Revisiting the Ultraviolet Absorption Cross Section of Gaseous Nitrous Acid (HONO): New Insights for Atmospheric HONO Budget.

Nitrous acid (HONO) is an important source of hydroxyl radicals (OH) in the atmosphere. Precise determination of the absolute ultraviolet (UV) absorption cross section of gaseous HONO lays the basis for the accurate measurement of its concentration by optical methods and the estimation of HONO loss rate through photolysis. In this study, we performed a series of laboratory and field intercomparison experiments for HONO measurement between striping coil-liquid waveguide capillary cell (SC-LWCC) photometry and incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). Specified HONO concentrations prepared by an ultrapure standard HONO source were utilized for laboratory intercomparisons. Results show a consistent ∼22% negative bias in measurements of the IBBCEAS compared with a SC-LWCC photometer. It is confirmed that the discrepancies occurring between these techniques are associated with the overestimation of the absolute UV absorption cross sections through careful analysis of possible uncertainties. We quantified the absorption cross section of gaseous HONO (360-390 nm) utilizing a custom-built IBBCEAS instrument, and the results were found to be 22-34% lower than the previously published absorption cross sections widely used in HONO concentration retrieval and atmospheric chemical transport models (CTMs). This suggests that the HONO concentrations retrieved by optical methods based on absolute absorption cross sections may have been underestimated by over 20%. Plus, the daytime loss rate and unidentified sources of HONO may also have evidently been overestimated in pre-existing studies. In summary, our findings underscore the significance of revisiting the absolute absorption cross section of HONO and the re-evaluation of the previously reported HONO budgets.

Elucidating the effect of HONO on O3 pollution by a case study in southwest China.

Photolysis of nitrous acid (HONO) is one of the major sources for atmospheric hydroxyl radicals (OH), playing significant role in initiating tropospheric photochemical reactions for ozone (O3) production. However, scarce field investigations were conducted to elucidate this effect. In this study, a field campaign was conducted at a suburban site in southwest China. The whole observation was classified into three periods based on O3 levels and data coverage: the serious O3 pollution period (Aug 13-18 as P1), the O3 pollution period (Aug 22-28 as P2) and the clean period (Sep 3-12 as P3), with average O3 peak values of 96 ppb, 82 ppb and 44 ppb, respectively. There was no significant difference of the levels of O3 precursors (VOCs and NOx) between P1 and P2, and thus the evident elevation of OH peak values in P1 was suspected to be the most possible explanation for the higher O3 peak values. Considering the larger contribution of HONO photolysis to HOX primary production than photolysis of HCHO, O3 and ozonolysis of Alkenes, sensitivity tests of HONO reduction on O3 production rate in P1 are conducted by a 0-dimension model. Reduced HONO concentration effectively slows the O3 production in the morning, and such effect correlates with the calculated production rate of OH radicals from HONO photolysis. Higher HONO level supplying for OH radical initiation in the early morning might be the main reason for the higher O3 peak values in P1, which explained the correlation (R2 = 0.51) between average O3 value during daytime (10:00-19:00 LT) and average HONO value during early morning (00:00-05:00 LT). For nighttime accumulation, a suitable range of relative humidity that favored NO2 conversion within P1 was assumed to be the reason for the higher HONO concentration in the following early morning which promoted O3 peak values.

Electrochemical synthesis of ferrate(VI) using sponge iron anode and oxidative transformations of antibiotic and pesticide.

Passivation of anode is a main challenge in the electrochemical synthesis of ferrate(VI) (FeVIO42-, Fe(VI)). A series of electrochemical approaches were employed including polarization curve, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS) to analyze the physicochemical processes involved in electrochemical synthesis of Fe(VI) using sponge iron and cast iron anodes. The results demonstrate that the sponge iron anode achieved higher yield of Fe(VI) compared to grey cast iron anode. The optimum condition to generate Fe(VI) using sponge iron was 35-50°C and 30mA/cm2. Significantly, the sponge iron anode could generate Fe(VI) for a long duration (>10h) under these conditions; possibly suitable for large scale synthesis of Fe(VI). The prepared Fe(VI) solution was used to treat antibiotic (sulfamethoxazole (SMX)) and pesticide (atrazine (ATZ)) in water. At a molar ratio of Fe(VI) to SMX as 20:1 in the pH range from 5.0 to 9.0, almost complete oxidative transformation of SMX could be obtained. Comparatively, oxidative transformation of ATZ was incomplete (∼70%) even when [Fe(VI)]:[ATZ]=87 at pH 5.0-9.0. Fluorescence spectra and cytotoxicity studies suggest that the oxidative transformation products of both SMX and ATZ possess lower toxicity than the parent antibiotic and pesticide, respectively.