Dimethylamine and Ammonia Measurements with Ion Chromatography During the CLOUD4 Campaign A

Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ; . 3 Hir- ; 1995 , 2004 ciency well , ffi Techniques Discussions (at a 100 pptv- Atmospheric Measurement 3 ). A key process of man and Hegg ff Kulmala et al. 2007 Co , ) on the ternary sulphuric acid ect on nucleation with sulphuric 3 nm) ( ff Kirkby > 2011 , ), demonstrated that NH 2395 2396 2000 , ) nucleation system ( 3 Kirkby et al. and DMA, which were protonated and retained on trace 3 ect on cloud properties ( ff Kulmala et al. ; O)/ammonia (NH 2 ). These particles can eventually grow to cloud condensation nu- 1999 , 2011 ) and dimethylamine (DMA) at low pptv levels. Sampling was performed by , 3 )/water (H mixing ratios reported were initially high du to an unintentional injection of NH 4 3 . DMA was injected intentionally to reach atmospherically relevant levels away SO 3 2 NH This discussion paper is/has been under review for the journal Atmospheric Measurement Techniques (AMT). Please refer to the corresponding final paper in AMT if available. The CLOUD project investigatesclimate the through influence of theirthese galactic e cosmic studies rays is (GCR)precursors the on and the nucleation theirsikko of growth et to new al. detectable particles sizes in ( the atmosphere from gaseous from sources (up toacid and 60 pptv) water at in 278 K. order to study its e 1 Introduction dissolving the gaseous NH cation concentrator columns as ammonium andabove dimethylaminium with 95 an %. e Thetime sampling allowed time a varied decreaselevel. between of 70 the and detection 210 limit min. for each A species longerThey down sampling then to recovered the to sub-pptv NH background levels around 10 pptv, with no further injection of clei (CCN) and influenceRecently indirectly published the CLOUD3 Earth’s data climate ( by modifying cloud properties. The CLOUD project investigatesation of the new influence particles in ofutilised an galactic together environmental with chamber cosmic a at rays sampling CERN. devicemonia Ion on developed (NH chromatography for the was CLOUD in nucle- order to measure am- Abstract Korhonen et al. (H level or less) increases nucleation rates by a factor higher than 100 to 1000 over the Dimethylamine and ammonia measurements with ion chromatography during the CLOUD4 campaign A. P. Praplan, F. Bianchi, J. Dommen, andLaboratory U. of Baltensperger Atmospheric Chemistry, Paul Scherrer Institute, VilligenReceived: PSI, 3 Switzerland February 2012 – Accepted:Correspondence 2 to: March 2012 J. – Dommen Published: ([email protected]) 23 MarchPublished 2012 by Copernicus Publications on behalf of the European Geosciences Union. Atmos. Meas. Tech. Discuss., 5,www.atmos-meas-tech-discuss.net/5/2395/2012/ 2395–2413, 2012 doi:10.5194/amtd-5-2395-2012 © Author(s) 2012. CC Attribution 3.0 License. 5 20 15 10 25 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ) ) ) 4 ). ). 3 SO ). 2 2011 2010 ect on 4 2011 2011 ( , ( ff Murphy , SO ect is de- 2 ff ) was used H , but also by 3 3 − ) or ozone (O · 2012 N), their e ( cm 3 7 Bzdek et al. ). A cation trap col- Bzdek et al. Kirkby et al. 1 − cm) was introduced by –10 6 and amines on surfaces. Ω VandenBoer et al. ). Furthermore, a recent cient to explain the nucle- ) and NH or R 3 ; where one, two or all three rotated to allow the elution 2 ffi 3 2 ) also reported enhancement ,R 1994 2012 2 2007 ( , Bianchi et al. , 2012 ( 0.05 K) with a relative humidity of 38 % ± ) from atmospheric samples with various was still not su + 4 3 ¨ ander et al. Yu et al. Tuazon et al. ect: even at pptv-levels, complete displace- ) and can therefore enhance even more neu- 2398 2397 ) in a 10-loop coil to allow for dissolution of the Murphy et al. ff 1 ; production with negligible thermal e − 4 electropolished stainless steel cylinder. A more Voigtl 2008 3 , 2001 SO 2 , O nucleation in the atmosphere. 2 /H ). Although the chamber temperature can be varied from 4 ´ ¨ en et al. a et al. SO and DMA 2011 2 ( 3 ¨ Kurt akel ( ) found that DMA was present at higher mixing ratios during nu- M 3 O) system. However, NH 2 2001 /H ( 4 by dimethylamine (DMA) occurs within seconds or minutes, changing the 3 ) showed that amines can form secondary organic aerosol (SOA), by acting Kupc et al. SO 2 ). It was specially designed to minimise the loss of NH ¨ 2007 a et al. ( 1 ects on the nucleation rate by several amines. 0.1 %) during CLOUD4. A debubbler separates the air and the water, which is pumped from the bottom of the CLOUD4 (June–July 2011) investigated the role of DMA in the formation and growth Because amines possess structural similarities with NH ¨ akel ff ± a second cation concentratortomatisation column was to necessary ensure as continuous the measurements. CLOUD chamber This cannot au- be accessed at all times 183 to 313 K, it( was kept constant at 278 K ( 2.2 Sampling of NH The same sampling probe as the one described in ber, it was mixed with airgaseous (0.8–2.1 species l into min the water. Withunflushed this by setup water, only so a that section sampling of losses 5 mm became tubing negligible. remained debubbler by a peristaltic pump. Thistrator water column was (TCC-2 passed through or a210 TCC-LP1, min trace Dionex), cation of concen- where sampling, cations theof were 10-port the retained. valve cations described After to 70 in the to Fig. analytical column while the sampling water was concentrated on Briefly, it consists ofsmall a orifice to 2-mm the diameter CLOUDa chamber. stainless peristaltic Ultra steel pure pump tubing water in (18.2 of theumn M stainless 140 (CTC-2, cm steel Dionex) length tubing was (0.25–0.80 additionally withfrom ml this used min a water to prior remove to the sampling. possibly As interfering the water cations reached the orifice to the CLOUD cham- The fibre-optic UV systemscribed for in H (Fig. 2.1 CLOUD chamber The CLOUD chamber isdetailed description a can 26.1 be m found in 2 Experimental surements performed for CLOUD4. tral and ion-induced H cleation events in boreal forestsnucleating compared species to or a non-event periods, speciesthat increasing making they growth it can rates a be of potential detected freshly faster formed at particles, 3 so nm. and was employed forused this for quantitative work. analysis are The described hereafter particular along with sampling the device results of and the the mea- IC method composition of sub-3 nm diameteraddition to bisulphate those clusters. clusters can NotM occur, only influencing their substitution, growth but rates also ( computational study suggests thatmolecules than amines NH are even more strongly boundfound to experimental H evidence forment of this NH e e of new particles. Ionand chromatography inorganic (IC) cations is like asampling ammonium methods method ( (NH often used to analyse amines ation rates observed under typical tropospheric conditions (10 hydrogen atoms are replaced by organicsecondary moieties (RNH organic aerosol formationet is al. increasingly subject of investigation. binary (H as bases and neutralisingparticipating acids in present gas in phase theto chemistry gas initiated form phase by low similar hydroxyl volatility radicals to products (OH NH (see also 5 5 20 25 15 10 25 15 10 20 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ] 4 + 3). (2) (1) . It SO 1 = 2 erence ): Sam- ff and [BH B 2003 ( p (isocratic). Re- ], 1 + − 100 pptv). From a ective Henry’s Law . The sampling was < ff 1 − is equal to the di Chang et al. B p for DMA. At this temperature, and between 17.8 and 21.1 min and DMA ( 3 1 3 , taking into account the pH of the − ∗ ). H 3 ciency relies on the e , of the analytes. The negative logarithm of ffi and amines, a second scrubbing system was a 2400 2399 K 3 is 9.90 at 278 K (Bates and Pinching, 1950) and 100 pptv each), assuming complete dissolution. ) is 10.64 at 293 K (Hall, 1957). + 4 + < and from 0.2 to 1.0 pptv for DMA (signal/noise , ( ] 3 + 3 and 81.3–150 M atm CS10 (Dionex) guard and analytical columns, respec- ) of NH B 3 [BH a p ® and both liquid flows were 0.5 ml min K + ciency for NH 1 ]). Equation (1) defines − ffi [B] + tubing of 1 mm diameter and 140 cm length. The air flow used for NH ])) of 14.7, corresponding to a pH of 7.3 for pure water (H = ® − ) 1 a ciency − K and 0 to 150 ng for DMA (Fig. log[H p ffi − 3 + a ][OH K + pH p − − , which depends on the degree of protonation of the species in solution ∗ pH is the partial pressure of base (B) in the gas phase. From the review 10 erent concentration levels, corresponding to injected amounts ranging from H CG10 and Ionpac ff + log([H B 10 p − ® (1 = ] = H + w = The method detection limit (MDL) depends primarily on the noise of the chro- To test the sampling e K ∗ [B] [BH between the total amount ofcan B be in derived the from system Eq. (here (1). 100 pptv) Considering and pure [BH solutions of each species, the amount Therefore [B] can be neglected in Eq. (1) and because theoretical point of view,constant, the sampling e and thus on pH ( solution and the dissociationthe constant, dissociation constant (p the one of dimethylaminium (DMAH H (p can be neglected).concentrations This of value DMA canMoreover, and increase the NH up degree to of(Eq. 7.5 protonation 2) at by of pH dissolving both 7.5: low species gas in phase solution is higher than 99 % 3.1 Sampling e The use of pureficient water for without measurements addition of of low an acidic mixing compound ratios is of assumed NH to be suf- where of Sander (1999),of Henry’s law 14.3–173 M atm constants atHawkes (1995) 278 K reports are a estimated negative to logarithm be of in the the self-ionisation range constant of water 3 Results and discussion 0 to 30 ng for NH matograms, but is influencedsampling by time). the sample Depending volumeranged (based on from 0.2 on instrumental to sampling conditions 3.7 pptv air and for flow NH sampling and time, the MDL ples were eluted with 40 mMtention methanesulfonic times acid varied (MSA) between at 8.8for 1 and ml DMA. 10.5 min min The for peaks NH obtainedCalibration from was the performed conductivity by detector directtion) were injection integrated of of manually. di aqueous standards (no preconcentra- consisted of a Teflon for this setup was 1alternated l min from one debubbler to the other using the valve system2.3 described previously. Ion chromatography (IC) A Dionex DX600 systemIonpac was usedtively. The for method used the was similar analysis to the of one the described in collected cations with to a minimum. No derivatisationto was the needed analytical and column the automatically samples at could the be end of directlyinstalled the eluted sampling in period. series at the end of the campaign as shown in the lower part of Fig. (e.g. when it is irradiated by the pion beam) and it reduced the required maintenance 5 5 10 20 15 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | . . , 3 6 3 3 3 − − and 10 10 3 ciency ciency × × , so that ffi ffi 3 VandenBoer , but no NH and between 3 at the present − 3 3 10 ciency is therefore × ffi . No DMA could be and DMA determined 1 3 ciency decreases, indicating ffi , as well as the ones corrected 3 mixing ratios decreased to values 3 ). Some values at the beginning of the 2003 2402 2401 , , the sampling e 3 − -free air, the NH 10 Krupa 3 ) is between 0.35 and 4.1 % for NH B × p ciency, the data before 1 July (marked with green color) ffi shows the mass flow controller settings for continuous DMA showed peaks in the blank samples during the second phase 6 3 ciency is governed by the residence time and not the gas-liquid in the sampling line. This ratio influences the sampling e ffi 3 − was not injected at a constant mixing ratio into the chamber, the same summarise the measured mixing ratios for NH 3 6 10 erent concentration levels, which can often be problematic ( × mixing ratio ranged mostly below 20 pptv, which corresponds to mixing ff shows the uncorrected mixing ratios of NH ). This was possible because of the cleanliness of the CLOUD chamber and 3 and DMA mixing ratios and 5 3 5 2011 , The NH The top panel of Fig. Blank values were obtained by directly sampling water instead of flushing it through Figure If the ratio drops below 0.25 Because NH tional to these settings. Indeed, the mixing ratios shown on the bottom panel of Fig. ratios found at remotemeasurements locations show ( higher values.After This several is days due ofwas to experiment, continuously an replaced where by unintentional the NH around injection air of 10 sampled pptv. NH fromconditions. the This CLOUD corresponded chamber to the background levelinjection of into the NH CLOUD chamber. It was expected that the DMA levels were propor- for background levels from thecussion sampling about water. sampling To take e were into corrected by account a the factor 2, previousIn because dis- the the liquid night to air from flowdata ratio 2 could was to around be 0.15 acquired 3 due July, to this an ratio interference in dropped the again chromatograms. below 0.25 Figures 3.3 NH with IC. The instrumentreliable was data not could be used acquiredbackground, at between which the 6 increased and very the 11 MDL. beginning July, due of to the an campaign elevated conductivity the and sampling no line. No peaking for the DMA whole could campaign, be so observedOn that from the no these other correction measurements was hand, dur- applied NH of to the the obtained campaign mixing (after ratio. sured 11 mixing July, ratios when were corrected thethe proportionally sampling column to time (which the depends was water on amount extended) concentrated water and on flow the and mea- sampling time) for this period. the absence of interfering peaks.the Only chromatograms but sodium well and resolved potassium from peaks the also peaks appeared of in interest. 3.2 IC method The use of the CS10DMA analytical column without from any Dionex allowed interferencehave the very separation of of di the NH peakset al. on each other, even when both species detected in the watercentration sampled was from close the to second 60is pptv system. at and least Because the 99 the detection %. limit measuredno Unfortunately, 0.6 the con- reliable pptv, second conclusion the system can sampling was be e contaminated drawn with for NH this species. DMA mixing ratio in the chamber (around 60 pptv) arethat depicted the on stripping the right. e equilibrium. Because somethey data were corrected were accordingly. recorded with a ratiotest lower could than not 0.25 besystem done. was Furthermore, set at the in end series of with the campaign, the a first second one sampling as shown in Fig. 0.06 and 0.12 % forexpected DMA. to be Under higher these than 95 conditionsratio % the overall. of sampling These 0.25 calculations e assumed aas liquid depicted to in air Fig. flow 4.the The left, value while of the the ratio values throughout obtained the by experiment is varying presented the on liquid to air flow ratio for a constant remaining in the gas phase ( 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | from ◦ ratios 3 ). Lower to 11 during 3 2010 − , , organics) can 3 10 × , corrections may need 3 − Benson et al. ; atmospheric levels range from ) is crucial for the understanding cient sampling line, could provide 3 3 − ffi 2006 , cm ) found outdoor mixing ratios of DMA 7 ) measured a broader range and slightly 2398 1995 ( Li et al. 2403 2404 2404 2003 130527) and by the EC Seventh Framework project ( ) found DMA levels of approximately 10 pptv with- 2403 , 2012. , while this ratio ranged from 4.6 (before 1 July) and by a factor 1.5 when the ratio was 3 , 2007. 2007 3 − ( − , 2010. 10 ¨ uz 10 × × , 1950. ). On the other hand, NH Chang et al. ) reported 0.5 and 1.8 pptv of DMA in urban and rural en- Aky Schade and Crutzen 2011 1992 135307 and 206620 This work was supported by the Swiss National Science Foundation ( , (in the night from 2 to 3 July), as previously discussed. The values 3 is also present at several orders of magnitude higher levels (ppbv) − 3 10 × Ge et al. doi:10.5194/amtd-5-2111-2012 cient to enhance nucleation rates by several orders of magnitude. The method ffi ¨ onberg et al. ¨ uz, M.: Simultaneous determination of aliphatic and aromatic amines in indoor and at low pptv mixing2130, ratios in the CLOUD chamber, Atmos. Meas. Tech. Discuss., 5, 2111– Studies at low temperature also need to be performed. However, for CLOUDGr cam- spectrometer for ambient measurementsdoi:10.5194/amt-3-1075-2010 of ammonia, Atmos. Meas. Tech., 3, 1075–1087, outdoor air samplesdoi:10.1016/j.talanta.2006.10.028 by gas chromatography-mass spectrometry, Talanta, 71, 486–492, doi:10.1021/ja01159a087 Usually, NH e.m.f. studies of the ammonium salt of a weak acid, J. Am. Chem. Soc., 72, 1393–1396, With the sampling system used, no separation of the gas and aerosol phaseDMA oc- mixing ratios correspond to atmospherically relevant levels away from the higher mixing ratios of DMA (1.9–34 pptv) at a suburban site in Seoul, Korea. Closer to vironments in Sweden. Bianchi, F., Dommen, J., Mathot, S., and Baltensperger, U.: On-line determination of ammonia of nucleation because suchbe su levels of certainpresented here, contaminants based on (e.g. IC and NH data making use down of to an sub-pptv e levels with 70 to 210 minpaigns time resolution. below 273 K,freeze the in sampling the sampling line line. needs to be adapted so that water does not agricultural sources, values could usually not be reported because of detection limitations. 4 Conclusions and outlook The analysis of trace gases at pptv-level (ca. 10 Benson, D. R., Markovich, A., Al-Refai, M., and Lee, S.-H.: A chemical ionization mass Aky of 21 pptv in theinto afternoon the and CLOUD 76 pptv chamber justmethylamine represented before and well sunrise. trimethylamine that The were range. levels alsoa of Moreover, present few DMA in hundreds at injected of all similar pptv). those levels (low studies, pptv levels to (project nos. 200020 CLOUD-ITN (MC-Initial Training Network No. 215072). References Bates, R. G. and Pinching, G. D.: Dissociation constant of aqueous ammonia at 0 to 50 a few hundreds of pptv to several ppbv ( province, Turkey, as well as strongly varying concentrations of various otherthan amines. the individual amines.in VandenBoer Toronto between et 1.6–20 al.the (2011) CLOUD4 reported campaign. The amines influence to ofrates such in NH a the level presence of DMA of on low nucleation NH3 and mixing growth Acknowledgements. ratio will be the subject of other publications. out large variation between summer and winter in six sampling sites in the Zonguldak the period from 21 to 24 July. curred. For totalto aerosol be mass considered, loadings to higherparticle take than phase. into 1 account µg m the ammonium and dimethylaminiumsources from the ( the measured mixing ratio dida not few drop pptv, slowly to decreasing. previousflow levels Data ratio but were was showed around multiplied a 0.15 by backgroundaround a of 0.2 factor 2 when thereported liquid for to both air species were in some cases very close to the MDL, in particular in followed this trend. However, after switching back from higher settings to lower ones, 5 5 25 25 15 20 15 20 10 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | , , ´ e, 2396 2396 ¨ 2397 a, M., 2397 ¨ a ˜ orrak, U., , 2011. ectively than , 2004. , 2011. ff , 2008. ¨ a, T., Tammet, ¨ aj doi:10.1034/j.1600- ¨ a, K., Sillanp ect of ammonia on ff 2396 2402 doi:10.1007/s10712-008- doi:10.1029/2005JD006275 2398 , , 2000. , 2003. ¨ a, M., Stozhkov, Y., Stratmann, F., 2403 doi:10.1016/j.jaerosci.2011.05.001 2396 production in aerosol chambers causing 2396 , 2011. 4 doi:10.5194/acp-11-767-2011 , 2011. ) on terrestrial vegetation: a review, Environ. ¨ ameri, K.: Chemical composition of aerosol doi:10.5194/acp-8-4095-2008 doi:10.5194/acp-11-8735-2011 3 SO 2 O in the atmosphere, J. Geophys. 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Chem. and their subsequent growth, Geophys. Res.2012. Lett., 39, L02807, Fig. 1. modified sampling system with two debubblers (bottom panel) for sampling e Tuazon, E. C., Atkinson, R., Aschmann, S. M., andVandenBoer, T. Arey, C., J.: Petro Kinetics and products of the Schade, G. W. and Crutzen, P. J.: Emission of aliphatic amines from animal husbandry Sander, R.: Compilation of Henry’s law constants for inorganic and organic species of potential Voigtl Yu, H., McGraw, R., and Lee, S.-H.: E 5 10 15 20 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | 2410 2409 , left panel) and dimethylamine (DMA, right panel). 3 Schematic of the concentrating system with two columns and a 10-port valve to en- Calibration plots for ammonia (NH Gray areas correspond to the range of experimental data. Fig. 3. Fig. 2. sure continuous measurements. While onechamber column sampling concentrates line the (red analytes line),ion coming chromatography the from (blue other the line). column can be eluted and the sample analysed by Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | 2412 2411 ) mixing ratios (in pptv): uncorrected (gray), corrected for 3 ciency (before 1 July, green), without correction required (1 to 6 July, dark blue) and ffi Liquid to air flow ratio from the sampling line used during the campaign (left panel). Overview of ammonia (NH sampling e Fig. 5. corrected for background levelsfunction (after through 11 the July, final light data. blue). The continuous line is a smoothing Fig. 4. The dotted line at 0.25occurs. indicates Measured the mixing ratio ratio for varying whichconcentration the complete (around liquid sampling to 60 of pptv) air dimethylamine in flow (DMA) ratio the while chamber sampling (right a panel). constant DMA Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | 2413 Mass flow controllers (MFC) settings (top panel) and summary of dimethylamine (DMA) mixing ratio (in pptv)data measured of the (lower second panel). half of A the logarithmic campaign (around scale 1 was pptv). used to visualise the Fig. 6.