Pharmaceuticals in STP effluents and their solar photodegradation in aquatic environment

Pharmaceuticals in STP e?uents and their solar photodegradation in aquatic environment

Roberto Andreozzi

a,*

,Marotta Ra?aele a ,Pax e us Nicklas

b

a

Univ.degli Studi di Napoli ‘‘Federico II’’,Fac.di Ingegneria,Dip.di Ingegneria Chimica,p.le V.Tecchio 80,80125Napoli,Italy

b

Gryaab––G €o teborg Regional Sewage Works,Karl IX:s v €a g,41834G €o teborg,Sweden

Received 19March 2002;received in revised form 7November 2002;accepted 7November 2002

Abstract

The presence of pharmaceutical compounds in surface waters is an emerging environmental issue.Sewage treatment

plants (STPs)are recognized as being the main point discharge sources of these substances to the environment.A monitoring campaign of STP e?uents was carried out in four European countries (Italy,France,Greece and Sweden).More than 20individual pharmaceuticals belonging to di?erent therapeutic classes were found.For six selected pharmaceuticals (carbamazepine,diclofenac,clo?bric acid,o?oxacin,sulfamethoxazole and propranolol)present in the STP e?uents,the persistence towards abiotic photodegradation was evaluated submitting them to solar experiments at 40°Nlatitude during spring and summer.Based on experimentally measured quantum yields for the direct photolysis in bi-distilled water,half-life times (t 1=2)at varying seasons and latitude were predicted for each substance.In salt-and organic-free (bi-distilled)water carbamazepine and clo?bric acid are characterized by calculated half-life times of the order of 100days at the highest latitudes (50°N)in winter,whereas under the same conditions sulphamethoxazole,diclofenac,o?oxacin and propranolol undergo fast degradation with t 1=2respectively of 2.4,5.0,10.6and 16.8days.For almost all studied compounds,except propranolol the presence of nitrate ions in aqueous solutions results in a re-duction of t 1=2.When present,humic acids act as inner ?lters towards carbamazepine and diclofenac,and as photo-sensitizers towards sulphamethoxazole,clo?bric acid,o?axocin and propranolol.ó2003Elsevier Science Ltd.All rights reserved.

Keywords:Pharmaceutical;Sewage treatment plant e?uents;Abiotic processes;Phototransformations;Sensitizers

1.Introduction

After intake,pharmaceuticals are excreted with urine or faeces to raw sewage in both an unchanged form and as metabolites.Recent studies in Germany and Swit-zerland have demonstrated that elimination of many pharmaceuticals in sewage treatment plants (STP)is often incomplete (Ternes,1998;Golet et al.,2001)and these are directly discharged to surface waters.The

presence of pharmaceuticals in the aquatic environment was reported as early as at the beginning of the 1980s (Waggott,1981;Watts et al.,1983;Richardson and Bowron,1985)and was later con?rmed (Ternes,1998;Hirsch et al.,1999;Zuccato et al.,2000;Ahrer et al.,

2001;€O

llers et al.,2001).This raises the question of what impact pharmaceutical residues have in the environ-ment,which in turn requires relevant data on exposure and e?ects on aquatic living organisms.Present knowl-edge is,unfortunately,far from adequate.In order to evaluate the exposure and e?ects of the particular pharmaceutical on aquatic organisms knowledge of both emission rates and the environmental fate of the com-pound in question is

prerequisite.

Chemosphere 50(2003)

1319–1330

https://www.sodocs.net/doc/fe16192513.html,/locate/chemosphere

*

Corresponding author.Tel.:+39-81-7682251;fax:+39-81-5936936.

E-mail address:randreoz@unina.it (R.Andreozzi).

0045-6535/03/$-see front matter ó2003Elsevier Science Ltd.All rights reserved.PII:S 0045-6535(02)00769-5

Generally speaking,both abiotic and biotic processes determine the fate of organic compounds in the aquatic environment.For any pollutant,including pharmaceu-ticals,abiotic transformations in surface waters may occur via hydrolysis and photolysis.Pharmaceuticals, usually designed for oral intake,are as a rule resistant to hydrolysis suggesting the mechanism of direct and in-direct photolysis as a primary pathway for their abiotic transformation in surface waters.While direct photoly-sis of chemical species is caused by direct absorption of solar light(Zepp and Cline,1977),the indirect photo-lysis involves natural photosensitizers like nitrate and humic acids.Under solar irradiation,these naturally occurring constituents can generate strong oxidant spe-cies such as hydroxyl radicals and singlet oxygen(Zepp et al.,1981).

On the other hand,humic acids absorbing solar ra-diation(Gao and Zepp,1998)may by inner?ltering reduce the rate of photodegradation of other organic species present in the aquatic environment.An addi-tional factor that strongly in?uences the rate of photo-degradation for any particular pharmaceutical present in the surface waters is the variation in the intensity of solar irradiance with both latitude and season.For a given latitude and the season,the spectral solar irradi-ance can be measured experimentally using pyranometer or can be found in specialized literature(Frank and Klop?er,1988;EPA,1996).

The aims of the present study were:(1)to identify pharmaceutical compounds in STP e?uents of four European countries with no previous record of pollu-tants of this type;(2)to evaluate the refractoriness of the selected pharmaceuticals present in these e?uents,to undergo abiotic photodegradation.The study was per-formed within the framework of the European Project ‘‘Ecotoxicological Assessment and Removal Technolo-gies for Pharmaceuticals in Wastewater––REMPHAR-MAWATER’’.2.Methods

2.1.Description of STPs and sampling.

The Ch^a tillon-sur-Chalaronne STP(S1-F),France, situated on the Dombes plateau,northeast of Lyon, serves a population of about6000and receives domestic and industrial(pharmaceutical,plastic and metal in-dustries)discharges.The annual treated volume is0.5 Mm3with an average in?uent BOD5of about120mg O2là1.Water treatment includes primary settling and activated sludge process.The e?uent is discharged to Chalaronne River.The Pierre B e nite STP(L1-F), France,situated in the South of Lyon where the Sa^o ne River and the Rh^o ne River meet,serves a population of about475000and receives domestic and industrial (pharmaceutical,chemical and food-processing indus-tries)discharges.The annual treated volume is48Mm3 with an average in?uent BOD5of about200mg O2là1. Water treatment includes primary settling and activated sludge process.The e?uent is discharged to the Rh^o ne River.The Iraklio STP(L2-GR),Greece,situated in Iraklio,Crete,serves a population of about164000and receives domestic discharges from Iraklio city.The an-nual treated volume is7.3Mm3with an average in?uent BOD5of about350mg O2là1.Water treatment includes primary settling and activated sludge process(BIO-Denitro system of KRUGER A.S.).The e?uent is discharged to the Cretan Sea.The Latina STP(M1-I), Italy,situated in Latina,Region of Lazio,serves a population of about45000and receives predominantly domestic discharges.The annual treated volume is6.9 Mm3with an average in?uent BOD5of about250mg O2là1.Water treatment includes primary settling and activated sludge.The e?uent is discharged to a system of arti?cial canals maintaining the water level of the surrounding land,before eventually reaching the Medi-terranean Sea.The Roma STP(L3-I),Italy,situated

in 1320R.Andreozzi et al./Chemosphere50(2003)1319–1330

the north of Rome,serves a population of about400000 and receives domestic and industrial discharges.The annual treated volume is73Mm3with the average in-?uent BOD5of about280mg O2là1.Water treatment includes primary settling and activated sludge.The ef-?uent is discharged to the river Tevere.The STP plant of Naples(L4-I),Italy,situated northwest of Naples,serves a population of about900000and receives predomi-nantly domestic discharges.The annual treated volume is69.5Mm3with an average in?uent BOD5of about250 mg O2là1.Water treatment includes primary settling and activated sludge.The e?uent is discharged to the Mediterranean Sea(Bay of Naples).Ryaverket(L5-S), owned by Gryaab,Sweden,is situated in G€o teborg and serves a population of about575000.Ryaverket addi-tionally treats wastewaters from small industries,hos-pitals and large industries.The latter encompasses food and beverage industries,fabricated metal production factories,equipment and machinery manufacturies,pa-per and chemical producers,plastic matting produc-ers and industrial laundries.Water treatment includes primary settling,chemical removal of phosphorus,ac-tivated sludge and biological nitrogen removal.The annual treated volume is120Mm3with an average in-?uent BOD7of about108mg O2là1.The e?uent is discharged to the G€o ta River estuary and further to Kattegatt.

Samples of the e?uents were collected in February–March2001for each individual STP.Grab samples for L2-GR,M1-I,L3-I and L4-I and24-h averaged?ow-proportional samples for L1-F and S1-F were cooled and immediately shipped for analysis by courier.A monthly averaged?ow-proportional sample from L5-S was kept frozen before analysis.

2.2.Chemicals

The following reference compounds(purity>97%by weight,CAS no.indicated)were purchased from Sigma–Aldrich and Promochem Standard Supplies:acebutolol (34381-68-5),aminopyrine(58-15-1),betaxolol(63659-18-7),beza?brate(41859-67-0),carbamazepine(298-46-4),cipro?oxacin(85721-33-1),clo?brate(637-07-0), clo?bric acid(882-09-7),diclofenac(15307-79-6),enox-acin(74011-58-8),feno?brate(49562-28-9),fenoprofen (31879-05-07),?urbiprofen(5104-49-4),gem?brozil (25812-30-0),ibuprofen(15687-27-1),ketoprofen(22071-15-4),lome?oxacin(98079-51-7),metoprolol(37350-58-6),naproxen(22204-53-1),nor?oxacin(70458-96-7), o?oxacin(82419-36-1),oxprenolol(6452-71-7),phenaz-one(60-80-0),propranolol(525-66-6),sulfamethoxazole (723-46-6)and trimethoprim(738-70-5).Acetonitrile, methanol,and water were of gradient grade(Chroma-solv,Riedel-de-Haen).Dichloromethane from Rathburn was GC grade.Formic acid,hydrochloric acid,triethyl amine and other reagents used in this study were of p.a. grade or better.

2.3.Chemical analysis

2.3.1.HPLC analysis

The aqueous samples(irradiation experiments)were analyzed using1100HPLC equipped with UV-VIS di-ode array detector(from Hewlett-Packard).Chromato-graphic separation was performed on reversed phase column(RP-C6Phenomenex,250mm?3:2mm i.d.). Analytes were separated isocratically(?ow rate of0.5 ml minà1)using solvents A(H2O:CH3OH:H3PO4500: 25:2)and B(CH3CN)in di?erent proportions:60%A and40%B for carbamazepine,propranolol,diclofenac and clo?bric acid,80%A and20%B for sulfamethox-azole and75%A and25%B for o?oxacin.

The molar absorptivities(Mà1cmà1)for di?erent pharmaceuticals were calculated from the UV absor-bances of standard solutions bu?ered at pH5.5mea-sured on UV–VIS spectrophotometer(HP8452A)using quartz cells(path length?1cm).

2.3.2.GC–MS analysis

Acidic and neutral pharmaceuticals were extracted from0.5to1l un?ltered acidi?ed wastewater samples VacMaster processing station(IST,Inc.,UK)using Isolute(IST,Inc.,UK)SPE cartridges(6ml,1g non-end-capped RP-C18).After extraction the cartridges were dried in a stream of nitrogen and eluted with3?4 ml of CH3OH:CH2Cl2(1:1)containing2%(C2H5)3N. Access of solvent(s)was removed using rotational vac-uum concentrator RVC2-18with CT02-50(both from Martin Christ,Germany)and the?nal volume was brought to1ml by addition of CH2Cl2.The extracts were divided in two fractions.The?rst one(100l l)was analyzed for carbamazepine,clo?brate,phenazone and aminopyrine.The second one(900l l)was evaporated to dryness and treated with an excess of diazomethane (€O llers et al.,2001).In this fraction clo?bric acid,dic-lofenac,feno?brate,fenoprofen,?urbiprofen,gem?bro-zil,ibuprofen,ketoprofen and naproxen were analyzed as their methyl esters.Analysis was performed using GC–MS(GCQ Plus,Thermoquest Inc.,USA)equipped with a temperature programmable injector.Standards and sample concentrates were injected using automatic sample injector A200S(CTC Analytics,Switzerland). A60-m?0:25-mm i.d.column coated with0.25l m chemically bonded phase HP-5(Agilent Technologies, USA)was used.Injector temperature was230°C, splitless mode(split open time4min).The GC pressure and temperature program:constant velocity of35cm sà1 of He,the initial temperature of80°C held in8min, then to280°C at5°C minà1,then to300°C at3°C minà1and held at300°C for5min.The ion source temperature and the transfer line temperature were held

R.Andreozzi et al./Chemosphere50(2003)1319–13301321

at180and at275°C,respectively.The analytes were detected and quanti?ed in selective ion monitoring (SIM)mode using the same masses as described by others(Ternes et al.,1998b).A calibration(5points) with standard solutions in CH2Cl2was used for quan-ti?cation.To determine absolute recoveries,samples of the e?uent wastewater from L5-S1were spiked with analytes(5and10l g là1)and concentrated as described above.Recoveries for the solid-phase extraction proce-dure for each individual pharmaceutical were evaluated by a comparison between peak areas from extracts of spiked samples and peak areas from a direct injection of the same concentration of the respective pharmaceutical. Concentrations of the pharmaceuticals in the unspiked wastewater have been taken into account.Extracts from 1l unspiked ultra-pure grade water(UHQII from USF Elga,UK)concentrated and treated as described above were used as blanks.

2.3.3.LC–MS analysis

Basic and neutral pharmaceuticals were extracted from0.8to1.0l un?ltered acidi?ed wastewater samples using Isolute(IST,Inc.,UK)SPE cartridges(15ml,1g mixed phase sorbent of C2/ENVt).The cartridges were ?ushed with ultra-pure grade water,dried under nitrogen ?ow and analytes were eluted with3?5ml of CH3OH containing2%(C5H5)3N.After removal of the excess solvent(s)in the vacuum concentrator the volume was brought to2ml using acidi?ed(HCOOH)ultra-pure grade water containing5–20%CH3CN.The eluates were centrifuged and?nally?ltered through0.45l m glass–?bre?lter.In all eluates,the presence of undissolved brownish residue was observed.The residue did not dissolve in CH3OH.Analysis of pharmaceuticals was performed using LC–MS.The LC system consisted of Surveyor HPLC(Thermoquest Inc.,USA)equipped with a quaternary pump,a vacuum degasser and an autosampler.Chromatographic separation was perfor-med on Genesis(250mm?2:1mm i.d.)column packed with4l m end-capped,base-deactivated RP-C18(Jones Chromatography Ltd.,UK).Chromatographic condi-tions were as follows:column temperature of50°C, solvents A(95%H2O;5%CH3CN;0.1%HCOOH)and B(CH3CNcontaining0.1%HCOOH),?ow rate200 l l minà1.Gradient program:isocratic100%A for1min, then to10%B in4min,then to15%B in10min,then to20%B in10min,then to55%B in10min and?nally to100%B in5min.The mass-spectrometric detection was performed on LCQ-Duo(Thermoquest Inc.,USA) equipped with electrospray.MS/MS data were acquired in ESItmode(capillary temperature230°C;sheath and auxiliary nitrogen gas?ows set to respectively60and20; source voltage4.50kV,source current80.00l A,capil-lary voltage29V).The collision energy required to produce the desired quantity of daughter ions in selective reaction monitoring(SRM)was individually optimized for each analyte.Detection(SRM)by a selective moni-toring of daughter ions(parent ion MHt!daughter ions monitored,with the underlined m=z being used for quanti?cation)was performed for the following phar-maceuticals:acebutolol(337:1!260:1,319:1),beta-xolol(308:1!231:1,254.2,266.2),carbamazepine (237:3!194:2),cipro?oxacin(332:1!288:2),enoxa-cin(321:1!257:3),lome?oxacin(352:1!308:2),meto-prolol(268:2!191:0),nor?oxacin(320:1!276:2), o?oxacin(362:1!318:2),oxprenolol(266:10!189:1, 206.1,225:1),propranolol(260:1!157:1,183:1,260.1), sulfamethoxazole(254:0!188:0,190.2,235.7,254.0) and trimetoprim(291:1!230:1,258.1,261.2,291.1). Phenazone and aminopyrine were detected in SIM mode monitoring their m=z189.0and232.1,respectively.

A calibration(5–10points)with standard solutions in acidi?ed distilled water containing5–10%CH3OH was used for quanti?cation.Absolute recoveries for the sol-id-phase extraction procedure were evaluated in the same manner as described above for acidic pharmaceu-ticals.Extracts from1l of unspiked ultra-pure grade water concentrated and treated as described above were used as blanks.

2.4.Irradiation experiments

Sunlight irradiation experiments were performed during spring and summer in Naples(40°N–14°E) in glass disk-reactors(width14:0cm?depth2:1cm) placed horizontally in a thermostated bath at25°C. Actinometry was carried out by using a solution of PNAP(2:0?10à5mol là1)and di?erent concentrations of pyridine(Dulin and Mill,1982).The pyridine con-centration was chosen to adjust the quantum yield of the PNAP(/ATT?0:0169?pyridine )to modify the rate of loss of PNAP to match the rate of consumption of the tested pharmaceutical(OECD,2000).UV-lamp irradi-ation was performed in an annular glass reactor equip-ped with a high pressure Hg lamp(UV12F Helios Italquartz)of a nominal power of125W with main emissions at305,313and366nm(manufacturer?s data). The radiation powers were4:33?10à7E sà1at305nm by H2O2actinometry(Nicole et al.,1990),7:97?10à7 E sà1at313nm by valerophenone actinometry(Zepp, 1989)and4:77?10à7E sà1at366nm by an UV digital radiometer,from UVP https://www.sodocs.net/doc/fe16192513.html,A.The irradiated volume of the reactor(V0)and the path length(l)were0.28l and 1.1cm respectively.The solutions were prepared using bi-distilled water and bu?ered at5.5with NaH2PO4and KH2PO4salts.An Orion960pH-meter with a glass pH electrode was used for pH https://www.sodocs.net/doc/fe16192513.html,mercial humate sodium salt(from Aldrich)was used as a sub-stitute for aquatic humic acids according to previous kinetic studies(Zepp et al.,1981).The initial concen-trations of photosensitizers were5and10mg là1for nitrate and5mg là1for humic acids according to OECD

1322R.Andreozzi et al./Chemosphere50(2003)1319–1330

guideline for testing of chemicals(OECD,2000).No reaction was observed for the pharmaceuticals in the pH range2.0–8.0in blank control experiments performed in the dark.

3.Results and discussion

3.1.Determination of pharmaceuticals

Absolute recoveries of the pharmaceuticals from the spiked e?uent wastewater(L5-S)are given in Table1. For the majority of pharmaceuticals the absolute recov-eries obtained in this study are su?ciently high(>60%) and are in agreement with the previously published data.The lowest recoveries were observed for gem?-brozil(46%),clo?brate(33%)sulfamethoxazole(40%)and three?uoroquinolones––enoxacin,nor?oxacin and cipro?oxacin(34–35%).Recoveries of>80%for the?u-oroquinolones reported by Golet et al.(2001),were obtained using mixed-phase cation-exchange SPE, which requires very low salt content in the e?uent sam-ple.This requirement,however,could not be ful?lled for L5-S due to a continuous industrial discharge of sodium chloride to its sewer and thus the procedure of Golet et al.(2001)could not be applied.Attempts to increase the recovery of sulfamethoxazole from40%to77–96% by decreasing the starting pH to2.5(Hartig et al.,1999) were undertaken but failed,the only result being a drastic decrease in the recovery of b-blockers and tri-metoprim.Taking into account the aim of the present study,e.g.to identify pharmaceutical compounds in STP e?uents,the recoveries obtained using the SPE con-centration procedures described above were judged to be

Table1

Absolute recovery(%)of spiked pharmaceuticals from di?erent types of water using SPE

Literature data This work STP

e?uent(L5-S)

Tapwater a Groundwater,

mountain spring water

STP e?uents

Gem?brozil4949–89b46

Feno?brate8677

Beza?brate9370–92b79

Clo?brate33

Clo?bric acid7771–82b100c75

Ibuprofen6781–82b97c83

Fenoprofen7179–90b82

Flurbiprofen80

Naproxen6854–91b90c83

Ketoprofen8077–94b78c77

Diclofenac7050–89b68c75

Phenazone8154d61(GC)71(LC) Aminopyrine7293d65(GC)71(LC) Acebutolol72

Metoprolol9693d95

Oxprenolol80

Propranolol8491d82

Betaxolol7091d81

Carbamazepine8046c89(GC)99(LC) Trimetoprim5587e75

Sulfamethoxazole2375e77–96f40

O?oxacin72g85

Lome?oxacin80g76

Enoxacin34

Nor?oxacin92g35

Cipro?oxacin97g34

GC,LC:enrichment and detection by GC or LC(see Methods).

a Sacher et al.(2001).

b Ternes et al.(1998a).

c€O llers et al.(2001).

d Ternes et al.(1998b).

e Hirsch et al.(1998).

f Harti

g et al.(1999).

g Golet et al.(2001).

R.Andreozzi et al./Chemosphere50(2003)1319–13301323

su?cient and therefore no additional attempts to im-prove the recoveries were undertaken.

While the?nal analysis of acidic and neutral(carb-amazepine,clo?brate,phenazone and aminopyrine) pharmaceuticals by GC–MS worked satisfactorily,the technique was found inappropriate for the basic ones and for?uoroquinolones.In order to analyze these compounds a method based on HPLC separation and MS detection was developed.The use of MS as the de-tector strongly limits the choice of a mobile phase.On one hand,the mobile phase should be volatile,prefera-bly not easily ionisable,and suppress the interaction of analytes and silanol groups,which results in peak tail-ing.On the other hand,the mobile phase should react with analytes to produce charged ions.In addition, a separation of such chemically and structurally di?erent compounds as b-blockers and?uoroquinolones requires a stationary phase which is both inert(highly deacti-vated)and exhibits su?cient retention time.Di?erent combinations of HPLC phases(hexyl,phenyl,amino, cyano,etc.),solvents(CH3CN,CH3OH,(CH3)2CO,etc.) and volatile bu?ers(HCOOH,CH3COOH,CF3COOH and/or their salts with ammonium or volatile amines) were tested.The best results were achieved with an oc-tadecyl base-deactivated high purity silica phase and a mixture of water and CH3CN,acidi?ed with0.1% HCOOH.Chromatographic separation worked su?-ciently well for most of the pharmaceuticals as illustrated in Fig.1a.Metoprolol,betaxolol and carbamazepine, not shown in Fig.1a were also well separated.When all the?uoroquinolones were present in the sample,they appeared as a cluster(Fig.1c,OFLtLOMtCIPtENtNOR).Additional chromatographic separation of these compounds should be considered very limited due to their structural and chemical similarities.However,it was possible to separate and quantify three of them, namely o?oxacin(m=z362.1),lome?oxacin(m=z352.1) and cipro?oxacin(m=z332.1)as shown in Fig.1c using MS detection(SIM mode,selective monitoring of parent MHtions).For the remaining nor?oxacin and enoxacin (Fig.1c,ENtNOR),producing very close molecular ions of m=z320.1and m=z321.1respectively(Fig.1c, ENtNOR),an ion-trap mass detector employed in this study was unable to resolve their peaks in SIM mode. The peaks could,however,be easily resolved in SRM mode detecting the daughter ions of m=z257.3for enoxacin and276.2for nor?oxacin(Fig.1c,ENand NOR).In addition to improved resolution,the detection in SRM mode resulted in a signi?cant reduction in the noise level of the baseline.This was particularly impor-tant for analysis of the pharmaceuticals in the real wastewater samples(Fig.1b).

3.2.Pharmaceuticals in STPs e?uents

Concentrations of pharmaceuticals found in this study together with literature data are given in Table2. The presence of o?oxacin,lome?oxacin,enoxacin,?ur-biprofen,acebutolol and oxprenolol in the e?uents from STPs,found in this work has to the best of our knowl-edge not been reported previously.Some pharmaceuti-cals(all antibiotics,gem?brozil,feno?brate,ibuprofen, naproxen,diclofenac,carbamazepine and the majority of b-blockers)were detected in almost every sample

of Fig.1.Chromatographic separation and MS detection of pharmaceuticals in a standard solution:(a)MS detection in SIM mode),in the wastewater from L4-I;(b)MS detection in SRM mode)and in a standard solution of?uoroquinolones and(c)MS detection in SIM and SRM modes.TMP,trimetoprim;OFL,o?oxacin;LOM,lome?oxacin;ACB,acebutolol,SFM,sulfamethoxazole;OXP, oxprenolol;PRP,propranolol;CIP,cipro?oxacin;EN,enoxacin and NOR,nor?oxacin.Chromatographic conditions are provided in Chemical analysis section.

1324R.Andreozzi et al./Chemosphere50(2003)1319–1330

the e?uent,which is probably a result of their high prescription extent and wide usage in Europe.On the other hand,clo?bric acid––the major metabolite of clo?brate,eto?brate and etofyllinclo?brate,previously reported as one of the most common pharmaceutical residues in e?uents from STPs and in natural waters in Germany(Ternes,1998),was only found in about half of the studied e?uents.When present in the e?uent, clo?bric acid was,however,detected in the same con-centration range as in Germany.One possible explana-tion may be that other drugs,like gem?brozil and feno?brate,have replaced the drugs metabolising to clo?bric acid.The detected presence of parent clo?brate, but not clo?bric acid,in one e?uent(L2-GR)is rather unusual and,at present,we do not have any explana-tion.Among b-blockers,betaxolol was not detected in any of the STP e?uents in this work in contrast to the previously published data for Germany(Ternes,1998) where its presence occurred in more than50%of all studied STPs.In addition,both metoprolol and pro-pranolol were found in lower concentrations than in Germany.As for antibiotics,our data for nor?oxacin and cipro?oxacin are in agreement with the Swiss data (Golet et al.,2001)but trimetoprim and sulfamethox-azole exhibit lower concentrations than reported for the e?uents from German STPs(Hirsch et al.,1999).The discrepancy is too large to be caused by the lower re-covery of sulfamethoxazole(40%in the present study) in comparison to the recovery of77–96%reported by Hirsch et al.(1999).O?oxacin and lome?oxacin were

Table2

Concentrations of pharmaceuticals(l g là1)found in the e?uents from STPs

France Greece Italy Sweden Median–

Maximum Germany and Switzerland (?literature data)

S1-F L1-F L2-GR M1-I L3-I L4-I L5-S

Lipid regulators

Gem?brozil 1.340.060.710.810.84 4.76 2.070.84–4.760.4–1.5

Feno?brate0.120.020.160.160.10.16n.d.0.14–0.16n.d.–0.03

Beza?brate n.d. 1.07n.d.n.d.n.d.0.91n.d.n.d–1.07 2.2–4.6

Clo?brate n.d.n.d.0.8n.d.n.d.n.d.n.d.n.d–0.8n.d.

Clo?bric acid n.d.n.d.n.d.0.68n.d.0.230.46n.d–0.680.36–1.6(n.d–0.06?) Antiphlogistics

Ibuprofen 1.820.020.050.180.020.027.110.05–7.110.37–1.2(<0.1–1.5?) Fenoprofen0.280.19n.d.n.d.n.d.n.d.n.d.n.d.–0.28n.d.

Flurbiprofen0.21n.d.n.d.n.d.n.d.0.34n.d.n.d.–0.34n.r.

Naproxen 1.730.51n.d.0.290.41 5.22 2.15 1.12–5.220.3–0.42(0.1–3.5?) Ketoprofen n.d. 1.62n.d.n.d.n.d.n.d.n.d.n.d.–1.620.20–0.38(n.d.–0.2?) Diclofenac0.410.250.890.47 1.48 5.45n.d.0.68–5.450.81–2.1(0.1–0.7?) Phenazone n.d.n.d.n.d.n.d.0.37n.d.n.d.n.d.–0.370.16–0.41 Aminopyrine0.43n.d.n.d.n.d.n.d.n.d.n.d.n.d.–0.43n.d.–1.0

b-Blockers

Acebutolol0.130.080.010.040.020.11<0.010.06–0.13n.r.

Metoprolol0.080.080.10.010.010.10.390.08–0.390.73–2.2 Oxprenolol0.050.020.010.01<0.010.03n.d.0.02–0.05n.r.

Propranolol0.010.040.010.010.010.090.010.01–0.090.17–0.29 Betaxolol n.d.n.d.n.d.n.d.n.d.n.d.n.d.n.d.0.06–0.19

Antiepileptic

Carbamazepine0.98 1.2 1.030.30.340.50.870.87–1.2 2.1–6.3(0.1–0.8?) Antibiotics

Trimetoprim0.040.020.080.040.030.130.050.04–0.130.32–0.66 Sulfamethoxazole0.090.070.090.01n.d.0.030.020.05–0.090.40–2.0

Antibiotics–?uoroquinolones

O?oxacin0.330.510.460.580.290.310.120.33–0.58n.r.

Lome?oxacin0.180.190.290.320.180.220.130.19–0.32n.r.

Enoxacin0.030.010.030.030.010.030.010.03–0.03n.r.

Nor?oxacin0.050.080.070.070.060.060.030.06–0.080.05–0.12?

Cipro?oxacin0.060.060.070.070.060.040.030.06–0.070.05–0.11?

n.d.:not detected;n.r.:not reported previously;literature data:median and maximum values(Ternes,1998;Hirsch et al.,1999)for Germany and concentration range(Golet et al.,2001;€O llers et al.,2001)for Switzerland.

R.Andreozzi et al./Chemosphere50(2003)1319–13301325

not found in the e?uents from STPs in Switzerland (Golet et al.,2001).In the present study,the concen-tration levels of o?oxacin and lome?oxacin are,on the contrary,much higher than for the other ?uoroquinol-ones.Concentrations of o?oxacin in the STP e?uents (0.12–0.58l g l à1)are actually close to the concentration (0.4l g l à1)found in untreated sewage from the regional hospital in Sweden (Johansson and Tysklind,2001).Based on the results above,a limited number of chemically and structurally di?erent pharmaceuticals frequently occurring in the STP e?uents were selected to study their persistence to abiotic photodegradation.These pharmaceuticals from di?erent therapeutic classes were carbamazepine,diclofenac,o?oxacin,propranolol and sulfamethoxazole.Among lipid regulators clo?bric acid was selected due to its widely reported presence in various aquatic compartments including surface and ground waters and even seawater of the North Sea (Stan

et al.,1994;Heberer et al.,1997;Buser and M €u

ller,1998;Ternes,1998).

3.3.Determination of quantum yield

The decay of the concentration of both the investi-gated substrate (S)and PNAP follows pseudo ?rst-order kinetics.Therefore,if the results collected during a single photolytic run are reported as lnS t =S 0vs.ln ?PNAP t =?PNAP 0a linear relationship is obtained:ln

S t S 0?k S k ATT ln

?PNAP t

?PNAP 0

e1T

For a ?xed latitude and season,the measured rate

constants,k S and k ATT ,depend on the reaction quantum yields (/S and /ATT )and molar absorptivities of the substrates and of PNAP:

k S ?/S

X

k

ee k L k TS e2Tk ATT ?/ATT

X

k

ee k L k TATT

e3T

where e k (l mol à1cm à1)are molar absorption coe?cients at wavelength k and L k is the average daily irradiance over wavelength interval centred at wavelength k (10à3E cm à2day à1).The product e k L k has the units of day à1.Values of L k and P

ee k L k TATT are reported in the litera-ture for di?erent seasons and decadic latitudes (Zepp and Cline,1977;EPA,1996).Rearranging Eqs.(2)and (3)will result in:/S P k ee k L k TS k S ?/ATT P

k ee k L k TATT

k ATT e4T

The quantum yields for the reaction with di?erent chemicals in bi-distilled water under sunlight irradiation can be derived by rearranging Eq.(4):

/S ?

k S k ATT /ATT P

k ee k L k TATT

P k ee k L k TS

e5T

In the present work,half-life times of the pharmaceutical at varying season and latitudes were calculated using the following equation:t 1=2?

ln 2k S ?

ln 2

/S P k ee k L k TS

e6T

From linear plots of lnS t =S 0vs.ln ?PNAP t =ln ?PNAP 0,

the ratios k S =k ATT were derived for o?oxacin,carb-amazepine,clo?bric acid and propranolol and used to evaluate their quantum yields (Table 3).

Because of their shorter characteristic reaction times it was decided to carry out photolytic experiments for diclofenac and sulfamethoxazole by using a high-pres-sure mercury vapor lamp.The evaluation of quantum yields was performed by a comparison of experimental data with the data calculated by integrating the follow-ing equation (De Laat et al.,1995):dS ?à2:3/0S

l 0X

k

ee S ek TI 0ek TT?S e7T

with k ?305,313and 366nm and the initial condition:?S ??S 0for t ?0./0S was assumed to be independent upon the wavelength k .

For each species,/0S has been estimated as the value which minimizes the objective function F :

F ?X N i ?1

eY i àC i T2

where N is the number of experimental data points for a single run and Y i and C i are respectively calculated and measured concentrations of the investigated species.For diclofenac,the measurements performed by submitting the aqueous solution to solar irradiation

Table 3

Quantum yields for the direct photolysis of the pharmaceuticals investigated in bi-distilled water at pH ?5:5Pharmaceutical Quantum yield Carbamazepine 4:77?10à5(sunlight)Propranolol 2:22?10à3(sunlight)Clo?bric acid 5:53?10à3(sunlight)O?oxacin

7:79?10à5(sunlight)Sulfamethoxazole 4:29?10à3(lamplight)a Diclofenac 3:13?10à2(lamplight)a Diclofenac

3:75?10à2

(sunlight)b

a

In agreement with Eq.(7)the unit of quantum yield is mol E à1.b

This value has been calculated from that found in the solar experiments (9:56?10à2)by taking into account the di?erence in the geometry of both types of reactors.

1326R.Andreozzi et al./Chemosphere 50(2003)1319–1330

were compared with lamplight irradiation experiments. Di?erences in the geometry of both types of the reactors were compensated by introducing the correction factor f de?ned as:

/0

S

?/S=f?9:56?10à2=2:55?3:75?10à2molEà1

The value of f was determined from lamplight irradia-tion of an actinometric solution of PNAP in pyridine to (/ATT?1:69?10à2?pyridine ?7:64?10à3)for which

an experimental/0

ATT ?3:00?10à3mol Eà1was found.

The value of the correction factor f obtained from this

experiment was f?/ATT=/0

ATT ?2:55.

A comparison between the values of quantum yield for diclofenac obtained from solar irradiation and lamp-light irradiation experiments showed good agreement (Table3)but both values are much lower than/S?0:22 reported by Moore et al.(1990).

Quantum yields for all six pharmaceuticals in the present study were used(Eq.(6))to predict half-life times for each species at varying seasons and latitudes (Fig.2a–c).3.4.E?ects of photosensitizers

To evaluate the e?ects of naturally occurring photosensitizers on photodegradation of chosen sub-strates,photolytic experiments(o?oxacin as an exam-ple,Fig.3)were carried out in the presence of nitrate and/or humic acids.Relative transformation rates ob-tained for the pharmaceuticals studied in this work and expressed as ratios between half-life time values (t1=2esensitizersT=t1=2edistillated waterT)are given in Table4.

As appears from the table the presence of nitrate in the aqueous solution enhances the rate of phototrans-formation for almost all investigated compounds but propranolol.The observed e?ect may be ascribed to the formation of HO radicals due to photolysis of nitrate. This e?ect has previously been reported(Zepp et al., 1987;Mack and Bolton,1999)for irradiation with k>280nm.

NOà

3

!h m NOà?

3

!NO?

2

tO?à!

H2O

NO?

2

tHOàtHO?The HO radicals formed in the reaction above would in turn react with the substrate:

R.Andreozzi et al./Chemosphere50(2003)1319–13301327

StHO?!products

In the solar irradiated aqueous solution containing a photodegradable substrate,e.g.a pharmaceutical,the added nitrate would thus account for an additional contribution to the substrate degradation.This addi-tional term may be expressed as the product between the kinetic constant of the OH radicals attack on the sub-strate S and the OH radicals‘‘steady-state’’concentra-tion:

k HO;S?HO?

SS

The kinetic constant k HO;S depends strictly on the nature of the substrate S whereas the second factor can be written as:?HO?

SS

?

rate of NOà

3

photolysis

HO;S

P

i i

with the term

P

k i?P i accounting for the reactions of OH radicals with other species present in the solution.

It is clear that the term‘‘rate of NOà

3

photolysis’’depends on the irradiating power available in the solu-tion which can be signi?cantly reduced when the sub-strate itself strongly absorbs in the same UV range as nitrate ions.Therefore,the e?ect exerted by the addition of nitrate on the phototransformation rates would strictly be dependent on the individual substance.

Besides pharmaceutical residues,even other species targeted by OH radicals,e.g.naturally occurring organic constituents,are present in real waters.For this reason, the e?ect caused by nitrate on the degradation rates of the pharmaceuticals found in this study should be in-terpreted just as a tendency no other organic molecules being present in solution during the runs but the sub-strate.

A more complex situation arises when humic acids are added to the solutions containing the pharmaceuti-cal.Humic acids are known to exert two opposite e?ects on the rate of photodegradation of organic molecules in water(Stangroom et al.,1998).

Due to their capability to absorb UV radiation in a broad range of wavelengths they can reduce the avail-able energy for the organic molecules present in the solution,thus acting as an inner?lter(Gao and Zepp, 1998).At the same time,the molecules of humic acids submitted to UV irradiation are promoted to a transient excited state(triplet state),in which they may react with oxygen in the solution forming reactive species as sin-glet oxygen(Haag and Hoign e,1986),or to react di-rectly with other organic species,thus promoting their phototransformation(Zepp et al.,1985;Canonica et al., 1995).The latter occurs only with substances able to support an energy transfer from molecules in their triplet states(Zepp et al.,1981).

The overall e?ect of humic acids on the phototrans-formation rate of an organic substance will therefore depend on the balance between these two opposite contributions.When humic acids act mainly as inner

Table4

Half-life times ratios of the pharmaceuticals in the presence and in the absence of photosensitizers(spring/summer sunlight) Compounds t1=2esensitizersT=t1=2edistillated waterT

With nitrate 5:0?10à3g là1With nitrate

10?10à3g là1

With nitrate

15?10à3g là1

With humic acids

5:0?10à3g là1

Diclofenac–0.622– 2.23 Sulfamethoxazole–0.235–0.326 Propranolol– 1.02–0.747 O?oxacin–0.120–0.198 Carbamazepine–0.4260.216 4.22 Clo?bric acid0.795––0.483 1328R.Andreozzi et al./Chemosphere50(2003)1319–1330

?lters,their addition will result in a decrease of the rate of photodegradation compared to the rate measured in bi-distilled water(as in the case of carbamazepine and diclofenac in the present study).On the other hand,if the promoting e?ect by humic acids prevails an en-hancement in the rate of phototransformation is ob-served(as in the case of o?oxacin,sulfamethoxazole, propranolol and clo?bric acid).

4.Conclusions

STP e?uents from four European countries(France, Italy,Greece and Sweden)with no previous record of pollutants of this type have been analyzed for the pres-ence of pharmaceutical residues.The analyses were per-formed using GC–MS and HPLC–MS/MS procedures developed in this study.More than20individual phar-maceuticals belonging to di?erent therapeutic classes have been found.Antibiotics,gem?brozil,ibuprofen, naproxen,carbamazepine and the majority of b-blockers have been detected in all samples.The presence of o?oxacin,lome?oxacin,enoxacin and?urbiprofen found in this study has not previously been reported in STP e?uents.In contrast to data published for Germany, betaxolol was not detected in any of the investigated STP e?uents,while trimetoprim and sulfamethoxazole were present in much lower concentrations than reported for the e?uents from German STPs.

The persistence to abiotic photodegradation has been evaluated for six selected pharmaceuticals among those found in the STP e?uents.Quantum yields for photo-degradation in salt-and organic-free water estimated for carbamazepine,diclofenac,clo?bric acid,sulphameth-oxazole,o?axocin and propranolol have been used to predict half-life times at varying seasons and latitudes. The results demonstrate that the photodegradation half-life times of carbamazepine and clo?bric acid are ap-proaching100days in winter at the highest latitudes (50°N),whereas under the same conditions sulfameth-oxazole,diclofenac,o?oxacin and propranolol undergo much faster degradations with t1=2respectively of2.4, 5.0,10.6and16.8days.The presence of nitrate ions in aqueous solutions(5.0–15.0mg là1)results in a reduc-tion of t1=2for the studied compounds,propranolol ex-cepted.Humic acids(concentration of5.0mg là1)act as inner?lters during the photodegradation of carb-amazepine and diclofenac and as photosensitizers for sulphamethoxazole,clo?bric acid,o?axocin and pro-pranolol.

Acknowledgements

The authors would like to acknowledge the Com-mission of the European Communities for the?nancial support of this work under Grant no.EVK1-CT-2000-00048.

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百事市场STP分析

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百事可乐的营销调研报告 委托单位：10无双营销 调研机构：最大风险 调研时间：2013.5.24

黑龙江东方学院 目录 1.引言 ···················································································································· - 3 - 2.数据分析与结果 ····································································································· - 3 - 2.1.数据分析········································································································· - 3 - 2.1.1性别及年龄差异··························································································· - 3 - 2.1.2广告策略 ······································································································ - 4 - 2.1.3百事的其他产品调查··················································································· - 4 - 2.1.4消费者的购买场所分析 ················································································· - 5 - 2.1.5百事可乐的广告代言人的调查数据分析····················································· - 6 - 2.1.6百事可乐的促销方式调查 ············································································· - 7 - 2.1.7整合营销传播的中心思想是在与消费者的沟通中 ······································· - 7 - 2.1.8满意度调查 ·································································································· - 8 - 2.2结果 ························································································································· - 9 - 2.2.1现有市场以年轻男性居多 ············································································· - 9 - 2.2.2消费者获知途径以广告为主·········································································· - 9 - 2.2.3最受青睐促销活动是买一赠一······································································ - 9 - 3.建议 ························································································································ - 9 - 3.1以广告宣传为主要载体···························································································· - 9 - 3.2产品代言人以年轻人喜爱的明星为主····································································· - 9 - 3.3将学生做为主要的销售群体···················································································· - 9 - 3.4推出健康型饮品······································································································· - 9 - 4.调研方法··············································································································· - 10 - 4.1调研目的 ··············································································································· - 10 - 4.2调查内容 ··············································································································· - 10 - 4.3调查方法 ··············································································································· - 11 - 4.4调查对象和调查范围························································································ - 11 - 4.5经费预算 ················································································································ - 11 - 4.6调查的时间进度安排 ····························································································· - 11 - 5.局限性说明··········································································································· - 12 - 5.1调查地点局限性····································································································· - 12 - 5.2调查对象局限性····································································································· - 12 - 5.3调查方法具有一定的局限性·················································································· - 12 - 5.4调查组员的局限性 ································································································· - 12 - 5.5调查样本局限性····································································································· - 13 - 6.附件及说明··········································································································· - 13 - - 2 -

关于可口可乐和百事可乐的渠道分析报告

渠道分析报告 ——关于可口可乐和 百事可乐的分析 参与人：张洁高蓓 刘艳樊永青 报告日期：2012年10月15日

目录 一、前言——————————3 二、调研概述————————3 三、公司背景————————4 四、调查目的————————5 五、调查结论————————5 六、启示——————————7 七、结论与建议———————7 八、附录——————————13

一、前言 目前，随着经济的发展，人们生活水平的不断提高，为满足顾客需求企业推出各种各样的饮料。我国的软饮料市场以碳酸饮料、瓶装水、茶饮料、果汁饮料和功能饮料为主。其中，碳酸饮料已进入成熟期，市场已被“两乐”基本瓜分完毕，两者合计占有率接近80％。但两家仍通过产品自身、价格、促销、以及渠道等不同的方面相互竞争。销售渠道决定着消费者能否顺利地购买到产品。渠道不畅，产品在销售终端铺开率不高，那么即使广告做得再好也是徒劳。两乐公司经过多年销售渠道的研究与实践，均形成了一套科学的渠道管理方式。但是为了更加详细地了解“两乐”的分销渠道，以及他们各自的优劣势我们组就对此在汉台区莲湖路展开了一次市场调研并进行渠道分析。 二、调研概述 1、调研目的：对选定区域内的所有饮料售点进行全面调查统计可口可乐和百事可乐饮料的铺货率，从而了解可口可乐和百事可乐的网点分布及销售情况，分析两家公司在渠道上的优劣。 2、调研对象：莲湖路所有销售点 3、调研方法：实地访谈法 4、调研经过：首先大家先每个人自己出几个问题，然后大家再一起从中选出几个精选问题，大家熟悉问题，再绘制一个表格以便记录收

集到的信息，复印四份，大家分工，两人去莲湖路的北边做调，两人在马路南边，这样经过一天的实地访谈调研，完成了任务。然后由高蓓开始做数据整理，刘艳，樊永青和张洁分项做调研报告，张洁最后整合并以word形式呈现，完成了最终的整个调研工作。 三、公司背景 可口可乐公司是全球最大的饮料公司，其系列产品畅销200多个国家和地区，拥有近400个饮料品牌。可口公司在全球生产超过2600种产品，每日销量超过14亿杯，并拥有全球最畅销软饮料品牌在前五名中的四个，包括可口可乐、健怡可口可乐、雪碧和芬达。 百事公司成立于1898年，是世界上最成功的消费品公司之一，其产品行销全球200多个国家和地区，拥有约157,000万雇员，公司2005年销售收入达320亿美元。在2005年公布的《财富》杂志全球500强和美国500强排名中，百事公司以营业收入292.61亿美元分列第172位和第61位，百事可乐商标价值突破1000亿美元。在饮料行业，可口可乐和百事可乐一个是市场领导者，一个是市场追随者（挑战者）。作为市场追随者，有两种战略可供选择：向市场领导者发起攻击以夺取更多的市场份额；或者是参与竞争，但不让市场份额发生重大改变。显然，经过近半个世纪的实践，百事可乐公司发现，后一种选择连公司的生存都不能保障，是行不通的。于是，百事可乐开始