Reactive oxidized nitrogen speciation and partitioning in urban and rural New York State

Figures & data

Figure 1. General schematic of oxidized and reduced nitrogen chemistry in the troposphere. Compounds that are most important to daytime and nighttime chemistry are in red and black, respectively

Table 1. Instrument information for the QC and PSP speciated NO_y measurements

Species	Organization(s)^1	Converters	Sampling details	Reference(s)
NO	ASRC	None	Manifold	Ninneman et al. (2017, 2019)
NO2		Photolytic (BLC)^2
NOy	ARA	Molybdenum	None	Arnold et al. (2007)
	ASRC (PSP only)			Ninneman et al. (2017, 2019); Schwab, Spicer, and Demerjian (2009)
	DEC (QC only)			NYS DEC (2015)
HNO3	ARA	Molybdenum	KCl denuder	Arnold et al. (2007)
	ASRC (PSP only)		NaCl denuder	Schwab, Spicer, and Demerjian (2009)
pNO3	ARA	Molybdenum	PM2.5 cyclone plus two denuders (one Na2CO3 and one C6H8O7)^3	Edgerton et al. (2006)
PNs	ARA	Thermal denuder plus BLC	None	Ninneman et al. (2017)
ANs

¹ASRC = Atmospheric Sciences Research Center; ARA = Atmospheric Research & Analysis, Inc.; DEC = New York State Department of Environmental Conservation.

²BLC = Blue Light Converter.

³Na₂CO₃ = sodium carbonate, C₆H₈O₇ = citric acid.

Figure 2. Map of the northeast United States with the Queens College (QC, black star) and Pinnacle State Park (PSP, blue star) sites indicated (adapted from D-Maps (2018))

Table 2. Estimated method detection limit (MDL) and overall uncertainty for each measured NO_y species. The estimated MDLs and overall uncertainties apply to hour-averaged data

Species (abbreviation)	Estimated method detection limit (MDL, ppt)	Estimated overall uncertainty (%)
Nitric oxide (NO)	26	19
Nitrogen dioxide (NO2)	121	20
Nitric acid (HNO3)	31	22
Particle nitrate (pNO3)	32 (QC), 37 (PSP)	28 (QC), 33 (PSP)
Peroxy nitrates (PNs)	32	24
Alkyl nitrates (ANs)	41	18
Reactive oxidized nitrogen (NOy)	74	10

Table 3. All-season median NO_y speciation, p-values for the seasonal median NO_x, HNO₃, pNO₃, PNs, and ANs concentrations that were determined using an analysis of variance (ANOVA) statistical method, and all-season median NO_y partitioning at QC and PSP

Parameter	Site	NO	NO2	NOx	HNO3	pNO3	PNs	ANs	NOyi	NOy
Concentration (ppb)	QC	0.97	10.02	10.99	0.49	0.24	0.62	0.94	13.28	13.95
	PSP	0.03	0.62	0.65	0.16	0.12	0.13	0.18	1.24	1.56
P-value	QC	NA	NA	< 0.01	0.37	0.17	0.17	0.01	NA	NA
	PSP	NA	NA	< 0.01	0.91	0.06	0.61	0.14	NA	NA
% Contribution to NOy	QC	6	71	77	4	2	5	7	95	NA
	PSP	2	40	42	10	8	9	12	81	NA

Figure 3. Seasonal median speciated (a) NO_y concentrations and (b) NO_z concentrations at QC from September 2016 to August 2018. Data that are 50%–75% complete (DJF 2017/8 pNO₃; MAM 2018 PNs and ANs) and less than 50% complete (DJF 2017/8 PNs and ANs; MAM 2018 pNO₃; JJA 2018 HNO₃) are denoted by the red and purple hatching, respectively. (c) Seasonal median NO_y partitioning at QC from September 2016 to August 2018. The dashed red line denotes 100% closure of the NO_y budget, and the x-axis is color-coded according to data usage. Reasons for missing data in (a) and (c) are outlined in the Methodology. See Table S1 for monthly numerical values and data completeness, respectively. In all figures, the combined uncertainty of the measurements is given by the black error bars

Figure 4. Seasonal median NO_x/NO_y ratio at QC from September 2016-August 2018. The dashed purple line denotes the median NO_x/NO_y ratio for the full measurement period. Reasons for missing data are outlined in the Methodology, and see Table S1 for monthly numerical values and data completeness, respectively. The combined uncertainty of the NO, NO₂, and NO_y measurements is given by the black error bars

Figure 5. (a) The diurnal variation of the hourly median NO_y speciation at QC during spring 2017. (b) The diurnal variation of the hourly median NO_z speciation at QC during spring 2017. (c) Same as (a), except for summer 2017. (d) Same as (b), except for summer 2017. (e) Same as (a) and (c), except for fall 2016–2017. (f) Same as (b) and (d), except for fall 2016–2017. In all figures, the combined uncertainty of the measurements is given by the black error bars

Figure 6. Seasonal median speciated (a) NO_y and (b) NO_z concentrations at PSP from June 2016 to August 2018. Data that are 50%–75% complete (MAM 2018 pNO₃) are denoted by the red hatching. (c) Seasonal median NO_y partitioning at PSP from June 2016 to August 2018. The dashed red line denotes 100% closure of the NO_y budget, and the x-axis is color-coded according to data usage. Reasons for missing data in (a) and (c) are outlined in the Methodology. See Table S2 for numerical values and data completeness, respectively. In all figures, the combined uncertainty of the measurements is given by the black error bars

Figure 7. Seasonal median NO_x/NO_y ratio at PSP from June 2016 to August 2018. The dashed purple line denotes the median NO_x/NO_y ratio for the full measurement period. Reasons for missing data are outlined in the Methodology, and see Table S2 for numerical values and data completeness, respectively. The combined uncertainty of the NO, NO₂, and NO_y measurements is given by the black error bars

Figure 8. (a) The diurnal variation of the hourly median NO_y speciation at PSP during spring 2017. (b) The diurnal variation of the hourly median NO_z speciation at PSP during spring 2017. (c) Same as (a), except for summer 2016–2017. (d) Same as (b), except for summer 2016–2017. (e) Same as (a) and (c), except for fall 2016–2017. (f) Same as (b) and (d), except for fall 2016–2017. (g) Same as (a), (c), and (e), except for winter 2016/7–2017/8. (h) Same as (b), (d), and (f), except for winter 2016/7–2017/8. In all figures, the combined uncertainty of the measurements is given by the black error bars

Figure 9. The diurnal variation of the hourly median NO_y partitioning at PSP during selected seasons. The dashed red line denotes 100% closure of the NO_y budget, and the combined uncertainty of the measurements is given by the black error bars

Figure 10. The diurnal variation of the hourly median NO_y partitioning at QC during selected seasons. The dashed red line denotes 100% closure of the NO_y budget, and the combined uncertainty of the measurements is given by the black error bars

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