Human spectrometry

Methods. As discussed in the previous chapter, a number of approaches have been used to assess the presence of potentially toxic trace elements in water. The approaches used in this assessment include comparative media evaluation, a human health and aquatic life guidelines assessment, a mass balance evaluation, probability plots, and toxicity bioassays. Concentrations of trace elements were determined by atomic absorption spectrometry according to standard methods (21,22) by the Oregon State Department of Environmental Quality and the U.S. Geological Survey. 

Figure 5.67 Reconstructed ion chromatograms for Idoxifene and internal standard (ds-Idoxifene using LC-ToF-MS for (a) double-blank human plasma extract, (b) extract of blank human plasma containing internal standard (IS), and (c) control-blank human plasma spiked with Idoxifene at 5 gml , the LOQ of the method. Reprinted from 7. Chromatogr., B, 757, Comparison between liquid chromatography-time-of-flight mass spectrometry and selected-reaction monitoring liquid chromatography-mass spectrometry for quantitative determination of Idoxifene in human plasma , Zhang, H. and Henion, J., 151-159, Copyright (2001), with permission from Elsevier Science.

Huelsemann F., Flenker, U., Koehler, K, Schaenzer, W. (2009). Effect of a controlled dietary change on carbon and nitrogen stable isotope ratios of human hair. Rapid Communications in Mass Spectrometry Vol 23, pp. 2448-2454. 

A new technique has been developed to analyze a- and (3-endosulfan concentrations in human urine (Vidal et al. 1998). Samples are mixed with a buffer solution and then passed through solid phase extraction cartridges for analysis using gas chromatography-tandem mass spectrometry (GC-MS-MS). 

GC/MS has been employed by Demeter et al. (1978) to quantitatively detect low-ppb levels of a- and P-endosulfan in human serum, urine, and liver. This technique could not separate a- and P-isomers, and limited sensitivity confined its use to toxicological analysis following exposures to high levels of endosulfan. More recently, Le Bel and Williams (1986) and Williams et al. (1988) employed GC/MS to confirm qualitatively the presence of a-endosulfan in adipose tissue previously analyzed quantitatively by GC/ECD. These studies indicate that GC/MS is not as sensitive as GC/ECD. Mariani et al. (1995) have used GC in conjunction with negative ion chemical ionization mass spectrometry to determine alpha- and beta-endosulfan in plasma and brain samples with limits of detection reported to be 5 ppb in each matrix. Details of commonly used analytical methods for several types of biological media are presented in Table 6-1. 

Vidal JEM, Arrebola PJ, Pemandez-Gufierrez A, et al. 1998. Determination of endosulfan and its metabolites in human urine using gas chromatography-tandem mass spectrometry. J Chromatogr 719 71-78. 

A glyceryl 2-aminoethylphosphonolipid has been isolated from Tetrahymenapyriformis and (45) has been detected by g.l.c.-mass spectrometry in both the lipid and proteinaceous fractions of human brain. The zwitterionic (45) was converted into volatile (46) by acetylation and methylation. Phosphonolipids derived from A-methyl-(45) have been synthesised by acetylation of A-methyl-(45) and subsequent conversion to the phosphorochloridate for the phosphorylation step. °... 

CANFIELD w K (1993). Study of beta-carotene metabolism in humans using 13C-beta-carotene and high precision isotope ratio mass spectrometry. Annals of the New York Academy of Sciences 691 86-95. 

DALLUGE J J, NELSON B c, THOMAS J B, WELCH M J and SANDER L c (1997) Capillary liquid chromatography/electrospray mass spectrometry for the separation and detection of catechins in green tea and human plasma , Rapid Commun Mass Spectrom, 11, 1753-6. 

Kucuk, O. et al.. Effects of lycopene supplementation in patients with localized prostate cancer, Exp. Biol. Med. (Maywood), 227, 881, 2002. van Breemen, R.B. et al.. Liquid chromatography-mass spectrometry of cis- and all-trans-lycopene in human serum and prostate tissue after dietary supplementation with tomato sauce, J. Agric. Food Chem., 50, 2214, 2002. 

For human studies, the choice of stable isotopes is limited because radioisotopes are associated with ionization radiation and thus with some potential harmful effects for humans. Studying the bioavailability of compounds labeled with stable isotopes requires complex techniques such as gas chromatography coupled with mass spectrometry (GC-MS), liquid chromatography coupled with MS (LC-MS), and atmo-... 

Kessler A, Siekmann L (1999) Measurement of urea in human serum by isotope dilution mass spectrometry. A reference procedure. Clin Chem 45 1523-1529. 

SlEKMANN L (1985) Determination of creatinine in human serum by isotope dilution mass spectrometry a definitive method in clinical chemistry. J Clin Chem Clin Biochem 23 137-144. Singer R, Danzer K (1984) Homogenitatsuntersuchungen von Festkorpem mit Hilfe linearer Regressionsmodelle. Z Chemie 24 339-341. 

Calcium exists in the human body as Ca(II) protein-bound and free Ca (II) ions (Dilana et al. 1994). For total extracellular Ca in plasma, serum and urine a definitive isotope dilution-mass spectrometry (ID-MS) method exist. Free Ca(II) in plasma/serum can be determined with PISE, but no definitive and reference methods exist. For Ca in faeces, tissue and blood flame atomic absorption (FAAS) is used widely. 

When pushed to the limit by overriding human health concerns, residue chemists have achieved detection limits of Ippt (Ingkg ) or even into the low ppqr (1 pg kg ) range. An example at the 1 ppt level is provided by methods for 2,3,7,8-tetrachlorodibenzodioxin (TCDD) in milk and TCDD in adipose tissue. Eor relatively clean matrices such as water and air, preconcentration on solid-phase adsorbents followed by GC or gas chromatography/mass spectrometry (GC/MS) can provide detection limits of 1 ng m and less for air (examples in Majewski and Capel ) and 1 ngL and less for water (examples in Larson et A summary of units of weight and concentration used to express residue data is given in Table 1. 

Guidance for Industry No. 118 Mass Spectrometry for Confirmation of the Identity of Animal Drug Residues DRAFT GUIDANCE June6,2001, US Department of Health and Human Services, Public Health Service, Pood and Drug Administration, Center for Veterinary Medicine, RockvUle, MD (2001). 

Goldstein SJ, Murrell MT, Janecky DR (1989) Th and U isotopic systematics of basalts from the Juan de Fuca and Gorda Ridges by mass spectrometry. Earth Planet Sci Lett 96 134-146 Goldstein SJ, Rodriguez JM, Lujan N (1997) Measurement and application of uranium isotopes for human and enviromnental monitoring. Health Phys 72 10-18... 

Schwarcz HP, Simpson JJ, Stringer CB (1998) Neanderthal skeleton from Tabun U-series data by ganuna-ray spectrometry. J Human Evol 35 635-645... 

Embrechts, J. Lemiere, F. Dongen, W. V. Esmans, E. L. Buytaert, P. van Marck, E. Kockx, M. Makar, A. Detection of estrogen DNA-adducts in human breast tumor tissue and healthy tissue by combined nano LC-nano ES tandem mass spectrometry. J. Am. Soc. Mass Spec from. 2003, 14, 482M-91. 

Dear, G.J., Fraser, I.J., Patel, D.K., Long, J., and Pleasance, S., Use of liquid chromatography-tandem mass spectrometry for the quantitative and qualitative analysis of an antipsychotic agent and its metabolites in human plasma and urine, /. Chromatogr. A, 794, 27, 1998. 

As a more sensitive detection method, MS can be very useful in amino acid determinations. For example, S-carboxymethyl-(R) cysteine or SCMC, is a mucolytic agent used in the treatment of respiratory diseases. The development of a method utilizing high performance IEC and atmospheric pressure ionization (API) mass spectrometry to quantify SCMC in plasma has been described.66 This method is simple (no derivatization needed), rapid (inn time 16 min.), sensitive (limit of quantification 200 ng/mL in human plasma), and has an overall throughput of more than 60 analyses per day. API-MS was used successfully with IEC to determine other sulfur-containing amino acids and their cyclic compounds in human urine.67 IEC has also been used as a cleanup step for amino acids prior to their derivatization and analysis by gas chromatography (GC), either alone or in conjunction with MS.68 69... 

Anacardio, R., Cantalini, M.G., De Angelis, F., and Gentile, M., Quantification of S-carboxymethyl-(R)-cysteine in human plasma by high-performance ion-exchange liquid chromatography/atmospheric pressure ionization mass spectrometry, /. Mass Spectrom., 32, 388, 1997. 

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