REFRACTORY METHYLATED ARSENIC COMPOUNDS IN ESTUARINE WATERS - TRACING BACK ELUSIVE SPECIES

被引:16
作者
DEBETTENCOURT, AM
FLORENCIO, MH
DUARTE, MFN
GOMES, MLR
BOAS, LFCV
机构
[1] UNIV EVORA,DEPT ECOL,P-7001 EVORA,PORTUGAL
[2] UNIV LISBOA COMPLEXO I,CTR ESPECTROMETRIA MASSA,P-1200 LISBON,PORTUGAL
[3] ESTACAO AGRON NACL,ITQB,P-2870 OEIRAS,PORTUGAL
关键词
ARSENIC; IDENTIFICATION; DCI MS/MS; HYDRIDE GENERATION; ARSENOBETAINE; ARSENOCHOLINE; METHYLARSENIC; CHLORINE; FLUORINE;
D O I
10.1002/aoc.590080109
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
Water from the Tagus estuary, Portugal, was concentrated and purified through evaporation, solvent extraction, ion exchange and HPLC, and peaks of refractory arsenicals were detected by difference between total arsenic (GFAA) and hydride-forming arsenic species (HG QF AA). DCI mass spectra of these fractions presented peaks at m/z 139, 157 and 159; the proportion of m/z 157 and 159 peaks, approx. 3: 1, suggested a chlorinated moiety. DCI MS/MS daughter-ion fragmentation of these peaks seems compatible with dimethylarsenic (cacodylic) acid and structures of the type Me2As(O)Cl or Me3As(OH)F. The refractory character of these fractions, however, cannot be explained by these structures. Further work with mixtures of halogen and arsenic species injected in the HPLC system showed that fluoride and iodide can shift DMA (dimethylarsenic) and TMAO (trimethylarsine oxide) to shorter retention times but not to Rf values similar to refractory arsenicals. These latter are attained by mixtures of sodium chloride + arsenobetaine, and sodium fluoride and chloride + arsenocholine. We suggest that peaks at m/z 139 and 157 correspond to fragments of a heavier refractory molecule mainly formed by halogenated betaines including chloro-arsenobetaine and chloro- and fluoro-arsenocholine.
引用
收藏
页码:43 / 56
页数:14
相关论文
共 23 条
[1]   DETERMINATION OF ARSENIC SPECIES IN NATURAL-WATERS [J].
ANDREAE, MO .
ANALYTICAL CHEMISTRY, 1977, 49 (06) :820-823
[2]  
ANDREAE MO, 1983, METHODS SEAWATER ANA, P218
[3]  
AYLETT BJ, 1979, ORGANOMETALLIC COMPO, V1
[4]  
CHAPMAN JR, 1986, PRACTICAL ORGANIC MA
[5]  
CHRISTAKOPOULOS A, UNPUB
[6]   DESORPTION CHEMICAL IONIZATION MASS-SPECTROMETRY OF ARSENIC COMPOUNDS PRESENT IN THE MARINE AND TERRESTRIAL ENVIRONMENT [J].
CULLEN, WR ;
EIGENDORF, GK ;
PERGANTIS, SA .
RAPID COMMUNICATIONS IN MASS SPECTROMETRY, 1993, 7 (01) :33-36
[7]  
CULLEN WR, 1989, APPL ORGANOMET CHEM, V3, P401
[8]   ON ARSENIC SPECIATION IN THE TAGUS ESTUARY [J].
DEBETTENCOURT, AMM .
NETHERLANDS JOURNAL OF SEA RESEARCH, 1988, 22 (03) :205-212
[9]   IMPROVEMENT OF SPECIATION ANALYSIS IN ENVIRONMENTAL MATRICES - IDENTIFICATION OF REFRACTORY ARSENICALS - SOME ANALYTICAL DIFFICULTIES [J].
DEBETTENCOURT, AMM ;
FLORENCIO, MHFS ;
VILASBOAS, LF .
MIKROCHIMICA ACTA, 1992, 109 (1-4) :53-59
[10]   REFRACTORY ARSENIC SPECIES IN ESTUARINE WATERS [J].
DEBETTENCOURT, AMM ;
ANDREAE, MO .
APPLIED ORGANOMETALLIC CHEMISTRY, 1991, 5 (02) :111-116