Influence of ammonia on sulfate formation under haze conditions

摘要

In the presence of hygroscopic material, stable aqueous droplets form at relative humidity below 100%. In this work, we examined the role and importance of NH_3 in SO_2 oxidation under haze conditions. Synthetic deposits composed mainly of NaCl and NaNO_3 were exposed to SO_2/NH_3/air gas mixture under controlled conditions, typical for heavily polluted atmosphere. In contrast to catalytic reaction by Mn(Ⅱ) in the absence of NH_3, which is self-limited, the production of sulfate in the presence of NH_3 at RH 80% increases considerably and linearly with time. The catalytic effect of Mn(Ⅱ) was observed only for NaNO_3 deposits. Non-catalytic SO_2 oxidation in the presence of NH_3 is negligible below the deliquescent relative humidity, i.e. RH<75%. Above this value a considerable increase of sulfate formation in a narrow range of relative humidity (75-80%) was noticed. We found out that the reaction rate is not proportional to the volume of condensed water; we suggest that available surface play a role in limiting the reaction. The rate of conversion for both pure salts at RH≥80% was found to be 1.1% h~(-1) ([SO_2] = 2 ppm, [NH_3] = 1 ppm, T = 10℃), which is more than an order of magnitude higher in comparison with our previous results on MnCl_2/NaCl and MnCl_2/NaNO_3 at RH = 80% in the absence of NH_3.