title: A sensitive flow-based procedure for spectrophotometric speciation analysis of inorganic bromine in waters.
abstract: A flow-based system with solenoid micro-pumps and long path-length spectrophotometry for bromate and bromide determination in drinking water is proposed. The method is based on the formation of an unstable dye from the reaction between bromate, 2-(5-dibromo-2-pyridylazo)-5-(diethylamino)phenol (5-Br-PADAP) and thiocyanate ions. A multivariate optimization was carried out. A linear response was observed between 5.0 and 100 µg L(-1) BrO3(-) and the detection limit was estimated as 2.0 µg L(-1) (99.7% confidence level). The coefficient of variation (n=20) and sampling rate were estimated as 1.0% and 40 determinations per hour, respectively. Reagent consumption was estimated as 0.17 µg of 5-Br-PADAP and 230 μg of NaSCN per measurement, generating 6.0 mL of waste. Bromide determination was carried out after UV-assisted conversion with K2S2O8 using 300 µL of sample within the range 20-400 µg L(-1) Br(-). The generated bromate was then determined by the proposed flow system. The results for tap and commercial mineral water samples agreed with those obtained with the reference procedure at the 95% confidence level. The proposed procedure is therefore a sensitive, environmentally friendly and reliable alternative for inorganic bromine speciation.
authors.affiliation: Centro de Energia Nuclear na Agricultura, Universidade de São Paulo, PO Box 96, 13400-970, Piracicaba, SP, Brazil.
authors.forename: Diogo L
authors.initials: DL
authors.lastname: Rocha
authors.affiliation: Centro de Energia Nuclear na Agricultura, Universidade de São Paulo, PO Box 96, 13400-970, Piracicaba, SP, Brazil.
authors.forename: Marcos C
authors.initials: MC
authors.lastname: Machado
authors.affiliation: Escola Superior de Agricultura "Luiz de Queiroz", Universidade de São Paulo, PO Box 9, 13418-970, Piracicaba, SP, Brazil. Electronic address: wanemelc@usp.br.
authors.forename: Wanessa R
authors.initials: WR
authors.lastname: Melchert
mesh_terms: D001391:Azo Compounds / Q000737:chemistry; D001965:Bromides / Q000737:chemistry; D001966:Bromine / Q000032:analysis*; D002712:Chlorides / Q000737:chemistry; D016014:Linear Models; D010100:Oxygen / Q000737:chemistry; D010777:Photochemistry / Q000379:methods; D015203:Reproducibility of Results; D013056:Spectrophotometry, Ultraviolet / Q000379:methods*; D013431:Sulfates / Q000737:chemistry; D013861:Thiocyanates / Q000737:chemistry; D014466:Ultraviolet Rays; D014867:Water / Q000032:analysis / Q000737:chemistry; D014874:Water Pollutants, Chemical / Q000032:analysis*; D014881:Water Supply
chemical_list: D001391:Azo Compounds; D001965:Bromides; D002712:Chlorides; D013431:Sulfates; D013861:Thiocyanates; D014874:Water Pollutants, Chemical; D014867:Water; C037882:2-(5-bromo-2-pyridylazo)-5-diethylaminophenol; D010100:Oxygen; D001966:Bromine
keywords: Bromate; Bromide; Long path-length spectrophotometry; Multi-pumping; Speciation; UV digestion