Application of an online ion-chromatography-based instrument for gradient flux measurements of speciated nitrogen and sulfur

Abstract. The dry component of total nitrogen and sulfur atmospheric deposition remains uncertain. The lack of measurements of sufficient chemical speciation and temporal extent make it difficult to develop accurate mass budgets and sufficient process level detail is not available to improve current air–surface exchange models. Over the past decade, significant advances have been made in the development of continuous air sampling measurement techniques, resulting with instruments of sufficient sensitivity and temporal resolution to directly quantify air–surface exchange of nitrogen and sulfur compounds. However, their applicability is generally restricted to only one or a few of the compounds within the deposition budget. Here, the performance of the Monitor for AeRosols and GAses in ambient air (MARGA 2S), a commercially available online ion-chromatography-based analyzer is characterized for the first time as applied for air–surface exchange measurements of HNO₃, NH₃, NH₄⁺, NO₃⁻, SO₂ and SO₄²⁻. Analytical accuracy and precision are assessed under field conditions. Chemical concentrations gradient precision are determined at the same sampling site. Flux uncertainty measured by the aerodynamic gradient method is determined for a representative 3-week period in fall 2012 over a grass field. Analytical precision and chemical concentration gradient precision were found to compare favorably in comparison to previous studies. During the 3-week period, percentages of hourly chemical concentration gradients greater than the corresponding chemical concentration gradient detection limit were 86, 42, 82, 73, 74 and 69 % for NH₃, NH₄⁺, HNO₃, NO₃⁻, SO₂ and SO₄²⁻, respectively. As expected, percentages were lowest for aerosol species, owing to their relatively low deposition velocities and correspondingly smaller gradients relative to gas phase species. Relative hourly median flux uncertainties were 31, 121, 42, 43, 67 and 56 % for NH₃, NH₄⁺, HNO₃, NO₃⁻, SO₂ and SO₄²⁻, respectively. Flux uncertainty is dominated by uncertainty in the chemical concentrations gradients during the day but uncertainty in the chemical concentration gradients and transfer velocity are of the same order at night. Results show the instrument is sufficiently precise for flux gradient applications.