An evaluation of the precision,and various sources of error,in daily and cumulative precipitation chemistry sampling

Experiments have been carried out to assess the precision and various potential sources of error in precipitation chemistry and deposition measurements made by the Acidic Precipitation in Ontario Study (APIOS). It was found that reproducibility of daily precipitation concentration measurements of S0₄ ^? and NO₃ ^? using colocated Aerochem Metrics samplers is 96% or better for 50% of the time, and 73% or better for 95 % of the time. For these parameters, MIC Type A 28-d samplers give reproducibilities of 94% or better 50% of the time, and 79% or better 95 % of the time. The reproducibility for the concentration of the other major ions, and loading (concentration times sample depth) is somewhat poorer. Concentration changes due to sample degradation or evaporative losses under field conditions are negligible or small on average, even for 28-d samples. For 28-d concentration measurements using MIC Type A collectors, errors due to evaporation amount to about 3% as an annual average, and 5% during the summer period. For S0₄ ^? and NO₃ ^?, overall long-term errors due to exposure under field conditions (including dry contamination and degradation due to chemical reactions), and sample handling, are less than 10%, at least for the techniques used in APIOS. A major potential source of error still to be quantified is unrepresentative sampling by automatic wet-only collectros (i.e., missing of initial portions of precipitation events due to sluggish sensor response, or less than 100% collection efficiencies of precipitation amounts).