Determination of triphenyltin hydroxide and its degradation products in water

Abstract

An analytical method has been developed for the simultaneous determination of triphenyltin hydroxide and its possible degradation products tetraphenyitin, diphenyitin oxide, benrenestannoic acid, and inorganic tin in water. The method Is rapid (one sample set per hour), sensitive to less than 0.01 wg/mL for most of the tin species, exhibits no cross-interferences between the phenyltins, and requires no elaborate equipment. The phenyltins are detected by electron-capture gas-liquid chromatography after conversion to their hydride derivatives, while inorganic tin is determined by a procedure which responds to tin(1V) oxide as well as aqueous tin(1V) cation, a procedure not previously described in the literature.Triphenyltin hydroxide (Duter) is a member of the organotin class of agricultural chemicals which also includes tricyclohexyltin hydroxide (Plictran) and triphenyltin acetate (Brestan), and is currently registered under a experimental-use permit in California as a fungicide in rice culture. As part of a study of the chemicals used in rice culture ( I , Z), we are examining the environmental fate of Duter (3).In order t o obtain information necessary to establish the fate of triphenyltin hydroxidefor example, photodegradation products and hydrolytic stability-it was essential to have an analytical method that (a) was capable of differentiating the parent compound and its degradation products, (b) was sensitive to sub-pg/mL levels in water, and (c) utilized readily available instrumentation. None of the over 140 methods concerning organotin analysis listed in a 1970 bibliography (4) or those in the more recent literature (5) adequately met these criteria. For example, the colorimetric procedures of Corbin (6, 7) were sensitive and utilized simple instrumentation but lacked specificity; the anodic stripping voltammetry method of Booth and Fleet (8) was specific for triphenyltin but required elaborate equipment; and the gas-liquid chromatography (GLC) procedure of Gauer et al. (9), while specific for various cyclohexyltin bromides, was not adaptable to the phenyltin analogues because of the low volatility of the phenyltin bromide derivatives.From previous studies on other organotin compounds ( I O , I I ) , it appeared that diphenyltin oxide (Ph2Sn0, where P h = phenyl), benzenestannoic acid (PhSnOzH), and inorganic tin would be likely degradation products of triphenyltin hydroxide (Ph3SnOH). (Current Chemical Abstracts nomenclature as follows: PhSnOzH, hydroxyoxophenyl stannane; PhzSnO, oxodiphenyl stannane; Ph,SnOH, hydroxytriphenyl stannane.) None of these compounds responded well to GLC, primarily because of their nonvolatile nature, and attempts to overcome this difficulty by conversion of the phenyltins to their corresponding halide, acetate, or methylether derivatives were unsuccessful. However, preparation of the hydride series, which are the most volatile and least ionic phenyltins possible, resulted in derivatives with excellent 'Present address, California Analytical Labs, Sacramento, Calif. 95814. Sc...

Degradation of the tri-n-butyltin species in water

“…This procedure yields quantitative recoveries for Bu3Sn+ (from either TBTO or Bu3SnCl), Bu2Sn2+, and BuSn3+ at pH 1-7; although Sn(IV) at pH 1 can be recovered quantitatively by this method, recoveries are low and variable at pH 5-7, probably because unextractable Sn02 is formed. The KHS04 fusion method of Soderquist and Crosby (1978) was occasionally used to solubilize Sn(IV) from Sn02, and this Sn(IV) in acid solution was extracted and analyzed as described above.…”

“…Periodically the whole volume of water in a tube, along with the inside surface of the tube, was extracted with tropolone in benzene and analyzed as indicated above. The water that had been extracted was replaced in its original tube and evaporated to dryness, and the residue fused with KHS04 (Soderquist and Crosby, 1978). The residue was dissolved in acid and extracted and analyzed as indicated above.…”

Butyltins and calmodulin: which interaction?

“…12 This speciation may also occur in the environment through biotransformation, due to microbial action and photochemical decomposition by ultraviolet irradiation. 13,14 One of the main toxic effects of organotin compounds is immunosuppression, in both vertebrates and invertebrates, through lymphocyte depletion and inhibition of chemotaxis and phagocytosis. 15 DBT and MBT appear to be less immunotoxic than TBT, since derivatives do not produce atrophy of lymphoid organs in mammals.…”

Determination of tributyltin by automated in-tube solid-phase microextraction coupled with HPLC-ES-MS

“…The most commonly used techniques for the determination of organotin compounds are gas chromatography (GC) followed by detection with ¯ame spectrophotometry, 4 electron capture (EC), 5 mass spectrometry (MS), 6 atomic absorption spectrometry (AAS) 7 and atomic emission spectrometry (AES). 8 Although GC has a high separation power and can be connected to very sensitive detectors, derivatization and clean-up procedures are required for analysis.…”