In-line optical subtraction using a differential Faraday rotation spectrometer for 15NO/14NO isotopic analysis

TL;DR

This paper introduces a dual-modulation Faraday rotation spectrometer with in-line optical subtraction for precise differential measurement of nitric oxide isotopologues, achieving high sensitivity and stability suitable for isotopic analysis.

Contribution

The work presents a novel in-line optical subtraction technique using a differential Faraday rotation spectrometer for improved isotopic measurement accuracy.

Findings

Achieved 3.1 ppbv/rt(Hz) sensitivity for 15NO

Demonstrated ~20 dB magneto-optical suppression

Maintained stability of differential signal up to ~500 seconds

Abstract

We present a dual-modulation Faraday rotation spectrometer with in-line optical subtraction for differential measurement of nitric oxide (NO) isotopologues. In-situ sample referencing is accomplished via differential dual-cell measurements, with 3.1 ppbv/rt(Hz) (15NO) sensitivity through 15 cm optical path length. Our system operates at 1.9x the shot-noise limit, with a minimum fractional absorption of 1.8e-7/rt(Hz). Differential measurement of both 14NO and 15NO are shown, yielding ~20 dB magneto-optical suppression. Noise analysis demonstrates stability of the differential signal up to ~500 s, with normalized ratiometric precision of 3.0 permil/rt(Hz) using 1 ppmv 15NO (or 272 ppmv 14NO at natural abundance). We rigorously model our differential method and demonstrate the utility of in-line calibration for precise isotopic ratiometry.