Carbon compounds quantification

Anthony, E. J., Bulewicz, E. M., Dudek, K. Kozak, A. 2002. The long term behaviour of CFBC ash-watersystems. Waste Management, 22,99-111. Bauer, C. F. Natlsch, D. F. S. 1981. Identification and quantification of carbonate compounds in coal fly ash. Environmental Science and Technology, 15, 783-788. 

Analytical Approaches. Different analytical techniques have been appHed to each fraction to determine its molecular composition. As the molecular weight increases, complexity increasingly shifts the level of analytical detail from quantification of most individual species in the naphtha to average molecular descriptions in the vacuum residuum. For the naphtha, classical techniques allow the isolation and identification of individual compounds by physical properties. Gas chromatographic (gc) resolution allows almost every compound having less than eight carbon atoms to be measured separately. The combination of gc with mass spectrometry (gc/ms) can be used for quantitation purposes when compounds are not well-resolved by gc. 

Simultaneous quantification of the herbicides atra2ine, sima2ine, terbut5la2ine, propa2ine, and prometryne and their principal metabohtes has been reported in natural waters at 3—1500 ng/L concentration (104). The compounds were enriched on graphiti2ed carbon black and analy2ed with hplc and a diode array uv detector. 

The identification and quantification of potentially cytotoxic carbonyl compounds (e.g. aldehydes such as pentanal, hexanal, traw-2-octenal and 4-hydroxy-/mAW-2-nonenal, and ketones such as propan- and hexan-2-ones) also serves as a useful marker of the oxidative deterioration of PUFAs in isolated biological samples and chemical model systems. One method developed utilizes HPLC coupled with spectrophotometric detection and involves precolumn derivatization of peroxidized PUFA-derived aldehydes and alternative carbonyl compounds with 2,4-DNPH followed by separation of the resulting chromophoric 2,4-dinitrophenylhydrazones on a reversed-phase column and spectrophotometric detection at a wavelength of378 nm. This method has a relatively high level of sensitivity, and has been successfully applied to the analysis of such products in rat hepatocytes and rat liver microsomal suspensions stimulated with carbon tetrachloride or ADP-iron complexes (Poli etui., 1985). 

Table 2.7 lists techniques used to characterise carbon-blacks. Analysis of CB in rubber vulcanisates requires recovery of CB by digestion of the matrix followed by filtration, or by nonoxidative pyrolysis. Dispersion of CB within rubber products is usually assessed by the Cabot dispersion test, or by means of TEM. Kruse [46] has reviewed rubber microscopy, including the determination of the microstructure of CB in rubber compounds and vulcanisates and their qualitative and quantitative determination. Analysis of free CB features measurements of (i) particulate and aggregate size (SEM, TEM, XRD, AFM, STM) (ii) total surface area according to the BET method (ISO 4652), iodine adsorption (ISO 1304) or cetyltrimethylammonium bromide (CTAB) adsorption (ASTM D 3765) and (iii) external surface area, according to the dibutylphthalate (DBP) test (ASTM D 2414). TGA is an excellent technique for the quantification of CB in rubbers. However, it is very limited in being able to distinguish the different types of... 

This is an analytical technique used to obtain accurate quantification of the principal compound constituents such as plasticiser, polymer, carbon black and inorganic species, by monitoring weight loss across a temperature range. 

GC is coupled with many detectors for the analysis of pesticides in wastewater. At the present time the most popular is GC-MS, which will be discussed in more detail later in this section. The flame ionization detector (FID) is another nonselective detector that identifies compounds containing carbon but does not give specific information on chemical structure (but is often used for quantification because of the linear response and sensitivity). Other detectors are specific and only detect certain species or groups of pesticides. They include electron capture,nitrogen-phosphorus, thermionic specific, and flame photometric detectors. The electron capture detector (ECD) is very sensitive to chlorinated organic pesticides, such as the organochlorine compounds (OCs, DDT, dieldrin, etc.). It has a long history of use in many environmental methods,... 

Gas chromatography is especially useful for gas-phase analysis of partial oxidation, hydrogenation, or hydroconversion products as in many cases a full carbon balance (educts, products, and all side products), in order to evaluate sample performance. As the detection and quantification of permanent gases such as N2, 02, CO, and C02 and also of higher boiling compounds are standard separation problems for gas chromatography, it is wise to employ the method regarding this problem. 

MS can measure the ratio between molar fractions of mass isotopomers. The ratio between two mass isotopomer pools of masses nti and m2 is defined in the present work as intensity ratio Jmi/m2- K identical with a mass spectral intensity ratio. If more than two mass isotopomer pools are assessed, their relative ratios, normalized to the sum, are named mass isotopomer distribution. The mass distribution of a compound can be thus obtained from the analysis of ions, which contain the intact carbon skeleton of the analyte. In the area of me-tabohc flux analysis, mass distributions of various metaboHtes have been assessed by MS. The major method used is GC/MS, whereby the analytes are deriva-tized into forms with desired physico-chemical properties such as increased volatihty, thermal stabiHty and suitable MS properties [62]. The mass of the formed derivate must be sufficiently high (usually above 175 apparent mass units) to avoid background interference [48]. To obtain the mass distribution of a compound, ions with the entire carbon skeleton of the analyte have to be present. For accurate quantification of the mass distribution of such ions, they should occur in high abundance and preferably be unique species, thus being formed by only one fragmentation pathway. 

Analytical methods for monitoring the compounds were developed or modified to permit the quantification of all 23 compounds of interest. As noted earlier, the compounds were initially studied in small-scale extractions by groups. This approach assured minimal interferences in the analyses conducted during the initial supercritical fluid carbon dioxide extractions. Table II summarizes the data on the recovery of organics from aqueous samples containing the compounds of interest at concentration levels listed in Table I when the sample preparation techniques and analytical methods described were used. For each experimental run, blank and spiked aqueous samples were carried through the sample prepration and analytical finish steps to ensure accurate and reproducible results. Analyses of sodium, calcium, and lead content were also conducted on selected samples by using standard atomic ab-... 

Azetidine-2-carboxylic acid (2) like proline gives an intense blue color with sodium nitroprusside in 10% acetaldehyde solution in the presence of sodium carbonate. 98,99 Upon usual acid hydrolysis (6M HC1, 110 °C, 24 h or more) as required for amino acid analysis, azetidine-2-carboxylic acid is completely decomposed, yielding mainly homoserine lactone, as well as other ninhydrin-positive compounds. 87,89,99 To enable an accurate quantification of this imino acid, azetidine-2-carboxylic acid peptides should be hydrolyzed by alkali (5M barium hydroxide, at 100 °C for 18 h 89 or 2 M sodium hydroxide at 110°C for 22h 100 ). There are extensive NMR spectroscopic data available 100-104 and the absolute configurations of A-acetyl-L-azetidine-2-carboxylic acid 105 and A-terf-butoxycarbonyl-L-azetidine-2-car-boxylic acid 106 have been determined by X-ray analysis. 

The radical "OH in surface waters is quickly consumed by organic compounds, bicarbonate, carbonate, and nitrite. It has a typically low steady-state concentration of around 10"16 M. For this reason it cannot be directly detected, and quantification in laboratory experiments is usually carried out by means of reactions of known kinetics. The formation of phenol from benzene, of 4-hydroxybenzoic from benzoic acid, and the disappearance of nitrobenzene are suitable systems if intermediate monitoring is carried out by liquid chromatography, while the disappearance kinetics of butyl chloride is suitable for headspace sampling and gas-chromato-graphic analysis [64]. 

Ultrafiltration was applied to examine the size fractionation of Al, Ca, Cu, Fe, K, Na, and Pb in white and red wines [91]. Metal determinations were performed on the unfiltered wine, the 0.45 p,m membrane-filtered wine and each ultrafiltrate fraction. Aluminum was determined by ET-AAS, while FAAS was employed for Cu and Fe. An electroanalytical technique, stripping potentiometry, was selected for Pb measurement, whereas flame photometry was chosen for K and Na quantification. Fractionation patterns were evaluated and discussed. Castineira et al. [92] combined on-line tangential-flow multistage ultrafiltration with a home-built carbon analyzer and ICP-MS for size fractionation of nonvolatile dissolved organic compounds and metal species in three German white wines. The study showed that the major part of the elements investigated (up to 25) were dissolved in the size fraction of < 1 kDa, with the exception of Ba, Pb, and Sr, which also appeared in other fractions. 

The chemical half-life of DMSP in seawater is >8 years (Dacey and Blough 1987), which results in high abiotic stability under natural conditions (moderate temperatures and pH). Therefore, most of the DMSP removal is through enzymatic processes. In the microbial food web, dissolved DMSP has many fates and several recent reviews on the microbial pathways and involved mechanisms have been published (Bentley and Chasteen 2004 Kiene et al. 2000 Lomans et al. 2002 Yoch 2002). They all show that DMSP can be readily used in a complex network of enzymatic conversions. This versatility indicates that this single compound is of major importance for the nutrition of the bacterial community. Indeed, several studies have shown that DMSP alone can contribute 1 to 15% of the total bacterial carbon demand in surface waters. Moreover, DMSP assimilation can satisfy most, if not all the, sulphur demand of marine bacteria (Kiene and Linn 2000 Simo et al. 2002 Zubkov et al. 2001). Since the focal point of this section is the quantification of DMSP removal, only the overall effects of the main pathways originating from DMSP (Fig. 1) will be discussed here. 

Due to the discovery of two further urinary metabolites of ramipril (the respective diketopiperazine derivatives of ramipril and ramiprilat), the above-described method was slightly modified (Schmidt et al. 1985). Instead of the rather time consuming second extraction step by means of a disposable Si column, the sample is cleaned by a liquid/liquid extraction step. After methylation of the compounds with diazomethane, the eluate is evaporated to dryness at 40 °C under N2 gas. Subsequently the residue is dissolved in n-pentane/diethyl ether (3 2. v/v) and washed with 5% hydrogen carbonate solution. After separation of the upper organic layer, this is evaporated to dryness at 40 °C under N2 gas and then treated with 1 mL n-hexane/TFAA (5%) as described before (Hajdu et al. 1984). This method allows the selective determination of ramipril and its three metabolites in human urine the limit of quantification amounted to 0.020 xg/mL for each of all four analytes. Using this assay, thousands of urine samples originating from phase I—III clinical studies were analysed. 

It was shown that the spectroscopic detection is influenced by the varying optical properties of the solvent and by the solvatochromic behavior of the nitroaromatic compounds at different CO2 densities. These specific effects have to be known for a accurate spectroscopic identification and quantification of analytes dissolved in sub- and supercritical carbon dioxide... 

Together with details of sample preparation and storage, an appropriate analytical method of known accuracy, precision, and sensitivity must be available for the quantification of the substance in the test solution and in the biological material. If these are lacking it is impossible to determine a true BCF. The use of radiolabelled test substance can facilitate the analysis of water and fish samples. However, unless combined with a specific analytical method, the total radioactivity measurements potentially reflect the presence of parent substance, possible metabolite(s), and possible metabolized carbon, which have been incorporated in the fish tissue in organic molecules. For the determination of a true BCF it is essential to clearly discriminate the parent substance from possible metabolites. If radiolabelled materials are used in the test, it is possible to analyse for total radio label (i.e. parent and metabolites) or the samples may be purified so that the parent compound can be analysed separately. 

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