Arsenic in urine

Landsberger S, Swift G, and Neuhoff J (1990) Nondestructive determination of arsenic in urine by epithermal neutron activation analysis and Compton suppression. Biol Trace Elem Res 26-27 27-32. 

Devoto 115)has described an indirect procedure for the determination of 0.1 ppm arsenic in urine. The arsenomolybdic acid complex is formed and extracted from 1 ml of urine at pH 2 into 10 ml of cyclohexanone. The molybdenum in the complex is then measured. Before extracting the arsenic, phosphate in the urine is separated by extracting the phosphomolybdic acid complex at pH 1 into isobutyl acetate. The direct determination of arsenic in biological material and blood and urine is best done using a nitrous oxide-acetylene flame 116>. The background absorption by this flame is low at 1937 A, and interferences are minimized due to the high temperature of the flame. 

R. B. Georgieva, P. K. Petrov, P. S. Dimitrov and D. L. Tsalev, Observations on toxicologically relevant arsenic in urine in adult offspring of families with Balkan endemic nephropathy and controls by batch hydride generation atomic absorption spectrometry, Int. J. Environ. Anal. Chem., 87(9), 2007, 673-685. 

The New Hampshire Department of Health and Human Services is determining blood mercury concentrations and related freshwater fish consumption, studying speciated arsenic in urine, and analyzing phthalates in urine and PBDEs in serum and breast milk (APHL 2004, 2006). In 2004, New Hampshire received about 300,000 to support its biomonitoring program (APHL 2004). 

Heitkemper, D., Creed, J., Davison, T., Caruso, J. and Fricke, F.L. (1989) Speciation of arsenic in urine using high performance liquid chromatography with inductively coupled plasma mass spectrometric detection./. Anal. At. Spectrom., 4, 279-284. 

When appropriately validated and understood, biomarkers present unique advantages as tools for exposure assessment (Gundert-Remy et al, 2003). Biomarkers provide indices of absorbed dose that account for all routes and integrate over a variety of sources of exposure (IPCS, 1993, 2001a). Certain biomarkers can be used to represent past exposure (e.g. lead in bone), recent exposure (e.g. arsenic in urine), and even future target tissue doses (e.g. pesticides in adipose tissue). Once absorbed dose is determined using biomarkers, the line has been crossed between external exposure and the dose metrics that reflect the pharmacokinetics and toxicokinetics of an agent (see section 5.3.3). 

Peter et al. [15] used an electrically heated quartz cell for the determination of arsenic in urine. Urine, 2 ml, was digested with 2 ml of nitric and perchloric acids (1 1). Aliquots of this solution were used for the subsequent arsine generation by sodium borohydride. The normal level of arsenic in urine was found to be less than lOppb. 

Atomic Absorption Assay for Arsenic in Urine In this method, the arsine generator is suitably connected to the atomic absorption spectrophotometer. 

The concentration of arsenic in urine from unexposed subjects is less than 0.05 ag/ml. In cases of chronic poisoning, values between 0.05 and 5 iLLg/ml may be found. Acute poisoning is usually associated with values in excess of 1 jLig/ml and may reach 20 ag/ml. 

FIGURE 20. Thin-layer chromatograms of arsenic in urine, faeces, blood and feed extract Au, authentic compounds A, arsenic acid B, DSMA C, DMAA (X, unknown). Faeces and urine are the second-day samples and blood is the fifth-day sample after treatment of MAF. The asterisk indicates the values in the faeces and blood are As /xg/g of sample weight and in the urine and feed are As g/10 g of sample weight. Reprinted with permission from Reference 178. Copyright (1978) American Chemical Society... 

Little available information on the organoarsenicals present in fish and other seafood may indicate that these compounds appear to be readily excreted in the urine in an unchanged chemical form, with most of the excretion occuring within 2 days of ingestion. Volunteers who consumed flounder excreted 75% of the ingested arsenic in urine within 8 days of eating the fish. 

The first requirement can be easily fulfilled by the preconcentration of the analyte before the analysis. Preconcentration has been applied to sample preparation for flame atomic absorption (25) and, more recently, for ICP (79,80) spectroscopy. However, preconcentration is not completely satisfactory, because of the increased analysis time (which may be critical in clinical analysis) and the increased chance of contamination or sample loss. Most important, however, a larger initial sample size is necessary. The apparent solution is a more sensitive technique. Table 2 lists concentrations of various metals in whole blood or serum (81,82) in comparison to limits of detection for the various atomic spectroscopy techniques. In many cases, especially for the toxic heavy metals, only flameless atomic absorption using a graphite furnace can provide the necessary sensitivity and accommodate a sample of only a few microliters (Table 1). The determination of therapeutic gold in urine and serum (83,84), chromium in serum (85), skin (86) and liver (87), copper in semen (88), arsenic in urine (89), manganese in animal tissues (90), and lead in blood (91) are but a few examples in analyses which have utilized the flameless atomic absorption technique. 

In routine analysis, arsenic in urine is usually determined. Recently, Karagas etal. (2002) proposed the use of toenail arsenic concentrations as a reliable biomarker of total As exposure reflecting arsenic intake by drinking water containing > 1 pg L kThe authors mentioned that urinary As may not be detected consistently in a population for which drinking water contents are primarily < 50 pg so that toenails may better provide risk information... 

Dang TMN, Tran QT and Vu KV (1999) Determination of arsenic in urine by atomic absorption spectrophotometry for biological monitoring of occupational exposure to arsenic. Toxicol Lett 108 179-183. 

Guo T, Baasner J and Tsalev DL (1997) Fast automated determination of toxicologically relevant arsenic in urine by flow injection-hydride generation atomic absorption spectrometry. Anal Chim Acta 349 313-318. 

Vahter M and Lind B (1986) Concentration of arsenic in urine of the general population in Sweden. Sci Total Environ 54 1-12. 

The table includes data for arsenic in the urine of nonexposed subjects (e.g. Smith et al., 1977 Buchet et al.. 1980 Norin and Vahter, 1981 Schierling et al., 1982 Valkonen et al.. 1983 Apel and Stoeppler, 1983 Stoeppler and Apel, 1984 Vahter and Lind, 1986 Foa et al.. 1987 Jensen et al.. 1991, Sabbioni et al.. 1992). Due to some intake of inorganic arsenic from marine food (seaweed) the inorganic arsenic in urine in Japan was reported to be somewhat elevated compared to data from Europe (Yamauchi and Yamamura, 1979). 

Total arsenic in urine was determined by the graphite furnace with Zeeman effect background correction. Using matrix modification with 5% nickel nitrate, sampie volumes of 20 /tL, charring up to 1500 °C, atomisation at 2800 °C. and using the standard addition method was reported to achieve a detection limit of 10 hqIL if the urine dilution factor (2) was considered (Edgar and Lum, 1983). 

The behaviour of As(lll) and As(V) in a graphite furnace during the individual steps of the temperature programme was studied by use of the radiotracer As for urine, human serum and hair solubilized with tetramethyl ammonium hydroxide (TMAH). Significant stabilization effects were observed if various metals, including nickel, were used as matrix modifiers. Thus experimental conditions for the determination of arsenic in urine, human serum and hair were optimized. For the determination of the hair soiution, charring at 1200 °C and atomization at 2400 °C were found to be optimal (Krivan and Arpadjan. 1989). 

Interlaboratory comparison studies have been reported on the analysis of total arsenic in urine in Canada (Savoie and Weber, 1983 Weber, 1986). Control samples were prepared by pooling urine samples from subjects ingesting seafood or As(lll) or by spiking urine samples with DMA or As(V). In the 1983-year study the average deviation from a "target value" (not further specified) was 30%. In the 1985-year study about 60% of the participating laboratories (about 40) reported results within 15% or 25, ug/L of the "target value". 

The results of an interlaboratory comparison programme operated since 1979 for several toxic substances in blood and urine by the Centre de Toxicologie de Quebec, Canada are summarized by Weber (1988). For urine arsenic, as for the other substances an increase of the number of participants with time could be seen. For arsenic in urine the relative standard deviation was concentration dependent and was lower for easily digested species (As(MI), As(V) than for resistant ones (e.g. seafood As). The success rate was approximately 60-70% for the inorganic arsenic and 40% for that of seafood origin. No chronological trend was apparent for the former but a slight downward trend could be seen for the latter. 

Apel, M., Stoeppler, M. (1983). Speciation of arsenic in urine of occupationally non-exposed persons, Proc. Int. Conf. Heavy Metals in the Environment. Vol. 1 p. 517-520, CEP Consultants, Edinburgh. 

Edgar, D.A. and Lum, K.R. (1983). Zeeman effect electrothermal atomic absorption spectrophotometry with matrix modification for the determination of arsenic in urine. Intern. J. Environ. Anal. Chem. 16, 219-226. 

Peter, F., Growoock, G. and Strunc, G. (1979). Determination of arsenic in urine by atomic absorption spectrometry with electrothermal atomization. Anal. Chim. Acta, 104, 177-180. 

TH Lin, YL Huang. Chemical speciation of arsenic in urine of patients with Black-foot disease. Biol Trace Elem Res 48 251-261, 1995. 

Gold miners had a number of arsenic-associated health problems including excess mortality from cancer of the lung, stomach, and respiratory tract. Miners and schoolchildren in the vicinity of gold mining activities had elevated urine arsenic of 25.7 p,g/L (range 2.2-106.0 p-g/L). Of the total population at this location, 20% showed elevated urine arsenic concentrations associated with future adverse health effects arsenic-contaminated drinking water is the probable causative factor of elevated arsenic in urine. 

Table I. Mean Concentration ( 1 Standard Deviation) of Arsenic in Urine from Forest Workers at 2, 3, 4, 7, and 8 Weeks of a 9-Week...

Table II. Mean Concentration of Arsenic in Urine from Forest Workers Applying MSMA or Cacodylic Acid via the Hack and Squirt Method in Operational Precommercial Tree Thinning (11)...

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