Improvements are provided in the detection of atmospheric vapors by ionizing them near ambient pressure, and analyzing them as ions. Lowest detection limits of parts per quadrillion (ppq) concentrations are enabled by a combination of improvements, including the use of a filter to remove occasional intense signal from explosive particles. Several sources of chemical background are identified and solutions for their reduction or elimination are presented. Gains in response time may be achieved by operating at elevated temperature. When the ionizer is an electrospray source, the use of high boiling point solvents is indicated. An increased selectivity is achieved by operating a differential mobility analyzer (DMA) in series with a mass spectrometer. However, ppq sensitivities require various improvements in the DMA system including a special coupling to the ionizer, controlling the temperature in the DMA pump circuit, avoidance of induction on the DMA electrodes from heating devices, etc.