Non-volatile marine and non-refractory continental sources of particle-phase amine during the North Atlantic Aerosols and Marine Ecosystems Study (NAAMES)

Abstract

Amines were measured by aerosol mass spectrometry (AMS) and Fourier transform infrared (FTIR) spectroscopy during the North Atlantic Aerosols and Marine Ecosystems Study (NAAMES) cruises. Both AMS non-refractory (NR) amine ion fragments comprising the AMS CxHyNz family and FTIR non-volatile (NV) primary (C–NH2) amine groups typically had greater concentrations in continental air masses than in marine air masses. Secondary continental sources of AMS NR amine fragments were identified by consistent correlations with AMS NR nitrate, AMS NR f44 (the contribution of AMS ion signal at m/z 44 (CO2+) to the total AMS NR organic mass (OM) signal), ion chromatography (IC) non-sea-salt potassium (nssK+), and radon for most air masses. FTIR NV amine group mass concentrations for particles with diameters <1µm showed large contributions from a primary marine source that was identified by significant correlations with measurements of wind speed, chlorophyll a (chl a), seawater dimethylsulfide (DMS), AMS NR chloride, and IC sea salt as well as FTIR NV alcohol groups in both marine and continental air masses. FTIR NV amine group mass concentrations in <0.18 and <0.5 µm particle samples in marine air masses likely have a biogenic secondary source associated with strong correlations with FTIR NV acid groups, which are not present for <1 µm particle samples. The average seasonal contribution of AMS NR amine fragments and FTIR NV amine groups ranged from 27±57 % amine from primary marine sources and 73±152 % secondary continental amine during early spring to 53±76 % amine from primary marine sources and 47±68 % secondary continental amine during winter. These results demonstrate that AMS NR and FTIR NV amine measurements are complementary and can be used together to investigate the variety and sources of amines in the marine environment.