Contribution-of-harbour-activities-to-levels-of-particulate-matter-in-a-harbour-area-Hada-Project-Tarragona-Spain.pdf

atmospheric environment 41 2007 6366 6378 contribution of harbour activities to levels of particulate matter in a harbour area hada project tarragona spain a alastueya n morenoa x querola m vianaa b art n anob j a luacesc j basorac a guerrad ainstitute of earth sciences jaume almera csic c llu s sole i sabar s s n 08028 barcelona spain bciemat av complutense 22 28040 madrid spain cport de tarragona passeig de l escullera s n 43004 tarragona spain dente pu blico puertos del estado av parteno n 10 28224 madrid spain received 5 september 2006 received in revised form 23 february 2007 accepted 16 march 2007 abstract the present study seeks to estimate the impact of harbour activities on pm10 levels based on a complete chemical characterisation of 90 pm10 samples periodically collected between september 2004 and september 2005 in the harbour of tarragona as part of the hada life program ec project interpretation of the time series of major and trace pm10 components allowed us to identify peaks of pm10 components related to the activities in the harbour a factor analysis of pm10 enabled us to identify the crustal traffi c secondary and sea spray sources and one other source related to the re suspension of materials handled in the harbour the multi linear regression analysis demonstrated a high anthropogenic contribution 62 for pm10 at the harbour mainly related to traffi c 34 of pm10 comparison with an earlier study using the same methodology at an urban background monitoring station in tarragona showed a good correlation for the annual average concentrations of most pm10 components at the two stations at the harbour higher concentrations were obtained for tracers p and mn and v and ni in a lesser extent of some mineral bulk cargo materials re suspension of loose materials by means of wind and or traffi c was identifi ed as one of the major contributors to pm10 in the harbour abatement strategies designed to reduce levels of pm10 in the harbour and nearby areas are provided r 2007 elsevier ltd all rights reserved keywords fugitive emissions source contribution pm10 trace elements air quality 1 introduction harbours which are often located close to urban areas may be at the root of problems related to atmospheric and water pollution and noise in the adjacent cities thus in the last decade a number of research studies have addressed the evaluation of the impact of atmospheric shipping emissions on air quality at local scale and on climate at regional scale studies by corbett and fischbeck 1997 corbett and koehler 2003 and endresen et al 2003 estimated the magnitude of shipping emis sions to the atmosphere a number of works have addressed the characterisation of emissions from article in press 1352 2310 see front matter r 2007 elsevier ltd all rights reserved doi 10 1016 j atmosenv 2007 03 015 corresponding author tel 34934095410 fax 34934110012 e mail address aalastuey ija csic es a alastuey ships and their estimation on proximal urban areas at local scale isakson et al 2001 cooper 2003 sinha et al 2003 saxe and larsen 2004 a major concern for harbour authorities is to identify the major sources and to estimate the impact of harbour activities on pm levels in the harbour and adjacent urban areas apart from the emission from ships other harbour activities such as loading unloading and transport of dusty loose materials may have a signifi cant impact on pm levels and therefore a potential effect on human health at nearby urban areas for example the unloading of soybean in bulk in the harbour of barcelona was related to increased numbers of asthma patients treated in emergency departments between 1981 and 1987 anto et al 1989 an estimation of the contribution of these sources related to the handling of dusty materials may help the harbour authorities to implement the appro priate measures for reducing levels of pm in the harbour the aim of this study carried out in the frame work of the hada project life program ec is to identify and to estimate the impact of harbour activities on ambient pm levels in the harbours the harbouroftarragona mediterraneancoast north east spain 4110 50n and 11140e was se lected for this study because of the high volume of solids in bulk handled 10650006 t in 2004 a detailed interpretation of the chemical composi tion of a representative set of pm10 samples collected at the tarragona harbour was carried out given the complexity of pm10 sources in this area sea spray local and external soil re suspension dust traffi candindustrialpetrochemicaland chemical emissions among others the results were compared with those results obtained for 2001 at an urban background monitoring station using the same methodology viana 2003 viana et al 2006 2 experimental sampling and measurements of levels of pm and gaseous pollutants were carried out at an air quality monitoring station belonging to the tarragona harbour authority which is located in the tarra gona harbour tha ms fig 1 sampling of pm10 was carried out from 22 09 2004 to 12 09 2005 by means of the en 1234 1 reference high volume sampler for pm10 tisch environmental 68m3h 1 at a rate of two 24h consecutive samples perweek movingdays theactualweekdays differingfromweektoweek equippedwith schleicher and schuell quartz microfi bre fi lters pm10 concentrations were determined by gravi metry and the fi lters were treated for chemical analysis following the methodology described by querol et al 2004a which allowed us to determine levels of 57 components in pm per sample this was based on the analysis of major and trace elements by icp aes and icp ms in a previously acid digested solution with hno3 hf hclo4 1 2 frac tion of each fi lter soluble anions by ion chromato graphy ammonium by colorimetry fia on water extractions of a 1 4 of each fi lter total c was determinedbymeansofalecoanalyser the contents of si and co3 2 were indirectly determined from the contents of al ca and mg on the basis of prior experimental equations 3 al2o3 sio2 1 5 ca 2 5 mg co2 3 the levels of cnonmineralwere obtained by subtract ing the ccarbonatefrom the direct ctotaldetermina tions the so2 4 marine was indirectly determined by stoichiometryfromthesolublenalevels so2 4 na 0 25 in accordance to the na so4 2 sea water ratio 8 33eqeq 1 drever 1982 om ec or organic matter plus elemental carbon was calculated by applying a 1 2 factor to the oc ec concentration turpin et al 2003 frac tions of blank fi lters were analysed for each batch of fi lter samples and the corresponding blank con centrations were subtracted from each sample a few mg of the reference material nist 1633b were added to a fraction of a blank fi lter to confi rm the accuracy of the analysis of the acidic digestions for mostelements relativeanalyticalerrorswere o10 with the exception of p and k for which a 15 errorwasdetermined thehigh volume sampling coupled with the analytical methodology article in press fig 1 location of the monitoring stations of the harbour authority of tarragona tha ms 2004 2005 and town of tarragona tub ms 2001 a alastuey et al atmospheric environment 41 2007 6366 63786367 allowedtoreachactualdetectionlimits o0 01ngm 3for most metals the main sources affecting the pm composition at the harbour of tarragona were identifi ed by applying a varimax rotated factor analysis fa in accordance with the methodology of thurston and spengler 1985 the factors with eigenvalues great er than one were identifi ed as particle sources on the basis of their loadings the respective quantitative contributions were then derived by applying a multi linear regression analysis mlra using pm concentration values as the dependent variable and absolute factor scores as independent variables the origin of air masses infl uencing the monitor ing stations for each day during the sampling period was interpreted on the basis of daily computed 5 day isentropic back trajectories using the hysplit model draxler and hess 1998 and ecmwf synoptic charts surface and upper levels further more african dust outbreaks affecting the iberian peninsula were also detected with the aid of daily toms nasaaerosolindexmaps skiron athens university and naaps naval research laboratory marine meteorology division mod elled dust concentration maps and seawifs nasa satellite imagery the record of the different activities carried out in the harbour for these periods was also considered in order to interpret the time evolution of selected elements specialattentionwaspaidtothe groups of elements identifi ed as tracers for specifi c operations in the harbour of tarragona moreno et al 2007 the results obtained in this study were compared with those obtained for 2001 at an urban back ground monitoring station tub ms in tarragona viana et al 2006 this site was located on the rooftop of a seven storey building 60m a s l in the city at a 1km distance from tha ms fig 1 see viana et al 2006 for details levels registered at this site may be considered as representative of the pollution levels in the city at this site pm10 and pm2 5 were sampled and characterised following the same methodology described above 3 results 3 1 chemical characterisation of pm10 at tha ms and comparison with tub ms table 1 shows the mean concentrations and the standard deviations obtained for major and trace elements in pm10 at the tha ms for the period 22 09 2004 12 09 2005 from the analyses of 92 24h samples results obtained for 2001 at tub ms viana et al 2006 and usual concentration ranges obtained at urban sites in spain querol et al 2004a are also presented the mean annual pm10 level obtained at the tha ms from gravimetric determinations was 40mgm 3 this concentration is slightly higher than that determined in 2001 at the tub ms 37mgm 3 querol et al 2004a viana et al 2006 major chemical components were grouped as crustal co3 2 sio2 al2o3 ca k mg fe p2o5 om ec sia secondary inorganic aerosols non marine so4 2 no3 nh4 and marine na cl marine so4 2 annual mean contributions in mgm 3and calculated for each of these groups of major components in pm10 at tha ms are presented in fig 2 the undetermined fraction whichaccountsfor23 ofpm10mass is attributed to water and hetero atoms derived from the organic constituents andrews et al 2000 crustalcomponent thisgroupofelements account for an annual mean of 11mgm 3 which represents 27 of pm10 this value is relatively high when compared with the mean concentration obtained at the tub ms in 2001 9 2mgm 3 24 table 1 and fig 2 this difference may be attributed to an increase in the crustal input in the area for 2004 2005 with respect to 2001 it could also be due to a higher contribution of crustal elements in the harbour which could be related to the handling of mineral solids in bulk relatively high contents of ca were measured at both sites the harbour and the urban monitoring site with annual mean concentrations of 1 9 and 1 8mgm 3 respec tively table 1 and daily mean values reaching up to 4 6mgm 3 these concentrations are in the range ofthosedeterminedforotherareasonthe mediterranean coast in spain but are markedly higher than those recorded in other areas in the iberian peninsula similarly the mean content of fe2o3at the harbour site 0 9mgm 3 is slightly higher than the one obtained at the urban site 0 6mgm 3 and it is in the upper range of the levels measured in spain 0 4 1mgm 3 table 1 secondary inorganic aerosols sia these com pounds annual mean of 10 3mgm 3 accounted for 25 of pm10 nonmarine sulphate being one of the most important constituents of pm10 annual mean of 5 1mgm 3 with daily concentrations ranging between 0 7 and 14 0mgm 3 nitrate presents an article in press a alastuey et al atmospheric environment 41 2007 6366 63786368 article in press table 1 mean concentration and standard deviation for major mgm 3 and trace elements ngm 3 in pm10 at the tha ms for the period 22 09 2004 12 09 2005 sampling period no samplestha ms 22 09 04 12 09 05tub ms 09 01 01 27 12 01range for urban background in spain 9290 meanst dev meanst dev mgm 3 pm104015371330 47 om ec8 24 68 83 44 11 co3 2 3 61 73 31 81 6 3 9 sio23 02 52 21 61 8 5 8 al2o31 00 80 80 60 7 1 9 ca1 91 01 81 11 2 0 k0 30 20 30 10 2 0 5 na1 00 71 20 60 4 2 3 mg0 30 10 30 10 15 0 7 fe2o30 90 50 60 30 4 1 0 so2 4 marine 0 30 20 30 20 2 0 9 so2 4 nonmarine 5 12 84 92 72 5 5 no3 3 62 93 92 91 4 3 1 cl 0 60 60 80 80 7 1 3 6 6 canaries nh4 1 61 61 51 31 3 2 determined 7810828 ngm 3 li0 60 80 40 20 2 0 7 p7673291718 32 480 huelva sc0 10 30 30 30 1 0 3 ti3131231420 85 v118865 15 cr42321 8 25 metallurgy mn33739610 25 85 metallurgy co0 30 20 20 10 2 0 5 ni63432 7 30 metallurgy cu2516332820 50 100 metallurgy zn3721352220 100 415 metallurgy ga0 20 20 20 30 2 0 4 ge0 30 20 10 20 1 0 3 as0 80 60 80 50 3 1 8 se0 40 50 50 50 3 1 1 rb0 80 50 80 50 6 1 8 sr5 73 24 82 72 6 y0 30 20 10 10 1 0 4 zr5 94 62 32 62 4 mo4 22 32 23 01 21 cd0 20 10 30 20 2 0 8 sn2 71 91 70 71 4 sb3 01 96 911 91 10 cs0 10 10 10 10 1 ba13812515 40 lree1 21 21 40 90 8 2 6 hree0 20 20 40 40 15 0 6 hf0 50 60 20 20 1 0 35 pb1211251810 60 bi0 30 30 20 40 1 0 5 th0 10 10 20 20 1 0 4 u0 20 20 30 50 2 0 5 data obtained for the tub ms in 2001 viana 2003 and range of levels of major and trace elements at urban background sites in spain also included querol et al 2004a a alastuey et al atmospheric environment 41 2007 6366 63786369 annual mean content of 3 6mgm 3 with daily values between 0 2 and 15mgm 3 these mean concentrations are also in the upper range of those determined for spain table 1 querol et al 2004a ammonium is present in concentrations between o0 1 and 9 5mgm 3 with an annual mean of 1 6mgm 3 there is a clear correlation between the concentration of sulphate and nitrate with those of ammonium r2 0 77 fig 3 with a marked excess of sulphate and nitrate the presence of acidic compounds or that of the partial association of sulphate and nitrate with other cations such as na or ca forming caso42h2o gypsum na2so4 nano3 or ca no3 2is deduced comparison with the results obtained at tub ms fig 2 showed similar concentrations of sia at both sites with a mean value of 10 2mgm 3 27 of pm10 at the urban site in 2001 table 1 and fig 2 the similarity of the contributions of these compounds in both localities is explained by the secondary nature of these compounds their fi ne grain size distribution and their longer time of residence and distance of transport in the atmosphere sea spray the mean annual contribution deter mined for sea spray is similar at both sites although it is surprisingly slightly higher at the tub ms 2 3mgm 3 than at the tha ms 1 9mgm 3 5 of pm10 fig 2 this difference may be attributed to inter annual variations sea spray levels usually recorded in mediterranean coastal sites in spain range between 2 and 4mgm 3 querol et al 2004a usually in atlantic coasts sea spray levels are higher by a factor of 2 with annual mean concentration of up to 7mgm 3 visser et al 2001 higher concentrations of sea spray have been determined in the canary islands 12mgm 3 querol et al 2004a carbonaceous particles om ec daily levels of organic matter and elemental carbon at the harbour varied between 1 4 and 22 3mgm 3 with an annual average of 8 2mgm 3 which accounts for 20 of pm10 this mean content was very similar to that determined for the tub ms in 2001 8 8mgm 3 23 trace elements the sum of the concentrations of allthetraceelementsanalysedaccountsfor 0 27mgm 3 273ngm 3 as the annual mean which contributes with o1 to pm10 it should be mentioned that although these measurements could not be considered as ambient air concentrations given that they were obtained in the inner part of the harbour annual mean concentrations of health concerning elements such as pb as cd and ni 12 0 8 0 2 and 6 1ngm 3 respectively were lower than the limit value established by the 1999 30 ec directive for pb annual mean of 500ngm 3 and the target values proposed by the 2004 107 ec directive for 2012 annual mean of 6ng asm 3 5ng cdm 3 and 20ng nim 3 the higher levels of pb registered at the tub ms in 2001 are related to article in press y 0 21x r2 0 77 y 0 27x 0 76 r2 0 83 0 5 10 05101520253035 so42 no3 nh4 fig 3 correlation between daily mean concentrations in mgm 3 of so4 2 no3 and nh4 pm10 tha ms 2004 2005 40 5 g m 3 11 0 27 8 2 20 10 3 25 9 2 23 1 9 5 crustalom ecsiamarineundeter pm10 tub ms 2001 37 4 g m 3 9 2 24 8 8 23 10 2 27 2 3 6 7 8 20 crustalom ecsiamarineundeter fig 2 pm10 levels and composition in mgm 3 in the harbour of tarragona tha ms for the period 22 09 04 12 09 05 and at an urban background site in the town of tarragona tub ms for an annual period 09 01 01 27 12 01 crustal co3 2 sio2 al2o3 ca k mg fe p2o5 om ec organic matter elemental carbon sia secondary inorganic aerosols nonmarine so4 2 no3 nh4 and marine na cl marine so4 2 undeter undetermined a alastuey et al atmospheric environment 41 2007 6366 63786370 the fact that leaded petrol was banned in spain in august 2001 the mean annual concentration of p in the harbour 76ngm 3 is clearly higher than at the tub ms site 29ngm 3 and may be consid ered high when compared with the mean concentra tions measured at other urban sites in spain table 1 in the range of that measured in huelva 480ngm 3 a site subject to the infl uence of the emissions of fertilizer plants querol et al 2002 alastuey et al 2006 in the remaining areas mean annual concentrations of p ranged between 18 and 32ngm 3 the content of mn 33ngm 3 may also be considered as relatively high when compared withthelevelsmeasuredatthetub ms 33ngm 3 and with the usual range obtained at urban sites in spain 10 25ngm 3 these high levelsofmnandpmayberelatedtothe composition of bulk solids usually handled in the harbour of tarragona mn mineral and phosphates moreno et al 2007 similarly levels of v and ni measured at the harbour site 11 and 6ngm 3 respectively were slightly higher than those ob tained at the tub ms 8 and 4ngm 3 respectively and at the top of the range determined for urban sites