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

. 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 C x H y N z family and FTIR non-volatile (NV) amine measured as primary (C-NH2) amine groups typically had greater concentrations in continental air masses than marine air masses. Secondary continental sources of AMS NR amine fragments were identified by consistent correlations to AMS NR nitrate, AMS NR m/z 44, IC non-sea salt 20 potassium, and radon for most air masses. FTIR NV amine group mass concentrations for particles with diameters <1 μm showed large contributions from a primary marine source that was identified by significant correlations with measurements of wind speed, chlorophyll a , seawater dimethylsulfide (DMS), AMS NR chloride, and ion chromatography (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 μm and <0.5 μm particle samples in marine air masses likely have a biogenic secondary source associated with strong 25 correlations to 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% primary marine amine and 73% secondary continental amine during Early Spring to 53% primary amine and 47% 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. picture of open-ocean amines for the region, this study compares online measurements of AMS non-refractory (NR) amine fragments by High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) to non-volatile (NV) primary amine groups by Fourier Transform Infrared Radiation (FTIR) Spectroscopy of size-resolved filters. Chemical and 70 meteorological tracers are used to associate the amine components with both primary and secondary processes and marine or continental sources. Together, the AMS NR amine fragments and FTIR NV amine groups provide a more complete picture of the varied aspects of amine-containing aerosol particles in the North Atlantic. NR amine fragments, but correlations of FTIR NV amine groups with primary marine tracers such as wind speed, IC sea salt, and seawater DMS, NR chloride, and chlorophyll a were higher than for AMS NR amine fragments. FTIR NV amine groups measured during marine periods were found to have largely primary sources for <1 μm particles but 415 secondary sources for <0.5 and <0.18 μm particles. Correlations with FTIR NV alcohol groups show the contribution of a primary source of non-volatile amine for aerosols with diameters <1 μm that had weaker correlations for <0.5 and <0.18 μm. Correlations between FTIR NV amine groups with both FTIR NV acid groups and IC MSA for particles <0.5 and <0.18 μm diameter revealed that secondary processes were a larger contributor for amine groups than in <1 μm particles.