Long path gas-phase absorption detector using a 235 nm deep-UV LED source for the determination of nitrite, nitrate and total dissolved nitrogen in waters

A gas-phase absorption detector (GPAD) was developed using a surface-mount 235 nm light-emitting diode (LED) as the light source. Modules for housing the LED and photodiode were three-dimensional printed. A stainless-steel tube was used as the detection cell. To perform long path absorption detection, a fused silica full-ball lens (5 mm diameter) was employed to collimate the light produced by the UV-LED with a viewing angle of 120°. The light attenuation coefficient ( α b ) was measured to be 0.025±0.001 cm −1 . The optimum path length with the maximum signal-to-noise ratio was obtained at ca. 80 cm. This result agreed with the theoretical calculation for optimum path length, i.e., 2/ α b . The GPAD was coupled with an automated analysis system and applied to detect nitrite in water. The automated system added citric acid and ethanol into a water sample, and nitrite was converted to gaseous nitrous acid (HONO), which has a strong absorption at 235 nm. The produced HONO was purged with air, followed by water removal, and then detected with the GPAD. The method was used to detect nitrate and total dissolved nitrogen (TDN) in water as well. Nitrate was reduced to nitrite through a photo-induced reaction with a conversion efficiency of ca. 60%. TDN was converted to nitrate by using an alkaline persulfate digestion method, followed by photoreduction to nitrite, and detected by using the automated system. The limits of detection were 0.4 μM, 3.9 μM, and 6.7 μM (94 μg N/L) for nitrite, nitrate, and TDN, respectively.