Organic pollutants in the effluents of large wastewater treatment plants in Sweden

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Per9am0n

0043-1354(95)00278-2

Wat. Re5. V01.30, N0. 5, pp. 1115-1122, 1996 C0pyr19ht • 1996E15ev1er5c1enceLtd Pr1nted 1n 6reat 8r1ta1n.A11r19ht5re5erved 0043-1354/96 $15.00+ 0.00

0 R 6 A N 1 C P 0 L L U 7 A N 7 5 1N 7 H E E F F L U E N 7 5 0 F L A R 6 E W A 5 7 E W A 7 E R 7 R E A 7 M E N 7 PLAN75 1N 5WEDEN N1CKLA5 PAX1~U5 6RYAA8--66te60r9 Re910na1 5ewa9e W0rk5, Kar1 1X:5 v/1.95-418 34 66te60r9, 5weden (F1r5t rece1ved January 1995; accepted 1n rev15edf0rm 0ct06er 1995)

A1~traet--Eff1uent5 fr0m the three 1ar9e5t WW7P5 1n 5weden were ana1y5ed f0r the pre5ence 0f 0r9an1c p011utant5 6y 6C-M5. Fr0m a t0ta1 0f 1371dent1f1edc0mp0und5 0n1y 10 were pr10r1typ011utant5. A 6r0ad 5pectrum 0f n0n-re9u1ated 0r9an1c p011utant5 f0und 1n the eff1uent51nc1udedar0mat1c hydr0car60n5, f00d and h0u5eh01d re1ated c0mp0und5, 501vent5, p1a5t1c15er5,f1ame retardant5, pre5ervat1ve5,ant10x1dant5 and wa5h1n9 and c1ean1n9 re1ated c0mp0und5. 7he c0ncentrat10n5 0f 1nd1v1dua1c0mp0und5 1n eff1uent5 0f a11 three WW7P5 were 1n the ran9e 0f 0.5-50 #9/1. Rather few p01nt-d15char9ed p0Uutant5 fr0m 5pec1f1c 1ndu5tr1e5 were pre5ent 1n the eff1uent5. 7he maj0r1ty 0f p011utant5 detected 1n the eff1uent5 were attr16uta61e t0 the 0vera11 u5a9e and d15char9e 0f chem1ca1 pr0duct5 1n m0dern 50c1ety. 7he5e p011utant5 0r191nate fr0m d1ffu5e 50urce5 and repre5ent ••a 6ack9r0und chem1ca1 p011ut10n 10ad•• 0f the rece1v1n9 water5 thr0u9h the d15char9e fr0m WW7P5 1n 1ar9e c1t1e5. C0pyr19ht • 1996 E15ev1er5c1ence Ltd. Key w0rd5--eff1uent5, wa5tewater treatment p1ant5, 0r9an1c p011utant5, chem1ca1 ana1y515,9a5 chr0mat09raphy, ma55 5pectr0metry

1N7R0DUC710N Pr0tect10n 0f the rece1v1n9 water5 fr0m p011ut10n 6y harmfu1 wa5te 15 the pr1mary 90a1 f0r the treatment 0f mun1c1pa1 and 1ndu5tr1a1 wa5tewater at mun1c1pa1 wa5tewater treatment p1ant5 (WW7P5). 7he eff1uent d15char9e 0f t0ta1 ph05ph0ru5, 8 0 D , and 1n 50me ca5e5 t0ta1 n1tr09en and 5u5pended matter fr0m WW7P5 15 re9u1ated 6y the nat10na1 and 10ca1 auth0r1t1e5 1n 5weden. N0n-re9u1ated parameter5 5uch a5 t0ta1 and m1nera1 011 and heavy meta15 are re9u1ar1y mea5ured 1n the 1nf1uent a5 a part 0f the WW7P5 v01untary pr09ram5. 7he ••reve1at10n•• 0f the fact that 5evera1 0r9an1c pr10r1ty p011utant5 fr0m the N0rwe91an pr10r1ty p011utant5 115t (5par5t01 et a1., 1983) were pre5ent 1n 0ne 5amp1e 0f wa5tewater and 1n 0ne 5amp1e 0f 51ud9e taken at 0ne W W 7 P 5tarted the em0t10na11y 10aded pu611c med1a de6ate 1n 5weden 1n 1988 (8a1m6r and Fr05t, 1990). 7h15 created an 1ntere5t f0r 0r9an1c p011utant5 1n the 1nf1uent5, eff1uent5 and 51ud9e5 0f WW7P5. 1nf1uent and eff1uent wa5tewater fr0m 66te60r9 Re910na1 5ewa9e W0rk5 ( 6 R Y A A 8 ) ha5 51nce then 6een re9u1ar1y ana1y5ed f0r the pre5ence 0f 0r9an1c p011utant5 (Pax6u5 et a1., 1992). 7he maj0r1ty 0f pr10r1ty p011utant5 ha5 e1ther never 6een detected 0r 0n1y detected 5p0rad1ca11y (Pax6u5 et a1., 1992). 7he 1ndu5tr1a1 eff1uent c0ntr01 pr09ram5 1n 66te60r9 have 6een 5ucce55fu1 1n reduc1n9 the d15char9e 0f ch10r1nated 501vent5, petr01eum-6a5ed 501vent5 and p-n0ny1phen01 p01yeth0xy1ate5 fr0m 1ar9er 1ndu5tr1e5 t0 the 5ewer 5y5tem (Pax6u5 et a1., 1991, 1992). 7he5e chem1ca15 were rep1aced 6y 0ther pr0d-

uct5 wh1ch d0 n0t c0nta1n 0r9an1c pr10r1ty p011utant5. H0wever, 11tt1eattent10n (1f any) ha5 6een pa1d t0 the a5pect 0f treata6111ty 1n mun1c1pa1 wa5tewater p1ant5 when 1ntr0duc1n9 new ••env1r0nmenta11y fr1end1y•• pr0duct5 (Pax~u5 and 5chr6der, 1996). 7h15 1mp05e5 a nece551ty f0r character15at10n 0f 1nf1uent5 and, e5pec1a11y, eff1uent5 w1th re9ard t0 0r9an1c c0ntam1nant5. A5 part 0f the pr09ram t0 chart 0r9an1c c0n5t1tuent5 1n the wa5tewater, 5amp1e5 0f eff1uent wa5tewater fr0m three 1ar9e5t WW7P5 1n 5weden were ana1y5ed u51n9 6 C - M 5 . 1 n the pre5ent w0rk the re5u1t5 0f th15 ana1y515 are rep0rted and d15cu55ed 1n term5 0f the 0r191n 0f 0r9an1c p011utant5 and the p05516111ty t0 c0ntr01 the1r d15char9e t0 5ewer5. DE5CR1P710N 0F FAC1L171E5 Henr1k5da1 5eWa9e 7reatment P1ant (H57), the 1ar9e5t p1ant 1n 5t0Ckh01m, 5erVe5 a p0pU1at10n 0f a60Ut 580,000 pe0p1e and rece1Ve5 the 1ndU5tr1a1 Wa5teWater fr0m Centra1 part 0f 5t0Ckh01m and 50Uthern 5U6Ur65 W1th 5Urr0Und1n9 mUn1C1pa11t1e5. 7he n0n-d0me5t1C C0ntr16Ut10n t0 the 1nf1Uent 15 d0m1nated 6y d15char9e5 fr0m a 6r0ad 5peCtrUm 0f m1dd1e-512ed 1ndU5tr1e5 and Car-Wa5h1n9 faC111t1e5. Lar9er 1ndU5tr1e5 1nC1Ude fa6r1Cated meta1 pr0duct10n, pharmaceut1ca1 and c1rcu1t 60ard pr0duct10n. Appr0x1mate1y 77.6 Mm 3 0f wa5tewater 15 treated annua11y at H 5 7 . 7 h e eff1uent 15 d15char9ed t0 5a1t5j6n (8a1t1c 5ea). 66te60r9 Re910na1 5ewa9e W0rk5 ( 6 R Y A A 8 ) , wh1ch 15 51tuated 1n 66te60r9, 5erve5 a p0pu1at10n 0f a60ut 550,000 pe0p1e and rece1ve5 m05t 0f the 1ndu5-

1115

1116

N1ck1a5 Pax6u5

tr1a1 wa5tewater 1n 66te60r9 re910n. Lar9er 1ndu5tr1e5 enc0mpa55 f00d and 6evera9e 1ndu5tr1e5, fa6r1cated meta1 pr0duct10n, e4u1pment and mach1nery, 1nc1ud1n9 car manufactur1n9, paper and chem1ca1 pr0duct10n, p1a5t1c matt1n9 pr0duct10n and 1ndu5tr1a1 1aundry. At 6 R Y A A 8 , appr0x1mate1y 120 Mm 3 0f wa5tewater 15 treated annua11y. 7he eff1uent fr0m 6 R Y A A 8 15 d15char9ed t0 the 6 6 t a R1ver e5tuary and further t0 Katte9att. 5j61unda 5ewa9e W0rk5 (55W), wh1ch 15 51tuated 1n Ma1m6, 5erve5 a p0pu1at10n 0f 247,000 pe0p1e and rece1ve5 m05t 0f the 1ndu5tr1a1 wa5tewater 1n the Ma1m6 re910n. Lar9er 1ndu5tr1e5 1nc1ude f00d and 6evera9e 1ndu5try (51au9hter1e5, meat pr0ce551n9, c0ffee etc.), pharmaceut1ca1 and f00d packa91n9 1ndu5try (can5), pr0duct10n 0f chem1ca15, p1a5t1c and ru66er, and 1ndu5tr1a1 1aundry. Appr0x1mate1y 44 Mm 3 0f wa5tewater 15 treated annua11y at 55W. 7he eff1uent 15 d15char9ed t0 0re5und. Water treatment pr0ce55 at a11 three WW7P5 1nc1ude5 mechan1ca1 treatment (pr1mary 5ett11n9) and 6101091ca1 treatment 1n an act1vated 51ud9e pr0ce55 (aerat10n and 5ett11n9). Wa5te 51ud9e 15 d19e5ted anaer061ca11y. 7he 0perat1n9 key parameter5 0f the WW7P5--the hydrau11c retent10n t1me (HR7), 5011d5 retent10n t1me (5R7) and f00d/m1cr00r9an15m5 rat10 (F/M) expre55ed a5 k9 C0D/(k9 5u5pended 5u65tance. day)~were wa5 f0110w5:4.8 h, 4.2d, 0.56 ( 6 R Y A A 8 ) ; 4 h, 2-3 d, 0.2-0.3 (55W) and 5-6 h, 2-3 d, 0.1 (H57). ME7H0D5

F10w pr0p0rt10na1 da11y c0mp051te 5amp1e5 0f eff1uent wa5tewater were c011ected 1n Decem6er 1993 (1 week at 55W, 1 m0nth at 6RYAA8) and January 1994 (1 week at H57). 0ne 5amp1eper p1ant wa5 prepared 6y c0m61n1n9 the da11y c0mp051te5. 7he 5amp1e5 (21 a114u0t5) were f11tered thr0u9h the 0.5/~m 91a55-f16re f11ter5 prev10u51y 6aked f0r 4 h at 450°C. 0r9an1c c0mp0und5 were c0ncentrated fr0m the water 6y u51n9 5011d pha5e extract10n 0n tw0 5e4uent1a11yc0up1ed C18 60nded pha5e Me9a 80nd E1ut cartr1d9e5 (Var1an, U.5.A.). 7he enr1ched p0rt10n 0f C0D c0rre5p0nded t0 a60ut 25% 0f the t0ta1 C0D 1n the 5amp1e5. 7he ad50r6ed 0r9an1c c0mp0und5 were 5e4uent1a11y e1uted w1th 4m1 0f hexane, d1ethy1 ether:hexane (1:1), d1ethy1 ether, methan01-water (1:1), methan01-water (8:2), and methan01. 7he pr0cedure wa5 prev10u51y rep0rted 6y 5chr6der (1989, 1991, 1993a,6). 1dent1f1cat10n and 4uant1f1cat10n 0f 0r9an1c c0mp0und5 1n th15 w0rk wa5 perf0rmed 6y 9a5 chr0mat09raphy ma55pectr0metry (6CM5). F0r 6C ana1y515 a 7herma1 De50rpt10n Un1t (7DU) fr0m 5upe1c0 1nc. wa5 u5ed t0 ref0cu5 0r9an1c c0mp0und5 t0 a narr0w-60re ad50rpt10n tu6e (Car60trap 301) 6y 1nject10n 0f 2-5 #1 0f the c0rre5p0nd1n9 e1uate. 7he 7DU 5erved a150 a5 an 1nject0r p0rt 0f the 9a5 chr0mat09raph 1nterfaced t0 the 6 C (Hew1ett Packard 5890) 6y a heated fu5ed-5111catran5fer 11ne.6C-M5 exper1menta1c0nd1t10n5:2 60 m x 0.25 mm 1.d. c01umn c0ated w1th 0.25/am chem1ca11y 60nded pha5e D8-5 (J•W 5c1ent1f1c, CA) 6e1n9 1nterfaced t0 the 7DU. 7he 6C temperature pr09ram: 30°C he1d 1n 15 m1n, then t0 300°C at 3°C/m1n, then 300°C f0r 15 m1n. 7he ma55-5peetr0meter (1NC05 50, F1nn19an MA7) wa5 0perated 1n e1ectr0n 1mpact m0de, 5cann1n9 fr0m 33 t0 600 u 1n 1 5ec0nd. 7he 10n 50urce temperature and the tran5fer 11ne temperature wa5 he1d at 150° and at 250°C,

re5pect1ve1y. 1dent1f1cat10n 0f 0r9an1c c0mp0und5 wa5 perf0rmed 6y 5earch1n9 1n the N157 M5-116rary (F1nn19an MA7), 1n the W11ey 116rary (8encht0p P8M, Pa115ade C0rp0rat10n, U.5.A.) a5 we11 a5 6y c0mpar150n 0f the 5pectrum f0r unkn0wn w1th 5pectra pu6115hed 1n the 11terature (8r0w5er fr0m 8encht0p P8M, Pa115adeC0rp0rat10n, U.5.A.). 5pectra 0f n0ny1phen01 eth0xy1ate5 were taken fr0m the w0rk 0f 619er et a1. (1981). 5em14uant1tat1ve e5t1mate5 f0r the c0ncentrat10n5 0f 1nd1v1dua1 c0mp0und5 were perf0rmed 6y ca1cu1at1n9the t0ta1 area 0f the 71C peak f0r the c0rre5p0nd1n9 c0mp0und and c0mpar150n w1th the area 0f a deuterated 5tandard (d8-naphtha1ene) added t0 e1uate5 pr10r 1nject10n. RE5UL75 AND D15CU5510N 0r9an1c c0mp0und5 1dent1f1ed 6y 6 C - M 5 and the 5tructure5 f0r 50me 0f them are 5h0wn 1n 7a61e 1 and 1n F19. 1. Fr0m a t0ta1 0f 137 1dent1f1ed c0mp0und5 0n1y 10 (N05 32, 45, 47-49, 95, 103, 104, 113, 119) are c1a551f1ed a5 pr10r1ty p011utant5. Apart fr0m the c0mp0und5 91ven 1n the ta61e a 1ar9e num6er 0f 5u65tance5 pre5ent 1n wa5tewater c0u1d n0t 6e p051t1ve1y 1dent1f1ed due t0 a 1ack 0f the1r reference 5pectra. F00d and h0u5eh01d re1ated c0mp0und5 7he pre5ence 0f 10n9-cha1n fatty ac1d5 and the1r methy1 and ethy1 e5ter5 (N05 20-26) 0r191nat1n9 fr0m human excreta, 50ap5 and f00d 0115 and fat5 ref1ect5 a 1ar9e pr0p0rt10n 0f d0me5t1c wa5tewater 1n the 1nf1uent5 f0r a11 three WW7P5. F0r examp1e, the h0u5eh01d c0ntr16ut10n t0 the t0ta1 d15char9e t0 6 R Y A A 8 , ca1cu1ated a5 C 0 D 15 m0re than 80%. 8e1n9 re1at1ve1y hydr0ph061c, the5e c0mp0und5 are ma1n1y attached t0 part1c1e5 (c0ncentrat10n 0f the ac1d5 and e5ter5 1n the unf11tered 1nf1uent 15 u5ua11y m0re than 500/~9/1). Acc0rd1n9 t0 Qu6m6neur and Marty (1994) the rem0va1 eff1c1ency 0f 6101091ca1 treatment pr0ce55 reache5 f0r fatty ac1d5 90% (d15501ved fract10n)-97% (part1cu1ate fract10n). Am0n9 1ntermed1ate 0x1dat10n pr0duct5 0f 11p1d5 f0und 1n the eff1uent5 1t 15 n0tew0rthy t0 ment10n 5evera1 fatty a1dehyde5 (n0t 5h0wn 1n the ta61e) w1th n0nana1 and decana1 d0m1nat1n9. 0ther c0mp0und5 0f d0me5t1c 0r191n are 5ter015 (an1ma1 f00d, faece5), caffe1ne (c0ffee, tea, 50ft dr1nk5) and 1nd01 (faece5). L1ke 11p1d5, the 5ter015 are eff1c1ent1y (m0re than 90%) rem0ved fr0m wa5tewater 1n 6101091ca1 treatment pr0ce55 (Qu6m6neur and Marty, 1994). Re1at1ve1y h19h c0ntr16ut10n5 0f 5ewa9e fr0m an1ma1 f00d 1ndu5try (51au9hter h0u5e5 and meat pr0ce551n9) 1n 55W 15 ref1ected 1n a 1ar9er num6er 0f 5ter015 and the1r h19her c0ncentrat10n5 1n the eff1uent. 1n c0ntra5t t0 11p1d5 and 5ter015, caffe1ne 15 m0re 501u61e 1n water thu5 6e1n9 rem0ved t0 a 1e55er extent 1n 6101091ca1 treatment. 7he d15char9e fr0m a c0ffee pr0ce551n9 1ndu5try c0ntr16ute5 t0 the much h19her c0ncentrat10n 0f caffe1ne f0und 1n the eff1uent 1n 55W. Ar0mat1c hydr0car60n5 Ar0mat1c hydr0car60n5 f0und 1n the eff1uent5 1nc1ude tw0 (N05 113, 119) pr10r1ty p011utant5 and

0r9an1c p011utant5 1n eff1uent5 0f 1ar9e ww7P5 ma1n1y 5u65t1tuted n0n-re9u1ated der1vat1ve5 0f d1-, tr1- and tetracyc11c pr10r1ty p0Uutant5. P01ycyc11c ar0mat1c hydr0car60n5 (PAH5) are 9enera11y re9arded a5 a c1a55 0f carc1n09en1c c0mp0und5, a1th0u9h the hea1th effect5 0f PAH5 vary w1th m01ecu1ar we19ht and 5tructure (D1pp1e, 1985). PAH5 are f0rmed 1n 1nc0mp1ete c0m6u5t10n pr0ce55e5, wh1ch 0ccur whenever 0r9an1c matter (w00d, c0a1, 011, etc.) 15 6urned. 7he 0r191n 0f PAH5 1n mun1c1pa1 wa5tewater 15 n0rma11y a5cr16ed t0 the d15char9e 0f petr01eum pr0duct5 and the d15char9e 0f ur6an 5t0rmwater run0ff c0nta1n1n9 PAH5 fr0m a5pha1t and car exhau5t part1c1e5 (7anaka et a1., 1990). 0ne 1mp0rtant 50urce 0f PAH5 wh1ch 15 0ften 0ver100ked 15 f00d (Lar550n, 1986). A5 dem0n5trated 6y Matt550n et aL (1991) the c0ntr16ut10n 0f h0u5eh01d5 can reach 50-60% 0f the t0ta1 5ewer 10ad f0r pyrene and phenanthrene. P1a5t1c12er5 and f1ame retardant5

A 9r0up 0f p1a5t1c12er5 c0nta1n5 6en2ene5u1f0nam1de5, e5ter5 0f hexand101c ac1d (ad1pate5), e5ter5 0f phtha11c ac1d and 5evera1 ph05phate e5ter5, w1th phtha1ate5 and ad1pate5 d0m1nat1n9 (N05 30, 32, 45, 47-49, 59, 60, 103-105, 107, 108). 7he maj0r1ty 0f p1a5t1c12er5 f0und 1n the eff1uent5 are pr10r1ty p011utant5 wh1ch are 5t1116e1n9 u5ed 1n many pr0duct5 f0r 1ndu5tr1a1 a5 we11 a5 h0u5eh01d app11cat10n5. Acc0rd1n9 t0 Matt550n et a1. (1991) the h0u5eh01d c0ntr16ut10n 0f phtha1ate5 and ad1pate5 acc0unt5 f0r m0re than 70% 0f the1r t0ta1 10ad t0 6 R Y A A 8 . 7he pre5ence 0f m0n0e5ter5 0f phtha11c and ad1p1c ac1d 1n the eff1uent 15 pr06a61y due t0 hydr01y515 0f the c0rre5p0nd1n9 d1e5ter5 0ccurr1n9 1n the treatment pr0ce55.7he ph05phate e5ter5 (N05 103-105) are u5ed a5 f1ame retardant p1a5t1c12er5 and a5 c0n5t1tuent5 1n hydrau11c f1u1d5. Even here the c0ntr16ut10n 0f h0u5eh01d5 t0 5ewer d15char9e 15 n0t ne9119161e, 6etween 10 and 50% (Matt550n et a1., 1991). Ch10r1nated ph05phate e5ter5 (N05 107, 108) are u5ed a5 f1ame retardant5 1n text11e5, p1a5t1c5 a5 we11 a5 1n 0ther pr0duct5. 2-Ch10r0ethan01 ph05phate t09ether w1th tr16uty1 ph05phate have 6een rep0rted 1n the eff1uent fr0m an 1ndu5tr1a1 wa5tewater treatment p1ant (K02awa et a1., 1992). 8en2ene5u1f0nam1de5 are u5ed a5 p1a5t1c12er5 1n p1a5t1c5, ru66er, pr0duct5 f0r pa1nt1n9 etc. 7he5e c0mp0und5 were n0t f0und 1n the eff1uent5 0f mun1c1pa1 WW7P5 1n New Jer5ey (C1ark et a1., 1991). H0wever, 5evera1 6en2ene5u1f0nam1de5 t09ether w1th tr16uty1 ph05phate have 6een rep0rted 1n 9r0und water5 c0ntam1nated fr0m a 1andf111 1n En91and (Jame5 et a1., 1986). Pre5ervat1ve5 and ant10x1dant5

Am0n9 pre5ervat1ve5 repre5ent1n9 c0n5t1tuent5 0f many pr0duct5 f0r 60th h0u5eh01d and 1ndu5tr1a1 app11cat10n, e5ter5 0f hydr0xy6en201c ac1d (para6en5, N05 40--43) were f0und 1n the eff1uent5. 5evera1 para6en5 are appr0ved a5 f00d add1t1ve5 1n 5weden. 5u65t1tuted phen015 and the1r der1vat1ve5, 5h0wn

1117

1n the ta61e (N05 14, 17, 91-93), are w1de1y u5ed a5 ant10x1dant add1t1ve5 1n p1a5t1c mater1a15 and 0ther pr0duct5. When 0x1d15ed, the5e c0mp0und5 are tran5f0rmed t0 c0rre5p0nd1n9 d1ene-0ne5 0r 4u1n0ne5 (d1ene-d10ne5), wh1ch a150 have 6een 1dent1f1ed 1n the wa5tewater (N05 83-89). 7he 5chemat1c examp1e 0f 5uch an 0x1dat10n react10n 15 5h0wn 1n F19. 2. 5evera1 5u65t1tuted phen015, 4u1n0ne5 and d1ene0ne5, f0und 1n the wa5tewater 1n th15 1nve5t19at10n have 6een rep0rted 6y Jun9c1au5 et a1. (1978) 1n the eff1uent fr0m a chem1ca1 manufactur1n9 p1ant, a5 we11 a5 1n the rece1v1n9 r1verwater and 5ed1ment5 (where 1n the reduc1n9 env1r0nment 4u1n0ne5 are c0nverted t0 c0rre5p0nd1n9 615phen015). 501vent5

7he 9r0up 0f 501vent5 f0und 1n th15 5tudy enc0mpa55e5 n0n-ch10r1nated a1c0h015, ether5 and ket0ne5 (N05 1, 4-8, 13, 19, 66-74). 7he5e c0mp0und5 are ma1n1y u5ed 1n 1ndu5tr1a1 de9rea51n9, c1ean1n9, 1ac4uer1n9 and c0at1n9 app11cat10n5. 5h0rt-cha1n ether5 are 0ften added a5 50 ca11ed c0-501vent5 1n ac1d1c water-6a5ed pr0duct5 f0r c1ean1n9 and de9rea51n9 0f a1um1n1um and 5ta1n 5tee1 5urface5 1n 1ndu5try. A1c0h015 and ether5, a5 c0n5t1tuent5 1n car 5hamp005 and de9rea51n9 pr0duct5, are a150 d15char9ed t0 5ewer5 fr0m aut0mat1c car-wa5h1n9 fac111t1e5.501vent5 6a5ed 0n a1c0h015, ether5 and ket0ne5 are c0n51dered 1e55 harmfu1 f0r human5 than petr01eum-6a5ed 0r ch10r1nated 0ne5, wh05e app11cat10n 15re5tr1cted 1n 5weden. 1n v1ew 0f the 9enera1 trend f0r 1ntr0duct10n 0f water-501u61e 6a5ed pr0duct5 1t may 6e expected that the 4uant1ty 0f 5uch 501vent5 d15char9ed t0 5ewer w111 1ncrea5e 1n the future. Dur1n9 treatment the maj0r part 0f the 501vent5 15 u5ua11y rem0ved thr0u9h v01at1115at10n and 5tr1pp1n9, wh1ch exp1a1n5 why many 501vent5 were n0t detected 1n the eff1uent5 0f H57 and 557. A 1ar9e d15char9e 0f a1c0h015, ether5 and ket0ne5 fr0m the car manufactur1n9 1ndu5try c0ntr16ute5 t0 the1r re1at1ve1y h19her c0ncentrat10n5 1n the 6RYAA8•5 eff1uent. 0d0rant5 and perfume5

A 9r0up 0f 0d0rant5 and perfume5 enc0mpa55 ma1n1y 5ynthet1c mu5k5 and terpene5 (N05 128, 129, 132, 133). Apart fr0m 6e1n9 perfume add1t1ve5 1n 1ndu5tr1a1 and h0u5eh01d pr0duct5, m1xture5 0f terpene5 are a150 50met1me5 u5ed a5 de9rea51n9 501vent5, rep1ac1n9 petr01eum-6a5ed 0ne5. 5ynthet1c mu5k5, 9a1ax011de5, are ma1n1y u5ed a5 0d0rant5 1n 1ndu5tr1a1 deter9ent5. 7he 9a1ax011de5 have 6een detected 1n 1ndu5tr1a1 eff1uent5, mun1c1pa1 51ud9e5 and 1n r1ver water5 1n the U.K. (Crath0rne et a1., 1989). 7he ma1n app11cat10n 0f mu5k ket0ne (N0. 129) 15, 0n the 0ther hand, a perfume add1t1ve t0 text11e wa5h1n9 f0rmu1at10n5 f0r the h0u5eh01d market. 8e1n9 per515tent, th15 c0mp0und 15 c0n51dered t0 6e env1r0nmenta11y p0tent1a11y harmfu1.

1118

N1ck1a5 Pax6u5 7a61e 1. C0mp0und5 1dent1f1ed 1n the eff1uent water fr0m H57, 6RYAA8 and 557 and the1r e5t1mated c0ncentrat10n5,/~9/1 (-- n0t detected) N0.

C0mp0und name

H57

6RYAA8

55W

0.5

7

--

- -

2

--

2.5

--

0.5 0.5

0.5 1.5

1.5 0.5

A1c0h015 and ether5

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

8utane, 2-meth0xy8utane, 1-ch10r0-4-meth0xy1,3-D10x01ane, 2,2-d1ethy1 Ethan01, 2-(2-eth0xyeth0xy)Ethan01, 2-[2-(2-eth0xyeth0xy)eth0xy]Ethan01, 2-(2-6ut0xyeth0xy)2-Pr0pan01, 1-(1-methy1pr0p0xy)2-Pr0pan01, 1-[2-(2-meth0xy- 1-methy1eth0xy)- 1-methy1eth0xy] Ether5 0f ethy1ene (PE6) and/0r pr0py1ene (PE6) 91yc01 1)ecane, 1,1•0xy615Methy1 d1pheny1 ether 815(2-pr0pan01)-6en2ene D1-t01y1ether 4-7ert-6uty1-phenet01e Pheny1p-(t-penty1) pheny1 ether 2-(4-tert-8uty1-0-t01y10xy) ethan01 7ert-6uty1 hydr0xy-an1501e (8HA) 4-7ert-6uty1-f1 -d1ch10r0phenet01e D1pheny1car61n01

- -

--

10

---

16

----

8

--

0.5

--

--

3

--

--

--

6.5

4.5 2 --

2.0 -0.5

- -

[

- -

--

--

0.5

--

--

0.5

1

0.5

0.5

4

- -

- -

Ac1d5 and e5ter5

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49

Fatty ac1d5 and the1r methy1 and et6y1 e5ter5 C12 C13 C14 C15 C16 C17 C18 Ethy1ene 91yc01 m0n001eate 0ctan01c ac1d, hexadecy1 e5ter 0ctan01c ac1d, 0ctadecy1 e5ter Hexaned101cac1d, 615(2-methy1pr0py1) e5ter Hexaned101cac1d, m0n0(2-ethy1hexy1) e5ter Hexaned101cac1d, 615(2-ethy1hexy1) e5ter 2-Pr0pen01c ac1d, 1,6-hexaned1y1 e5ter 2-Pr0pen01c ac1d, 0cty1 e5ter Pentan01c ac1d, 3-0x0-, d1ethy1 e5ter Pr0pan01c ac1d, 2-methy1-, 2-ethy1-1-pr0py1-1,3-pr0paned1y1 e5ter 8en201cac1d, methy1 e5ter 8en201cac1d, 2-ch10r0-, methy1 e5ter 8en201cac1d, 3,4-d1meth0xy-, methy1 e5ter 8en201cac1d hydr0xy-, methy1 e5ter (methy1 para6en) 8en201cac1d hydr0xy-, ethy1 e5ter (ethy1 para6en) 8en201cac1d hydr0xy-, pr0py1 e5ter (pr0py1 para6en) 8en201cac1d hydr0xy-, 6en2y1 e5ter (6en2y1 para6en) 1,2-8en2ened1ear60xy11c ac1d, m0n0ethy1 e5ter 1,2-8en2ened1car60xy11c ac1d, d1ethy1 e5ter 1,2-8en2ened1car60xy11c ac1d, m0n06uty1 e5ter 1,2-8en2ened1car60xy11c ac1d, d16uty1 e5ter 1,2-8en2ened1car60xy11c ac1d, 6uty1 pheny1methy1 e5ter 1,2-8en2ened1car60xy11c ac1d, 615(2-ethy1hexy1) e5ter

0.5 <0.5 18 6 76 1.5 20

0.5 <0.5 17 2 48

5

28 5

1

8 --

3 3 12

2 20 8 15 0.5 3

1 <0.5 19 6 99 1.5 26 42 6 2 3 9

0,1 --

0.3 <0.1 <0.1 0.2 1 0.5 3 4 11 6 10

--

0.2 <0.1 11 8 20 22 17 17

0.2 0.3 <0.1 0.3 0.5 0.5 6

N1tr09en c0nta1n1n9 c0mp0und5

50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

1nd01e Caffe1ne 8en20th1a201e 2-M0rph011n0th106en20th1a201e Qu1n011ne, 2,6-d1methy1F0rmam1de, N,N-d16uty11-Pr0panam1de, N-ethy1-N-methy12-Pr0peneam1de, 2-methy1-N-pheny1 8en2am1de, N-(1,1 -d1methy1ethy1)-3-methy18en2¢ne5u1f0nam1de, N-¢thy1-4-methy18en2ene5u1f0nam1de, N-6uty18en2•nam1ne, N,N,4-tr1methy11,3,5,7-7etraa2atr1cyc10[3.3.1.1 (3,7)]d¢¢ane 1H-Pyrr01e-2,5-d10ne, 3-ethy1-4-methy12,5 -Pyrr011d1ned10ne, 3-methy12-Pyrr011d1n0ne, 1-methy1-5-(3-pyr1d1ny1)-

<0.1

2 <0.1

2 --

1.5

33

<0.1

1.5

4 4 1.0 <0.1

0.5 6 0.5

--

0.2

1

3

--

0.5

1

<0.1 --

14

Ket0ne5 and ene-0ne5

66 67 68 69 70 71 72

2-Pentan0ne, 4-methy13-Pentan0ne, 2-methy13-Penten-2-0ne, 4-methy1 2-Hexan0ne Cyc10hexan0ne Cyc10hexan0ne, 4-methy1Cyc10hexan0ne, 4-(1,1 -d1methy1ethy1)-

0.5 0.5 0.5 1

•

m

m

0.5 6 <0.1 1

1

8

7a61e 1--c0nt1nued

0r9an1c p011utant5 1n eff1uent5 0f 1ar9e WW7P5

1119

7a61e 1--c0nt1nued N0. 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89

C0mp0und name

H57 6RYAA8

2-Pr0pan0ne, 1-phen0xy2-0ctan0ne, 1-pheny14-0eten-3-0ne 3-8uten-2-0ne,4-pheny18en20phen0ne Ethan0ne, 2,2-d1meth0xy-1,2-d1pheny1Ethan0ne, 1-(3-methy1pheny1)Ethan0ne, 1-[4-(1-hydr0xy- 1-methy1ethy1)pheny1]9,10-Anthracened10ne 6-Meth0xy-3,4-d1hydr0-1(2H)-naphtha1en0ne 2-Cyc10hexen-1-0ne, 2-methy1-5-(1-methy1etheny1)2,5-D1-tert-6uty1-2,5-cyc10hexad1ene-1,4-d10ne 4-Cyc10pentene-1,3-d10ne, 4-(3-methy1-2-6uteny1)2,6-D1-150-pr0py1-2,5-cyc10hexad1ene-1,4-d10ne 2,6-D1-tert-amy1-2,5-cyc10hexad1ene-1,4-d10ne 2,6-D1-tert-6uty1-4-methy1¢ne-2,5-cyc10hexad1ene-1-0ne 2,6-D1-tert-6uty1-4-ethy1ene-2,5-cyc10hexad1ene-1-0ne

55W

--

2

--

--

- -

5

- -

- -

- -

4

11

--

0.5

48

---

--

16

1

--

4

0.5

- -

--

- -

10

--

0.5

--

--

- -

2

- -

2

3

0.5

1

14

1

7

6

--

0.5

12

--

--

0.5

--

Phen015 90 91 92 93 94 95 96 97 98 99 100 101 102

Phen01 2,6-D1-150-pr0py1-4-methy1phen01 2,6-D1-tert-6uty1-4-ethy1phen01 2,6-D1-tert-6uty1-4-methy1phen01(8H7) 0cty1phen01 (0P) N0ny1phen01 (NP) 2,4-D10cty1phen01 D¢cy1phen01 5-Ch10r0-2-(2,4-d1ch10r0phen0xy)phen01 0cty1phen01 eth0xy1ate (0PE01) 0cty1phen01 eth0xy1ate (0PE02) N0ny1phen01 th0xy1ate (NPE01) N0ny1phen01 eth0xy1ate (NPE02)

103 104 105 106 107 108

7r16uty1 ph05phate 7r1pheny1ph05phate 2-Ethy1hexy1d1pheny1 ph05phate 2-8ut0xyethan01 ph05phate 2-Ch10r0pr0pan01 ph05phate 2-Pr0pan01,1,3-d1Ch10r0-, ph05phate

--

--

5

14

- -

1

0.5

0.5

3 0.3

0.5 --

- -

0.5 1.5 0.5 11 6

0.5 1 - -

17 0.5 --

2

----

- -

0.5 ---

1

0.5

0.5

3 --28 4 1

----<0.5 <0.5

Ph05ph0ru5c0nta1n1n9c0mp0und5 2 3 2 19 3 3

Ar0mat1c hydr0car60n5 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127

Naphtha1ene,d1methy1Naphtha1ene,methy1pr0py11,1•-81pheny1, d1methy11,1•-81pheny1, ethy1Anthracene/Phenanthrene Methy1d16en20th10phene 2,8-D1methy1d16en20th10phene Anthracene/Phenanthrene methy1 (d1fferent 150mer5) Anthracene/Phenanthrene d1methy1 (d1fferent 150mer5) Retene Pyrene Pyrene,methy1- (d1fferent 150mer5) Pyrene,methy1, methy1ethy1- 0r tetramethy11,1•-D1pheny1ethane 1-(H)-1ndene, 1-pheny1methy1ene9H-F1u0ren-9-0ne 2-Anthraceneam1ne Acr1d1ne,9-methy1-/D16en2(6,f)a2ep1ne 0ctahydr0phenanthrene, d1methy1-, 150pr0py1-

128 129 130 131 132 133 134 135 136

6a1ax011de5 Mu5k ket0ne 2(1H)Phenanthren0ne, hexahydr0-7-meth0xy, tr1-methy1M0rph1nan-6-01,7,8-d1dehydr0-4,5-ep0xy-3-meth0xy-17-methy1 ~ -Cad1nene R1muene Ch01e5tan015 Ch01e5ter015 Ch01e5ta-d1en015 Ch01e5ta-d1en-0ne5

M15ce11ane0u5

137

1

0.5

--

3 2

-0.5

--0.5 0.5

1

--

--

--

5

- -

- -

2

--

3

1

-3 2

--

-<0.5 --

1

0.5 2.5 1

1

--

1

--

0.5

--

0.5 0.5

---

---

--

--

9

1

--

0.5

--

6 5

1 2

--

--

- -

•

--

0.5

--

--

0.5 0.5

0.5 0.5

--

--

--

--

0.5 -2 1 0.5 ]

--

0.5 4 0.5 6 11

Wa5h1n9 and c1ean1n9 re1ated c0mp0und5

cha1n ac1d5 ment10ned a60ve, the1r a1ky1 e5ter5 (N05

1n term5 0 f 4uant1t1e5, the wa5h1n9 a n d c1ean1n9 re1ated c 0 m p 0 u n d 5 are, after f00d re1ated 0ne5, the 5ec0nd 1ar9e5t 9 r 0 u p 0 f 5u65tance5 d15char9ed t0 5ewer5. D0me5t1c 5ewa9e 15 d0m1nated 6y the 10n9-

28, 29) f r 0 m 50ap5 a n d eth0xy1ated e5ter5 (N0. 27) 0r191nat1n9 f r 0 m 114u1d h a n d w a 5 h pr0duct5. F r 0 m a 9 r 0 u p 0 f 1ndu5tr1a1 n0n-10n1c 5urfactant5 a n u m 6 e r 0 f e5ter5 (N05 33-35), ether5 0 f P E 6

and PP6,

1120

N1ck1a5 Pax6u5

n0. 5 2

n0.53

cH3

n0.62

n0.65

n0.118

CH--CH2

N02 CH~t-C4H9

c20 . N°

3 = CH3 n0.129

0H n0.131

5 n0.132

1-C3H7 CH3 CH3 n0.133

cH,,y, H

0

~

n0. 134

H0" v ~ 1 n0. 135

01 ~ n0. 137

F19. 1. 5tructure5 0f 50me c0mp0und5 fr0m 7a61e 1. a1ky1phen015 (N05 94-97) and eth0xy1ated a1ky1phen015 (N05 99-102) were f0und 1n the eff1uent5. A1th0u9h 1n 9enera1 n0t t0x1c f0r mamma15, 50me 5urfactant5 can 6e very t0x1c t0 a4uat1c 0r9an15m5 (Lew15, 1991). Fr0m an ec0t0x1c01091ca1 a5pect, the m05t cr1t1ca1 c0mp0und 15 n0ny1phen01 (NP) wh1ch 1n 5weden 15 c1a551f1ed a5 a pr10r1ty p011utant. 7he u5a9e 0f NP eth0xy1ate5 (NPE05) 1n 1ndu5tr1a1 app11cat10n5 (n0t u5ed 1n h0u5eh01d deter9ent5) 15 re5tr1cted, 6ut unf0rtunate1y ha5 n0t cea5ed 1n 5weden. Acc0rd1n9 t0 Ahe1

(PE6 and PP6) app11cat10n5, c0ntr16ute5 0n1y part1y t0 the1r pre5ence 1n the eff1uent5. A5 dem0n5trated 6y 5chr6der (1993c) the c0mp0und5 0f P E 6 and P P 6 type are hard1y e11m1nated 0r de9raded 1n 6101091ca1 treatment pr0ce55e5 6ut add1t10na11yf0rmed fr0m the 610chem1ca11y 1nduced 60nd c1eava9e 0f p01yeth0xyand pr0p0xy1ated n0n-10n1c 5urfactant5. 1n the 6101091ca1 treatment pr0ce55 p01y91yc015are 0x1d15ed t0 c0rre5p0nd1n9 ac1d5. 7he 0x1dat10n 0f the term1na1 hydr0xy1 funct10n 0f p01yethy1ene 91yc01 ether5 0ccur5 acc0rd1n9 t0 the react10n:

R -- (0CH 2C H > ). -- 0 C H 2CH 20H--• R -- (0CH)2 C H > ). -- 0 C H 2C ~

"o H

et a1. (1994) pure NP 15 n0t pre5ent 1n c0mmerc1a1 m1xture5 0f NPE05, 6ut 15 f0rmed fr0m the 1atter 1n the wa5tewater treatment pr0ce55. 1t 15 p055161e that d10cty1- and decy1phen01 f0und 1n the eff1uent5 are a150 f0rmed 1n 5ame manner a5 NP fr0m the c0rre5p0nd1n9 p01yeth0xy1ated 0r pr0p0xy1ated der1vat1ve5. A5 f0r m0n0- and d1eth0xy1ated NP (NP1E0, NPE2E0), the5e are 60th part1y rem0ved and part1y f0rmed fr0m h19her eth0xy1at10n de9ree NPE05 1n the treatment pr0ce55 (Ahe1 et a1., 1994). 0cty1phen01 (0P) and 0PE05, f0und 1n the eff1uent 1n H57 are expected t0 6ehave 1n the treatment pr0ce55 51m11ar1y t0 NPE05. 7he re1at1ve a6undance 0f N P E 0 01190mer5 1n the eff1uent5 0f three WW7P5 w1th the d0m1nat1n9 N P E 0 2 (7a61e 1) 15 1n a9reement w1th the re5u1t5 0f Ahe1 et a1. (1994) 06ta1ned f0r 5ewa9e treatment p1ant5 1n 5w1t2er1and. P01y91yc01 ether5, PE65 and PP65, f0und 1n the eff1uent5 0f a11 three WW7P5 repre5ent a 5pec1a1 ca5e. 7he d15char9e t0 5ewer5 0f the5e c0mp0und5, w1de1y u5ed 60th 1n h0u5eh01d (ma1n1y PE6) and 1ndu5tr1a1

(R = H 0r a1ky1 9r0Up)

wh1ch re5u1t5 1n the f0rmat10n 0f h19h1y per515tent ac1d1c meta6011te5, that have 6een rep0rted t0 d0m1nate the eff1uent 0f a 1ar9e-5ca1e treatment p1ant 1n Aachen (5chr6der, 1993c). 51m11ar ac1d1c meta6011te5 (F19. 3) der1ved fr0m P E 6 and P P 6 and 1ntermed1ate meta6011te5 c0nta1n1n9 a1dehyde term1na1 9r0up c0u1d 6e 1dent1f1ed 1n the eff1uent5 1n the pre5ent 5tudy. 7he 51mu1tane0u5 pre5ence 0f p01y91yc015, the1r a1dehyde and ac1d1c meta6011te5 1n the eff1uent5 1nd1cate5 that the p01yeth0xy- 0r pr0p0xy1ated 5urfactant5 are 0n1y part1y 0x1d15ed 1n the treatment pr0ce55, pr06a61y due t0 the 5h0rt re51dence t1me.

1ndu5tr1a1 p01nt-d15char9ed c0mp0und5 7he 0r191n 0f 5evera1 p011utant5 (N05 3, 10, 52, 53, 55, 62, 77, 81, 106) 1n the eff1uent5 can 6e 1dent1f1ed a5 p01nt d15char9e5 fr0m 5pec1f1c1ndu5tr1e5. A chem1ca1 fact0ry, runn1n9 a new "env1r0nmenta11y m0re fr1end1y•• (e.9. w1th0ut the u5e 0f ch10r1ne) pr0ce55 c0ntr16ute5 t0 a 1ar9e extent t0 the pre5ence 0f decane

0r9an1c p011utant5 1n eff1uent5 0f 1ar9e ww7P5

.0 x

1121

R = CnH2n+ 1

R

Xt

R

~

X2

H0-; CH30-;C2H50-

0

CnH2n+1

~

CnH2n

F19. 2. 0x1dat1ve f0rmat10n 0f d1ene-d10ne5 (Xj--5aturated a1ky115 tran5f0rmed t0 the un5aturated 0ne) and d1ene-0ne5 (X~--0xy9enated 5u65t1tuent5 are tran5f0rmed t0 ket0ne) fr0m c0rre5p0nd1n9 phen011c c0mp0und5. 7he 5aturated a1ky1 R rema1n5 unchan9ed.

ether, anthracened10ne and f0rmam1de (N05 10, 55, 81) 1n the eff1uent 0f 6 R Y A A 8 . D1ethy1 d10x01ane (N0. 3) a5 a 6y-pr0duct 15 d15char9ed t0 the 5ewer fr0m a fact0ry pr0duc1n9 5ynthet1c a1kyd re51n5. A p055161e 50urce 0f methenam1ne and m0rph011n0th106en20th1a201e (N05 53, 62) 15 the eff1uent wa5tewater fr0m ru66er 1ndu5try wh1ch repre5ent5 a 519n1f1cant pr0p0rt10n 0f the 1ndu5tr1a1 5ewa9e 10ad 1n 55W. 8en20phen0ne (N0. 77) w1th1n a ran9e 0f 0.5-2.0/~9/1 ha5 6een rep0rted 1n the eff1uent5 0f 60th a W W 7 P 10cated 1n a rura1 area w1th0ut kn0wn 1ndu5tr1a1 c0ntr16ut10n 0f wa5te t0 the 51te and the 0ne 1n an 1ndu5tr1a1 area (C1ark et a1., 1991). 7h15 c0mp0und 15 w1de1y u5ed a5 an act1vat0r, harder etc, 1n 1ndu5tr1a1 pr0ce55e5 1nv01v1n9 5urface c0at1n9 and c010ur pr1nt1n9 app11cat10n5.8en20phen0ne (7a61e 1) 15 pre5ent 1n re1at1ve1y h19h c0ncentrat10n5 1n the eff1uent5 0f tw0 WW7P5 (H57, 6 R Y A A 8 ) and n0t detected f0r the th1rd 0ne, 1nd1cat1n9 a 10ca11ndu5tr1a1 d15char9e. 7he exact 50urce 0f 6en20phen0ne 1n the wa5tewater 15, at pre5ent, n0t kn0wn. 8ut0xyethan01 ph05phate (N0. 106), f0und 1n the eff1uent5, 15 u5ed

45

m

1n many 1ndu5tr1a1 pr0duct5 (add1t1ve, def0amer, c0501vent). H0wever, 0ur 0wn re5u1t5 fr0m ana1y515 0f 1ar9er 1ndu5tr1e5 (unpu6115hed re5u1t5) 1nd1cated that 60th th15 c0mp0und and 6en20th1a201e (u5ed a5 c0rr0510n 1nh161t0r) were a550c1ated w1th d15char9e fr0m 1ndu5tr1e5 dea11n9 w1th fa6r1cated meta1 pr0duct10n. N0te, that the5e p011utant5 were detected 1n the eff1uent5 0f tw0 WW7P5 w1th re1at1ve1y h19h 1nput5 0f 5ewa9e fr0m th15 part1cu1ar type 0f 1ndu5try (H57 and 6 R Y A A 8 ) . 7he pre5ence 0f m0rph1nan der1vat1ve (N0. 131) 1n the eff1uent 0f 55W can 6e a5cr16ed t0 1t5 d15char9e fr0m a 1ar9e pharmaceut1ca1 1ndu5try. W W 7 P 5 and re9u1at10n5

7he c0ncentrat10n5 0f 1nd1v1dua1 c0mp0und51n the eff1uent5 0f a11 three WW7P5 are 1n the ran9e 0f 0.5-50 #9/1, wh1ch 151n a9reement w1th the re5u1t5 f0r WW7P5 rep0rted 6y C1ark et aL (1991). 7he va5t maj0r1ty 0f the detected p011utant5 0r191nate fr0m d1ffu5e 50urce5 due t0 0vera11 u5a9e and d15char9e 0f chem1ca1 pr0duct5 1n m0dern 50c1ety. A1th0u9h the

n=5:221 -1 n=4:177-1 n=3:133 -1 n=2:89 -1

PE6

e9

r-k=4:221 [•" k=3:177 ~-k=2:133 1•" k=1:89

M , , ,,

, . . . .J;

. .

. ,1

. . , , ,,

. . , , ,..

, . . . . . . . . .

, .

. .

H- (0CH2CH2)n - (0CH2CH2)k - 0CH2CH3

103

45 55

1.11

,7

1 .............

1,,F

. 1. J ..... , . . ,1. ... . ,J

1,•1 ,1

,, .

,

.

,.

.J .j,~9.

J

757 108 . . . . 116,,

1.

1,~1f2 ,~r.t,~..~,;.~

,

1~

~

. . . .

.

Ac1d1c meta6011te P P 6

142 .....

161 ,

, 174 ,

199 1 2 0, ,3

219

-0CH2CH

1~

k=2:175 -

k=1:117

~59

H- (0C11••1CH2)n " (0~HCH 2)k "-0~HCH 3

2,9 . . . .

+- (0CH2CH2)k

"•1

117-~1--

n=1:59

117

55

.,1

H()~C-CH21~(0CH2CH2)n

n=2:

72

1

. . . . . .

•9 .............

n = 3:175

43

m

n=3: 191-1

Ac1d1c meta6011te P E 6

r

CH3

1

M/2

H0••

CH3

CH3

n=2:189-1 73 n=1:131-1 CH3 ~H3

cH3

C83

F19. 3. Ma55 5pectra (1eft) 0f the c0mp0und5 wh05e 5tructure5 were a5519ned t0 PE6 and PP6 and the1r ac1d1c meta6011te5. Fra9mentat10n pattern5 (r19ht) repre5ent 5tructura1 un1t5 and the1r ma55e5 (n and k--num6er 0f eth0xy 0r pr0p0xy 9r0up5) c0rre5p0nd1n9 t0 ma55 fra9ment5 (M/2) 1n the 5pectra.

3

1122

N1ck1a5 Pax6u5

1nd1v1dua11ndu5tr1a1 5ewa9e 10ad pr0f11e5 are d1fferent f0r a11 three WW7P5, there 15 a certa1n 51m11ar1ty 6etween H 5 7 and 6 R Y A A 8 1n term5 0f the pre5ence and c0ncentrat10n5 0f 5evera1 5pec1f1c p011utant5 (N05 77, 106). Each mun1c1pa1 W W 7 P 1n 5weden ha5 the 1e9a1 p05516111ty t0 10ca11y re9u1ate 5pec1f1c 1ndu5tr1a1 chem1ca15 1n 1t5 1nf1uent w1th1n 1t5 1ndu5tr1a1 c0ntr01 pr09ram5 0r, 1n the w0r5t ca5e 51mp1y refu5e t0 treat wa5tewater c0nta1n1n9 ha2ard0u5 chem1ca15. 0 n the 0ther hand, a 6r0ad 5pectrum 0f p011utant5 5h0wn 1n the ta61e 0r191nate5 fr0m d1ffu5e 50urce5. 7h15 9r0up 0f p011utant5 may 6e c0n51dered a5 ••a 6ack9r0und chem1ca1 p011ut10n 10ad•• 0f the rece1v1n9 water5 thr0u9h the d15char9e fr0m WW7P51n 1ar9e c1t1e5.1n re5pect t0 the1r 0r191n the e11m1nat10n 0f a p055161e harmfu1 effect 1n the env1r0nment f0r part1cu1ar p011utant5 can 6e ach1eved 0n1y 6y re5tr1ct10n5 0n the1r u5a9e app11ed at the nat10na1 1eve1.

A4uat1c Env1r0nment•• C057 641 (Water P011ut10n Re5earch Rep. 3), Chan1a, 6reece. Jun9c1au5 6. A., L0pe2-Av11a V. and H1te5 R. A. (1978) 0r9an1c c0mp0und5 1n an 1ndu5tr1a1wa5tewater: a ca5e 5tudy 0f the1r env1r0nmenta1 1mpact. Env1r0n. 5c1. 7echn01. 12, 88-96. K02awa 7., Wuek1 7., K06aya5h1 H. and Mat5u1 5. (1992) Mana9ement 0f t0x1c5 f0r the Fuka5h16a 1ndu5tr1a1wa5tewater treatment p1ant 0f the Ka5h1ma petr0chem1ca1 c0mp1ex. Wat. 5c1. 7echn01 25, 247-254. Lar550n 8. (1986) P01ycyc11c ar0mat1c hydr0car60n5 1n 5wed15h f00d5. A5pect5 0n ana1y515, 0ccurrence and 1ntake. Ph.D. the515, 5wed15h Un1v. 0f A9r1cu1tura1 5c1ence5, Upp5a1a, 5weden. Lew15 M. A. (1991) Chr0n1c and 5u61etha1 t0x1c1t1e5 0f 5urfactant5 t0 a4uat1c an1ma15: a rev1ew and r15k a55e55ment. 1•Vat. Re5. 25, 101-113. Matt550n J., Aver9Ard 1. and R061n50n P. (1991) Pr10r1ty p011utan5, heavy meta15 and ma1n c0n5t1tuent5 1n the d0me5t1c 5ewa9e fr0m tw0 re51dent1a1 area5 1n 60then6ur9 (1n 5wed15h). Vatten 47, 204-211. Pax6u5 N., R061n50n P. and 8a1m6r P. (1991) 50urce5 and 0ccurrence 0f 0r9an1c m1cr0p011utant51n wa5tewater and 5ewa9e 51ud9e 1n 66te60r9, 5weden. 1n 7reatment and

REFERENCE5

(Ed1ted 6y L•Herm1te P.), pp. 405~,11. E15ev1er App1. 5c1., L0nd0n. Pax6u5 N., R061n50n P. and 8a1m6r P. (1992) 5tudy 0f 0r9an1c p011utant5 1n mun1c1pa1wa5tewater 1n 66te60r9, 5weden. Wat. 5c1. 7echn01. 25(11), 249-256. Pax6u5 N. and 5chr6der H. Fr. (1996) 5creen1n9 f0r n0nre9u1ated 0r9an1c c0mp0und5 1n mun1c1pa1wa5tewater 1n 66te60r9, 5weden. 1n pre55. Qu6m6neur M. and Marty Y. (1994) Fatty ac1d5 and 5ter015 1n d0me5t1c wa5tewater5. Wat. Re5. 28, 1217-1226. 5chr6der H. Fr. (1989) H0chdruckf1115519ke1t5chr0mat09raph1e 9ek0ppe1t m1t 7andemma55en-5pekr0metr1e--E1ne 5chne11e und 2ukunft5we15ende Ana1y5enmeth0de 1n der Wa55er- und A6wa55erana1yt1k. V0m Wa55er 73, 111-136. 5chr6der H. Fr. (1991) P01ar, hydr0ph111c c0mp0und5 1n dr1nk1n9 water pr0duced fr0m 5urface water. J. Chr0mat09r. 554, 251-266. 5chr6der H. Fr. (1993a) P011utant5 1n dr1nk1n9 water and wa5te water. J. Chr0mat09r. 643, 145-161. 5chr6der H. Fr, (19936) Fe5tpha5enextrakt10n m1t 5e1ekt1v E1ut10n 1n Ver61ndun9 m1t ma55en5pektr05k0p15che5 Detekt10n--E1ne v1e1ver5prechende V0r9ehen5we15e 6e1 der Unter5uchun9 v0n A6w/155ern auf p01are, 0r9an15che 1nha1t55t0ffe. V0m Wa55er 80, 323-339. 5chr6der H. Fr. (1993c) 5urfactant5: n0n-610de9rada61e, 519n1f1cantp011utant5 1n 5ewa9e treatment p1ant eff1uent5. J. Chr0mat09r. 647, 219-234. 5p~r5t01 5. P., Urda1 K., Dran95h01t H. and 6j~5 N. (1983) Pr10r1ty p011utant5 1n N0rway. 5taten5 f0ruren5n1n95t115yn (N0rwe91an Env1r0nmenta1 Pr0tect10n A9ency) Rep. 83 02 02-1. 7anaka H., 0nda 7. and 09ura N. (1990) Determ1nat10n 0f p01ycyc11c ar0mat1c hydr0car60n5 1n ur6an 5treet du5t5 and the1r 50urce mater1a15 6y cap111ary 9a5 chr0mat09raphy. Env1r0n. 5c1. 7echn01. 24, 1179-1186.

U5e 0f 5ewa9e 51ud9e and L14u1d A9r1cu1tura1 Wa5te5

Ahe1 M., 619er W. and K0ch M. (1994) 8ehav10ur 0f a1ky1phen01 p01yeth0xy1ate 5urfactant5 1n the a4uat1c env1r0nment--1. 0ccurrence and tran5f0rmat10n 1n the 5ewa9e treatment. Wat. Re5. 28, 1131-1142. 8a1m6r P. and Fr05t R. C. (1990) Mana91n9 chan9e 1n an env1r0nmenta11yc0n5c10u5 50c1ety: A ca5e 5tudy, 60then6ur9 (5weden). Wat. 5c1. 7echn0L 22(12), 45-56. C1ark L., R05en R. 7., Hartman 7h. 6., A1a1m0 L. H., L0u15 J. 8., Hert2 Ch., H0 Ch1-7an9 and R05en J. D. (1991) Determ1nat10n 0f n0nre9u1ated p011utant5 1n three New Jer5ey pu611c1y 0wned treatment w0rk5 (P07W5). Re5. J. 1Vat. P011ut. C0ntr01 Fed. 63, 104-113. Crath0rne 8., D0na1d50n K., Jame5 H. A. and R09er5 H. R. 7he determ1nat10n 0f 0r9an1c c0ntam1nant5 1n UK 5ewa9e 51ud9e5. 1n 0r9an1c C0ntam1nant51n Wa5te Water, 51ud9e and 5ed1ment. 0ccurrence, Fate and D15p05a1 (Ed1ted 6y Qua9he6eur D., 7emmerman 1. and An9e1ett16.), pp. 45~55. E15ev1er App1. 5c1., L0nd0n. D1pp1e A. (1985) P01ycyc11c ar0mat1c hydr0car60n5: an 1ntr0duct10n. 1n P01ycyc11c Ar0mat1c Hydr0car60n5 and Carc1n09ene515 (Ed1ted 6y Harvey R. 6.), pp. 1-17, Am. Chem. 50c., Wa5h1n9t0n, D.C. 619er W., Eur1p1de5 5. and 5chaffner Ch. (1981) Per515tent 0r9an1c chem1ca15 1n 5ewa9e eff1uent5: 1.1dent1f1cat10n0f n0ny1phen015and n0ny1phen01eth0xy1ate56y 91a55cap111ary 9a5 chr0mat09raphy/ma55 5pectr0metry. Chem05phere 10, 1253-1263. Jame5 H. A., 61650n 7. M. and M00re K. (1986) 0r9an1c m1cr0p011utant5 1n c0ntam1nated and c0ntam1nated 9r0undwater5. 1n 8ehav10ur and 7ran5f0rmat10n 0 f 0r9an1c P011utant5 1n 6r0undwater 7reatment, Pr0c. W0rk5h0p w1th1nthe framew0rk 0f W0rk1n9 Part1e5 3 and 4 0f the C0ncerned Act10n ••0r9an1c M1cr0p011utant5 1n