Heterogeneous uptake of ammonia and dimethylamine into sulfuric and oxalic acid particles

Sauerwein, Meike; Chan, Chak K.

doi:10.5194/acp-17-6323-2017

Cited by 24 publications

(30 citation statements)

References 77 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Besides, 8 % of amine-containing particles contained ammonium while 25 % of ammonium-containing particles contained amines in summer, suggesting a possible contribution of ammonium-amine exchange reactions to the low abundance of ammonium in amine-containing particles at high ambient RH (72 ± 13 %) in summer. In addition, the presence of aminium salts affects the water activities and osmotic coefficients of aqueous solutions, which may influence the calculation of pH using aerosol thermodynamic models (Sauerwein et al, 2015). Furthermore, it should be noted that the measured pH of bulk ambient aerosols may not be representative of the actual single-particle acidity.…”

Section: Discussionmentioning

confidence: 99%

“…Due to their strong basicity and water solubility, LMW amines can undergo acid-base reactions with sulfuric and nitric acid to form aminium salts (Angelino et al, 2001;Sorooshian et al, 2007;Pratt et al, 2009), which has been found to enhance new particle formation beyond the amounts produced from reactions between acids and NH 3 alone (Kurtén et al, 2008;Berndt et al, 2010;Place et al, 2010;Wang et al, 2010). In addition, once partitioned into the particle phase, these LMW aliphatic amines can enhance aerosol particle hygroscopicity (Chu et al, 2015;Sauerwein et al, 2015). Furthermore, amines can be oxidized by OH radicals, NO 3 radicals, and O 3 in the atmosphere to form semi-volatile and non-volatile compounds, some of which are highly toxic (Lee and Wexler, 2013), and which contribute to secondary organic aerosol (SOA) mass (Murphy et al, 2007;Malloy et al, 2009).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Characteristics and mixing state of amine-containing particles at a rural site in the Pearl River Delta, China

Cheng

Huang²,

Chan

et al. 2018

Atmos. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

Abstract. Particulate amines play an important role for the particle acidity and hygroscopicity and also contribute to secondary organic aerosol mass. We investigated the sources and mixing states of particulate amines using a single-particle aerosol mass spectrometer (SPAMS) during summer and winter 2014 at a rural site in the Pearl River Delta, China. Amine-containing particles accounted for 11.1 and 9.4 % of the total detected individual particles in summer and winter, respectively. Although the increase in amine-containing particle counts mostly occurred at night, no obvious correlations between amine-containing particles and ambient relative humidity (RH) were found during the sampling period. Among the three markers we considered, the most abundant amine marker was 74(C2H5)2NH2+, which was detected in 90 and 86 % of amine-containing particles in summer and winter, followed by amine marker ions of 59(CH3)3N+, and 86(C2H5)2NCH2+ which were detected in less than 10 % of amine-containing particles during sampling period. The amine-containing particles were characterized by high fractions of carbonaceous marker ions, carbon–nitrogen fragments, sulfate, and nitrate in both summer and winter. More than 90 % of amine-containing particles were found to be internally mixed with sulfate throughout the sampling period, while the percentage of amine particles containing nitrate increased from 43 % in summer to 69 % in winter. Robust correlations between the peak intensities of amines, sulfate, and nitrate were observed, suggesting the possible formation of aminium sulfate and nitrate salts. Interestingly, only 8 % of amine particles contained ammonium in summer, while the percentage increased dramatically to 54 % in winter, indicating a relatively ammonium-poor state in summer and an ammonium-rich state in winter. The total ammonium-containing particles were investigated and showed a much lower abundance in ambient particles in summer (3.6 %) than that in winter (32.6 %), which suggests the ammonium-poor state of amine-containing particles in summer may be related to the lower abundance of ammonia/ammonium in gas and particle phases. In addition, higher abundance of amines in ammonium-containing particles than that of ammonium in amine-containing particles suggests a possible contribution of ammonium–amine exchange reactions to the low abundance of ammonium in amine-containing particles at high ambient RH (72 ± 13 %) in summer. The particle acidity of amine-containing particles is estimated via the relative acidity ratio (Ra), which is defined as the ratio of the sum of the sulfate and nitrate peak areas divided by the ammonium peak area. The Ra was 326 ± 326 in summer and 31 ± 13 in winter, indicating that the amine-containing particles were more acidic in summer than in winter. However, after including amines along with the ammonium in the acidity calculation, the new Ra′ values showed no seasonal change in summer (11 ± 4) and winter (10 ± 2), which suggests that amines could be a buffer for the particle acidity of ammonium-poor particles.

show abstract

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Characteristics and mixing state of amine-containing particles at a rural site in the Pearl River Delta, China

Cheng

Huang²,

Chan

et al. 2018

Atmos. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

show abstract

“…During 15 May-25 September 2013, the average concentrations (ranges) of NH 3 , SO 2 , and NO x were 36.2 (0.1-862.9), 5.0 (0-86.8), and 15.4 (2.7-67.7) ppb, respectively. As listed in Table 1, the concentration of NH 3 at the NCP rural site was lower than that reported at Asian and African urban sites such as Lahore (Pakistan; Biswas et al, 2008), Colonelganj (India; Behera and Sharma, 2010), and Cairo (Egypt; Hassan et al, 2013) but higher than those from other areas in China, Europe, and North America (Plessow et al, 2005;Yao et al, 2006;Lin et al, 2006;Walker et al, 2006;Hu et al, 2008;Meng et al, 2011Meng et al, , 2014Shen et al, 2011;Schaap et al, 2011;Makkonen et al, 2012;Behera et al, 2013;Gong et al, 2013;Li et al, 2014). For example, the NH 3 at the NCP rural site was higher than that found at the Shangdianzi regional background station in the NCP (Meng et al, 2011), Lin'an regional background station in the Yangtze River Delta (YRD) in eastern China (Meng et al, 2014), and the rural site in Beijing (Shen et al, 2011).…”

Section: Overview Of Concentration Levels Of Measured Speciesmentioning

confidence: 70%

Response to referee #2

Meng¹

2017

Preprint

View full text Add to dashboard Cite

The real-time measurements of NH 3 and trace gases were conducted, in conjunction with semi-continuous measurements of water-soluble ions in PM 2.5 at a rural site in the North China Plain (NCP) from May to September 2013 in order to better understand chemical characteristics of ammonia and the impact of secondary ammonium aerosols on formation in the NCP. Extremely high NH 3 and NH + 4 concentrations were observed after a precipitation event within 7-10 days following urea application. Elevated NH 3 levels coincided with elevated NH + 4 , indicating that NH 3 likely influenced particulate ammonium mass. For the sampling period, the average conversion / oxidation ratios for NH + 4 (NHR), SO 2− 4 (SOR), and NO − 3 (NOR) were estimated to be 0.30, 0.64, and 0.24, respectively. The increased NH 3 concentrations, mainly from agricultural activities and regional transport, coincided with the prevailing meteorological conditions. The high NH 3 level with NHR of about 0.30 indicates that the emission of NH 3 in the NCP is much higher than needed for aerosol acid neutralisation, and NH 3 plays an important role in the formation of secondary aerosols as a key neutraliser. The hourly data obtained were used to investigate gas-aerosol partitioning characteristics using the thermody-namic equilibrium model ISORROPIA-II. Modelled SO 2− 4 , NO − 3 , and NH 3 values agree well with the measurements, while the modelled NH + 4 values largely underestimate the measurements. Our observation and modelling results indicate that strong acids in aerosol are completely neutralised. Additional NH + 4 exists in aerosol, probably a result of the presence of a substantial amount of oxalic and other diacids.

show abstract

“…These field observations emphasize the important role of acid-base reactions in the partitioning of amines from the gas phase to the particle phase. Recent laboratory studies have revealed that the exchange between amine gases and particulate NH 3 and/or ammonium also contributes substantially to amine content and results in a depletion of NH 3 and/or ammonium in the particle phase (Lloyd et al, 2009;Bzdek et al, 2010;Qiu et al, 2011;Liu et al, 2012;Chan and Chan, 2013;Chan, 2016, 2017;Sauerwein and Chan, 2017); however, the significance of such exchange reactions in the ambient environment has not been fully explored. Therefore, the influence of ammonia and particle acidity on the distribution of amines in the particle phase should be studied comprehensively through field measurements.…”

Section: Introductionmentioning

confidence: 99%

“…amine-containing particles in summer, and only a very small ammonium peak was detected in winter. The low ammonium signal in ECOC amine-containing particles may have been due to the exchange of particulate ammonium for gas-phase amines(Lloyd et al, 2009;Qiu et al, 2011;Chan and Chan, 2012;Chan and Chan, 2013; Chan, 2016, 2017;Sauerwein and Chan, 2017). In both summer and winter, the mass spectra of BB amine-containing particles showed carbonaceous markers and secondary ions similar to those found in ECOC amine-containing particles, withadditional distinct ion peaks at m/z 23 [Na] + and BB markers at m/zs -59 [C 2 H 3 O 2 ] -, -71 [C 3 H 3 O 2 ] -, and -73 [C 3 H 5 O 2 ] -.…”

mentioning

confidence: 99%

Characteristics and mixing state of amine-containing particles at a rural site in the Pearl River Delta, China

Chen¹,

Huang²,

Chan³

et al. 2018

Preprint

Self Cite

View full text Add to dashboard Cite

Abstract. Particulate amines play an important role for the particle acidity and 43 hygroscopicity and also contribute to secondary organic aerosol mass. We investigated 44 the sources and mixing states of particulate amines using a single-particle aerosol 45 mass spectrometer (SPAMS) during summer and winter 2014 at a rural site in the 46 Pearl River Delta, China. Amine-containing particles accounted for 12.8 % and 9.2 % 47 of the total detected individual particles in summer and winter, respectively. only 6.7 % of the total amine-containing particles were found to be mixed with 57 ammonium, while in winter this percentage increased to 55 %. The ammonium-poor 58 state of amine-containing particles in summer may have been caused by the 59 displacement of particle-phase ammonium by amine uptake, which was more efficient 60 in summer at higher ambient RH (72 ± 13 %) than in winter (63 ± 11 %). In 61 ECOC-type amine-containing particles, the time series of the amine peak area and the 62 sum of the nitrate and sulfate peak areas were similar in both summer and winter, 63 suggesting the formation of aminium sulfate and nitrate salts. The particle acidity of 64 ECOC-type amine-containing particles was represented by the relative acidity ratio 65 (R a ), which was defined as the ratio of the total sulfate and nitrate peak areas to the 66 ammonium peak area. The R a decreased from 348 ± 335 and 28 ± 14 to 10 ± 5 and 9 ± 67 2 in summer and winter, respectively, after including amines along with the 68 ammonium in the acidity calculation, suggesting that it is reasonable to consider 69 amines when estimating particle acidity.

show abstract

Heterogeneous uptake of ammonia and dimethylamine into sulfuric and oxalic acid particles

Cited by 24 publications

References 77 publications

Characteristics and mixing state of amine-containing particles at a rural site in the Pearl River Delta, China

Characteristics and mixing state of amine-containing particles at a rural site in the Pearl River Delta, China

Response to referee #2

Characteristics and mixing state of amine-containing particles at a rural site in the Pearl River Delta, China

Contact Info

Product

Resources

About