Determination of Benzothiazole and Alkylphosphates in Water Samples from the Great Lakes Drainage Basin by Gas Chromatography/Atomic Emission Detection

Abstract

Benzothiazole, tri-n-butylphosphate tris(2-chloroethyl)phosphate, tris((β-chloro-propyDphosphate and two isomers of this last chemical were detected in all archived water extracts collected from permanent sampling stations located at Fort Erie, Niagara-on-the-Lake and Wolfe Island. The archived samples initially extracted using a Goulden large sample extractor (GLSE) after centrifuging, were analyzed using gas chromatography/atomic emission detection (GC-AED) for P-, S-, and N-containing compounds. All samples also contained atrazine and metolachlor whose concentrations had previously been determined using gas chromatography/mass spectrometry (GC/MS). The concentration values of atrazine in the 38 archived samples as determined by the AED method were similar to those determined by the GC/MS method. However, the concentrations of metolachlor in the 38 archived samples calculated from the GC/AED generally differed by a factor of 2 relative to concentrations determined for the extracts by GC/MS. The atrazine and metolachlor concentrations determined by GC/AED were in the range 12-141 ng/L compared to 10-89 ng/L determined using GC/MS. The trialkylphosphate concentrations were in the range 5-23 ng/L and the benzothiazole concentrations were in the range 1-10 ng/L. Other archived samples from the St. Lawrence River above and below Montréal also contained the above five trialkylphosphates and benzothiazole, as did fresh samples from the eastern and western basins of Lake Erie. Nonpolar fractions from silica gel cleanup of the St. Clair River sample extracts contained none of the compounds of interest, but the compounds were found in the methanol eluates of the cleanup column material. One sample collected from the middle of Lake Huron contained tris(2-chloroethyl)phosphate. Rain samples collected about Lake Ontario contained benzothiazole and the alkylphosphates.

Identification of Volatile and Extractable Chloroorganics in Rain and Snow

“…Haloalkyl phosphates are used as flame retardants in polymers (37,38), and the occurrence of such compounds in rainwater samples has previously been noted by our study team (23,25) and by Scott and co-workers (24), who analyzed samples collected in urban areas close to Lake Ontario in Canada. In addition, Aston and co-workers (39) found such compounds in pine needles in the Sierra Nevada Mountains in the United States.…”

“…Identification. It has already been reported elsewhere ( − ) that tris(2-chloroethyl)phosphate can occur in rain and snow. The GC-AED runs in the present study showed that extracts obtained by liquid−liquid extraction of precipitation normally contained a chlorinated compound with a retention time that was identical to that of tris(2-chloroethyl)phosphate (Figure ).…”

“…A number of scientists have studied the occurrence of chlorinated C2-C4 hydrocarbons (3,16,17) and haloacetic acids (3,(18)(19)(20)(21)(22) in precipitation. Recently, the first results regarding chlorinated alkyl phosphates in rain and snow were published (23)(24)(25).…”

Identifying New Persistent and Bioaccumulative Organics Among Chemicals in Commerce

“…Several related phosphates, tri(t-butylphenyl) phosphate (CASRN 31570-04-4), trihaloalkyl phosphates [e.g., tris(2-chloropropyl)phosphate, CASRN 6145-73-9] and triphenyl phosphine (CASRN 603-35-0) are also in the list of 610 compounds but were not included in the priority list because of low predicted BCFs. Nevertheless, there is evidence for environmental contamination by some of these compounds in the Great Lakes , . Some tris-(chloroalkyl) phosphates may be replacements for penta-BDEs , so we foresee increased use.…”

Transformation of Benzothiazole in Estuarine Sediments

“…Several BT derivatives are double photonic and/or nonlinear optical materials of possible value in high speed memory and information retrieval (Zheng et al, 2001; Abbotto et al, 2002). Benzothiazole and some of its derivatives have been identified in lacustrine, riverine, and estuarine water globally (Kumata et al, 2000; Scott et al, 1996, Louter et al, 1994; Bester et al, 1997; Bester, 1998), and as major constituents of organic nitrogen in agricultural soils (Leinweber and Schulten, 1998).…”