Contants lists availabe at ScianeaDirect Science of the Total Environment ELSEVIER journal homepage: www viae.com/locate/scitotany Assessment of PM2.5 sources and their corresponding level of uncertainty in a coastal urban area using EPA PMF 5.0 enhanced diagnostics 'M. Manousakas**, H. Papaefthymiou, E. Diapouli *, A. Migliori‘, A.G. Karydas “4, I. Bogdanovic-Radovic, K. Eleftheriadis* «Mac fet eet De: og pew Soc HIGHLIGHTS GRAPHICAL ABSTRACT + Results showed thatthe neve tools in PAF 5.0 are very usfil inthe case of smal datases| + The appiestion of the appropiate con straints may be needed to reduce the Totational ambiguity of the solution for small daases| +The case of biomass burning revealed that sources ith high seascnal vari- we.5 Source Contribution abity are vulnerable to resampling Secondary Suites {ecinigues in small datasets sea at + Biomass burning (11) shipping (10%) oping Emissions se salt (9), sultes (34%), mineral ee dust (28) ad vehi emissions (343) sm lomass Burning Vehicle Emisions 1 Mineral Dust ARTICLE INFO ABSTRACT ‘ct Dazasets hat nclude only the PM elemental composition and no other important constituents such 3s ons and eee ay 2015 (0G should be treated catfully when ued for source apprtionient. This works Gemonstating how asoure Reeve form August 2016 apportionment study utlizing PF 5.0 enhanced diagnostic tol can achieve an improved soltion wi dct ee mE ‘entad levee of uncertainty for such dataset. The wnceainy ofthe solution ieraely reported in sxece apo ‘ionment stules or itis reported partly Reporting the uncertain ofthe solution is very impertant especialy a nthe ase of smal datasets, PMB. samples collected in Patas ducing the veut 2011 were wed. The concent ‘dons of 22 elements (2 = 11~3) wete determined using PIXE Soutce apportionment analss revealed hat ewan PM: emision sources were bmass burning (11%), sea salt (8%), shiping emissions (105), vehicle emissions Source pporbonment (33%), mneral dust (2) and secondary slates (33) while unaccounted mass was 3 Atha Ptascity ce Paso. {erislactedin avery close proximity to te ty shatbot. he contibuton of sipping originating emissions was ~ Caesponding autor ‘mates manssmanpadesokrtosg(M Mancusi). poo 10.106 scnten 2016.09.07 UUD687)@ 2018 leer BV. Al gh sei156 Mi Maroulis tal Since of the Tt Ewionment 5742017) 155-154 reas. FP weeny 1 Introduction Particulate ar pollution has been associated with adverse effets on hhurman health. PM isa chemically non-specific pollutant, and may orig- inate from various emission source types. Thus its toxicity may well vary depending on its source and chemical composition. IPM toxicity is determined with respect to source types. the regulation of PM can bee implemented more effectively (Ito etal, 2006). Several factor analy- ‘sis and source apportionment methods have been developed to appor- tion sources of ambient PM2.5. Estimates of resulting source ‘contributions have subsequently been used in epidemiological studies {investigate the association betwveen source-specific PM2.5 and health (cioumourtzoglou et al. 2014). Given the impact of such air quality standards, itis very important to lower and assess the uncertainty of the results (Hopke etal, 2008; Kioumourtzoglou eta, 2014). Greece is located atthe Eastern Mediterranean basin whichis char- acterized as air pollution hotspot, located atthe crossroad of air masses ‘coming. from Asia, Eutope and AMrica (Karanasiow and Mihalopoulos, 2013). Because ofthe particular characteristics of the location, PM in, the area can originate from a variety of sources both local ancl regional. Biomass burning Amis etal,2012; Saraga etal, 2015) trai related processes, dust resuspension (Athanasopoulou etal, 2010}, industrial ‘activities, transported Saharan dust are some of the most common, Soufees inthe area (Grigoropoulos etal, 2009; Karanasiou etal, 2008; ‘Amato et al, 2016). In addition to those sources the climate conditions ‘of the area (low precipitation, high solar activity} favor the accumula tion of pollutants and the formation of secondary paticles For example ‘model simulations inicate that SO> is transported in the Mecitertanean basin where sulfate is produced due to intense photochemical activity (Piksidas et al, 2013). The aforementioned reasons coupled with the ‘weather concitons lead to high PM background concentrations in the area, with high impact on human health in urban areas (Ost etal, 2014), Although Greece is a coastal country with several harbors of various sizes and shipping emissions have been already identified (Karanasiow cet al, 2009; Amato etal, 2016) as a source, itil remains to be ade- ‘quately quantified. This source is active when the ships are in dock, as ‘wellas when they ae at sea. In particular, 70% of ship emissions are es timated to occur within 400 km ofthe mainland (Endresen etal, 2003), Another compleaity is that ships in many cases use old engine technol ‘ogy and thatthe fuel quality used is poor. Heavy ol usually contains high level of sulfur when compared with the diesel used for passenger ‘cats and residential heating in most European countries (Fridell et al 2008 Receptor modeling using aerosol chemical composition datas ate liable method that can provide information on aerosol sources (Belis et al, 2013) Positive Matrix Factorization (PME) {Paatero and Tappert. 41994), is a receptor model that has been successfully applied to many areas with different characteristics (Querol et al, 2001; Kim etal 2003; Johnson et al, 2008a; Moon et al, 2008; Cohen et al, 2009; ‘Amato et al, 2016; Liang et al, 2016). PMI introduces a weighting ‘scheme taking into account errors ofthe data points, which are used 2 point by point weights. Adjustment ofthe corresponding eror est ‘mates als allows it to handle missing and below detection limit data “Moreover, non-negative constraints are implemented inorder to obtain ‘more physically meaningful factors. The latest PME version available by USEPA, is designed to overcome some ofthe weakppints ofthe previous ‘versions of the model, providing better tools to investigate the rotation al ambiguity of the factors, PME 5.0 for the first time effers three never before quantified As rotational stability shard tobe achieved when a small datasets used the ottional Sail the solution was thoroughly evalted. A naber of constraints were applied othe solution inorder to reduce rotatinal ambiguity (© 2016 Elsevier BY All rights reserved. rmthods for estimating uncertainty in factor analytical modal: boot- Strap (85 also available onthe previous versions ofthe model), ds- placement of factor elements (DISP), and bootstrap enhanced by displacement of factor elements (BS-DIP} (Psatero etal, 2014) The uncertainty of PMF analysis due to random errors and rotational ambi- sity can be reduced by applying these metho inthis study a small dataset was used to igentify FM. sources ina rer-sie coastal Greek ty. The elements determined nthe sam bles by PIKE were namely Na, Mg. Li CLK, Ca, Tt, VC, nF, Ni {4.7m As SPs, Coan Ge. The concentration fall he clement ex cept fm SP Ga. Co and Ge was used asa variable in the model. This dataset was used as an example of how small datasets of PX elemental ‘omposton could be treated and more importantly how the ncetin- {yo the results could be evaluated and reported. The tol offered by PMS were wed in order to evaluate the rotational tai of theo Tuto, As rotational sti is hard to be achieved when aver sll datasets used, a number of constants were wsed in the solution, 30 that the stability is maintained as high as possible, The application of constraints reduces the ottiona space (Hopke, 2016). Small dataset ead to another implication Is had to obtain representative source profiles without an appropriate number of samples, For example, in the manu of PM it suggested that for atmosphere PM at least 10D samples are necessary. The aplication of some constraints can 3gain improvethe rotational stability and asst towardsobtaining meaning fulsotion 2. Experimental 21. Sampling Fatras is a medium size city located in Peloponnese peninsula (Fig 1). Patras’ population according tothe last census (2011) was 168.034 citizens. Is residential area with low industrial activity, ‘wich is mainly located in the industrial zone atthe southeastern out” skirts ofthe city. Two commercial ports are lacated in the atea, the north orokl port andthe south or new port. Te new por started oper- sting at 11-Jun-2011, and it s wed mainly by passenger and cargo fetes sailing italy. About 1.5 milion passengers per year isestimated to travel using Patras’ pots. Trafic inthe citys high especially during rush houts. Public transport fleet is composed mainly of buses of very ‘ol technology Olive groves are located in the surouncing area of the ‘iy. Scrap wood originating fom agricultural activities fs commonly used by houschokis in close proximity to the ity. ‘The sampler was installed inthe vty center, onthe oot ofa high public building 20.) located the centrality square Thesampling, site at this location allowed representative sampling of urban air fom any direction. The site was selected because strong influence by neaoy Sources such as trafic was minimal when compared toa kerbside sta- tion. Hence. the samples collec! would he representative ofthe eeat- er urban area and not be overwhelmed by the contribution of only one source. Te sampler used wa 3 low volume sampler model FRM 2000 by Rupprecht Pataschnick, This sampler is designed according to USEPA dizective CFR 40, PMZ5 samples were collected onto Teflon membrane filters Whatman PTFE 47 mim diameter with 1 ym pore size. The filter isa PTFE membrane (4 mgicm) with polypropylene backing. The samples were collected over 224 h sampling interval (Grom 00:00 to 23:58). Al ilters were weighed before and after sam- Plingto determine the collected PM2.S mass using a Sartorits PB211D rirobalance (readability of. ya) (Manousakas etal, 2014), BeforeFig ni: Paras lation et: samping an postions P25 sources lacton ‘weighing. the fters were equilibrated for24h inside custom designed chamber with automated’ controls cesigned to maintain environmental conditions at a constant air temperature of 20 °C and constant RH of 50% Ta avoid static electricity interference the balance was equipped ‘with a 210Po static eliminator. The filters were loaded into clean poly siyrene Pett dishes and transferred tothe sampling site. A number of, samples were collected throughout 2011 and 55 of them were selected to be analyzed by PIXE. Ater the analysis the concentration of 22 ele- ‘ments were determined and 17 of them was used as input on the ‘model (Na, Mg, Al, Si, C, K, C2, i, V, Cr, Mn, Fe, NiCu, Zn and As). ‘The samples analyzed by PIXE were selected to equally represent the ‘warm and cold season ofthe sampling period The concentration of black catbon (BC) inthe collected filters was, {determined by optical analysis using a Smoke Reflectometer (Model 43 Smoke Stain Reflectometer, Diffusion Systems LTD). The method followed is described in detail elsewhere (Manousakas et al, 2013} 22. Flemental analysis, PE Particle Induced X-ray Emission (PIXE) was used for elemental anal~ ysis ofthe Samples. PXE has many advantages for elemental analysis of Particulate Matter it provides rapit multielemental analysis capable to detect a large numberof elements from Z = 11 (Na) and heavier, in ‘eluding all the crustal and important anthropogenic elements. The ad- vantage of a single analytical technique isthe lower possibility fora random error. If random error does occur in a PIXE measurement it ‘is highly likely to affect all elements in a given sample, which makes it ‘much easier to locate and treat accordingly. OF course thete are draw: backs as wel. Iris not possible to determine all the useful PM compo- nents need in soufce apportionment analysis such as ions, organic carbon or some specific tracets such as levoglucosan (Kostenidou et al, 2015) ane carbonate (Karanasiou et al, 2011) witha single analy 1. The lack of those very important PM components in the analysis is very possible to lead to a solution not easily interpretable and with high levels of uncertainty. Thus its veryimportantto evaluate and reduce the uncertainty. PIXE measurements were performed atthe Laboratory for fon Beam, Interactions, Rudjer Boskavie Institute, Zagreb Croatia. A mass calibra tion ofthe PIXE set-up has been performed utilizing Micromater thin standards evaporated on thin Nueleapore (polycarbonate) filters “Micromatter standards are known to have 45% uncertainty on areal ‘mass concentrations (Calzola etal, 2008}. One multielemental stan. dard (Vienna Dust Standard Vos, Air particulate matter on filter media) has also been measured, PIXE set up and the calibration tech- nique is described in cetailin (Manousakas etal, 2015). 2.3, Positive Matrix Factorization (PAF) ‘The basic equation that refers to the solution of the mass balance problem is common forall the utilized multivariate receptor models in- cluding PME: Xij= Sealy + ot o Where Xyis the concentration of species j measured on samplei, pis the ‘numberof factors contributing tothe samples, fs the concentration of| species jin factor profile k, gis the relative contribution of factor kto sample i, and gis error ofthe PME model forthe j species measured ‘on sample i The values of gu. and fy are adjusted until a minimum value of @ fora given p is found. Qis defined as te 4s Bee 2 Wheres the uncertainty of the jy species concentration in samplei.n isthe number of samples, and mis the numberof species In some cases other auxiliary equations can be add inorder to inclu a priori infor- ‘mation such as well-known chemical profiles for certain sources (Paatero anal Hopke, 2008; Lia etal, 2015) The auxiliary equations de fine the auxiliary part Q* of object function Q: a-ha Ee 6 enumerates the auxiliary equations. The residuals of auxiliary equations are denoted by , while s, denotes the ‘softness’ of v auxil iary equation, which is usally provided by the user (Paatero, 1999) ‘Those awaliary equations can be applied to the solution in the form of constraints. Constraints can allow us identify 2 free rotation ofthe solu tion with better physical meaning than the original solution In addition to that a number of rotations blocking zero values can be introduce! to the matrix increasing thus the rotational stability of the solution In the current study Sc, , G3, Co ancl Ge were set as “bad” and thus were excluded from the analysis and Cr and As as “weak”, PM2.5 con. centration was set a8 total variableArange ofsolutions were examined with different number of factors (4-8), but 6 factors were the maximum number of factors correspond. ing to meaningful sources. If the factors were increased some profiles ‘were split creating profiles with no physical meaning, while the rota tional instability ofthe solution increased significantly. The data uncertainty was calculated by taking into account thre ind vidual errors: analytical error, PIXE calipation error and sampling eter. ‘The inal uncertainty used in the model was the total uncertainty plus 1/3 LOD (Polissar etal, 1998; Lee etal, 2002; Kim and Hopke, 2004; Li ‘etal, 2004; johnson et al, 2006). The modeling uncertainty was adjust- ft 9%, Values that were much lower than LOD were substituted by 1/2 LOD and the uncertainty was set a 5/6 ofthe LOD value ‘Small datasets (number of cases close 50) pose an extra challenge ‘when used for PM because the solution is strongly afecte by rotation ambiguity and the overall uncertainty is increased, Previous versions ‘of PMF offered only bootstrapping” asa tool to estimate the effect of random errors and to some extent the rotational ambiguity in the dataset Fpeak was a function fr estimating the lower limit of retaional uncertainty (Reffet al, 2007), Thelatest version gives the user more a¢- vanced tools to evaluate rotational ambiguity, namely the displacement (DISP} and the bootstrap displacement (BS-DISP) methods. BS esti ‘mates the random errors on the matrix, while DISP explicitly explores the rotational ambiguity (Paatero et al, 2014). BS-DISP being a combi- nation of the two methods estimates both random errors and rotational ambiguity. When the rotational ambiguity of the solution is high the identity ofthe resolved factors may be exchanged or swapped during DisP anil BS-DISP runs. Ths is expressed in the diagnostic result as 2 ‘number of factor swaps In addition, the number of cases used in BS- DisP is reported, which expresses the number of accepted resamples. Irallcases were accepted this number is equal to 1 (base run) plus the ‘number of bootstrap, ‘Aste base run revealed that the solution had high rotational amb suity indicating no wel-defined solutions, same physical and chemical constraints were applied in order to artive at 2 more stable solution. Ro- {ational ambiguity can be reduced among other ways by constraining individual factor elements, either scores and/or loadings, towards ero values, prescribing values for ratis of certain key factor elements (Paatero et ab, 2002). It must be emphasized that application ofthese {echniques must be based on some external information about accept- able or eviclence based factor profiles, The base run can be modified (constrained) by the following methods: by setting some factor ele ments to 2 fixed value, by speeilying lower and/or upper limits, by pulling 2 factor element towards a certain value and by setting an equa- tion such as aratio, amass balance equation ora custom equation. Some constraints are considered strong sch as setting a variable ona fixed value because they can perturb the model results significantly. Pulling towards a value has the advantage that ithe equation is incompatible ‘with the result (0 changes too much), then the pulling will fall sort of the target value (Paateto and Hopke, 2008). In other words ifa free ro- tation isnot available then the pulled factor will never reach the user defined outcome. Setting constraints in the form of equations such as 2 ratios regarded as rather strong constraint but alesser one than set- ting 2 particular value For all other constraints apart from setting acer- tain value the model offers the option to set the maximum allowed dQ% change. Giving low maximum dQ change ensures that significant per turbation of the model rests are less probable ‘After constraints were applied BS results incicated very good repro 5 tralian in particular ie/break wear (such as Cu and Zn), indicating possible influence by non-exhausttrafMe emissions as well Secondary Inorganic aerosols are formed from the reaction of H:S04(g) andl HINOs(g) with NH, giving (NH.);S0, and_NH,NOs accordingly (Stowell et a, 2003: Squizzate et al, 2013). The main tracers ofthis source are SO: "and NHL} but NOs may also be present in the source profile, when the fctor represents inorganic aerosols in general rather than secondary sulfates exclusively (Yin et al, 2005; Viana etal 2008), Since the formation of (NH,).60, and NH,NO, is usually favored indifferent seasons, the concentrations of these two secondary species io not have high correlation and they tend to be apportioned in sepa- rate factors, Because the concentration of major ions was not available in the current dataset, § was used as the main tracer to identify this source, a practice that has been previously applied in other studies (Marcazzan etal, 2003), The absence ofthe major ions and especially Mineral Dust Vehicle Emiasions Biomass Buming s Shipsing Emissions sea Salt, 1 Secondary SutatesSecondary Sulees Mm Vebile Emissions ome Burning inert Dust ie. Sours contbutons andthe te vary NOs can ad some implications tothe results because the mass of the secondary nitrates can be apportioned to others sources such as trafic tr biomass burning. Secondary sulfates represent a high percentage in the mass of PM25 in Greek urban environments with regional origin. ‘This result is in agreement with those reported forthe Greater Athens Area (Pateraki etal, 2012; Mantas etal, 2014: Dimitri etal, 2015}. Secondary sulfates are in many cases attributed to long range transport evens (Viana etal, 2008), Previous studies have stated that sulfates are ingredients ofthe “aged!” air masses, because the oxidation of SO> to 80; is slow (Quetol etal, 1998}, and thus this aerosol component is ‘more related to transported than local pollution (Fleftheriadis eta, 11998; Ricard and Jafirezo, 2002; Schaap et al, 2004; Saffati etal 2012). High sulfate concentrations due to tansport have been known toinfluence Greece, 2s documented by the high levels observed in back- sround areas inthe Aegean {Gerasopoulos eta, 2006; Lazarcis etal, 2006), This source has the highest contribution along with vehicle emis sions (721 yg/m?, accounting for 33% of total PM2.5 mass on average, Fig), ‘The factor representing sea salt has been identified by the high con- tribution of Na and Mg. Sea spray is commonly identified asa source of PM and especially PM 10 in southern European Countries (Viana eta. 2008; Bove et a, 2016). Cis present inthe factor but in much lower ‘concentration than expected forseasaltby stoichiometry. The CI dep. tion inthe factor indicates thatthe sea salt cannot be characterized as fresh but rather as aged, Fresh sea salt i almost exclusively found at the coarse particle faction (Eleftheriadis etal, 2014), and that is prob, ably the reason why fresh sea salt is not identilied as a source despite that sampling inthis study took place in very close proximity to the sea. Seasaltas a contribution of 8 which remains very stable through cut the seasons ‘Shipping emissions are identified by the high presence of Nand Vin, the factor along with the presence of Fe.All of them are common tracers of crude ol burning (Karanasiou etal, 2009; Argyropoulos eta, 2013) ‘This source is common in the Mediterranean region (Waked etal 2014; ‘Amato et al, 2016). As mentioned before the ratio of V/Ni was constrained to 3for this factor {was 2.6 in the initial base run), which isan indicative value for shipping emissions in the Mediterranean re- sion, BCis presentin the factor as expected in all combustion processes Since there are no refineries or oil powered plants inthe area itis safe to say thatthe contribution of this source ean be attributed to shipping alone, The contribution of this source i 10% of PA2.5 an anual basis and is higher curing the warm season probably because ofthe higher vessel related ativity that peaks during that period. Biomass burning is resolved mainly by the presence of high K con- centrations and to 2 lesser extent by presence of Clin the factor (Diapoul etal, 2014). As mentioned biomass burning in the area of Pa tras is related mainly to farming processes, and specifically to scrap ‘wood burning t olive groves and agricultural firesin the region. In ad- dition to that, due to the economic crisis andthe inereased prices of die- sel (diesel based central heating was the most common means of {domestic eating in Greece), biomass burning use for domestic heating has dramatically increased in the last years (Saffar et al, 2013). K in fresh smoke isin the form of KCI which explains the high abundance ‘ofthis element in the factor (Viana tal, 2012). Addliionally itis quite ‘common that plastic waste is burned in fires along with the biomass, leading to fesh particle formation with up to 21% concentration of Cl (Kostenidou etal, 2013). This source has 11 contribution and is man ifested almost exclusively in the cold season (Table 1), Vehicle exhaust emissions are traced by the high percentage of BCin the factor ani the lower presence of Cu, Zn, K, and Cr. A vehicle non-ex- haust factor has not been identified, probably because ofthe elevated positon ofthe sampler and the small numberof samples. The elevated Position ofthe sampler made resuspension sources ess influential. ‘2ddition, non-exhaust emissions generally contribute more to coarse rather than fine particles. The chemical profile obtained for this vehicle ‘exhaust Source, consists mainly of BC. The old technology buses, which are the only means of public transport the city, 2s well as the many trucks that circulate in the port area, are expected to influence this source the most. The contribution of this source is 33% and itis higher ‘on the cold period of the year probably due to the lower inversion layer, which limits the dilution of vehicular emissions during the winter season (Khillae andl Sarkar, 2012). ‘Mineral dust a well-defined factor identified by the high concen. tration of the crustal elements such as Al, Si, Ca, Ti and Fe. Al, Si, Ca and Tare expected to originate mainly ftom this Source. The contribu- tion ofthis source is very small (28) anc! stable throughout the year. Even though this source is not expected to have high contribution in M25 (Fleftheriagis and Colbeck, 2001) iis expected that itis also in- fluenced by the high sampling location. Generally no correlations are expected tn exist between the sources _as each source contriputes aerasol to the receptor independently from ‘others. Examination ofthe scatter plot of secondary sulfates and ship ping emissions contributions, reveals a lower edge in the datapoints in- ‘cating that for high shipping emissions the secondary sulfates are also high (Fig. 5). Ships can emit SO5 whichis transformed very fast to sul- fates (Kim and Hopke, 2008; Pandolfiet al, 2011). Combustion of resid ual oil wil also produce particles containing vanadium (V) andl nickel (Ni), Vanadium reaets with the oxygen from the combustion air surplus ‘creating V20- that forms layers on the heat exchanger and other boiler and stack surfaces. The VaO5 acts as a catalyst in the temperature range of 500-800 °C, accelerating the $0; formation, $0; formed by this mechanism can exceed the aroun produced in the flame by a fac tor oftwo or three (Kim and Hopke, 2008). Therefore par of secondary flies” sak emisine buming emissions cut ‘mal 72 19 aa waa 03 Warm 35. 7 a tea 03M Mansa Scie othe Teta Secondary Sulfates (g/m?) 2 Shipping Emissions (yig/m*) Fi. sce plot herween secondary sults an shiping emisons. A ot) sulfates may be associated with shipping emissions. The absence of $ from the shipping emissions might be another indication that partially shipping emissions are recognized by the model as secondary sullates. ‘The lack of ons inthe analysis makes it hard for factors suchas seconel- ary sulfates to be very “selective”. That means that even though this source can be identified because ofits high contribution, probably $ originating from other processes is also accumulated in the factor. 32, Result evaluation ‘The constrained applied first helped “clear” the factor profile from the “noise” that is present in the form of elements that ate not related to the source itself. This problem is of course more pronounced in the «case of small datasets and especially when the constituents included inthe analysis represent only a smal fraction of total PM mass. The el- ements of crustal origin being pulled up in the mineral factor and BC pulled up inthe biomass buming factor are examples ofthe first type fof constraints. The second type ate constraints applied for reducing the rotational ambiguity of the factors. Rotational ambiguity is de- creased when a sullicient number of zera values in G and F matrixes are present (Paatero and Hopke, 2008). Assigning fed values to either For Gwuil have the same result as zero values but it might be a more subjective choice. Known elemental ratios fixed for certain source pro- files and BC pulled to zero are examples ofthis type of constraints In Tables 2 and 3 the results from the uncertainty tools offered by PM 5.0 are presented. The results provided in Table 2 are basedi on PM2.5 concentration foreach source. Mineral dusthas high uncertainty i Sovieonmen 574 (2017) 135-164 1 as expected by the low contributing mass concentration of this source. For secondary sulfates and vehicle emissions the results are quite stable a8 indicated by the three rotational tool. The higher uncertainty for BS and BS-DISP indicates that a numberof peak events affect these factors ‘Those events might not be resampled in the BS runs leading to higher ‘uncertainty. The time series of 24h source contributions presented in Fig. reveals that such events do exist. A matte of discussion is wheth- lersuch events should be considered as outliers and be subsequently re- ‘moved from the analysis. tis noted here that after te frst model run the results were evaluated in order to locate any possible outliers in the dataset. After the convergence of the PMF algorithm the program calculates the residuals and identifies the points of bad fit (Paatero and Tapper, 1994). For the small number of such cases identified, theircorresponding uncertainties were increased thus their significance inthe fiting was decreased. Events of episodic nature such as forest fires or intense long range transport events may appear a5 outliers but if they are down weighted, then a serious modeling ertor is made leading to loss of eitical information (Paatero etal, 2014). Sea salt seems to have a similar uncertainty level as secondary sul- fates and vehicle emissions, with BS test yielding the highest uncer- tainty. Unlike the sources discussed so far. in the case of sea salt resampling is not assured for both low {or even zero values} and peak events instead of peak events only, affecting the uncertainty Shipping emissions seem to be more sensitive to BS-DISP even though BS and DISP when tested separately produce similar sesults, Generally speaking sources identified only by a small number of elements are much more sensitive to DISP based analysis Biomass burning has the highest uncer- ‘ainty for all three tests. Biomass burning has either very high (cold sea- son) or very low/zero (warm season) contributions and itis identified ‘mainly by one element {K), thus it is very sensitive both to resampling and displacement. Generally speaking high uncertainties are to be ex. pected when small datasets ate sed (Paatero etal, 2014) ‘The uncertainties provided by the rotational tools correspond to pro- ‘le uncertainties. The uncertainty given on Table 2 regarding PM2.S ap- plies also to estimates of average PM2.5 conteibution from each factor because all modeling is performed under the constraint that average G Values must be normalized for each factor with respect to mass (Paatero etal. 2014). straightforward method to calculate uncertainty for individual (24-h) contribution values doesnot yetexist although in- {ercomparison studies has given some indications towards this direc- tion (Belis et al, 2015). An approach using regression analysis Is propased inthis work. The errr ofthe source contribution wasealeulat- fe based on the standard errr ofthe coefficients ofa multiple regres- sion between the dally PM2.5 concentration {independent variable) Unesrtity te ea or M2 mas omcntation (4 Boseyaue _BS3th__BSmedion ES ESDP BSDKPaenme _BSDSPOSH _DSPMn_DSPaetae _ DSPMax Sevsat 18 oo 3a 0 2 a 09 rn 26 Shipping emisions 22 es aa ut a9 “2 16 2 a Bimassourang 23 05s 05 5 36 2 a rr Minerals a as 0 3 es ai ae a ‘Uncen tous res for specie clemens uses tras pacar sources, Where: 80. ta MID net secondary sites SEAS HI shipping emission BI iomsssbusing VEE veil ex Soure_aaevahe A550 Wmedan 605i ESDSPSIH ESDSPaenge _ESOSPGSH _OFMn_DiPawrage STN Ss su am) a—a0 ry 1250 ven 1296 1512 Ne SA 02m Tisai ae nis oi a0 Das visit 00 .noa amass mo 2 004 0.003 004 kK poz azo as 08 nae naw om aan baa ne VER 10) e589 HD nis 120 ro 1387 vat SMD 02 02am ams nae 36 28 oa dasa aa182 Mi Maroulis tal Since of the Tt Ewionment 5742017) 155-154 ‘ables Sours oaubuton nd carrespoding enor Secondary sates 72 ar Scout 9 a Shipping emsions 2 a ‘Bhomass uring 2A a Vetideemisons n a Mineral dust on 03 «ai the six source contributions for any given day (depenslent va ‘bles)- The regression approach assumes thatall the factors that explain the mass are identified. However, ia significant portion of the mass that is not directly correlated withthe species that are in the PMFanalysi is missed, the source contributions will be overestimated. This might be {an important source of additional uncertainty. Results are shown in, Table 4, I must be noted that this method captures only one past of the uncertainty, because it daes net include the error arising from the profile uncertainty and the rotational ambiguity. Using this method ‘we can investigate how well the dally contributions can recreate the daily PM mass. Since the corclation of the model predicted mass and the true PM mass is high (R? = 0.80) itis believed that this method ‘could provide an estimate of this uncertain. ‘The errors calculated by this method are quite low indicating good ‘model fit. Mineral dust because ofits very low contribution has a high ‘error assigned to its contribution. In Table 3 the uncertainty of the main elements used as tracers for ‘each source are presented. Those results are very useful because they ‘are needed in order to evaluate which factots may be more reliably at- tributed to sources, by showing which components were fitted conti- ‘dently and which components were too uncertain (o be considered for ‘soutee identification. al elements uncertainies are considered reason- ably low and thus the factors can be indeed identified 3s specific PM. Sources. The only element that shows quite high uncertainty for BS is K probably because ofthe variability mn concentrations thas, making, it very sensitive on resampling. DISP result for the same element is much more stable 4.Conclusions A seall dataset of 55 samples was used in order to identify the sources of PM. in Patras The target ofthe study, apart ram source identification and characterization, was 0 evaluate the stability ofthe Solution resulting rom the use of ama dataset, sing the ols fered by PME5.0, When no constants ae apple, the results rom the base run were characterized by high uncertainty, othe extent that no Sores could be atributed tothe factors. Aer the application ofthe Constraints the sotion was tale and cole be interpre ins mean- ingfl manner ‘The constants applied were in the form of elerental ratios ain particular for shipping emissions (V — 3 Ni= 0) and for biomass burning (S~ 05 K'= 0} ALS. Ca and 7 were pulled up maximally inthe mineral dust source, BC was pile up in biomass ring anf nally BC wassetto zero in mineral Gust The change in Qafter the ppl ‘ation ofthe constants was lw (1 Six sourees were identified and were namely biomass burning (11%, shipping emissions (10%), sea sal (93), secondary sulfates (34), mineral cist (2%) and vehicle emissions (34%). Tisis the fst time thatthe contribution of sipping emissions ts quantified in a (Greek urban area with port. This information canbe used forthe deve. ‘pment of more elfctive measures for theimproverentaf the air qual ity ofthe ares, 1S, DSP and BS-DISP results showed thatthe prof uncertainty for the elements ued as tracers for factor entation vs ite low pro viding strong evidence forthe identification othe actos PM. cOn- “entation inthe prafles has high uncertainty in som cases, a fact thats attributed mainly tothe small dataset and the high level of uncer- tainty assigned to PM2.5 when set as total variable (uncertainty is t- pled in that case). The case of biomass burning revealed that Sources ‘with high seasonal variability are especially vulnerable to resampling, techniques in small datasets ‘Overall the results indicate thatthe use of the tools offered by PME 50 and the consideration of appropriate constraints significantly im prove the solution even for data sets of limited number ef samples. I isvery importantto fully report the uncertainty of the solution in source apportionment studies especially i'small datasets ate used. In any case it should be noted that this work does not encourage the use of small datasets, and datasets with a larger number of samples should be used ‘whenever posible, Acknowledgements ‘This work has been supported by the European Community as an n- tegrating Activity “Support of Public and industrial Research Using fon Bean Technology (SPIRIT under EC contract no. 227012. nancial up- port from the EnTeC FP7 Capacities program (REGPOT-2012-2013-1, FP7, 1D: 655 316173) and K. Karatheodori program (Grand D165) are also acknowledged. References ‘Amat, Alay, A. Karama, A Lael F Nava S, Cael Ge ay 2016 ‘ARUSE-LIFe +: harmed PM Speciation and source apportionment Be Southern Eiropean tes As. Chem Py 1 3268-3308, Amin, Wate, Kaze. Cerspauls E Hetertes K Vekous et “22012 mpac the 2009 Aten whe son the cuit a uaa Abe ‘es Eeon tert} 46 sever Ld pp. 596-544. ps dadery 0.1018) Smosen 20417085 ‘Annepeuos ©. GrgratosT, Vous M, Sanat, C, 2013 Oc. Concerns and Soute ppoivonment ef PMO nd wsoeated eet ad ene pees 9 hte burning power generation are of sober Cease Eason Sc Pat Res. Ine 0 (10)-7214-7250 [ted 2014 Jan 30}- Avda Wome) Hp. nL nitseipabmed 1360497 ‘Abzssopolb,, Tonbrou M, Risell AC. Kanai A, Ethers K, Dane, 1h: 2010. plementation of oad and soi cust emission paanetnzatons I he {ensol ade Che sppcatons ver he eater Athens oan sea sete y aural scares Ceopty ex Aion 115 (17 1-2 tel CA argon Lane BA2013 Hope eel view an metanaiof “et pareulst mater sure apportionment sing receptor modes in Eo. ‘Anes avo interme ever tp cited 204 Jan 3,694 108. vale from: tik chever comorebievespy 19522310120 10580 Beli CA. Pema D, Karel F Prova, Lane A. Ceol, Metal 201, “yaeir thoy ts anesthe plone neues our sport: tment mocel sn tremparsn sernes Smos Esra Ineo] 118 Hacer Tee," pp. 5-44 Avallble row tpfinknghubelsevercomytetneve/p ove, Mi rote, P- cao Caso FCaal Ferme, eta, 2016 Pato sauce mens inte Wlesembestenaeam mex. Enon. 125, 1-15 Caimi G. Chr, Laat Maer fina, Sa eta, 208 PRE ae “also areas moter samples am ne artery a ‘wih Miter Atoms iteret) May ated 265 1024011 Aaa om hp Akungueheveccanfetieve piso l6RsORO 72. ‘Gang MoT. Chen, YC, Lee CT Cheng Ct Tak Yo, Chang, So al 2015 Ap Prtoment ofthe seus fh ie parse ae eaten events 3 ‘fevelopngaroropots i Taoyuan Tatwan enon Pot [grat] 214 seer tad pe at-261 Avable (rin pakinghubeleve- com feheve pl ‘cohen, DD. ster E FS. Pr, M Thompson. C, FCB P 209, Rrgepining ane Sure opetoamen othe pre ohana Man y BA and Petts {hear study XeRaySpecrom. 381), 18-25. hp xden 101002 1012 Ja etd 2013 Fe a Dap E opin, O Kiley, Vat SPersansev, Tino, Metab "24 Fkypeachemsa chucterzston of ape eras uring sro ale Tange transpet to Gress fom ate cle wiles in Risse ad surounding te {bors Super 2010. Ans Even interne Elsevier et oted 014 De 2 Sosos-404 Avalble tom’ Mp, Mabrghubslsene:comjetievepl Dimou. Remounda F, Mantas, Kemomenos 2015. Spatil dation of eure stan of P25 by conentraton weighed ajar (CWT) made pee inPM25 eanensabon and compostin dat Atos Ene inten] 16 sever [ee pp 138-195 Avalaietom hp: paw scenecredtcomisoencalp eters Cale, 2001, Conse tmenpherc aera: ie ction face ‘ment mae Eman 53) S100.1M Manoa a Scene othe Teta evant 574 (2017) 135-164 18 feria Bas. Zama CoB Manas N. 198 Jun Atpospeicaerosl ‘ne gaseouspedesin Aen ree los Enavan 32 (12). 2183-211 alle rom hp nnghsene ecm rete S135275OSTEDN- Elthernin Ie HMO, Lymperopaioa T-Karansou, A Raz P- Cchoenkub nc temporal vty of sae weslved stmospheric serosl ms concertos ‘ne wateeslble spent Aes medoplean ea Aunos Env [noe sever ed Now ted 2014 Dee T7252", Avalie em ht keh event pS1I5225101400807 sin Sora ames J Daten SD eae 1, een Geophys Res. 108 (D171 4560 hapa on 1O.1 0292002100288 eed oIsyan 14, dsl Stem E Petron, 2008 Primary parties sip emis, Amon Ei ron), 1160-1068 Fe [ates 2014 Ape 24 rats from ep ang. ‘hevecom/erieveptS133225100700968. CersopsE Kova, aaa PVekouss, M. Put J Mieputos ‘zn rigin nd varity of paca mater (Pit) mast concentrations ber the Eistre Mectenranean Atos. xvion 0 (25, 179-4500 Aug ated 2014 May 6] Availble fom hip linking tsevier com rereveipy Stasza3inoso4on [Gigpropoulbs KN, Nats Pr Fereminos G, 208 stil sntin of Tae PM 1 dig Saran dst poesia Athens Gece AS Res 359-52 Hope, PK. 2016 A view af eer tndelg metho fo soue: appertionnent "At Waste Nagase: Asoc 7247. hpcedotorg 11080 109521472016 1 0603 amo Hopke PK. ka K Mt T Chistesen WE, toh, DJ, Henry Ret by 2008 PM source apotionten’ an health effect 1 Inteteomparson source apportion neat ess) apa Scena Epo 15 (3, 775-286. a. Chistes Wf atu Dd Henry RC, Thuton . 2006 Pl source par ‘onment and eat efect:2. An estas of neteted varity asso ‘ons between sourceapportoned fine particle mass and duly mortally In ‘Washington DC | Expa Sa Eon, Eel 200, 30-510. Jobson ce Ze Mab, LT Mois Me, Yet a 2006 Ny 198 ere amponhen sere approninent nthe Neco Cay erp Ars ‘th PAE PESASTIMG ane mlivarate saya, Aton Chem Py Dass (3), 53057-4022 Ava fom tp po ats ene physscss 8 997/208 Johnsen KS, coy Bh Zen By Mtn LT Allin Ml. Ne tl 2005 May 19. Refs zampanic an sore apprtonient inte Neco Cy Metra Area ‘th PAE PESASTIM ane multe saya, Aten Che Psp. Dass (3), [Tar-a023 Avie om ame comp cn 27 2008 ranma Mop 2011 Arquette ser Md ‘tenes: Vana, MCE) Han ion Che 25 Spm ern pp, 21-278 avanasiou, AAPA Sefer K 2409 Assesment of sour appeicament by ste Na Facaebon anasis on Ae ane couse ua sere se atone, ‘Ameston tere ener Jl [ces 2013 e121 38595. Ava {Ble rom ne: Minkingh ener ean fee pS 195223 1085, armas, Dipl cova FHetherinteK W M ler, A. ea 201 ‘On mecaanieston of atmosphere crbnate abn by thermatepil anass potas Anas Meas Tech 4 (1), 2009-240 iar P'S, Sak 52012 Aston inalbe metalic ares of ei ‘eirouton sure apportionment ane nets Ames Pat Re 3. 46-38] [eine 2018 Mar 1] Raabe mbps esmespres em icesobme}/ EaeLAMm-t2o04pet um. £ Hope, 2004 Source ponent offi pres a Washign. DC iaag temperature sesolvedeabon factions Jr Waste Mata Assoc 54 ‘773-785. oor 0 1080 04752892004 APO ul eed 2014 Ap 4. im, EHopke, Pk 208. See charaterzaton of anbent ie prices at mule Stes inthe Seale re. Atos. ron. 2 (28), 7~2086 Acted 2014 May 27) Aad on Bhagat en ees p32 108005067, Lane Es Hope, Pk Stuer. Sepa, LE Caborm C. 2003 Soaee ‘entiation of? nan aid Norwest J. iy by postive marx creation ‘tos Hes ct, 291-308 May fee 2013 Feb 20] Ava fom ity finkingbescsevier circ Sosa0es4300025, ‘oumourzogiou MA. Col, Domne F. Koutakis, ,Schwar,.Suh H.2014 “The pact of acur: enteten unreal onthe ec of ave apeiie P25 thon amine: rcs tryst on, ML apo Sa Ene Eel {ernet| 244) Nature Publishing Group pp, 365-71. po. 101038, bona osteno, £, KaksonoudsC. Tact Mlawrars E_Rasel LM, SN 201, ‘imo Chem Pi: Dace (1) 728-Tagbiter 19 ote 201) Mar] fom {rom hp stor chem: pcan 12221201 osteo, Foto K,Hasonos,C Taboo, M, Witt, 5, Heth Kc Ss 2013 Sources and chemea chariteroatn of ogni eel inet = ‘mer inthe essem Medtemacan Amos Che. Pye 1318) 11335-1137. Lacan M, ethers K Sob Coe. Kall, G, Drossins, Ys et al 2005 (Dyas offic pres and photon ant i the Ester Meaeranean (SUB [KO Ames. Ean A 5214-5228 Oet fated 2014 De 8) Arallae fam ‘hep nkigbublrvercomretneve/ps 1922510300302, we JH Yo ¥, Tupi, 8) Hopke PA, Pat, RL ay, AJ 2002 at to of sources contig to nda ponl trol Ale Waste Manag ‘Asse 5210) 186-1205. or10 0801017328820 170930 et Tetee 2014 Apr 1.2. Hop, PC Musi, Quests Dutewic Va, Schwa. eta, 204 Sates ‘alin ute cnpoiton i New Yok cy. Aas En. 3 (38). 5521-8529 wwaaesk Qe am He uc aca inp eeoS tE tas my ci sent Er buts 20% Gn st Souresancmbaent Ar Coneeotation Levels at egalopoks Cty (Southem Greece) icin teat tease ay Stace ry Sisson Sede atcha ge teat Sora ee eta Wana a ata Shes vi an. cap ce vation thon tai a sect Yt a oo Sag a se ft ttn ia ac Sanne out A tt id Gen runs et ele eta Se li cer a a eines aunt ib pat eacaet peat a ERE nl ae et ito eaidaat A amceecaea eae li eat ey eet es cap St ataot acter a a Sotho sl gt Ree Ri ie io in pe nahin Sw Se a ng ih Sweeter Sel co a oe nt nc th en see oe ete i 1, 8 ve i te nap main amg te falatfeote aA7 M Maroulis tal Since of the Tt Ewionment 5742017) 155-154 Samar A, Daher. N. Samar, Vous, D. Kowa, A Mano etl, 2013. nese ‘roms burnin de tthe cen ess m Greece nis vase mpacton wt fertine out) Thosson Eon Sea Teck 3 (4723) SIMO Den healdk fom ip rani pre. Surge DE. Mabophts, A Knaalaon 5 abl A; Dupo Eerie 3, 2013 Apt unestigen of Hooton mas concent ache ‘alana dunnga pera fextensve replace tse In Atbers. Ase Ar Qa Res 15 (7), 2885-2895 Ava fom. Mp: pav.angoneDot php eT AKG usta one skeen 22015 sep Moran nn en nM Deine Bs 208 Sonny (Gem: Phy 4 (3) 857-874 Jun 13 Avail rom p/w ata chen py. seus 2004 Sowata 5 Mauek M, Brel A Pll, Tart, Rempasen Gy, 201 ctor cetemaning he oration face snr aeran set he oat ay Atmos chem. Phys. 19 (4) 19271899 Fe 19 [eed 2014 Mar ipo am hither che: pine 1927201 ‘tcl W/L Kus Eererian V-tree, MIC, Cho, JC Watson. Je 2D The Fesure Vay secondary aoe sty He mods of the onan of [noganicseconary aero an precisors er sehwester so Anes, Even 537, 525-534 Fe [ated 20E¢ Ape 23] Ava HIgh tse. emntetev 8135223102085, ‘ana M, Rubich a]. Quel. Alstry,A, Harta, RAE Hophe, PX HOE Soue pporanieat of pclae mater it Ewope: Ave of ethos and results Aerosol S39 (10) 227-849 Oe ed 2013 Jan 30] Arai fom inka eee cone suz1450208001078 Viana Anat F Aston A. Quer X, Moreno, Dex Santon, SC 2008, “Chemie aes of partie rms om sennecil shipping. Enso Se ‘eco 14,15), 9472-747 Ot, Ava om poche pomediseasi63. ia eee, At, E.Azstue, 2. QueolX, Maren Tt a, 2013. Edens of emats uring aeresls ithe Birclona uh envrontent curing winter ti ‘Atmos nan tert] 7 Hei i pj 818 (te 2014 Sep 9 alee fom hip inlonghac ever eine ps1 1222110120125 ‘aang i isromungt Cole A Quel Degree el 2014 Im Patol marine trnpetemisonsen coal ar qa ineorope: Ams Eo Sacer cpp. 9105 un oe 201 Jun 3 alae om ht kg Wiad fase O, Aleman Lat CPt J. Daou Tea 2014 Soares ap Portonment of PMO wa north-west Europe regional wan backround Ste {lens France) wing poste max tcoiation a ning ema ogee emia mes. Chem Phys 147), 3525-36 ‘in Jen, AG, Hania RM. Jenne, WME, Fzpatic Me a 2008. ao eomponentcompeston of uban Pi an Pun ela Atos Res 78 {G4 1400165 Dee eee 2014 Fe 21] Avaabe om Mp aninghubeleter. omuretevep0 1680850500 24,