The organoarsenic species, monomethylarsonic acid (l), dimethylarsinic acid (2), arsenobetaine (3) and arsenocholine (4), have received considerable scrutiny.They are found in the environment and have very different toxicity; 1 and 2 are quite toxic whereas 3 and 4 are relatively non-toxic. 2 is used as a herbicide. Bacteria and fungi can methylate inorganic arsenic to form 1 and 2 while 3 is the principal metabolite of ingested arsenic in fish.Very little mass spectrometric work has been done on 1 and 2, and all the work was done using gas chromatographylmass spectrometry. Since both 1 and 2 are non-volatile, conversion to the hydride,' iodide,2 trimethylsilyl' or methylthi~glycolate~ derivative was necessary. Electron impact mass spectra have been recorded by volatilizing/partially pyrolyzing 3 on a solid No molecular ion of 3 was seen in all cases, and the spectra bore a strong resemblance to that of tetramethyl arsonium ion.s We are not aware of any published electron impact mass spectrum of 4. More informative spectra were obtained by using field desorptionG8 and fast atom bombardment (FAB).'."In this communication, we wish to report the results of a study on these organoarsenicals using two soft ionization procedures: atmospheric pressure chemical ionization and electrospray (ES).
EXPERIMENTALA triple quadrupole mass spectrometer (SCIEX TAGA 6000 prototype) equipped with an atmospheric pressure chemical ionization (APCI) source, a heatednebulizing liquid interface (SCIEX) and a laboratorybuilt electrospray interface was used. When the electrospray interface was used, the APCI source was detached. The design of this interface is quite similar to that of Henion et al., the most significant differences being that we use a 33 and a 22 gauge hypodermic needle tubing (Hamilton) for liquid and gas delivery, respectively. Collision induced dissociation (CID) measurements were carried out using argon under essentialiy single collision conditions at a thickness of about 1 . 8~ 10'4cm-2, and at collision energy (laboratory frame) of 55 eV.Organoarsenic solutions, generally at about 10-100 ppm arsenic, were prepared in 50150 methanol/
' NRCC 28578Author to whom correspondence should be addressed. or ethanollwater containing usually 0.01 M acetic or phosphoric acid. Solutions were either introduced continuously or valved in as a liquid plug, using a reciprocating pump [Waters 60001 at a rate of 1 mL/min for the heated-nebulizer or 50 vL/min for the electrospray interface. When the valve injection method was used, identical solvent mixture was used for the organoarsenic samples and the carrier stream.
RESULTS AND DISCUSSIONOf the four species studied, 2, 3 and 4 showed good response in the positive ion mode; no response was seen from solutions of 1, whether acidic or basic, in either positive or negative modes.For 2, the most intense ion seen was due to the protonated molecule at mlz 139. Other ions of note are the [MH-H20+CH30H]+ adduct (mlz 153, when using methanol as solvent, Fig. 1) and the [MH-H20+CH,CH2OH]+ adduct ...