Mineralogy-and-origin-of-atmospheric-particles-in-the-industrial-area-of-Huelva-(SW-Spain).pdf

atmospheric environment 39 2005 6777 6789 mineralogy and origin of atmospheric particles in the industrial area of huelva sw spain j m bernabe m i carretero e gala n dpto cristalografi a mineralog a y qu mica agr cola universidad de sevilla apdo 553 sevilla spain received 31 march 2005 received in revised form 30 june 2005 accepted 18 july 2005 abstract the mineralogy of atmospheric particles at the confl uence of the tinto and odiel rivers south of huelva a highly industrialized city in the sw spain was characterized in view to identify source origins in spite of the small amount of sample collected mineralogical characterization was performed by x ray diffraction polarized light microscopy and scanning electron microscopy with eds analysis system using an adequate sample preparation methodology sedimentable sp and aerosols particles were sampled an one week basis every two months for one year quartz calcite and feldspars were found to be the major minerals in both fractions and phyllosilicates dolomite and gypsum were also identifi ed in lower content minor mineral particles included barite apatite sphalerite and pyrite sem studies revealed the additional presence of chalcopyrite in both sp and aerosols and of chalcocite covellite halite and sylvite in the latter siderite hematite and ankerite were only detected in the sp fraction the concentrations of the previous minerals increased in summer by effect of the limited rain and the resulting scarcity of atmosphere washing non mineral particles detected by sem in sp and aerosol fractions included spherical biological and compositionally complex particles the main source of mineral particles was found to be the soil suspension in addition to the metallurgical and fertilizer production industries in the area r 2005 elsevier ltd all rights reserved keywords mineralogy sedimentable particles aerosols x ray diffraction scanning electron microscopy 1 introduction the atmospheric particulate material has been subject of many studies most of them have been chemical in scope torfs and van grieken 1997 querol et al 1998 2002 chabas and lefe vre 2000 a lvarez mota 2001 brewer and belzer 2001 bernabe et al 2003 bogo et al 2003 also some authors have used scanning electron microscopy sem with x ray energy dispersive eds to examine particles in morphological and chemical terms or elucidate their mineralogy esbert et al 1996 umbr a et al 1999 chabas and lefe vre 2000 bernabe and carretero 2003 however there are not many mineralogical analyses of atmospheric particles esteve et al 1997 querol et al 1999 queralt et al 2001 ekosse et al 2004 the mineralogy of atmospheric particles may be in some cases more useful than their chemical composition article in press 1352 2310 see front matter r 2005 elsevier ltd all rights reserved doi 10 1016 j atmosenv 2005 07 073 corresponding author fax 34954557141 e mail address carre us es m i carretero with a view to establishing their origin and their potential effects on human health whether adverse e g silicosis asbestosis lung cancer or favourable e g neutralization of acid aerosols however the mineralogy of particles is more diffi cult than their chemical characterization in the case of small amount of sample as it sometimes occurs in sedimentable and aerosol fraction in this case the problems of the mineralogical characterization of atmospheric parti cles could be avoided with the use of both x ray diffraction xrd and sem techniques employing an adequate sample preparation methodology the city of huelva sw spain is in a heavily industrialized environment including metallurgical chemical and petrochemical industries also it is under the infl uence of the sea the atlantic ocean andsubjecttoinputsofnaturalatmospheric particles of both local agricultural soils beaches and external origin northern africa studies on atmospheric particles in huelva have allowed their characterization in terms of chemical composition potential origin and in some cases deducing the mineralogy querol et al 2002 bernabe and carretero 2003 bernabe et al 2003 de la rosa et al 2003 sa nchez de la campa 2004 however no mineralogy study of particulate material in this area has been reported the aim of this work was to characterize the atmospheric mineral particles from the industrial environment of huelva sw spain in a view of establishing their source origins 2 methodology and sampling approach samples were collected on an one week basis in may july september and november 2000 and in januaryandapril2001 usingtwosampling instruments placed at the top of a turret 14m high one of the instruments fig 1a was used to collect sedimentable particles sp a funnel of 20cm i d attached to a 1 l polyethylene collection bottle containing 1ml of formaldehyde was used for this purpose a metal ring was placed at a distance of 5cm around the funnel in order to avoid contam ination by bird droppings after collection of samples the funnel was rinsed with exactly 50ml of de ionized water to remove dry depositions which were fi ltered over whatman 41 paper in order to separate insoluble suspended particulate matter sp from the soluble sp fraction the other instrument fig 1b was used to collect aerosol particles aerosols were collected by a fi ltering unit with a cap inlet intended to avoid collecting rain and sedimentable particles that was connected to a low volumepump 1m3h 1 polycarbonate fi lters nucleopore membranes 47mm in diameter and 0 4mm in pore size were used for this purpose a gas fl ow meter was placed behind the pump the chemical composition of the soluble sp fraction was determined as follows a chloride by titrimetrywithsilvernitrate usingpotassium chromate as indicator b carbonate and bicarbo nate with hcl using phenolphthalein and methyl article in press fig 1 sampling devices to collect a sedimentable particles and b aerosol particles j m bernabe et al atmospheric environment 39 2005 6777 67896778 orange as indicators c sulphate by turbidimetry using barium acetate as precipitant d nitrate by uv vis spectrophotometry and e cations by aas ca2 mg2 or aes na k sulphate and nitrate were quantifi ed on a zuzi 4210 50 uv vis spectrophotometer and cations on a perkin elmer analyst 1000 spectrophotometer the chemical results were subjected to statistical analysis themineralogicalcompositionofboththe insoluble sp fraction and aerosols was determined by powder x ray diffraction xrd polarized light microscopy and sem the xrd technique was implemented on a philips pw 1130 90 instrument with an automatic slit at 20ma 40kv and using a ni fi ltered cu karadiation the x ray powder diffraction patterns were collected by a scan speed of 2 min 1at a time constant of 2 and a paper speedof1cm 2y 1from31 to601 2y a quantitative approach was realized on the basis of highest characteristic refl ections for each crystalline phase sedimentable particles were extracted from the fi lters by using acetone from a syringe particles were then concentrated by evaporating the acetone and placed on the sample holder by means of a pipette afraction of theaerosol fi lters was examined directly on a glass sample holder the sem technique was implemented on a jeol jsm 5410 instrument equipped with an analytical system consisting in a si li energy dispersive spectro meter link system isis instrument mounted with a pentafet detector with a be thin window operated at 20kv elements with zona were not detected sp after their concentration with acetone were placed on a graphite microscope stub with double adhesive carbon tape studding both a representa tive fraction of the whole sample and individual particles previously selected based on their mor phology with the aid of a binocular magnifi er the aerosol fi lters were studied placing a fraction of them on a graphite microscope stub with double adhesive carbon tape samples were coated with carbon secondaryandback scatteredelectron images were used in the study of the samples the insoluble sp fraction was additionally examined under a binocular magnifi er and a nikon alpha phot 2 ys2 petrographic microscope in this case the samples were previously suspended in water prepared on a glass sample holder and coated with a thin glass adelta tloggerweatherstation equipped with wind speed and direction tempera ture relative humidity and sunlight sensors in addition to a rain meter was placed near the sampling instruments to record data on an hourly basisthroughoutthesamplingperiod may 2000 april 2001 additional meteorological and pollution data were obtained from the environment council of the andalusian regional government and the local weather centre of huelva 3 study area the study area named punta del sebo is located at the confl uence of the rivers tinto and odiel sw spain the area fig 2 is approxi mately 5km far from both the city of huelva in the north and the atlantic ocean in the south from a geological point of view the province of huelva is located at the western end of the guadalquivir basin igme 1995 during the upper neogene underwent strong sedimentation of carbonateandsiliciclasticmaterialsoverlaying unconformably a paleozoic and mesozoic base ment the paleozoic materials take part of the iberian pyritic belt hesperian massif and are located approximately 40km far from the sampling zone this unit contains volcanic sedimentary sul phide deposits of a high economic importance and worldwide known ruiz de almodovar and sa ez 1992 miocene pliocene sediments consist of bio clastic calcarenites and carbonates clays marls and sandstones civis et al 1987 1994 mayoral and pendo n 1986 1987 this sedimentary succession is more than 400m thick being overlapped uncon formably by detrital sands conglomerates qua ternary materials this facies known as the high alluviallevel pendo nandrodr guez vidal 1986 1987 the study area has an oceanic mediterranean climate under the infl uence of the ocean the average climatic year has a typical annual tempera ture with a short range winters are mild the mean annual temperature is above 101c and so are summers mean temperatures are in the region of 251c and highs rarely exceed 401c the mean relative humidity is 64 and ranges from 52 in julyto76 indecember monthlymeans precipitation is moderate 500 600lm 2annually and occurs largely in winter summers are mostly dry sunlight hours exceed 3000 in some places the prevailing winds are dictated by the topography of the land they fl ow along the rivers tinto and odiel nw and ne components and are also infl uenced by the proximity to the atlantic ocean sw article in press j m bernabe et al atmospheric environment 39 2005 6777 67896779 component data from local weather centre of huelva since 1960 huelva has undergone heavy indus trialization with three large chemical areas encom passingalargenumberofchemicaland petrochemical industries fig 2 bolivar 1995 namely a the punta del sebo industrial area which gathers most of the fertilizer production indus tries the major emissions of these industries are po3 4 f so2 4 and nh 4 in addition to solid and liquid residues rich in po3 4 f so2 4 fe3 and cu2 that accumulate in large phospho gypsum ponds very near the urban area of huelva fig 2 there is also strong metallurgi cal activity that releases so2 h2so4 as sb pb zn sn and other metals as well as a thermal power plant that uses gas and or fuel oil and releases no no2 co2and so2into the atmosphere b the nuevo puerto chemical area which encompasses petrochemical industries sodium hydroxide chlorineandchlorinederivative sodium hypochlorite hydrochloric acid chlor omethane production industries tio2pigment industries and ammonia and urea industries these industries release so2 no no2 ni v cl and ti mainly c the tartesos industrial area which consists largely of paper production industries that use the sulphate pulping method and release h2s and so2mainly a comparison of the mean monthly levels of various atmospheric pollutants no no2 so2 pm10 and o3 measured by the andalusian atmo spheric pollution monitoring and control network environmentalcouncil andalusianregional government fig 3 reveals a seasonal variation pattern the no and no2levels follow similar trends the latter however occurs at higher con centrations both rising in winter and falling in summer ozone exhibits the opposite trend by effect of the tropospheric photodissociation of no2into no and o under the action of near visible photons l 380nm the reaction of atomic oxygen with o2atmospheric produces o3 the pm10 particle concentration also rises during summer so2ex hibits no seasonal variation pattern its levels however have gradually decreased over the last few years article in press fig 2 location of the study area j m bernabe et al atmospheric environment 39 2005 6777 67896780 4 meteorological data for the studied period the meteorological data for the studied period were quite similar to those for the average climatic year during the sampling period temperatures ranged from 131c in january to 221c in july mean weekly values and relative humidity from 62 in april to 98 in november also mean weekly values table 1 there was precipitation in may 15lm 2one day followed by seven without precipitation september 6lm 2the last day which was the only rainy day of that month and november 131m 2 collected over 7 of the 8 sampling days no meteorological data of sunlight and rainfall for january could be recorded because the equipment was broken by the heavy rain the overall precipitation for this month was 114lm 2 data from local weather centre of huelva the wind direction was strongly infl uenced by the topography of the land with nw and sw as the prevailing components fig 4 5 sedimentable particles sp 5 1 insoluble sp fraction the minerals detected in the insoluble fraction of sp consisted largely of quartz calcite and feldspars accompanied by dolomite phyllosilicates and barite inlowerproportions minorphasesincluded apatite sphalerite pyrite siderite hematite and ankerite table 2 all of which were detected by xrd in lower proportions detected only by sem werealso identifi edaspossiblygypsumand chalcopyrite and other non mineral particles in cluding spherical biological and compositionally complex particles quartz was the major mineral phase detected throughout the sampling period but particularly in spring and summer it occurred as particles of variable size 25 120mm and shape ranging from highly eroded reworked grains with weathered outer textures and subrounded shapes fig 5b to scarcely round spherical mineral grains feldspars were detected mainly in summer either as sodium plagioclases or potassium feldspars fig 5c with a mean grain size article in press table 1 meteorological data for the sampling period obtained in situ with the delta t logger weather station mean weekly values sampling period rh t c sunlight kwm 2 rainfall lm 2 wind directionwind speed ms 1 max min mean max min mean maxmeanpredominantsecondarymaxminmean may8861722519211 240 5915n nwsw62 14 july8368762421220 830 60w sw nws73 34 8 september8151672219210 720 496w swn nw n new s sw 4 12 63 2 november9986981613160 570 413w sws6 61 64 3 january976780161213n d n d n d w sw w nw n8 63 55 8 april8050622216180 960 590n nwne5 62 63 5 n d no data fig 4 wind direction during the sampling period fig 3 mean monthly levels from 2000 to 2002 of various atmospheric pollutants measured in the industrial area of huelva datafromenvironmentalcouncil andalusianregional government j m bernabe et al atmospheric environment 39 2005 6777 67896781 of 50mm phyllosilicates were detected mainly in september they occurred as individual particles or aggregates ranging from 10 100mm to 1mm in size mean basal diameter fig 5a calcite was the second most abundant mineral phase and detected in all samples table 2 fig 5d its content increasing in september lower propor tions of other carbonates such as dolomite january and april siderite september january and april and ankerite may july and september were also detected table 2 sphalerite was detected in low proportions by xrd in july and in particles roughly 15mm in diameter by sem also in april fig 5e pyrite was detected by xrd at very low levels in november and january apatite particles 50 100mm in size fig 5f were detected only in summer barite particles ca 30mm in size fig 5g were observed in large amounts in april and at lower levels in may july and november hematite was detected in september january and april and invariably in very low proportions the semtechnique revealedtheadditional presenceof a sandcaparticles possibly gypsum fig 5h that were unevenly shaped and 80 100mm in size occasionally they contained p traces possibly as phosphogypsum b chalcopyr ite particles s fe and cu ranging from 10 to 50mm in size fig 5i c other silicates composed by si al fe and or zn figs 5j and k d non mineral particles including spherical biological and compositionally complex particles spherical parti cles consisted of c or c and s they were encountered throughout the sampling period but particularly in july september and november these particles were opaque black coloured irides cent and 20 100mm in size under the binocular magnifi er and optical microscope also they exhibited a spongiform texture by sem fig 5l biological particles were highly structured and exhibited complex regular textures consisting of pollen grains and diatoms figs 5m and n compositionally complex non mineral particles that contain a lot of elements that cannot be attributed to a mineral given they are composed mainly by p pb ti fe br sb or cr among other elements fig 5o 5 2 inorganic soluble sp fraction the chemical analysis of the soluble fraction of sp table 3 revealed high mean concentrations of hco 3 0 88meql 1 and na 0 85meql 1 rela tive to cl so2 4 and ca2 mean values from 0 31 to 0 50meql 1 as well as low concentrations of no 3 k and mg2 less than 0 15meql 1on average the calcium sodium and bicarbonate concentrations increased in may ju