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Water samples were collected and analyzed for conductivity, pH, temperature and trihalomethanes (THMs) during the fall of 2014 at two monitored municipal drinking water source ponds. Both spot (or grab) and time weighted average (TWA) sampling methods were assessed over the same two day sampling time period. For spot sampling, replicate samples were taken at each site and analyzed within 12 h of sampling by both Headspace (HS)- and direct (DI)- solid phase microextraction (SPME) sampling/extraction methods followed by Gas Chromatography/Mass Spectrometry (GC/MS). For TWA, a two day passive on-site TWA sampling was carried out at the same sampling points in the ponds. All SPME sampling methods undertaken used a 65-µm PDMS/DVB SPME fiber, which was found optimal for THM sampling. Sampling conditions were optimized in the laboratory using calibration standards of chloroform, bromoform, bromodichloromethane, dibromochloromethane, 1,2-dibromoethane and 1,2-dichloroethane, prepared in aqueous solutions from analytical grade samples. Calibration curves for all methods with R2 values ranging from 0.985–0.998 (N = 5) over the quantitation linear range of 3–800 ppb were achieved. The different sampling methods were compared for quantification of the water samples, and results showed that DI- and TWA- sampling methods gave better data and analytical metrics. Addition of 10% wt./vol. of (NH4)2SO4 salt to the sampling vial was found to aid extraction of THMs by increasing GC peaks areas by about 10%, which resulted in lower detection limits for all techniques studied. However, for on-site TWA analysis of THMs in natural waters, the calibration standard(s) ionic strength conditions, must be carefully matched to natural water conditions to properly quantitate THM concentrations. The data obtained from the TWA method may better reflect actual natural water conditions

Comparison of Spot and Time Weighted Averaging (TWA) Sampling with SPME-GC/MS Methods for Trihalomethane (THM) Analysis