Journal of Chromatography A, 1094 (2005) 122129

Determination of endocrine-disrupting phenand y s

ss s, M.arch Ins, Canadhore Ro

July 20r 2005

Abstract

The occurrence, fate, and effects of phenols with endocrine-disrupting properties as well as some pharmaceuticals and personal-care productsin the environment have frequently been discussed in recent literature. In many cases, these compounds were determined by using individualmethods which can be time-consuming if results for multiple parameters are required. Using a solid-phase extraction procedure with an anionexchanger inand effluentand tert-butyapplied to thsalicylic acimethods. Us 2005 Else

Keywords: E

1. Introdu

In the lhas been deffects of oaters [1,2].potential totem in wild[3]. Collec(EDCs), thehold chemchlorinatedbisphenol A

CorresponE-mail ad

0021-9673/$doi:10.1016/jthis work, we have developed and optimized a multi-residue method for the extraction of 21 phenols and acids in sewage influent. The phenols and acids were then selectively eluted in separate fractions and were converted into pentafluoropropionyl (PFP)ldimethylsilyl (TBDMS) derivatives, respectively, for gas chromatographymass spectrometric (GC/MS) determination. Whene sewage samples under study, the results for nonylphenol, bisphenol A (BPA), triclosan (TCS), 17-estradiol (E2), estrone (E1),d, ibuprofen, naproxen, diclofenac, and a few other acidic drugs were consistent with those determined previously by individualing the same procedure, we also report, for the first time, the occurrence of 2-phenylphenol and parabens in those sewage samples.vier B.V. All rights reserved.

ndocrine-disrupting chemicals; Phenols; Pharmaceuticals; Personal-care products; Sewage

ction

ast two decades, a great deal of research effortevoted to the identification, occurrence, fate, andrganic contaminants found in municipal wastew-Among these organics, chemicals that have thedisrupt the normal functions of the endocrine sys-life, fish, and humans have drawn special attentiontively known as endocrine-disrupting chemicalsy encompass a wide range of industrial and house-

icals such as polychlorinated biphenyls (PCBs),insecticides, alkylphenols and their ethoxylates,(BPA), etc. Pharmaceuticals used for humans,

ding author. Tel.: +1 905 336 6266; fax: +1 905 336 4420.dress: bill.lee@ec.gc.ca (H.-B. Lee).

farm animals, and fish have also been identified as emerg-ing environmental pollutants [4]. Many classes of com-mon prescription and non-prescription drugs, including anal-gesics, anti-inflammatories, antiepileptics, -blockers, antibi-otics, etc., are discharged into sewage systems at the endof their application-cycles. The environmental concentra-tions of many pharmaceuticals and personal-care products(PPCPs) have also been documented in detail [46].

The occurrence of EDCs as well as PPCPs in munici-pal sewage effluent and other environmental samples couldnegatively impact the health of the ecosystem and humans.The environmental occurrence of EDCs has been implicatedin the feminization of fish, sex transposition of wildlife, andhormone-related cancers in humans [7]. The detection of car-bamazepine, a commonly prescribed antiepileptic, in influentand effluent samples at nearly the same concentrations exem-

see front matter 2005 Elsevier B.V. All rights reserved..chroma.2005.07.070personal-care products in sewage bgas chromatographyma

Hing-Biu Lee a,, Thomas E. Peart aa Aquatic Ecosystem Protection Research Branch, National Water Rese

867 Lakeshore Road, Burlington, Ont.b Wastewater Technology Centre, Environment Canada, 867 Lakes

Received 25 April 2005; received in revised form 15Available online 5 Octobeols, acidic pharmaceuticals,olid-phase extraction andpectrometryLewina Svoboda b

titute, Environment Canada, P.O. Box 5050,a L7R 4A6ad, Burlington, Ont., Canada L7R 4A6

05; accepted 18 July 2005

H.-B. Lee et al. / J. Chromatogr. A 1094 (2005) 122129 123

plifies that a persistent drug could survive existing wastewatertreatments [8]. As carbamazepine and other pharmaceuti-cals are biologically active compounds, their presence inaquatic ecohealth if thsuggests thanti-inflamtion of vultmonitor theenvironmen

In respoprojects inoped separtert-octylphand its memaceuticalphase octahave beenabove EDCwith goodnols and acin the sameinfluent, thoccasionallSuch coexsion in thederivatizaticartridgessuccessfullin the envan optimizacids in sea subsequeand acids.extract andapplication

2. Experim

2.1. Chem

All stanparabens, 2triclosan (estrone (E1Table 2, asrecovery stproducts oreagents, pN-t-butyldiSTFA) withe same cstandard aCanada).

Table 1Phenols included in this study and their characteristic ions (as PFPderivatives)

l Retentiontime (min)

Molecularion, m/z

Characteristic ions, m/z

l paraben, 5.51 298 298, 267

paraben, EP 6.10 312 312, 284, 267l paraben, PP 7.06 326 285, 284, 267paraben, BP 8.27 340 285, 284, 267nylphenol, 7.09 316 316, 197, 169

ylphenol,7.76 352 352, 281, 253

ylphenol, 8.79.9 366 366, 309, 295, 281, 267,253

onylphenol, 11.71 366 366, 253, 254

enol A, BPA 13.52 520 520, 506, 505enol A-d16 13.43 534 534, 517, 516san, TCS 14.19 434 434, 254, 252e, E1 16.10a 416 416, 372, 359stradiolstradiold3lined iodifferen

Sampl

om Mnt saplants

nto (thda. Th00 to over 1,000,000. All samples were mixtures of

ential and industrial wastewaters in various proportions.were collected by plant staff, transported immediatelyr laboratory, and extracted upon arrival. If same-dayction could not be achieved, the samples were stored atin the dark and extracted within 48 h of their arrival.

2pharmaceuticals included in this study and their characteristic ions

DMS derivatives)phar-

ticalsRetentiontime (min)

Molecularion, m/z

Characteristicions, m/z

ric acid, CFA 9.15 328 273, 271, 143fen, IBP 9.51 320 264, 263lic acid, SYL 10.65 366 351, 310, 309brozil, GFB 13.70 364 307, 244, 243rofen, FNP 14.36 356 300, 299xen, NPX 15.67 344 288, 287, 185san, TCS 16.41 402 347, 345, 200rofen, KTP 17.61 368 312, 311, 295amic acid, TFN 18.75 375 320, 318, 244enac-Na, DCF 19.06 409 354, 352, 214ethacin, IDM 25.46 471 414, 370, 139(surrogate) 11.56 334 279, 277, 249lined ions were used for quantitation.systems presents a potential hazard to humaney contaminate our drinking water. A recent studyat wide-spread veterinary use of diclofenac, anmatory drug, is indirectly causing the near extinc-ures in South Asia [9]. Hence, there is a need tolevels of EDCs and PPCPs in sewage and othertal samples.nse to the specific needs of different researchthe past, analytical methods have been devel-

ately for EDCs such as 4-nonylphenol (NP) andenol (OP) [10], BPA [11], 17-estradiol (E2)

tabolites [12], as well as those for acidic phar-s [13]. Generic adsorbents such as the reversed-decylsilane (ODS), the Oasis HLB, and othersapplied by many workers to the extraction of thes and PPCPs in water and wastewater samplessuccess [1418]. In those cases, however, phe-ids were eluted from the cartridge by methanolfraction. For a complex matrix such as sewage

e non-selective ODS/HLB enrichment proceduresy yielded an extract with excessive coextractives.tractives would lead to the formation of emul-back extraction steps, reduced yields in chemicalon, and interference in GC/MS analysis. Recently,packed with anion exchangers have also beeny applied to the extraction of acids and phenolsironment [19]. In this work, we shall describeed method for the extraction of 21 phenols andwage samples using an anion exchanger, withnt elution procedure to fractionate the phenolsThis multi-residue procedure produces a cleanerminimizes sample preparation time in screening

s.

ental

icals and reagents

dards including the phenols listed in Table 1 (the-phenylphenol, the alkylphenols, BPA, BPA-d16,TCS, 5-chloro-2-(2,4-dichlorophenoxy)phenol),), E2, E2-d3, the acidic pharmaceuticals listed inwell as 2,3-dichlorophenoxyacetic acid (2,3-D, aandard used for the acidic pharmaceuticals) weref SigmaAldrich Chemicals. The derivatizationentafluoropropionic acid anhydride (PFPA) andmethylsilyl-N-methyltrifluoroacetamide (MTB-th 1% TBDMSCI, were also purchased fromompany. 4-n-Nonylphenol (nNP) was a Pestanalvailable from Riedel-deHaen (through Supelco

Pheno

MethyMP

EthylPropyButyl2-Phe

PHP4-tert-

OctOP

4-NonNP

4-n-NnNP

BisphBisphTricloEstron17-E17-E

E2-

Undera A

2.2.

FreffluementToroCana100,0residTheyto ouextra4 C

TableAcidic(as TBAcidicmaceu

ClofibIbuproSalicyGemfiFenopNaproTricloKetopTolfenDiclofIndom2,3-D

Under, E2 14.84a 564 564, 401-d3, 14.81a 567 567, 404

ns were used for quantitation.t temperature program was used for the estrogens.

e collection and storage

ay to July 2004, 24 h composite influent andmples were collected from eight sewage treat-located in Burlington, Galt, Guelph, Mississauga,ree plants), and Waterloo in southern Ontario,ese cities have populations ranging from less than

124 H.-B. Lee et al. / J. Chromatogr. A 1094 (2005) 122129

2.3. Solid-phase extraction (SPE) of samples

Immediately before extraction, a sewage sample was fil-tered throufritted, all-gwas addedvent cloggi2,3-D, 0.5were spiketo ca. pH 3ple, a 6 mLwas conditiby 10 mLmanifold (Swas siphonand 15 mLtion was ccartridge wacetate solusodium ace100 mL witlowed by sfraction) anpharmaceuderivatizati

2.4. Derivpharmaceu

To the pof NaOAcwere addedusing nitroadded andnot to drynThe pentaflformed byat room temcedure [11of 1 mL inchromatogof the estroextract wa[12]. The pby petroleuin 250L oand E1.

After thto the acidorated to dTo the resiSTFA withreacted at 7the TBDMextracted indichlorome

a final volume of 1 mL in iso-octane for the GC/MS analysisof the acidic pharmaceuticals.

GC/Mmaceu

systemgraphtive D. Chrved bm thure prure, 7/min/min

he anain holC, 5 o 300acidi

in holC, 5 o 300e injeas (hles inwith

ron-imfor thra of t00. Seuantitcteris

esults

Optim

e Oapoly

ange f3 or

s andactionntagee wasert theongly

me profoundte solcircumo fracmethagh a 90 mm GF/C filter (1.2m retention) with alass filtration device under a slight vacuum. Celiteas a filter aid, particularly for the influent, to pre-ng. To each litre of the filtered sample, 2.5g ofg each of nNP and BPA-d16, and 0.05g E2-d3

d as recovery standards. The sample was acidifiedwith sufficient HCl. Meanwhile, for each sam-

, 150 mg Oasis MAX SPE cartridge (Waters Corp.)oned by washing with 4 mL of methanol followedof water at pH 3. With a solid-phase extractionupelco Visiprep 57044 or equivalent), the sample

ed through the cartridge at a flow rate between 10/min by adjusting the vacuum. When the extrac-omplete, the cartridge was dried for 1 min. Theas then washed with 5 mL of a methanol/sodiumtion prepared by dissolving 0.41 g of anhydrous

tate (NaOAc) in 5 mL of methanol and made up toh water. The washing was discarded. This was fol-equential elution with 5 mL of methanol (phenold 10 mL of 2% formic acid in methanol (acidic

tical fraction). Both fractions were collected foron.

atization of phenols and acidicticals

henol fraction, 25L of a methanolic solution(0.25 g of anhydrous NaOAc in 25 mL methanol). It was evaporated to ca. 500L in a 40 C bathgen. Then 1 mL of methyl tert-butylether wasthe volume was further reduced to 100L but

ess. This procedure was repeated two more times.uoropropionyl (PFP) derivatives of phenols werethe reaction of the extract with 100L of PFPAperature for 20 min according to an earlier pro-

]. The products were made up to a final volumeiso-octane for the analysis of phenols by gas

raphymass spectrometry (GC/MS). If an analysisgens was needed, an aliquot of the above methanols evaporated to dryness and reacted with PFPAroducts were washed by a base, back extractedm ether, evaporated to dryness, and redissolvedf iso-octane for a separate GC/MS analysis of E2

e addition of 250L of 2% NH4OH in methanolic pharmaceutical fraction, the solvent was evap-ryness, again in a 40 C bath using nitrogen.due, 50L of acetonitrile and 75L of MTB-1% TBDMSCI were added. The mixture was then5 C for 30 min. At the completion of the reaction,S derivatives were washed with water and backto 3 mL of hexane and then 3 and 2 mL of 10/90thane/hexane (v/v). The products were made up to

2.5.phar

AmatoSelecworkachie0.25peratperat30 C15 CFor ta 1 m200 260 tof thea 1 m190 260 t

Thrier gSampmodeElectusedspect506the qchara

3. R

3.1.

Thmodeexchto pHforminteradvatridgconv

be strin sohaveacetasuchin twwithS analysis of phenols and acidicticals

consisting of an Agilent Model 6890 gas chro-, Model 7683 autosampler, and Model 5973 Massetector was used for the GC/MS analysis in this

omatographic separation of all derivatives wasy a Restek Rtx-5Sil MS (30 m, 0.25 mm I.D.,ickness) column using the following three tem-ograms. For the analyses of phenols: initial tem-0 C, with a 1 min hold, oven temperature ramps,from 70 to 150 C, 5 C/min from 150 to 190 C,from 190 to 270 C, and a 5 min hold at 270 C.lyses of estrogens: initial temperature, 70 C, withd, oven temperature ramps, 30 C/min from 70 toC/min from 200 to 260 C, and 30 C/min fromC, and a 10 min hold at 300 C. For the analysesc pharmaceuticals: initial temperature, 70 C, withd, oven temperature ramps, 30 C/min from 70 toC/min from 190 to 260 C, and 15 C/min fromC, with a 5 min hold at the final temperature.ction port temperature was 250 C and the car-

elium) flow rate was kept constant at 1 mL/min.1L aliquots were injected in the pulsed splitlessa 1 min hold of injection pulse pressure at 30 psi.pact ionization mass spectrometry (EI/MS) was

e detection of phenols and acids. Full-scan masshe derivatives were obtained over a range of m/zlected ion monitoring (SIM) was employed for

ative analyses of the target compounds, and thetic ions used are listed in Tables 1 and 2.

and discussion

ization of the extraction procedure

sis MAX cartridge was made up of a mixed-mer sorbent with both reversed-phase and anion-unctionalities. When a water sample was acidified

less, phenols and acids were in the unionizedso they would be adsorbed by the reversed-phases similar to an ODS cartridge. In order to takeof its anion-exchange properties, the MAX car-washed, at the end of extraction, by a base toacids into their anionic forms so that they wouldattached to the NR3+ groups in the sorbent. Whilecedures a strong base such as NaOH was used, wethat only a small quantity of a methanol/sodium

ution was sufficient for this conversion. Understances, selective elution of the phenols and acids

tions could be achieved. Elution of the cartridgenol removed only the less acidic phenols (along-

H.-B. Lee et al. / J. Chromatogr. A 1094 (2005) 122129 125

side other neutral coextractives) which were mainly adsorbedby the reversed-phase groups of the sorbent. For the elu-tion of the more acidic pharmaceuticals, a mixture of 2%formic acidback to unbeing a triunable to cmethanol,from 5 tofractions vof the totalin influentsamples, retate this ubas the acidi

In the ea(

126 H.-B. Lee et al. / J. Chromatogr. A 1094 (2005) 122129

Table 3Percent recovery of phenols and acidic pharmaceuticals from spiked distilledwater samples

Compound Spiking level(g/L)

Mean SD (%)

Spiking level(g/L)

Mean SD (%)

Methyl paraben 1.0 87 4 0.1 89 6Ethyl paraben 1.0 92 4 0.1 93 5Propyl paraben 1.0 96 4 0.1 96 4Butyl paraben 1.0 99 5 0.1 93 52-Phenylphenol 2.5 96 2 0.25 93 44-tert-Octylphenol 1.0 94 3 0.10 95 54-Nonylphenol 10.0 102 5 1.0 104 64-n-Nonylphenol 0.5 95 3 0.5 93 4Bisphenol A 1.0 98 3 0.1 99 5Bisphenol A-d16 0.5 99 3 0.5 102 4Estrone (E1) 0.10 105 6 0.010 109 717-Estradiol (E2) 0.10 89 5 0.010 95 5E2-d3 0.050 90 4 0.050 91 5Clofibric acid 1.0 98 3 0.1 94 5Ibuproffen 1.0 87 4 0.1 86 4Salicylic acid 1.0 97 3 0.1 95 6Gemfibrozil 1.0 99 4 0.1 97 5Fenoprofen 1.0 98 3 0.1 96 4Naproxen 1.0 101 3 0.1 103 5Triclosan 1.0 93 5 0.1 96 5Ketoprofen 1.0 102 4 0.1 105 6Tolfenamic acid 1.0 99 5 0.1 96 4Diclofenac-sodium 1.0 99 3 0.1 104 6Indomethacin 1.0 107 5 0.1 110 72,3-D 2.5 93 3 2.5 98 5Means of fou

Among thethe highestIt ranged finfluent an

Fig. 1. A GC/MS/SIM chromatogram of a sewage influent extract, showingthe phenols as their PFP derivatives.

ffluentmediactivelg/L,

Table 4ConcentrationSewage treatmplanta

A influentA effluentB influentB effluentC influentC effluentD influentD effluentE influentE effluentF influentF effluentG influentG effluentH influentH effluentMinimum (inMaximum (inMedian (influMinimum (efMaximum (eMedian (efflu

a Located inr replicates and standard deviations.

phenols included in this study, NP was found atconcentrations in the sewage samples (Table 4).

the ewithrespe0.14rom 2.72 to 25.0g/L (median 14.6g/L) in thed from 0.32 to 3.21g/L (median 0.70g/L) in

of these meof the alkyl

s of selected phenols in sewage influent and effluent samplesent MP

(g/L)EP(g/L)

PP(g/L)

BP(g/L)

PHP(g/L)

OP(g/L)

0.63 0.12 0.86 0.12 5.19 3.240.02

H.-B. Lee et al. / J. Chromatogr. A 1094 (2005) 122129 127

Fig. 2. A GC/the phenols as

by the elev[21], this hof accumuthese lipop

In contrvery few rphenylphenlong been upersonal-careferred toexhibit estrfound, at ng[22]. It hacation of punderarm aopment. Mdetected inbeing the mcentrationscontrast, thent sampledetection li

2-Phenyin hospitalsprocessing

Again,were muchthe effluent

The occand of itssamples [12and derivat

eral procedure could have been used for their determination.However, in order to achieve a detection limit of 0.001g/Lfor the estrogens, a final volume of 250L (equivalent to a

entration factor of 4000 based on a 1 L sample) for ale extract was needed in the procedure. Similar to theous findings, the observed median concentrations for E21 in the influent samples were 0.009 and 0.016g/L,

ctively. Due to the rapid degradation of E2 and E1 underic conditions, their median concentrations in the efflu-

amples were further reduced to 0.002 and 0.005g/L,ctively.

Acidic pharmaceuticals in municipal wastewaterles

ven acidic pharmaceuticals, namely, ibuprofen, sali-acid, gemfibrozil, naproxen, ketoprofen, diclofenac, andethacin, were consistently detected in the influent and

nt samples (Table 5). In contrast, clofibric acid, feno-n and tolfenamic acid have not been detected in thissamples. As mentioned earlier, the anti-bacterial agent

san is split between the phenol and acid fractions andherefore necessary to quantitate this compound in bothons.uprofen, salicylic acid, and naproxen were the moredant acidic pharmaceuticals in the influent (Fig. 3),respective median concentrations of 6.77, 6.86, andg/L in the samples. For the effluent (Fig. 4), naproxenbuprofen were detected at higher levels than the other, withMS/SIM chromatogram of a sewage effluent extract, showingtheir PFP derivatives.

ated levels of these contaminants in the sludgeuge reduction appeared to be mainly the resultslation onto sludge rather than biodegradation ofhilic compounds.ast to the alkylphenols, BPA, and TCS, there wereeports on the occurrence of the parabens and 2-ol in the Canadian environment. Parabens havesed as preservatives in foodstuffs, cosmetics, andre products. However, these compounds are alsoas endocrine-disrupting chemicals, as they allogenic activities. Recently, parabens have been

conc

samppreviand Erespeaerobent srespe

3.5.samp

Secylicindomefflueprofeset oftricloit is tfracti

Ibabunwith2.76and idrugs/g levels by LC/MS/MS, in human breast tumorss then led to the speculation that regular appli-araben-containing personal-care products to thend breast area could influence breast cancer devel-ethyl, ethyl, n-propyl, and n-butyl parabens wereall influent samples, with the n-propyl parabenost abundant chemical in the samples (with con-from 0.2 to 2.43g/L, median 0.73g/L). In

ese parabens were virtually absent in the efflu-s as their levels were either close to or below theirmit of 0.01g/L (Table 4).lphenol, commonly used as a surface disinfectant, nursing homes, commercial laundries, and foodplants, was also detected in the same samples.the observed concentrations of 2-phenylphenol

higher in the influent (median 2.58g/L) than(median 0.05g/L).

urrence of E2, the most potent female hormone,major metabolites has been reported in sewage,14]. As these compounds were extracted, eluted,ized alongside the other phenols, the same gen-

Fig. 3. A GC/the acidic pharespective median concentrations of 0.82 and

MS/SIM chromatogram of a sewage influent extract, showingrmaceuticals as their TBDMS derivatives.

128 H.-B. Lee et al. / J. Chromatogr. A 1094 (2005) 122129

Table 5Concentrations of selected acidic pharmaceuticals in sewage influent and effluent samples

Sewage treatment planta IBP (g/L) SYL (g/L) GFB (g/L) NPX (g/L) KTP (g/L) DCF (g/L) IDM (g/L)A influent 7.16 8.03 0.30 1.73A effluent 0.22 0.12 0.08 0.46B influent 10.21 5.76 0.14 6.03B effluent 0.17 0.09 0.15 0.36C influent 4.10 10.2 0.38 2.84C effluent 0.12 0.32 0.24 0.95D influent 7.67 7.96 0.20 2.43D effluent 0.11 0.01 0.19 0.69E influent 4.63 2.82 0.27 1.88E effluent 2.17 0.23 0.29 2.31F influent 6.37 4.91 36.53 2.94F effluent 0.62 0.15 2.09 2.54G influent 4.95 3.78 0.24 3.45G effluent 0.50 0.11 0.19 1.57H influent 7.48 12.7 0.12 2.68H effluent 0.39 0.16 0.09 0.69Minimum (influent) 4.10 2.82 0.12 1.73Maximum (influent) 10.21 12.7 36.53 6.03Median (influent) 6.77 6.86 0.26 2.76Minimum (effluent) 0.11 0.01 0.08 0.36Maximum (effluent) 2.17 0.32 2.09 2.54Median (effluent) 0.31 0.14 0.19 0.82

a Located in southern Ontario, Canada (see Section 2).

0.31g/L. These concentrations suggest a >85% removalof the two drugs by the sewage treatment processes. Therelatively low concentrations of salicylic acid found in theeffluent samples were probably due to the instability ofthis compound in sewage samples [13,23]. The levels ofthe acidic

Fig. 4. A GCthe acidic pha

confirmedsewage [13proceduretion of thedrugs.

Concl

multifor t

, perspharmaceuticals found in this study have further3.6.

Adatedticals/MS/SIM chromatogram of a sewage effluent extract, showingrmaceuticals as their TBDMS derivatives.

with endoccompoundsa cartridgeprovided bmonly usedseparate grtives in eacmatrices supermitted pderivativessensitivitymethod wafor alkylphin this studworks usindure is thethe previouparametersgenerated sand butyl psewage sam0.06 0.05 0.430.06 0.10 0.490.08 0.18 0.420.04 0.08 0.360.11 0.15 0.220.06 0.12 0.140.06 0.09 0.130.04 0.08 0.080.09 0.19 0.160.06 0.16 0.170.15 2.45 0.330.09 0.25 0.180.07 0.18 0.360.04 0.16 0.180.07 0.08 0.030.04 0.07 0.040.06 0.05 0.030.15 2.45 0.430.08 0.17 0.280.04 0.07 0.040.09 0.25 0.490.05 0.11 0.18

our previous findings on the same compounds in], as those results were obtained with a differentusing the Oasis HLB cartridge and the forma-

trimethylsilyl (TMS) derivatives of the acidic

usions

-residue method has been developed and vali-he determination of selected acidic pharmaceu-onal-care products, and a wide variety of phenols

rine-disrupting potentials in sewage samples. For

such as phenols and acidic PPCPs, the use ofwith anion-exchange groups for extraction has

etter selectivity than those with the more com-C18 groups. Elution of phenols and acids into two

oups has produced an extract with less coextrac-h fraction, which would be beneficial for complexch as sewage samples. This procedure has alsohenols and acids to be converted into different

, so that further enhancement in selectivity andcould be made in the final analysis. When thiss applied to influent and effluent samples, resultsenols, BPA, estrogens, and acidic drugs obtainedy were consistent with those reported in previousg individual methods. This multi-residue proce-refore a useful and more efficient alternative tos methods, especially when results for multipleare required. The application of this method hasome of the first results of methyl, ethyl, propyl,arabens as well as 2-phenylphenol in Canadianples.

H.-B. Lee et al. / J. Chromatogr. A 1094 (2005) 122129 129

Acknowledgements

The staffs of sewage treatment plants included in this workare gratefully acknowledged for their effort in sampling.

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Determination of endocrine-disrupting phenols, acidic pharmaceuticals, and personal-care products in sewage by solid-phase extraction and gas chromatography-mass spectrometryIntroductionExperimentalChemicals and reagentsSample collection and storageSolid-phase extraction (SPE) of samplesDerivatization of phenols and acidic pharmaceuticalsGC/MS analysis of phenols and acidic pharmaceuticals

Results and discussionOptimization of the extraction procedureDerivatives of phenols and acidic pharmaceuticalsMethod performance: accuracy, precision, and method detection limitsPhenolic compounds in municipal wastewater samplesAcidic pharmaceuticals in municipal wastewater samplesConclusions

AcknowledgementsReferences