Determination of Atmospheric Organosulfates Using HILIC Chromatography with MS Detection A

Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ). Trace 10 % for 3 − ± , ), followed by 2 3 sample extrac- − 2.5 , E. Geddes 1 , Z. Baker samples collected 10–11 July 2013 in 1 2.5 ) and lactic acid sulfate (1.4–2.9 ngm 12589 12590 3 − 8 % for extraction by sonication and 98 , S. Kundu ± 1 2 , E. A. Stone 1 ciency and precision of two methods of ambient PM cient method of separating and quantifying organosulfates is used to ffi , and T. Humphry ffi 2 This discussion paper is/has beenTechniques under (AMT). review Please for refer the to journal the Atmospheric corresponding Measurement final paper in AMT if available. Department of Chemistry, Chemistry Building,Chemistry University Department, of Iowa, Truman State Iowa University, City, Kirksville, IA MO 52242, 63501, USA USA extraction by rotary-shaking. Sonication wasits determined better to be precision. the AnalysisCentreville, superior of AL, method USA ambient for during PM the Southeastence Atmosphere of Study hydroxyacetone (SAS) sulfate confirms the infate pres- ambient was aerosol the for most the abundant first compound time. measured Glycolic (ranging acid 8–14 ngm sul- evaluate the e 1 2 Received: 23 October 2014 – Accepted: 20Correspondence November to: 2014 E. – A. Published: Stone 17 ([email protected]) December 2014 Published by Copernicus Publications on behalf of the European Geosciences Union. Abstract Measurements of organosulfates insecondary ambient organic aerosols aerosol provide (SOA) insightthropogenic formation pollutants. to from Organosulfates the mixtures have, extent of however,to proved of biogenic analytically measure. gases challenging This and an- studycation presents of a organosulfatesnegative sensitive based electrospray new upon ionization analytical ultra-performance mass methodration liquid spectrometry for is the chromatography (UPLC-ESI-MS/MS). based quantifi- with amide The upon sepa- stationary hydrophilic phase interactionand that methyltetrol-derived liquid organosulfates. The provides chromatography method excellent ispounds: (HILIC) validated methyl retention using with sulfate, six ethyl of model sulfate, an com- benzyl carboxy-organosulfates sulfate, sulfate, and hydroxyacetone sulfate, glycolic lactic acid acidpure sulfate. organosulfate A potassium straightforward saltsThis protocol for highly for use e preparation as of quantification standards highly is presented. tion. Spike recoveries averaged 98 K. Richards hydroxyl acetone sulfate (2.7–5.8 ngm amounts of methyl sulfate were detected,detected. while ethyl Future sulfate and research benzyl will sulfatestandards, were focus not expansion on of the this development UPLC-MS/MSapplication of to of additional include this more organosulfates method targetenvironments. to molecules, assess and temporal the variations in organosulfates in ambient Determination of atmospheric organosulfates using HILIC chromatography with MS detection A. P. S. Hettiyadura Atmos. Meas. Tech. Discuss., 7, 12589–12615,www.atmos-meas-tech-discuss.net/7/12589/2014/ 2014 doi:10.5194/amtd-7-12589-2014 © Author(s) 2014. CC Attribution 3.0 License. 5 20 10 15 25 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ) − S 7 O 11 H 5 ) and 2-methyltetrol sulfate (C − S 6 12591 12592 O ). It has been suggested that they are a signifi- 3 − 3 H 2 )ESI) mass spectrometry (MS) (Olson et al., 2011; SO − − O − ) (Kundu et al., 2010; Staudt et al., 2014). However, this mode of LC − 4 ) (Gao et al., 2006; Surratt et al., 2007a) and aromatic organosulfates − 7 SO 7 H NSO 7 16 H Chemical identification and quantification of organosulfates requires the analytical Due to the atmospheric abundance of organosulfates and their importance in SOA Atmospheric organosulfates are SOA compounds that contain a characteristic sul- 10 (e.g. C non-volatile in the environment. Hence, theygraphic cannot techniques be separated and usingprocess gas must chromato- (e.g. be liquid approached chromatographyhave using (LC) applied a or reversed-phase condensed-phase capillary LCwater-soluble separation electrophoresis). to and Prior aqueous methanol-extractable studies et atmospheric aerosol al., samples components 2003; Stone that to etrely range fogwater al., upon from 2012; (Cappiello a Surratt non-polar ettaining stationary al., higher-molecular 2008). phase Reversed-phase weight, and separationsC polar monoterpene-derived that mobile nitro-oxy phase organosulfates are (e.g. successful in re- separation of target analytesOrganosulfates from are the strongly inorganic acidic aerosol (Guthrie, matrix 1978) and and are from consequently each anionic other. and of organosulfates in thecharge negative (Romero mode, and because Oehme, 2005; theseused Surratt compounds to et determine carry al., organosulfate a 2007a).teristics, exact High-resolution negative masses, and MS chemical may abundance formulas, be (AltieriShalamzari structural et charac- et al., al., 2013; Staudtet 2008; et al., Laskin al., 2013). 2014; A et Surratt majorthe al., et limitation glaring al., in 2009; lack 2008; the of Pratt Tao quantification et authentic and et al., quantification speciation 2014; standards. al., of Zhao organosulfates 2013; is separation is not optimized for lower-molecularfor weight example and glycolic highly polar acid organosulfates; sulfate (C 2010), and capillary electrophoresis (CE)negative and electrospray liquid ionization chromatography (LC) (( coupled with Surratt et al., 2008; Yassine et al., 2012). ESI MS is especially sensitive to the detection formation, analytical methods have beenby developed Fourier to transform detect infrared them2003), spectroscopy in ambient (FTIR) in-situ aerosol (Hawkins single et al., particle 2010; mass Maria et spectrometry al., (Farmer et al., 2010; Froyd et al., cant component of fine particulate organic2010; matter Shakya (Frossard et and al., Peltier, 2011;Turpin, 2013; Hawkins 2012). et Stone Laboratory al., et chamber al., experimentsfrom 2012; have biogenic demonstrated volatile Surratt organic that et compounds SOAol al., (BVOCs, formed [MBO], 2008; e.g. monoterpenes, isoprene, Tolocka and 2-methyl-3-buten-2- and sesquiterpenes)acid, in contain the a presence large of organosulfate oxidantsSurratt and component et sulfuric (Chan al., et 2007b; al., Zhang 2011; et Iinuma al., et 2012a, b, al., 2014). 2009; are retained less than 2.5organic min and acids, co-elute polyols, with and numerouslytes other inorganic with organosulfates, sulfate small other (Stone compoundsto et competition may al., for lead 2012). ionization toaration, Co-elution (Reemtsma such negative of and as biases These, ana- hydrophilic in interactiondesigned 2003). liquid their Other to chromatography ESI modes retain (HILIC), of response are moleculesIrgum, specifically LC 2006). due with HILIC sep- ionic chromatography has and previously polar been shown functional to groups retain (Hemstrom hydroxycar- and fate ester functional group (R 1 Introduction On a large scale, particulatetive balance matter directly (PM) by in scattering the andand atmosphere absorbing indirectly impacts solar radiation the by (Jacobson earth’s et acting1993). radia- al., PM as 2000) also cloud contributes condensationcular to nuclei and negative (CCN) respiratory human (Novakovcomposition diseases health of and outcomes, (Davidson PM Penner, can such et aidof as al., in air cardiovas- the resources. 2005). identification Secondary Knowledge of organicactions PM aerosol of of sources (SOA) and the gaseous is better formed precursors chemical management It in that remains the yield atmosphere one products by of re- thatbecause the partition of most its to poorly chemical understood the complexitymixtures. PM particle and sources the phase. fact (Foley that et it al., forms 2010), in in complex part environmental 5 5 15 10 20 25 15 20 25 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ) C, ◦ 2.5 ciency ffi cient in the separa- ffi 378.2029, Sigma-Aldrich) , desolvation gas flow rates of m/z 1 − )ESI mode was performed on a mi- resistivity). All other reagents and sol- − Ω cient sample preparation protocol for the ffi ciencies of ultra-sonication and rotary shak- ffi 12594 12593 LC/MS grade) and ultrapure-water was prepared on- ™ C, cone gas flow rate 30 Lh , from samples that were collected in Centreville, Alabama ◦ 2.5 . Data were collected from a mass range 40 to 400 with V geometry in 1 − et al. (2001). To synthesize a sulfate ester, 1 molar equivalent (eq) of the ap- ff High-resolution MS analysis in the negative ( The objective of this study was to develop an accurate and sensitive method of quan- This study presents the development and validation of a new analytical method to source temperature 110 550–650 Lh dance) were filtered out.was A used small for lock peptide mass (Val-Tyr-Val, correction. 2.2 General procedure for the synthesisEach of sulfate organosulfates ester standard was synthesizedof using Ho a general method derivedpropriate from alcohol that was added with stirring to 15 mL of dry pyridine in a round bottom reflectron mode. Signals below a threshold level (set at 5–18 % of the relative abun- vents were obtained from FisherAcrosAnalysis and was used conducted without by further Atlantic purification.collected Microlabs Elemental on in a Norcross, Bruker GA ARX-400 and NMR NMR spectrometer spectra with were acrOTOF 5 mm spectrometer broadband probe. (Bruker Daltonics).voltage 2.6 The kV (benzyl ESI sulfate) conditions and15 V 2.8 used kV (benzyl (for include other sulfate), capillary 5colic standards), 30 acid V sample sulfate) cone (methyl and voltage 35 sulfate, V ethyl (hydroxyacetone sulfate), sulfate, desolvation lactic temperature 350 acid sulfate and gly- 2 Materials and methods 2.1 Chemicals, reagents, and general methods Six organosulfate standards werecommercially-available: methyl used sulfate in (sodiumand method methyl ethyl sulfate, sulfate development, (sodium 99 two %, ethyl sulfate, Acros of Sigma-Aldrich).according Lactic Organics) to which acid sulfate Olson were was et prepared acid al. sulfate (2011). were Benzyl synthesized sulfate,from as hydroxyacetone Fisher described sulfate, Scientific below. and (Optima Acetonitrile glycolic site (ACN) (Thermo, was BARNSTED EasyPure-II; purchased 18.2 M Organosulfates with aromatic,quantified keto-, with hydroxyl-, triple and quadrupoletion mass carboxyl- curves spectrometric prepared functional detection from commercially-available groups (TQD) orto against synthesized are quantifying standards. calibra- these In compounds, addition the new method is shown to be e tifying highly-polar atmospherically-relevant organosulfates usingphy for HILIC separation chromatogra- and tandemcommercially mass available and spectrometry laboratory-prepared for pure detection.this standards Used combination of in enables the concert organosulfates, the with manner facile of separation, identification, smalllected and samples from quantification the of of atmosphere. This highly all method polar, provides a ionic, means of and assessing the nonvolatile e organosulfates col- separate highly-polar and ionic organosulfatesraphy by (UPLC) ultra-performance using liquid an chromatog- HILIC stationary phase modified with amide functional groups. boxylic acid organosulfates, such asare glycolic among acid the sulfate and mostet lactic abundant al., acid 2011). atmospheric sulfate, which organosulfates quantified to date (Olson of extracting organosulfates fromaccurately measuring fine organosulfates particulate in ambient matter aerosol. deposited on filters and for tion of other major organosulfatesstandards present in are the not southeastern yet Unitedextraction available. States, and A for pre-concentration which highly of organosulfates e samples from is fine reported, particulate and matter the (PM extraction e ing are compared. Alsosulfate reported in here ambient areduring PM the the first Southeast measurements Oxidant of and Aerosol hydroxyacetone Study (SOAS). 5 5 25 20 10 15 15 10 20 25 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | : + K − 4 SO 7 the cation H 7 ff (relative intensity, 4.84 (s, 2 H); 7.25– ), 96.9588 (100.00), − 6 1 63.59; 172.20. HR-MS m/z − SO 1 3 − H 8.45; 56.01; 67.54; 127.42; ppm 2 )ESI) 1 δ − ppm − δ ppm δ (relative intensity, %): 187.0072 (81.75, m/z 12596 12595 2.10 (s, 3 H); 4.26 (s, 2 H). 13C-NMR (400 MHz, 1 C, and the resulting white solid was recrystallized )ESI) : C 18.74, H 2.62, S 16.68. Found: C 18.57, H 2.55, ◦ − − + K ), 96.9564 (96.86), 80.9609 (50.19), 79.9533 (100.00). − 5 C) overnight. Potassium benzyl sulfate formed in the ppm − 5 ◦ δ 5 SO 5 SO − 5 H 3 H 3 26.47; 71.05; 206.39. HR-MS (( 1 − (relative intensity, %): 154.9650 (10.00, C ppm C, and then titrated to pH 2 using 3 M HCl, before enough ethanol was δ ◦ ), 95.9497 (100.00), 80.9636 (15.74). Analysis calculated for C 4.54 (s). 13C-NMR (400 MHz, DMSO-d6): m/z − 4 1 − SO 7 )ESI) H ppm 7 − (( exchange resin and rinsing,ration the at water 40 was reducedadded to to about make 10 an mLboiling 80 via % ethanolic rotary ethanol solution evapo- as solution.acid in The sulfate the product formed previous was as syntheses. thenrinsed The colorless crystallized with potassium needles from salt cold that the of 90 werewith % glycolic glycolic collected ethanol. acid by sulfate, The and vacuum gave needles filtration elementalprotonation analysis gave of and results the NMR fitting carboxylic approximately and 50 acid % δ mass moiety. Yield: spectra 45 %; consistent 1 H NMR (400 MHz, DMSO-d6): ions. The exchange wasester conducted dissolved by in making water awater and slurry to approximately with maintain 80 a the equivalents slurry. pyridinium Afterunder of salt filtration, vacuum resin, the of at using water the was no appropriate removed more via than rotary 40 evaporation %): 152.9836 (21.94, C S 16.79. 2.2.3 Glycolic acid sulfate, potassium salt The isolation of thelar potassium manner salt to of that glycolic of hydroxyacetone acid sulfate, sulfate except was that conducted after in filtering a o simi- from a boiling 80 %of ethanol benzyl solution, sulfate. including Theneedles a potassium hot that filtration salt were step of collectedThe as hydroxyacetone by needles in sulfate the vacuum proved formed synthesis to filtrationNMR as be (400 and colorless MHz, analytically rinsed DMSO-d6): pure withDMSO-d6): hydroxyacetone cold sulfate. 90 Yield: % 35 ethanol. %; 1 H Analysis calculated for C mother liquor as colorlesswith needles that cold were 90 collected % byYield: vacuum ethanol. 1.648 g filtration The and (75 %); rinsed needles 1 proved H NMR to (400 be MHz, analytically DMSO-d6): pureC benzyl sulfate. flask under nitrogen. Todine that sulfur clear, trioxide colorless complex was mixture,was added slightly stirred at more for once than 8 and h,distillation the 1 after under resulting eq vacuum, which cloudy of and white the pyri- varying mixture the solution in resulting was color clear clear. from oil TheThe colorless (the conversion pyridine to pyridinium to was salt the slight removed potassium of yellow,the via salt was the esters. and converted ester), the to crystallization the procedures potassium varied form. among 2.2.1 Benzyl sulfate, potassium salt To synthesize thebeen potassium removed salt via ofsolved distillation benzyl in under approximately sulfate, vacuum, 10pH once mL the was the of resulting above distilled pyridine 11. clearous water Then, solvent yellow solution. 50 and oil mL had The titrated of resulting wasand with ethanol solution dis- quickly 1 (neat) (approximately vacuum M was 75 filtered KOH %gave added to until ethanol) to no remove was the the a proton heated remainingthen small to or aque- amount placed boil carbon of in stark NMR a white spectrum freezer precipitate when that ( analyzed. The mother liquor was 7.41 (m, 5 H).127.59; 13C-NMR 128.13; (400 MHz, 137.56. HR-MS DMSO-d6): (( C 37.15, H 3.12, S 14.17. Found: C 36.64,2.2.2 H 2.93, S Hydroxyacetone 14.10. sulfate, potassium salt The isolation of theing potassium Dowex 50WX8-200 salt cation of exchange hydroxyacetone resin sulfate that was had accomplished been us- charged with potassium 5 5 25 20 15 10 10 15 25 20 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | 1 − LV, Caliper ) were ob- 2 ® er (10 mM, pH 9) ff C for 18 h to remove ◦ ) flow rate at 900 Lh 2 : C 11.27, H 1.18, S 15.04. C, desolvation temperature of ◦ + 1.5 was collected on quartz fiber fil- K − 6 C and the mobile phase flow rate 2.5 ◦ SO , 5510, Branson) or an orbital shaker 2.5 1 − H 2 , desolvation gas (N 1 quartz fiber filters) and 7 spiked samples, for − 12598 12597 2 cient to elute the analytes. To re-equilibrate the ffi C using an evaporation system (TurboVap ◦ in Centreville, AL filter samples and field blanks (totaling 15 cm 2.5 2.5 ) flow rate at 100 Lh 2 . 1 − . A 5 µL injection volume was used for quantitative analysis of sam- 1 100mm, 1.7 µm particle size; AQUITY UPLC, Waters) equipped with − ciency of extraction by sonication and rotary shaking, a series of quality × ffi er (10 mM, pH 9) in acetonitrile and ultra-pure water (95 : 5, by volume) ff was collected at the Southeastern Aerosol Research and Characterization C, cone gas (N ◦ 2.5 Organosulfates were detected by a TQD MS (ACQUITY, Waters) equipped with an each authentic standard transition are provideda in capillary Table 1. voltage Other of ESI 2.7 conditions kV, include source temperature of 150 ESI source in the negativeitoring ion (MRM) mode. mode, The in detectorfragmented which operated in the in molecular multiple the reaction ionquadrupole. second mon- was Optimized selected quadrupole MS in conditions and the (cone product first voltages and quadrupole, ions collision were energies) used selected for in the third column prior to thephase next A injection, the from solvent 11(needle program wash) to was consisted 11.5 of returned min acetonitrile to and and 100 water % was (80 mobile held : 20, constant v/v). until 14 min. The wash solvent in ultra-pure water. AA solvent was gradient maintained at was 100 usedconstant % for until to 2 min, 11 elute min, then the which decreased analytes: to was 85 mobile su % phase from 2 to 4 min and held 450 was 0.5 mLmin ples and standards. Theacetate optimized mobile bu phase Aand (organic) mobile consisted phase of B ammonium (aqueous) consisted of ammonium acetate bu 2.5 Separation and detection of organosulfates Organosulfates were separated using antosampler, and UPLC thermostatted (equipped column with compartment,USA). quaternary ACQUITY The UPLC, pump, separation Waters, au- was Milford, optimized usingumn a (2.1mm bridged ethylene hybrid (BEH) amide col- which standards were spiked ontration of to 100 blank µgL quartz fiber filters to achieve a final concen- a pre-column. The column was maintained at 35 control samples were extractedsisted by of each 4 method. laboratory These blanks quality (of control 5.3 cm samples con- 75.0076 (30.50). Analysis calculated for C PM Found: C 11.58, H 1.18, S 15.13. 2.3 Collection of PM (SEARCH) network site induring Centreville, the Alabama SOAS (CTR)and field from nighttime study. 1 (20:00–07:00) Sample schedule. June Awas collection to medium-volume used sampler followed 15 to (URG the July collect Corporation) particles 2013 coated daytime aluminum with (08:00–19:00) cyclone aerodynamic operating diameter at ofters 92 2.5 (90 Lpm. µm mm PM by diameter, Pall way Life of Sciences) a were Teflon- pre-baked at 550 2.4 PM sample extraction and preparation Sub-samples of PM organic material. Pre-and post-samplingrotameter. flow All rates filters were werefilters handled measured in using with plastic petri clean-techniques, a dishes whichpre-cleaned calibrated lined included with stainless storage pre-cleaned steel aluminum of foildark. forceps. and One Post-sampling, manipulation field with filters blank was were collected for stored every frozen five samples. in the tained using standardized filter punchesmerged of in known 10.0 area. mL These of sub-samples acetonitrilefor were and sub- ultra-pure 20 min water (95 by : 5, ultra-sonication by volume) (60 and sonicsmin extracted (125 rpm, VWR). Extractsters were (0.45 filtered µm through pore polypropylene size).purity membrane Filtrates nitrogen gas syringe were (5 reduced psi) fil- atLife in 50 Sciences) volume and then to to 500 aration µL final system under volume (Reacti-Therm of ultra-high III 100 TS-18824 µLTo using and test a Reacti-Vap the I micro-scale e 18825, nitrogen evapo- Thermo Scientific). 5 5 25 20 15 10 15 10 25 20 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | , 1 − 3 − O m/z 3 H at ered to 2 96) that ff − 3 SD) were × m/z 80) that forms at q − 4 m/z at q − 3 )ESI conditions are shown − solution. er is maintained at a relatively 1 ff − 89), respectively, which form from . All data were acquired and processed m/z 1 − , − 3 97 transitions, respectively. For quantitative O 5 > 12600 12599 H 3 10) of 25.0 µgL SD) and the limit of quantification (10 = × n 97 and 169 > that were prepared in organic mobile phase. Reproducibility of 1 − ) flow rate at 0.05 mLmin 2 97) that is postulated to form via a cyclic syn-elimination pathway m/z at − 4 75) and methyl glycolate ions (C Under the optimized conditions that provided the best resolution of analytes, the The charge state of organosulfates plays a key role in their retention on the BEH The MS/MS method was optimized for the detection of each analyte. The source con- aqueous portion of thefate mobile phase standards increased within 5–20 % 8 min and (Table eluted 1 the six and organosul- Fig. 2). The mobile phase was bu sitions were optimized for eachthat analyte, relied except solely for on ethylanalysis 125 sulfate of and compounds lactic with two acid transitions, sulfate the corresponding signals3.2 were summed. HILIC separation Analytes were separated onpounds. a In BEH HILIC amide chromatography,tionary water column in phase, that forming the retains a mobile extremelyin hydrophilic phase polar layer the is (Strege, com- organic adsorbed 1998) mobile into tonitrogen phase which electrons the partition polar to sta- compounds (Alpert, thetrogen carbonyl 2007). atom, oxygen The promoting imparts delocalization strong acolumn dipolar of partial as interactions. the the positive Polar amide aqueous analytes charge fraction are2008). on of eluted the the mobile from ni- phase the increases (Grumbach et al., 2004, pH 9 with 10 mMtionary ammonium phase acetate and to analytes. maintain However,unit a the consistent actual closer charge pH to state of onet the neutral the mobile al., due sta- phase 2001; may to be Espinosadeprotonate the 1 carboxylic et pH high acids al., organic groups 2000).pH in content values A glycolic of greater acid slightly the than sulfate basictonated, and 5, mobile increasing pH lactic silanol the phase was acid thickness groups (Canals selected of sulfate.tention in the At to of the adsorbed completely polar stationary hydrophilic layer, compounds phase and (Jandera, are increasing 2008). similarly re- The depro- bu amide column. At pH 9, glycolic acid sulfate and lactic acid sulfate are fully depro- high ionic strength,and compensating organosulfates, by for providing ammonium repulsion ions2007; between to Storton pair et the with al., silanol anionic 2010). groups silanol (McCalley, groups and collision gas (N 81) that forms fromion (HSO the heterolytic cleavage of the S-O bond, and the bisulfate an- (Attygalle et al., 2001).of Notably, methyl the sulfate, bisulfate because anion therestracted. is Glycolic is absent acid no sulfate in and C2 lactic the position acid MS/MS sulfate from spectra spectrum which contain glycolate a (C hydrogen may be ab- forms from the homolytic cleavage of a C-O bond, the bisulfite anion (HSO m/z using MassLynx software (versionwas 4.1). determined The using linear300.0 a range and of series 500.0 µgL each of authenticthe standard MS standard solutions method was at determined based 0.5, on seven 1.0, replicate injections 25.0, of 50.0, the 100.0 100.0, µgL from the homolytic cleavage of an O-S bond, the sulfate radical (SO the heterolytic cleavage ofmentation O-S of bond benzyl and sulfate is are2013). discussed resonance elsewhere stabilized. (Attygalle The et al., MS/MS 2001; frag- Kundu et al., ditions (collision energy and cone voltage) used in MRM are given in Table 1. Two tran- solution. The limit of detection (3 obtained from multiple injections ( in Fig. 1. Formulas wereMS/MS. assigned Major to fragment precursor ions and included product ions the using sulfite high-resolution radical (SO 3 Results and discussion 3.1 MS/MS fragmentation and optimization Product ion spectra given bytic methyl acid sulfate, ethyl sulfate, sulfate, and hydroxyacetone glycolic sulfate, lac- acid sulfate under applied ( 5 5 10 20 15 25 15 20 25 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | m/z 10 %. Both ± . LOD and LOQ ranged from Centreville, AL are 1 − 2.5 erent organosulfates formation path- ff ) are baseline resolved. The separa- 15 % for 95th percentile values and did − ± S ) (Gomez-Gonzalez et al., 2008; Surratt 7 − O S 7 11 12602 12601 O H 7 5 0.995), as shown in Table 1. The linearity require- H 5 ≥ 2 cient at resolving other organosulfates present in at- R ffi 215 (C , respectively. The relative standard deviation (RSD) was 211 (C 1 − m/z 2 charge, and are retained 7.84 and 7.57 min, respectively. − m/z ) and − S 7 8 % and for rotary shaking ranged 79–122 % and averaged 98 O , and for all other compounds across 25.0–300 µgL 9 ± 1 cient and reproducible methods for extracting organosulfates from filters. The − H 5 ffi SD) 98 Extraction by sonication and rotary shaking were both tested, and were both found The UPLC method is also e ± methods were found to be accurate within 100 to be e results of seven replicate extractions of theshown in six Fig. organosulfates 4. in Overall, a spike standard recoveries( solution for are sonication ranged 83–121 % and averaged not introduce artifacts into extraction.with Sonication narrower had ranges the of advantage results of andfor better lower the precision RSD. extraction Consequently, of sonication ambient was selected aerosol samples from filter3.5 media. Application to ambient aerosol Concentrations of organosulfates quantified inprovided ambient in Table PM 2. Glycolic acid sulfate was the most abundant compound measured, with negative artifacts, duedegrade to certain the organic formation compounds ofshaking, (Mutzel hydroxyl on et radicals the and al., othernot heat, 2013; hand, subject which Riesz is to can et these considered potential al., to problems. 1985). be a Rotary milder method of extraction that is 2.5–3.0 % for the firstsulfate four and compounds 6 to % elute, for and lactic increased acid to sulfate, which 16 %3.4 were for retained glycolic longer acid on Optimization the of column. extraction It has been previously shown thatesters methanol and converts should carboxy-organosulfates to be methyl 2011). avoided Instead, in ACN quantitative and analysis waterin (95 of : this organosulfates 5, (Olson by study. volume) et Twotigated: were al., methods used the as of commonly the extracting extracting used2007a) solvent organosulfates and methods from rotary of the shaking. sonication Extraction filters (Gao by were et sonication inves- al., has 2006; previously Surratt been et associated al., 1.9–3.9 and 6.3–13.2 µgL mospheric aerosols that aretheir expected strong to MS have signals.from high As isoprene shown atmospheric in epoxide abundances Fig. (IEPOX) duewith 3a, (Gomez-Gonzalez to a six et methyltetrol precursor al., sulfate ion isomers 2008; of derived Surratt et al., 2008) tonated; each carrySingly-charged a organosulfates – methyldroxyacetone sulfate, sulfate ethyl – sulfate, elute benzylresolved. sulfate, within and the hy- window of 0.58–0.88 min, and are baseline- tion of these isomers bywhich this these method IEPOX-derived is organosulfate isomers superior2012). co-elute to The in reversed resolution phase two of chromatography, peaks in individual (Stonebecause IEPOX-derived et organosulfate their al., isomers separation is will significant, products support that future may quantification prove of useful individual in isoprene elucidating SOA di ways (Surratt et al., 2010) andthe because greatest IEPOX-derived organosulfates organosulfates have signals generated 2013). in Two additional prior organosulfates field derived from studies isoprene,213 (Froyd with et precursor (C ions al., of 2010; Lin et al., et al., 2008) shownsolved in by Fig. this 3b method. and Futureidentifying c, and study respectively, quantifying were should these retained target two improving although compounds. resolution not and fully ultimately 3.3 re- Method validation The goal of methodthe development quantification was of to organosulfatesconditions in develop were ambient a applied to aerosol. robust a Optimized and serieshighly UPLC of linear sensitive authentic and calibration protocol organosulfate curves MS/MS standards, for ( andment produced was met for methyl sulfate500 µgL and ethyl sulfate across concentration ranges of 25.0– 5 5 15 20 25 10 10 15 20 25 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | , 3 − , re- sam- 3 − 2.5 0.1 ngm 1 ngm ± ± 2 and 8 0.2 and 2.7 ± ± enberg, J. H., Lewandowski, M., Ed- ff cient, with sonication providing better preci- 12604 12603 across six locations, lactic acid concentrations ffi 3 − , and a 3-fold or greater enhancement of glycolic acid 3 − We thank Thilina Jayarathne and Sean Staudt for collection of PM cial views of the USEPA. Further, USEPA does not endorse the purchase of ffi , compared to the measured organosulfates. HILIC chromatography is a promis- 2.5 ney, E. O., Kleindienst, T. E., Jaoui,Knipping, M., E. Edgerton, M., E. and S., Tanner, Seinfeld, R.of J. L., secondary H.: Shaw, S. organic Influence L., aerosol of Zheng, from aerosol M., beta-caryophyllene,doi:10.5194/acp-11-1735-2011, acidity Atmos. 2011. on Chem. Phys., the 11, chemical 1735–1751, composition tion of charged solutes and2007. selective isolation of phosphopeptides, Anal. Chem., 80, 62–76, Oligomers formed through in-cloudties, methylglyoxal and reactions: mechanisms chemical investigated composition,mos. by Environ., proper- 42, ultra-high 1476–1490, resolution 2008. FT-ICR mass spectrometry, At- mass spectra of organic sulfate anions, J. Chem. Soc.,HPLC. Perk. T. 6. 2, pH 498–506, 2001. measurementsmatogr. with A, the 911, 191–202, glass 2001. electrode in methanol–water mixtures,Facchini, J. M. Chro- C., and Fuzzi,pounds S.: in Molecular fogwater characterization by ESI-MS/MS, of Environ. the Sci. water-soluble Technol., organic 37, com- 1229–1240, 2003. Acknowledgements. Altieri, K. E., Seitzinger, S. P., Carlton, A. G., Turpin, B. J., Klein, G. C.,Attygalle, and A. Marshall, B., A. Garcia-Rubio, G.: S., Ta, J., andCanals, Meinwald, I., J.: Oumada, Collisionally-induced F. dissociation Z., Rosés, M., and Bosch, E.:Cappiello, Retention A., of De ionizable Simoni, compounds E., on Fiorucci, C., Mangani, F.,Chan, Palma, M. P., N., Trufelli, Surratt, H., J. D., Decesari, Chan, A. S., W. H., Schilling, K., O Alpert, A. J.: Electrostatic repulsion hydrophilic interaction chromatography for isocratic separa- ples and Ann MarieOxidant Carlton, and Jose Atmosphere Study Jimenez, (SOAS) andfor in providing Allen Centreville, us Alabama. Goldstein with We for lactic alsosistance organizing acid thank with sulfate. the Frank and We Keutsch Southeast training also in thankThis the Lynn research University Teesch is of and funded Iowa Vic by High Parcell theber Resolution for US 83 Mass their EPA 540 Science Spectrometry 101. as- to Facility. Its Achieverepresent contents Results (STAR) the are program grant solely o num- theany responsibility commercial of products the or grantee services and mentioned do in not the necessarily publication. References with 10–11 July daytime and nighttime concentrations of 14 spectively. Hydroxyacetone sulfate, quantifiedsecond-most for abundant the compound measured first at time levels of in 5.8 this study, was the respectively. Lactic acid sulfatetrations, and and benzyl methyl sulfate sulfateagreement and were with ethyl observed those sulfate of at weretrations Olsen lower not in et the detected. concen- range al. These ofin (2011) results 1.9–11.3 ngm who the are report range in of glycolic 0.4–3.8 acid ngm sulfate concen- A UPLC-MS/MS method forveloped the quantification and of validated atmospherica organosulfates for was variety the de- of purpose lower-molecular-weightcarbonyl organosulfates of and containing evaluating carboxy alkyl, the functional benzyl,pounds groups. ambient hydroxyl, used In concentrations in addition of methodaration to of validation, resolving a the the range HILICfor six of the separation model isoprene-derived preparation holds com- organosulfates. of promiseor In filter for rotary comparing samples the shaking for two sep- organosulfates weresion. procedures Initial quantification, proven measurements both indicate to that sonication be hydroxyacetonePM sulfate is e relatively abundant in ing analytical techniquethe for complex the aerosol separation matrix.highly-sensitive When of MS/MS coupled organosulfates with detection, from authentic itcation one standard and provides development another speciation an and of and improveclass atmospheric of organosulfates. technique compounds Improved for will measurements the advancemechanisms. of the this quantifi- understanding of SOA precursors and formation sulfate relative to lactic acid sulfate. 4 Conclusions 5 5 30 20 15 25 10 15 25 10 20 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ects on sulfuryl ff ects and medium e ff er, A., and Andreae, M. O.: Diurnal variation in the ff 12606 12605 enberg, J. H., Kleindienst, T. E., Edney, E. O., Blockhuys, F., Van ff , R. H., Larsen, P., and Hengge, A. C.: Isotope e ff transfer reactions, J. Am. Chem. Soc., 123, 9338–9344, 2001. of organosulfates from reactive11, uptake 7985–7997, of 2009. monoterpene oxides, Phys. Chem. Chem. Phys., aerosols: review and state of the science, Rev. Geophys., 38,and 267–294, implementation 2000. into multidimensional chromatography1437, concepts, 2008. J. Sep. Sci., 31, 1421– water-soluble inorganic ions, organicnitrogen carbon in and biomass isotopic burning aerosols compositionsAerosol from of Sci., the 41, total LBA-SMOCC 118–133, carbon campaign 2010. in and Rononia, Brazil, J. and quantitation of aromatic organosulfatesChem. in Phys., ambient 13, aerosols 4865–4875, in doi:10.5194/acp-13-4865-2013, Lahore, 2013. Pakistan, Atmos. ganic compounds inEnviron. biomass Sci. Technol., burning 43, 3764–3771, aerosols 2009. using high-resolution massBudisulistiorini, spectrometry, H., Sexton, K. G., Vizuete, W., Xie, Y., Luecken, D. J., Piletic, I. R., Ed- bridged hybrid particles for1518, hydrophilic 2008. interaction chromatography, J. Sep. Sci., 31,56, 1511– 2342–2354, 1978. acids, sulfates, and organosulfates ineast processed continental Pacific organic Ocean aerosoldoi:10.1029/2009jd013276, over during 2010. the south- VOCALS-REx 2008, J. Geophys.1821, Res.-Atmos., 2006. 115, D13201, Alsenoy, C., Maenhaut, W.,photooxidation and of Claeys, isoprenechromatography/(-) M.: electrospray and ionization Characterization mass unsaturated of spectrometry, J.382, organosulfates fatty Mass 2008. Spectrom., from acids 43, 371– the in ambient aerosoldrophilic interaction using chromatography using liquid silicaand enhanced columns ESI-MS for sensitivity, the LC retention GC of N. polar Am., 22, analytes 1010–1023, 2004. health: a review, Aerosol Sci. Tech., 39, 737–749, 2005. scales and theChem., retention 72, of 5193–5200, acids 2000. and bases withJimenez, acetonitrile–water J. mobile L.: Response phases, offates Anal. an and aerosol mass implications spectrometer for to atmospheric2010. organonitrates chemistry, and P. organosul- Natl. Acad. Sci. USA, 107, 6670–6675, war, G., Young, J. O., Gilliam,Incremental R. testing C., Nolte, of C. the G.,sion Community Kelly, 4.7, J. Multiscale Geosci. T., Gilliland, Air Model A. Dev., Quality B., 3, (CMAQ) and 205–226, modeling Bash,, doi:10.5194/gmd-3-205-2010 J. system 2010. O.: Quinn, ver- P. K., and Bates, T. S.:ticles Springtime from European Arctic and haze Asian contributions combustion of,doi:10.1029/2010JD015178 sources, submicron J. 2011. Geophys. organic Res.-Atmos., par- 116, D05205, Wennberg, P. O.:aerosol mass, Contribution P. Natl. of Acad. Sci. USA, isoprene-derived 107, 21360–21365, organosulfates 2010. feld, to J. H.: free Characterizationern of tropospheric United polar organic States: componentsdoi:10.1029/2005jd006601, identity, 2006. in origin, fine and aerosols evolution, in J. the Geophys. southeast- Res.-Atmos.,Lewandowski, 111, M., D14314, O Iinuma, Y., Boge, O., Kahnt, A., and Herrmann, H.: Laboratory chamber studies on the formation Jacobson, M. C., Hansson, H. C.,Jandera, Noone, P.:Stationary phases K. for hydrophilic J., interaction chromatography, and their characterization Charlson, R. J.: Organic atmospheric Kundu, S., Kawamura, K., Andreae, T. W., Ho Kundu, S., Quraishi, T. A., Yu, G., Suarez, C.,Laskin, Keutsch, A., F. Smith, N., J. and S., Stone, and E. Laskin, A.: J.: Molecular Evidence characterizationLin, of Y. H., nitrogen-containing Zhang, H. or- F., Pye, H. O. T., Zhang, Z. F., Marth, W. J., Park, S., Arashiro, M., Cui, T. Q., Grumbach, E. S., Diehl, D. M., and Neue, U.Guthrie, J. D.: P.:Hydrolysis The of esters application of oxy of acids – novel pKa valuesHawkins, 1.7 µm for strong L. ethylene acids, Can. N., J. Chemistry, Russell, L. M., Covert, D. S., Quinn,Hemstrom, P. P. and K., Irgum, and K.: Bates, Hydrophilic interaction T. chromatography,Ho S.: J. Sep. Carboxylic Sci., 29, 1784– Grumbach, E. S., Wagrowski-Diehl, D. M., Mazzeo, J. R., Alden, B., and Lraneta, P. C.: Hy- Davidson, C. I., Phalen, R. F., andEspinosa, S., Solomon, Bosch, P. A.: E., and Airborne Rosés, particulate M.: matter Retention and of ionizable human Farmer, compounds D. K., on Matsunaga, HPLC. A., 5. Docherty, K. pH S., Surratt, J. D., Seinfeld, J. H., Ziemann, P. J., and Foley, K. M., Roselle, S. J., Appel, K. W., Bhave, P. V., Pleim, J. E., Otte, T. L., Mathur, R.,Frossard, Sar- A. A., Shaw, P. M., Russell, L. M., Kroll, J. H., Canagaratna, M. R., Worsnop, D.Froyd, R., K. D., Murphy, S. M., Murphy,Gao, D. S., M., Surratt, de Gouw, J. J. D., A., Knipping, Eddingsaas, E. N. M.,Gomez-Gonzalez, C., Y., Surratt, Edgerton, and J. D., E. Cuyckens, F., S., Szmigielski, R., Shahgholi, Vermeylen, R., M., Jaoui, M., and Sein- 5 5 15 20 25 30 10 30 10 25 15 20 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | 12608 12607 enberg, J. H., Jaoui, M., Kleindienst, T. E., Edney, E. O., ff enberg, J. H., Lewandowski, M., Jaoui, M., Maenhaut, W., ff ect of acidity on secondary organic aerosol formation from isoprene, ff enberg, J. H., Lewandowski, M., Jaoui, M., Flagan, R. C., and Seinfeld, J. H.: Evidence for ff Claeys, M., Flagan, R. C., andorganic Seinfeld, aerosol, J. J. H.: Organosulfate Phys. formation Chem. in A, biogenic 112, secondary 8345–8378, 2008. Hersey, S. P., Flagan, R.revealed C., in Wennberg, secondary P.107, O., organic 6640–6645, and aerosol 2010. Seinfeld, formation J. from H.: isoprene, Reactive P. intermediates Natl.Laskin, Acad. J., Sci. Laskin,ganic USA, A., aerosols from and Shanghai Yang, andtrospray Los X.: ionization Angeles high-resolution Molecular urban areas mass11001, characterization by 2014. spectrometry, nanospray-desorption of Environ. elec- organosulfates Sci. in Technol., 48, or- 10993– Environ. Sci. Technol., 46, 7978–7983, 2012. weak and strong organic acids in atmospheric aerosols by capillary electrophoresis/mass Environ. Sci. Technol., 41, 5363–5369, 2007b. enst, T. E., Edney, E. O., O Zhang, X., Weber, R., Surratt, J. D.,aerosols: and synthesis, Stone, characterization, E. A.: and Aromatic abundance, organosulfates Atmos. in Environ., atmospheric 94, 366–373, 2014. atmospheric aerosols at Four Asian locations, Atmos. Environ., 47,tion 323–329, in 2012. hand dishwashing2010. liquid using an HILIC-UV methodology, J. Sep. Sci., 33,of polar 982–987, compounds for natural product drug discovery, Anal. Chem.,O 70, 2439–2445, 1998. and Seinfeld, J. H.: E organosulfates in secondary organic aerosol, Environ. Sci. Technol., 41, 517–527, 2007a. ney, E. O., Bartolotti, L.organic J., aerosol Gold, formation A., and fromP. Surratt, isoprene Natl. J. Acad. photooxidation D.: Sci. in Epoxide USA, the as 110, a presence 6718–6723, precursor of 2013. to nitrogen secondary oxides, bert, B. J.: SourcePacific Regional signatures Aerosol of Characterization carbon ExperimentJ. (ACE-Asia) monoxide Geophys. Res.-Atmos., submicron and 108, aerosol organic 8637, types, ,10.1029/2003jd003703 doi: functional 2003. groups intive Asian to reversed-phase liquidChromatogr. chromatography A, 1171, for 46–55, the 2007. analysis of ionisable compounds?,quantification J. of SOA bound peroxides, Atmos. Environ., 67, 365–369,nuclei 2013. concentrations, Nature, 365, 823–826, 1993. Smith, L. M., andstability, Keutsch, and F. quantification N.: in Hydroxycarboxylic ambient acid-derived aerosol, organosulfates: Environ. Sci. synthesis, Technol., 45, 6468–6474,cloud 2011. water above the Ozarks’ isoprene source region, Atmos. Environ., 77,trospray 231–238, ionization-tandem 2013. mass spectrometryacids, for Anal. Chem., the 75, analysis 1500–1507, of 2003. aquatic fulvic andand nonaqueous humic solutions, Environ. Health Persp., 64, 233–252, 1985. atmospheric aerosols?, J. Atmos. Chem., 52, 283–294, 2005. Environ. Sci. Technol., 47, 9332–9338, 2013. Van der Veken, P., Maenhaut,organosulfates W., related and to Claeys, secondarySp., M.: organic 27, Mass aerosol 784–794, 2013. spectrometric from isoprene, characterization Rapid of Commun. Mass Tao, S., Lu, X., Levac, N., Bateman, A. P., Nguyen, T. B., Bones, D. L., Nizkorodov,Tolocka, M. S. P.and A., Turpin, B.: Contribution of organosulfur compounds to organicYassine, aerosol M. mass, M., Dabek-Zlotorzynska, E., Harir, M., and Schmitt-Kopplin, P.: Identification of Surratt, J. D., Chan, A. W. H., Eddingsaas, N. C., Chan, M. N., Loza, C. L., Kwan, A. J., Surratt, J. D., Gomez-Gonzalez, Y., Chan, A. W. H., Vermeylen, R., Shahgholi, M., Kleindi- Surratt, J. D., Lewandowski, M., O Staudt, S., Kundu, S., He, X., Lehmler, H. J., Lin, Y. H., Cui, T.Stone, Q., E. Kristensen, K., A., Glasius, Yang, M., L., Yu, L.Storton, M., E., Exarchakis, J., and Waters, T., Rupakheti, Hao, Z., M.: Parker, B., Characterization and Knapp, of M.: Lactic organosulfates acid in quantita- Strege, M. A.: Hydrophilic interaction chromatography-electrospray mass spectrometry analysis Surratt, J. D., Kroll, J. H., Kleindienst, T. E., Edney, E. O., Claeys, M., Sorooshian, A., Ng, N. L., Maria, S. F., Russell, L. M., Turpin, B. J., Porcja, R. J., Campos, T. L., Weber, R.McCalley, J., D. and V.: Is Hue- hydrophilic interaction chromatography with silica columns a viable alterna- Mutzel, A., Rodigast, M., Iinuma, Y., Böge, O., andNovakov, Herrmann, T. H.: and An Penner, improved J. method E.: for Large the contributionOlson, of C. organic N., aerosols Galloway, to M. cloud-condensation- M., Yu, G., Hedman, C. J.,Pratt, Lockett, K. M. A., R., Fiddler, Yoon, M. T., N., Stone, Shepson, E. P. B., A., Carlton,Reemtsma, A. T. G., and and Surratt, These, J. A.: D.: Organosulfates On-line in coupling of size exclusionRiesz, P., chromatography Berdahl, with D., and elec- Christman, C. L.: FreeRomero, radical generation F. and by ultrasound Oehme, in M.: aqueous Organosulfates – aShakya, new K. component M. of and humic-like Peltier, R. substances E.: in InvestigatingShalamzari, missing M. sources S., of Ryabtsova, sulfur O., Kahnt, at A., Fairbanks, Vermeylen, Alaska, R., Herent, M. F., Quetin-Leclercq, J., 5 5 25 30 20 15 10 15 20 25 10 30 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ) (%) 1 − ) (µgL 1 − LOD LOQ RSD enberg, J. H., Klein- ff 2 R ) (µgL 1 − 0.03 25.0–500.0 0.9980.03 2.6 25.0–500.0 0.9980.02 3.4 25.0–300.0 8.6 0.9950.02 3.9 25.0–300.0 11.2 2.9 0.996 2.5 2.60.02 13.2 25.0–300.0 3.0 0.995 8.7 3.90.01 25.0–300.0 3.0 0.998 13.0 1.9 5.9 6.3 15.6 ± ± ± ± ± ± 12610 12609 ), limit of detection (LOD), limit of quantification (LOQ), and voltage energy time (min) (µgL (V) (eV) 2 R 97 2681 42 12 18 0.78 97 0.58 2875 16 26 7.57 18 7.84 80 36 18 0.88 80 32 18 0.66 96 14 9697 20 20 97 14 − 3 m/z O − 4 − 3 − 4 − 4 − 4 . . . . 3 cient ( − 3 − 3 − 4 − 4 H and 2 ffi 111 SO 125 HSO 187 HSO 153 SO 169 HSO 155 C − 4 − 4 − 5 − 6 − 6 m/z − 4 SO SO SO SO SO SO 5 7 5 5 3 and 3 H H H H H 2 7 3 3 2 Mass spectrometry parameters for MRM transitions of UPLC-MS/MS, linearity, C dienst, T. E., Gilman, J., Kuster,Russell, W. C., L., de Kaser, Gouw, L., J., Park, Jud,Goldstein, C., W., A. Schade, Hansel, H., G. A., Seinfeld, W., Frossard, J. Cappellin,as A. H., L., tracers A., Gold, for Karl, A., secondary T., Kamens, organic Glasius,in R. aerosol M., the M., (SOA) Guenther, atmosphere, formation and A., Environ. from Surratt, Sci. 2-methyl-3-buten-2-ol J. (MBO) Technol., D.: 46, Organosulfates 9437–9446, 2012a. Gold, A., Kamens,methacrolein R. photooxidation: M., roles and ofviron. Chem., NOx Surratt, 9, level, 247–262, J. relative 2012b. D.: humidity Secondary and aerosol organicmasses acidity, aerosol and En- molecular formation formula from trometry, Atmos. identification Chem. using Phys., ultrahigh-resolution 13, 12343–12362, FT-ICR doi:10.5194/acp-13-12343-2013 , mass 2013. spec- spectrometry and ultra-high-resolution Fourier transform iontrometry, cyclotron Anal. resonance Chem., mass spec- 84, 6586–6594, 2012. stein, A. H., Guenther,aerosol formation A., via Jimenez, 2-methyl-3-buten-2-ol photooxidation: J. evidencetive of L., uptake acid-catalyzed of Gold, reac- epoxides, A., Environ. Sci. and Technol., 1, Surratt, 242–247, J. 2014. tensen, D.: K., Secondary Campuzano-Jost, P., organic Day, D. A., Jimenez, J. L., Jaoui, M., O Lactic acid Glycolic C EthylBenzyl C C Hydroxy- C Compound Precursor ion Product ionMethyl Cone CH Collision Retention Linear range sulfatesulfate sulfateacetonesulfate SO sulfate SO acidsulfate HSO HSO Zhang, H. F., Lin, Y. H., Zhang, Z. F., Zhang, X. L., Shaw, S. L., Knipping, E. M.,Zhao, Weber, R. Y., J., Hallar, A. G., and Mazzoleni, L. R.: Atmospheric organic matter in clouds: exact relative SD (RSD) ofsition, 7 MRM replicate signals standard were injections. summed For prior compounds to with quantification. more than one tran- Table 1. squared correlation coe Zhang, H., Zhang, Z., Cui, T., Lin, Y.-H., Bhathela, N. A., Ortega,Zhang, J., H. F., Worton, Worton, D. D. R., R., Lewandowski, M., Gold- Ortega, J., Rubitschun, C. L., Park, J. H., Kris- 5 10 15 20 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ) mea- 3 − ∗ ∗ 0.1 0.1 1 0.04 ± ± ± ± BDL BDL 168.9797 154.9650 152.9836 124.9912 m/z

110.9753

96.9564

80.9609 80.9649 96.9598 96.9588 96.9584 95.9499 ∗ ∗ 2 8 0.2 1.4 0.2 2.7 0.05 0.34 89.0220 79.9571 79.9558 75.0076 ± 60 80 100 120 140 160 180 60 80 10079.9533 120 140 160 180 60 80 100 120 140 160 180 60 80 100 120 140 160 180 60 80 100 120 140 160 180 ± ± ±

0 0 0 0 0

80 60 40 20 80 60 40 20 80 60 40 20

80 60 40 20 80 60 40 20 %Relative Peak Intensity Peak %Relative %Relative Peak Intensity Peak %Relative Intensity Peak %Relative %Relative Peak Intensity Peak %Relative 100 Intensity Peak %Relative 100 100 100 100 H 12612 12611 OH O (08:00–19:00) (20:00–07:00) 153 O O O O 125 O O 111 S O 80/81 80 S O O O S 97 O 80/81 89 75 97 O O O 97 97 O O O 96 O S S O O O O O 169 155 A) spectrum Structure ion product ofmethyl and sulfate B) spectrum Structure ion product sulfate ofethyl and C) Structure and product ion spectrum StructureC) sulfate product ion of hydroxyacetone and spectrum Structure sulfate D) acid product ion of lactic and E) Structure and product ion spectrum of glycolic acid sulfate Glycolic acid sulfateLactic acid sulfate 14 2.9 Benzyl sulfateHydroxyacetone sulfate 5.8 BDL Ethyl sulfate BDL CompoundMethyl sulfate 10 Jul – Day 0.70 10–11 Jul – Night BDL – below detection limit. ∗ from Centreville, AL in 2013. 2.5 Production spectra of organosulfates standards generated by Q-ToF MS/MS of a di- Ambient concentrations of organosulfates with analytical uncertainties (ngm Figure 1. rectly infused standard solution. Table 2. sured in PM Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper |

Response of glycolic and lactic acid sulfate (a.u.) 5.0e+4 4.0e+4 3.0e+4 2.0e+4 1.0e+4 0.0 2.5e+5 2.0e+5 1.5e+5 1.0e+5 5.0e+4 0.0 ) - ) ) 7 - - 7 7 SO SO SO 11 7 9 H H H 5 5 5 2013 12614 12613 215 (C 211 (C 213 (C Retention time (min.) time Retention a mixed standard containing six organosulfates at Retention time (min.) m/z m/z m/z (a) methyl sulfate methyl sulfate ethyl benzyl sulfate sulfate hydroxyacetone sulfate acid glycolic sulfate acid lactic A) C) B) 012345

2e+5 1e+5 0 1e+4 5e+3 0 4e+4 2e+4 0 Response (a.u.) Response A) Standard Solution Standard A) an ambient aerosol sample. Responses of glycolic acid sulfate (GAS) and B) Centreville, AL - Summer 01234567891011 (b) Figure 2 1.6e+6 1.2e+6 8.0e+5 4.0e+5 0.0 1.2e+6 8.0e+5 4.0e+5 0.0

MRM chromatograms of and Extractedion chromatograms of isoprene-derived organosulfates qualitatively iden- Response (a.u.) Response 1 − Figure 2 Figure Figure 3. tiﬁed in andaytime ambient (08:00–19:00). aerosol sample collected in Centreville, AL on 10 July 2013 during the 100 µgL lactic acid sulfate (LAS) are shown on the right axis. Figure 2. Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | sonication and (a) 7 each) extracted by = n 12615 Comparison of spike recovery samples ( rotary shaking. Figure 4. (b)