Electrospray ionization mass spectrometry (ESI-MS) was applied for the char
acterization of inorganic polyphosphates [orthophosphate, pyrophosphate, tr
ipolyphosphate, trimetaphosphate, and tetrapolyphosphate]. The high selecti
vity of ESI-MS allows the detection of different polyphosphate species with
out preseparation by ion chromatography or capillary electrophoresis. Furth
ermore, ESI-RIS does not require the incorporation of W-absorbing chromopho
res into the analytical method for the detection of phosphates, unlike conv
entional UV-chromatographic methods. Limits of detection by ESI-MS were est
imated to range from similar to 1 to 10 ng/mL. The quantification of polyph
osphate samples as single-component and multicomponent mixtures was investi
gated. Linear signal response for single-component samples ranged from the
limit of detection to similar to 10 mu g/mL. Quantification of polyphosphat
e in streamwater is demonstrated using the standard addition method. The ef
fect of multi-polyphosphate components and salts on signal response was als
o studied. For concentrations less than 2.0 mu g/mL, signal response from a
tetrapolyphosphate sample was comparable to those obtained from tetrapolyp
hosphate-tripolyphosphate mixtures. Signal response obtained from tetrapoly
phosphate in the presence of tripolyphosphate or NH4NO3 at higher concentra
tions (similar to 50 mu g/mL and 35 mu g/mL, respectively) was significantl
y lower relative to single-component standards (similar to 40%-70%).