FCN/FDH/Pt electrodes, respectively. The slope of the linearity was about 80 nA/mM and 450 nA/mM, respectively. 

One of the most commonly used detection systems in a gas chromatography laboratory is the electron capture detector. The first paper [25] to be published demonstrating the use of an electron capture detector with supercritical fluid chromatography showed that with supercritical fluid chromatography sensitivity to about 50pg minimum detection limit on column was obtainable. 

A wide variety of commercial equipment is available for detection of hazardous chemicals, including a number of chemical warfare agents. For example, ion mobility spectroscopy is used to detect nerve, blister, and blood agents. The Chemical Agent Monitor is a portable, hand-held point detection instrument that uses ion mobility spectrometry to monitor nerve or blister agent vapors. However, minimum detection limits are approximately 100 times the acceptable exposure limit for nerve agents, and approximately 50 times the acceptable exposure limit for blister agents. 

The method detection limit is, in reality, a statistical concept that is applicable only in trace analysis of certain types of substances, such as organic pollutants by gas chromatographic methods. The method detection limit measures the minimum detection limit of the method and involves all analytical steps, including sample extraction, concentration, and determination by an analytical instrument. Unlike the instrument detection limit, the method detection limit is not confined only to the detection limit of the instrument. 

Optimal assessment of the minimum detection limit would require a design x well below the current standard concentrations and including the blank. 

Figure 1.4 Comparison of the application ranges of techniques that are sensitive to nearsurface strains. Minimum detection limits are plotted against depth resolution of the measurement. XRD X-ray diffraction DOR differential optical reflectometry. RBS Rutherford back scattering MEIS medium energy ion scattering TEM transmission electron microscopy...

Polished thin sections or iron oxides grains polished in epoxy mounts were analyzed using Universite Laval CAMECA SX-100 5-VVDS electron microprobe under a beam of 15 kV at 100 nA, using a range of natural and synthetic standards. After counting over the peak for 20 to 30 sec, background is measured on both sides for 10 sec. These settings yield minimum detection limits (mdl) as low as 20 ppm for elements such as K, Ca, Al, Si, Ti and Mg, 50 ppm for Mn, Cr and V, 200 ppm for Cu,... 

Elemental mass distribution - The aerosol sampled by the LPI for elemental analysis was impacted on coated mylar films affixed to 25 mm glass discs. The mylar had been coated with Apiezon L vacuum grease to prevent particle bound. The LPI samples were sent to Crocker Nuclear Laboratory for elemental analysis by PIXE using a focused alpha particle beam of 3 to 4 mm diameter. Nanogram sensitivities for most elements were achieved with the focused beam. A detailed description of the PIXE focused beam technique applied to LPI samples can be found in Ouimette (13). Based upon repeated measurements of field samples, the estimated measurement error was about 15-20% or twice the minimum detection limit, whichever was larger. 

Poorer accuracy is to be expected at the low levels because the uncertainty of the measurement rises as the minimum detection limit is approached. Laboratory B reported better overall accuracy than laboratory A, particularly for the OCs. 

Atmospheric argon-37 has been measured in the counter at a concentration of about 40 times the estimated cosmic particle concentration. The minimum detectable limit for measuring argon at 10 atm. for a 1000-minute counting is 0.1 d.p.m./meter3 air, or about two times the cosmic particle-produced concentration in the troposphere. It should be possible to measure cosmic particle produced argon in the stratosphere. 

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