Sampling for mercury at subnanogram per litre concentrations for load estimation in rivers

Estimation of constituent loads in streams requires collection of stream samples that are representative of constituent concentrations, that is, composites of isokinetic multiple verticals collected along a stream transect. An all-Teflon isokinetic sampler (DH-81) cleaned in 75??C, 4 N HCl was tested using blank, split, and replicate samples to assess systematic and random sample contamination by mercury species. Mean mercury concentrations in field-equipment blanks were low: 0.135 ng??L-1 for total mercury (??Hg) and 0.0086 ng??L-1 for monomethyl mercury (MeHg). Mean square errors (MSE) for ??Hg and MeHg duplicate samples collected at eight sampling stations were not statistically different from MSE of samples split in the laboratory, which represent the analytical and splitting error. Low fieldblank concentrations and statistically equal duplicate- and split-sample MSE values indicate that no measurable contamination was occurring during sampling. Standard deviations associated with example mercury load estimations were four to five times larger, on a relative basis, than standard deviations calculated from duplicate samples, indicating that error of the load determination was primarily a function of the loading model used, not of sampling or analytical methods.