General comments
Li et al. present warm season measurements of HONO and related trace gases at a measurement site in Beijing, China. According to these authors, these data and analysis fill a measurement gap for the seasonal understanding of HONO in Beijing. As such, the data and analysis are a reasonable contribution to the literature on this subject and the related topics of the contribution of HONO to free radicals, oxidation capacity, and urban air pollution. It can be published in ACP subject to the comments below.
As with previous literature on this topic, the authors find a large missing or unknown source of HONO. The authors analyze the magnitude of this source, and try to assess the mechanisms that may produce it. This is the weakest part of this paper and one that should undergo major revision. The presented correlations do not appear to support any of the proposed mechanisms. Rather than trying to provide evidence for these sources, the authors would do better to simply evaluate the magnitude of each based on the available data and assess the extent to which each can explain the observations. There do not appear to be meaningful correlations that would support any given explanation for the unknown HONO source, but an analysis of the size of each would still be informative. See specific comments below for recommendations.
There are several other major revisions required – see the specific comments below. Of particular importance are the explicit recognition of vertical gradients in HONO, and the related topic of the contribution of HONO to the OH budget.
This paper has already been reviewed by two other reviewers. One recommended rejection on the basis of NO2 measured by a molybdenum converter. The authors have addressed this concern, although they could go further with an uncertainty budget for the corrected NOx and all measurements. See specific comments. The second reviewer recommended major revisions based on lack of clarity and consistency in the analyses. I concur with this reviewer, and my recommendations are similar to those of this reviewer. The authors have addressed some of these comments, but have not fully addressed them. See specific comments below.
Specific comments:
Line 15: Define the emission factor in the abstract – i.e., relative to NOx or some other component of vehicle emissions.
Line 17: Conversion frequency in the abstract appears to be a first order rate constant. If so, quote as such, and don’t give in units of % per hour but rather in s-1. Also check this unit as it seems quite slow as given.
Line 50-52: OH + NO is not normally a net source of HONO as it is balanced by photolysis to create a null cycle that does not affect OH or NOx.
Line 94: NO2 hydrolysis is not the only potential interference in LOPAP instruments for HONO. For example HO2NO2 is known to interfere with HONO in these systems. Can the authors provide more detail on the phrase “subtracted by a deployed dual channel absorption system” and explain how this corrects for interferences in the LOPAP method ?
Line 102: Does this imply an uncertainty in the analysis that is greater below 7 ppb of NOx ? Is an uncertainty budget given ? What, in general, is the uncertainty of all the measurements quoted in this paragraph ?
Line 117: What is the uncertainty associated with estimating OH via equation 1 ? See comments above re: uncertainty budget.
Line 123: Is there a reference to the nighttime OH at 2e-5 ? This is quite a high number. Does this matter for the subsequent analysis? What is the source of nighttime OH at this level ? A sustained OH of this magnitude would require a large, non-photolytic source. If not important to the subsequent analysis, suggest neglecting nighttime OH.
Line 171-174: The premise is hard to follow here – why should HONO sources remain constant ? HONO should follow NOx (stated earlier), so variation in NOx should lead to varaiton in HONO.
Line 211: Provide more justification for the use of 2 µg m-3 to exclude biomass burning. For example, what is the ratio of HONO / K+ that would allow assessment of biomass burning as a source of HONO ?
Line 251: The OH concentration at night is taken from literature and not observed. Is this level consistent with the observed NO and NO2 ? Such high levels of NOx would have the effect of greatly reducing nighttime OH, so the literature values would also have to have similar NOx levels. The high inferred levels of OH are not plausible without also demonstrating that there is a large OH source. Absent such an analysis, the nighttime HONO source from OH + NO should be omitted. It is almost certainly the case that the quoted values are an upper limit, perhaps a large upper limit, to the actual contribution of this reaction at night.
Line 308-310: Vertical gradients in HONO are well known (e.g., multiple references from Stutz et al., see below, VandenBoer et al. 2013). Why would vertical transport be negligible ?
Line 366-367: If the phenomenon is not evident in four of the five months, then it is clear that there is not evidence for it. The conclusions should clearly state this finding rather than impying that it operates in June only.
Line 371-374: The analysis is very confusing. There is a correlation of the unknown source with the product of jNO2, NO2 and PM2.5 that is evident only in June ? If so, there is no evidence for such a source, and the conclusion should state this. Additionally, none of the R values (which all produce r2 well under 0.5) are convincing. The assumed variations account for far less than half of the observed variability (r2 values all well smaller than 0.5).
Line 375-381: Similar comment to above. The correlations presented offer no evidence for the source being tested. One could instead simply calculate the magnitude of the source based on previous literature and compare this to the observed Punknown. The observations themselves appear to provide no evidence.
Line 389: Same comment. Based on the correlation coefficients presented, the conclusion should be that there is no evidence for this source, but that it could contribute based on prior literature.
Line 407-409: The conclusion is flawed, since the source should not vary from month to month without an obvious mechanism. A more likely explanation is simple variation in the data, which can simply be presented as an average and standard deviation rather than as a time varying source. This comment was prominent in previous reviews and should be addressed.
Section 3.4.3: There is an important caveat missing in this section in that it pertains to the OH source at the altitude of the measurement. Since vertical gradients in HONO are well known (see above) but not measured here, the analysis must be specified as a local analysis at a fixed height rather than characteristic of the entire mixed layer. The actual contribution to OH is smaller, and likely much smaller, than shown here when integrated across the mixed layer.
Also in this section, there is no comparison to the photolysis of formaldehyde, a large and known HOx source in urban areas. Presumably this is due to the lack of formaldehyde measurements. If so, this should be clearly stated, and it should also be stated that the analysis is not a full HOx buddget.
Lines 418-420: What is P OH-O3 ? Is this O3 photolysis to O1D followed by reaction with water vapor ?
References
Pinto, J.P., J. Dibb, B.H. Lee, B. Rappenglück, E.C. Wood, M. Levy, R.Y. Zhang, B. Lefer, X.R. Ren, J. Stutz, C. Tsai, L. Ackermann, J. Golovko, S.C. Herndon, M. Oakes, Q.Y. Meng, J.W. Munger, M. Zahniser, and J. Zheng, Intercomparison of Field Measurements of Nitrous Acid (HONO) during the SHARP Campaign. Journal of Geophysical Research: Atmospheres, 2014: p. 2013JD020287.
Stutz, J., B. Alicke, and A. Neftel, Nitrous acid formation in the urban atmosphere: Gradient measurements of NO2 and HONO over grass in Milan, Italy. Journal of Geophysical Research-Atmospheres, 2002. 107(D22).
Wang, S., R. Ackermann, and J. Stutz, Vertical profiles of NOx chemistry in the polluted nocturnal boundary layer in Phoenix, AZ: I. Field observations by long-path DOAS. Atmos. Chem. Phys., 2006. 6: p. 2671-2693.
Wong, K.W., H.J. Oh, B.L. Lefer, B. Rappenglück, and J. Stutz, Vertical profiles of nitrous acid in the nocturnal urban atmosphere of Houston, TX. Atmos. Chem. Phys., 2011. 11(8): p. 3595-3609.
Wong, K.W., C. Tsai, B. Lefer, N. Grossberg, and J. Stutz, Modeling of daytime HONO vertical gradients during SHARP 2009. Atmos. Chem. Phys., 2013. 13(7): p. 3587-3601.
Wong, K.W., C. Tsai, B. Lefer, C. Haman, N. Grossberg, W.H. Brune, X. Ren, W. Luke, and J. Stutz, Daytime HONO Vertical Gradients during SHARP 2009 in Houston, TX. Atmos. Chem. Phys., 2011. 12: p. 635-652.
VandenBoer, T.C., S.S. Brown, J.G. Murphy, W.C. Keene, C.J. Young, A.A.P. Pszenny, S. Kim, C. Warneke, J. de Gouw, J.R. Maben, N.L. Wagner, T.P. Riedel, J.A. Thornton, D.E. Wolfe, W.P. Dubé, F. Öztürk, C.A. Brock, N. Grossberg, B. Lefer, B.M. Lerner, A.M. Middlebrook, and J.M. Roberts, Understanding the role of the ground surface in HONO vertical structure: High resolution vertial profiles during NACHTT-11. J. Geophys. Res., 2013. 118(17): p. 10155-10171.
Young, C.J., R.A. Washenfelder, L.H. Mielke, H.D. Osthoff, P. Veres, A.K. Cochran, T.C. VandenBoer, H. Stark, J. Flynn, N. Grossberg, C.L. Haman, B. Lefer, J.B. Gilman, W.C. Kuster, C. Tsai, O. Pikelnaya, J. Stutz, J.M. Roberts, and S.S. Brown, Vertically resolved measurements of nighttime radical reservoirs in Los Angeles and their contribution to the urban radical budget. Environ. Sci. Technol., 2012. 46: p. 10965-10973. |