water research 47 (2013) 1317e1328 Available online at www.sciencedirect.

com SciVerse ScienceDirect

journal homepa e! www.elsevier.com"locate"watres Partitioning of polycyclic aromatic hydrocarbons, alkylphenols, bisphenol A and phthalates in landfill leachates and stormwater Yuliya Kalmykova a'*, Karin Bjorklund h, Ann-Margret Stromvalla, Lena Blomc a Department of ivil and !nvironmental !ngineering, Chalmers "niver#ity of $e%&nology, 412 96 'ot&en(urg, S)eden b Department of ivil !ngineering, $&e "niver#ity of British Col mbia, 62!" Applied #cience $ane, %anco &er, B'C', anada %6( 1)4 c *ater and +ecycling ,ffice of 'ot&en(urg ity, 4"4 24 -othenb rg, #weden a r t i c l e info Article history. +ecei&ed 12 / ly 2"12 +ecei&ed in re&ised form 26 0o&ember 2"12 Accepted 21 0o&ember 2"12 A&ailable online 2" 2ecember 2"12 3eywords. ,rganic poll tants 4ydrophobic 2issol&ed Colloid 2issol&ed organic carbon #tormwater $andfill leachate abstract Partitioning of organic poll tants is essential to their fate, mobility and remo&al from water and soil' (o st dy the partitioning beha&ior of selected alkylphenols, bisphenol A, phtha5lates and polycyclic aromatic hydrocarbons 6PA4s7, a method for separating the tr ly dissol&ed and colloidal phase of organic poll tants was de&eloped, &erified and applied to samples of landfill leachate and stormwater from rban areas and waste5sorting sites' Alkylphenols,bisphenolA,phthalatesandPA4sweredetectedinallthe ntreatedsamples 6total concentrations7, most of the filtered samples and fre8 ently in the colloid5bo nd phase' Concentrations of alkylphenols and PA4s in rban stormwater were one order of magnit de lower than in the landfill leachates and stormwater from waste5sorting sites' (he difference between total, dissol&ed and colloid5bo nd concentrations in the water samples was not statistically significant for any phenols or phthalates, b t for three of the PA4s9 naphthalene 6mostly dissol&ed7, phenanthrene and fl oranthene 6mostly partic 5 late7' (hese res lts indicate that in landfill leachates and stormwaters, organic poll tants are predominantly attached to colloids and:or tr ly dissol&ed in contrast to their e;pected strong sorption to partic late matter' ,cc rrence and concentrations of poll tants in dissol&ed and colloid5bo nd phases correlated negati&ely with the 3 ' 4owe&er, e&en highly hydrophobic compo nds were fre8 ently detected in filtered samples, i'e' the dis5 sol&ed phases, and it is s ggested that the organic content in the colloids decreases the compo nds< partition to particles' (he res lts confirm that the 3 &al es of specific organic poll tants well describe the compo nds partition5binding process to dissol&ed organic carbon 62,C7 colloids' , r findings call for a re5assessment of the organic poll tants< mobility and associated risks' (his knowledge can also ser&e as a base for selecting efficient treatment methods for stormwater and landfill leachates'
,* ,*

# 2"12 =lse&ier $td' All

rights reser&ed'

1'

>ntrod ction

>n this st dy, partitioning of selected alkylphenols, bisphenol A, phthalates and polycyclic aromatic hydrocarbons 6PA4s7 in

landfill leachate and stormwater is in&estigated' (he s bstances ha&e been selected based on their e;pected occ rrence in rban water streams and potential negati&e effects on a8 atic en&ironments' Alkylphenols e incl ding 45

? Corresponding a thor' (el'. $466"7@1AA22162' =5 mail address. y liyaBchalmers'se 6C' 3almyko&a7' ""4@51@!4:D e see front matter # 2"12 =lse&ier $td' All rights reser&ed' http.::d;'doi'org:1"'1"16:E'watres'2"12'11'"!4

1@11 water resear ch 47 (2013) 1317e 1328 n o n y l p h e n o l 6 4 5 0 P 7, 4 5 t5 o ct y l p h e n o l 6 4 5 t5 , P 7 a n d 4 5 t5 b t y l5 p h e n o l 6 4 5 t5 B P 7 e b is p h e n o l A 6 B P A 7, p h t h al at e s a n d P A 4 s h a & e p r e & i o sl y b e

en reported in wastewater, rban snow, r noff and landfill leachate 6BEoFrkl nd et al', 2""9, 2"119 #a GncheH5A&ila et al', 2""99 #lack et al', 2""!9 )gheib et al', 2"117' (he s bstances< bi8 ito s occ rrence in rban water streams is a reflection of their widespread se and prod ction in society' (he PA4s are emitted from comb stion and petrole m so rces whereas the phenols and phthalates are emitted mainly from cons mer prod cts and b ilding materials 60eilson, 19919 BEoFrkl nd, 2"1"7' As se&eral of the selected PA4s, phenols and phthalates show ac te to;ic, carcinogenic and estrogenic effects on a8 atic organisms, their occ rrence in leachate and stormwater may pose a threat to recei&ing water 8 ality

6=CB, 2"1"9 0eilson, 19919 #er&os, 19999 #taples et al', 199Aa7' As many organic compo nds are hydrophobic by definition, it is often ass med that they can be remo&ed from the water phase thro gh remo&al of particles' >n addition to the a8 eo s and partic late phase, organic poll tants may also adsorb to colloids, sometimes referred to as Ithe third phaseJ' #t dies ha&e shown that organic compo nds may adhere to organic colloids in marine waters, gro ndwater and soil 6Chin and -schwend, 19929 3an and (omson, 199"9 #himiH et al', 19919 %illholth, 19997' $ee and 3 o 619997 ha&e for synthetic sol tions analytically 8 antified the effect of dissol&ed organic carbon 62,C7 presence on the decreased partitioning of organic poll tants to

t h e s o li d p h a s e' A s a n e ; a m p le , f o r a 2 , C c o n c e n tr at i o n o f 2 ! m g : $ , t h e r el at i & e d e c r

e a s e i n t h e p a rt it i o n o f o r g a n ic p o ll ta n ts t o p a rt ic la te s w a s a s h i g h a s @ " " K f o r a c o m

po nd with log 3,* % 6 6$ee and 3 o, 19997' 3nowledge on partitioning of organic poll tants in rban waters will assist in estimation of their mobility, to;icity and associated risks 62itoro et al', 19917' (he bioa&ailability of organic poll tants has been shown to depend on their form9 the fraction binding to 2,C tends to show lower bioa&ail5 ability to a8 atic animals than the tr ly dissol&ed fraction 64aitHer et al', 19917' ,n the other hand, 2,C colloids may act asa carrier for organic poll tants and enhance their transport, i'e' colloid5 facilitated transport, in gro ndwater, soil and other poro s media 6/aradat et al', 2""97' Beca se colloid5bo nd poll tants ac8 ire different charge, siHe and stoichi5 ometry compared to tr ly dissol&ed compo nds

they may tra&el thro gh particle and adsorption filters 6#himiH et al', 19919 Lorstner et al', 2""19 3almyko&a et al', 2"1"7' (h s, treatment methods for landfill leachates and stormwater need to be selected based on knowledge of organic poll tants partitioning' (he importance of in&estigating the partitioning of organic poll tants between the tr ly dissol&ed, colloidal and partic late phases has also been stressed in a re&iew on s rface water 8 ality monitoring programs by %ignati et al' 62""97' *astewater s s ch as stormwater and landfill leachate are different regarding the origin and acc m lation of organic poll tants, and the specific chemical and physical composition of the waters' (he poll tant content of

la n d fi ll le a c h at e s r e fl e ct s t h e h is t o ri c al s e o f c h e m ic al s i n t h e s o ci et y, w h e r e a s st o r m w at

e r is a si n k f o r c h e m ic al s c rr e n tl y i n s e' # t o r m 5 w at e r c o m p o si ti o n & a ri e s w it h st o r m e & e

nt and catchment

area 6BEoFrkl nd et al', 2""97, and landfill leachates &ary in composition depending on the type of waste, year of deposition, and the age of the landfill 63Eeldsen et al', 2""27' Anaerobic conditions, which may be e;pectedin landfills, ha&e been shown to pre&ent or retard the degradation of phthalates 6C an et al', 2""29 #taples et al', 199Ab7' 4owe&er, st dies by both 3Eeldsen et al' 62""27 and Ba n et al' 62""47 s ggest that degradation of phthalates in landfills or leachates may occ r' Alkylphenolic compo nds may degrade nder both aerobic and anaerobic conditions 6>sobe et al', 2""19 Changetal', 2""47' Alkylphenol etho;ylate degradation was ass med to ha&e taken place in a 2anish landfill, where Ba n et al' 62""47 co ld not detect any nonylphenol etho;ylate

is o m e rs b t o n l y t h e d e g r a d at i o n p r o d ct n o n y l p h e n o l et h o ; y c a r b o ; y la te ' A n g el i d

a k i et al ' 6 2 " " " 7 s h o w e d t h at P A 4 s w e r e b i o d e g r a d e d n d e r b o t h a e r o b ic a n d a n a e r

obic conditions in landfilled sewage sl dge' Anaerobic degradation of PA4s is, howe&er, in most cases slower than aerobic degradation 6=riksson et al', 2""@7' (he aim of this st dy is to in&estigate the partitioning of selected alkylphenols, bisphenol A, phthalates and PA4s in landfill leachate and stormwater samples' (he obEecti&es are to. i7 determine concentrations of poll tants in the total, dissol&ed and colloidal fractions9 ii7 in&estigate whether occ rrence in different fractions can be e;plained by the poll tants< physico5 chemical properties and:or by certain properties of the in&estigated waters' (he hypotheses are that. i7 the PA4s, 450P, 45t5,P and the high molec lar weight 64M*7 phthalates are

adsorbed to particles in the a8 atic en&ironment 6Cing et al', 2""@9 Co sins et al', 2""@9 Mackay and Callcott, 199179 ii7 the &C6 phthalates, the alkylphenol eth;oylates, BPA, 45t5BP and 45t5 pentylphenol 645t5PP7 are fo nd partly dissol&ed in water d e to their higher water sol bility and iii7 organic compo nds may show higher than e;pected water sol 5 bility in landfill leachates and stormwater d e to the presence of 2,C' 2' =;perimental 2'1' #ampling $eachate samples were collected at fo r landfills in the -othenb rg region, #weden' (he Br daremosse n landfill was in se 19@6e19A6 and contains a mi;t re of ho sehold and ind strial waste with a

h i g h o r g a n ic c o n te n t' A t t h is si te f o r s a m p le s w e r e c o ll e ct e d . B + 1 e r a w le a c h at e, B + 2 e le

a c h at e a ft e r o il s e p a r at o r, B + @ e le a c h at e a ft e r o il s e p a r at o r a n d s e d i m e n ta ti o n p o n d , a

nd B+4 e a separate ntreated raw leachateflow' Atthe #oFrmossenlan dfill,in se 19@1e19A1 with mainly high organic content ind strial waste, a raw leachate sample 6#+7 was collected' ,ne sample 6L$7 of raw leachate was collected from the most recently constr cted LlaFskebo landfill 62""@7,

containing ind strial waste and contaminated soil with an organic content below !K' (he (agene landfill has been in se since 19A4 and contains resid es from m nicipal solid waste incineration 6raw leachate sample (A17' >n one section of the landfill, sewage sl dge was deposited ntil the 191"s 6raw leachate sample (A27'

water research 47 (2013) 1317e1328 2'2'

1@19 # t o r m w at e r w a s c o ll e ct e d at 4 o g s b o a n d # k r a p p e k a rr w a st e 5 s o rt i n g si te s 6 4 B a n d # 3 7, w h ic h h a n d le p r e d o m i n a n tl y i n d st ri al a n d b l k y w a st e' ( h e w a st e is le ft n c o & e r e

d, sometimes for e;tended periods, before being sorted and transported to a final destination' #tormwater was also collected from rban areas. sewers draining a motorway with an ann al a&erage daily traffic of N1! """ &ehicles at -arda 6-17, and from the /arnbrott area with a maEor road, ho sing and small5 scale ind strial s rfaces 6/27' All waters were grab sampled and collected in dark sol&ent rinsed glass bottles, kept at +4 C and directly sent to the laboratory for chemical analysis' Lor all landfill leachates and stormwater st died in this proEect, data on other chemical parameters than organic poll tants are presented in # pplementar y (able #1' (hese data show that se&eral of the general meas red parameters, concentrations are in the same order for

all the different wastewaters' (he most important differences are that the landfill leachates contain m ch higher concentrations of main elements s ch as for e;ample Ca, Le and Mn, n trients and Cl' (he stormwater samples, on the other hand, show m ch

h i g h e r c o n c e n tr at i o n s o f t o ; ic tr a c e m et al s a s C d, C r, C , P b, 0 i a n d ) n' ( h e r e s lt i n ( a b le

# 1 al s o i n d ic at e t h at la n d fi ll le a c h at e s h a & e h i g h e r c o n c e n tr at i o n s o f t o ta l o r g a n ic c a r

bon 6(,C7, often correlated to high 2,C concentration, whereas the stormwater ha&e m ch higher concentrations of solid particles meas red as total s spended solids 6(##7' #eparati on of fraction s >ncl ded in the st dy are 16 specific PA4s, 45t5 octyl5 and 45 nonylphenol and their etho;ylates, three phenols and eight phthalates, see (ables 1 and 2 and # pplementar y (able #2' (he total, particle bo nd, colloid bo nd and

tr ly dissol&ed concentrations were determined for all compo nds, following a proced re modified and de&eloped from the determination of colloidally associated PA4s in water sing C11 solid5phase e;traction 6#P=7 disks 6Brown and Peake, 2""@7' (he determi5 nation of organic poll tants was performed in steps as follows. (otal concentratio ns were determined on nfiltered samples sing sol&ent li8 idO li8 id e;traction 6$$=7'

I I

(able 1 e AnalyHed phenol and phthalate 6mg:l7 total concentrations, n mber of samples 6n7 and samples with concentrations abo&e the detection limit 6Pd'l'7 in the c rrent st dy, compared with water 8 ality standards and res lts from screenings of r noff and landfill leachate' Compo nd (his st dya +ange n 6Pd'l 1@ 1@ 1@

45 0onylphenol monoetho;ylat 45tert5

45 0P 45t5

6median7 Q"'1OA'@ Q"'1O@'6 Q"'"1O1'@

standards g idelines AA:MAC "'@:2'":1 "'1:0A

,ctylphenol monoetho;yla 45tert5 45tert5 Bisphenol A 2imethyl 2iethyl 2i5n5b tyl B tyl benHy 2i5625 phthalate 2i5n5octyl 2iisononyl 2iisodecyl a All analy sis data for each speci fic samp le are a&ail able in (able #2 in the # ppl emen tary >nfor matio n' b =n&ir onme ntal 8 alit y stand ards in the field of water polic y 62""1 7 and *ater R ali ty - id elines for the Prote ction of A8 a tic $ife 6CC M=, 2"117 ' c AA. ann

al a&erage9 and MAC. ma;im m allowable concentration for inland s rface waters9 $(. freshwater, long term e;pos re' d 0onylphenol and its etho;ylates' e = 0o a&ailable standard or g ideline' f 0A = not applicable' g / nestedt et al' 62""@7 and BEorkl nd et al' 62""97' h n'a' = 0ot analyHed' i Cerne et al' 62""A7' E ,man and / nestedt 62""17' k ? = 0ot reported' i'e' the n mber of samples abo&e the d'l' was not reported' (he detection limit was 1 ng:l as indicated by the minim m &al es 6i'e' Q17'

6 m e d i a n 7 a All analysis data for each specific sample are a&ailable in (able #2 in the # pplementary >nformation' b =n&ironmental 8 ality standards in the field of water policy 62""17 and *ater R ality - idelines for the Protection of A8 atic $ife 6CCM=, 2"117' c AA. ann al a&erage9 and MAC. ma;im m allowable concentration for inland s rface waters9 $(. freshwater, long term e;pos re' d 0A = not applicable' e = 0o a&ailable standard or g ideline' f / nestedt et al' 62""@7' g BbL incl ded, BkL e;cl ded' 0aphthalene Q"'" se @ 47 1e"' n 7 (20 0AP !" e 1 6Q"' C 1 13) "'"2e@'1 6"'"!7 "17 4 6 131 11 C 6 7e1 116117 647 Q 7 "'1:" "' " 328 2'4:0A :1'1 '4:"' " ' 1 " Acenaphthylene "12 Ll o e @ (able the n 6Pd'l'7 d 2 e AnalyHed specific PA4 total concentrations 6mg:l7, n mber of samples 6n7 and samples with concentrations abo& the detection limit 6Pd'l'7 in the c rrent st dy, compared with water 8 ality standards and res lts from screenings of r noff and landfill leachate' ACC rene "' : L$S @ 0 Q"'"1e"'"9 Q"'" 1 A 6Q"'"17 1e1' 6" : 1 '" e 11 6@7 6"'" @7 B 17 1 e e 116A 16 n Acenaphthene 7 A7 H "'1:1 e o AC= :"'"4 B T Pyre e a Q"'"1e1'1 ne n U 6Q"'"17 PC+ H p Q"'" oT y 11 6!7 1e"' b, r 91 kU e e:e:!'1 6"'" fl n Ll oranthene !7 e 1161 or B L$ 7 a a e: e: nt P Q"'"1e1'! 6"'"27 "'"2 h Q ! e " 116A7 BenH n ' oTaUa e " "'1:1:@ nthra B 1 Phenanthrene cene b e BaA k " P4= Q"'" L ' 1e"' Q 2 Q"'"1e1'4 6"'117 @2 "' " 6"'" " 6 11 697 27 1 Q 11 e " e:e:"'4 667 "' ' Anthracene e: e: 4 " "'"1 1 1 A0( 1 6" 7 Chry '" 1 1@2" wat er rese arch a n d f i l l l e a c h a t es, #w ed enh +
d

1 n Q 6@7 " "'" !:" '1: "'" 1! Be nH oTg ,h,i Upe ryl en e BP C Q"' "1 e"' 12 6Q "'" 17 11 6@7 % "'" "2: 0 A: e ' 2'@' >nd en oT1 ,2, @5 cdU pyr en e >0 P Q"' "1 e"' "9 6Q "'" 17 11 2i be nH oTa ,hU ant hra ce

17 Q"'"1O"'"A 6Q"'"17 Q"'"@O "'"9 6Q"'"@7 Q"'"1O"'"@ 6Q"'"17 Q"'"1O "'"2 6Q"'"17

2 2 6 ? 7 i 2 " 6 ? 7 2 " 6 ? 7 2 " 6 ? 7 2 " 6 ? 7 2 " 6 ? 7

2 " 6 ? 7 2 " 6 ? 7 2 " 6 ? 7 2 " 6 ? 7 2 "

6 ? 7 2 " 6 ? 7 2 " 6 ? 7 2 " 6 ? 7 2 " 6 ? 7

V 2issol&ed concentratio ns, comprising tr ly dissol&ed and colloid5 bo nd organic poll tants, were determined on samples passed thro gh "'A | xm glass5 fiber filters, followed by $$=' V Particle5 bo nd concentratio ns were calc lated thro gh mass balances by s btracting dissol&ed concentratio ns from total concentratio ns'

V (r ly dissol&ed concentratio ns of PA4s and phthalates were determined sing the e;tract adsorbed onto C11 #P= disks 6pre5 filtered samples7 and the colloid5 bo nd concentratio ns were calc lated thro gh mass balances by s btracting tr ly dissol&ed concentratio ns meas red on the #P= disks from dissol&ed concentratio ns'

VL o r t h e p h e n o l i c c o m p o n d s t h e f i l t r a t e s p a s s i n g t h r o g h t h e C
1

# P = d i s k s 6 p r e 5 f i l t e r e d s a m p l e 7 w e r e m e a s r e d t o d e t e r 5 m i n e c

olloid5bo nd concentratio ns while the tr ly dissol&ed concentratio ns were calc lated thro gh mass balances 6s btracting colloid5 bo nd concentratio ns meas red on the #P=5 filtrates from dissol&ed concentratio ns7' (he proced re for the separation of the colloid5 bo nd fraction described abo&e has been &erified as follows. 1"" |xg 0Ps (echnical mi;t re was added to 1l of tap water, both with and witho t addition of 1"" mg 2,C as h mic colloids 6prepared according to Llorence, 19127, to ser&e as a model5 colloid phase' All filtrations, e;tractions and chemical analyses were

cond cted as described below' (he C11 material sed in the #P= disks in this st dy has already been &erified for separation of colloid5bo nd PA4s and other colloid5 bo nd hydrophobic organic compo nds in freshwater 6Brown and Peake, 2""@7' =;tracti on and chemica l analysis Lor the 8 ality ass rance, blank samples were e;tracted for all the proced res9 internal standards were sed and for phenolic compo nds also d plicate sampling, e;tractions and chemical analysis were carried o t' (he dissol&ed and colloid5 bo nd concentrations were determined for pre5filtered 6"'A mm glass fiber, -L:L *hatman7 samples' 2'@'1' PA4 and phthalates Lor the analysis of total and dissol&ed

c o n c e n tr at i o n s, s e p a 5 r at o r y f n n el $ $ = w a s p e rf o r m e d o n 1 " " " m l s a m p le s f o ll o w i n g

t h e S # = P A st a n d a r d iH e d m et h o d @ ! 1 " C w it h s o m e m o d if ic at i o n s' , n e m l o f a s rr o g at e s p i

king sol tion, corre5 spondingto2 mgpyrene5d1" 691 Atom K2, #igmaeAldric h7 and 1 mg benHyl benHoate 60=A(, # pelco7, was added to the original sample bottle and mi;ed thoro ghly' A mi;t re of 1.1 cyclohe;ane and

ethylacetate 6both 4iPer#ol& C4+,MA0, +M for 4P$C, %*+7 was sed for e;traction' (he e;tracts were concentrated by a rotary e&aporator to w1" ml' Lor determining the tr ly dissol&ed concentrations in pre5filtered

water research 47 (2013) 1317e1328

1@21 s a m p le s, o n e m l o f t h e s rr o g at e s p i k i n g s o l ti o n , w a s a d d e d t o t h e o ri g i n al s a m p le b o tt le s a n d m i ; e d t h o r o g h ly ' ( h e s a m p le s w e r e e ; tr a ct e d t h r o g h c o n d it i o n

ed C11 #P= disks 6@M =mpore7 following the proced re in the S# =PA standardiHed method @!@! with a few modifications, and the 1.1 cyclo5he;ane and ethylacetate mi;t re was sed as el tion sol&ent' All e;tracts 6both from $$= and #P=7 were dried by filtrations thro gh a col mn bed of anhydro s sodi m s lfate 699WK, ChemP r7, and red ced to 1'" ml by 02 and analyHed by -COM# following standardiHed proced res' 2'@'2' Phenolic compo nds (otal and dissol&ed, i'e' pre5filtered thro gh "'A X ;m glass fiber 6-L:L *hatman7, concentrations for phenolic compo nds were determined by an $$= proced re and -COM# standardiHed proced re at a commercial laboratory' Lor the analysis of colloid5bo nd compo nds, 1""" ml of pre5filtered

6"'A X;m glass fiber, -L:L *hatman7 samples were e;tracted at the Chalmers laboratory sing the C11 #P= disks and following the same proced re as described abo&e, b t no s rrogate sol tion was added in this step' (he remaining filtrates were collected and sent to the commercial laboratory, where the samples were acidified by concentrated 42#,4, internal standards added and the samples $$= three times with 1" ml dichlorometha ne' (he e;tracts were concentrated by rotary e&aporation followed by drying thro gh 0a2#,4, and e&aporation to 1'" ml by 02' (he e;tracts were analyHed by -COM# following a standardiHed proced re' >n se&eral of the samples, higher concentrations were detected in the filtered compared to total samples, and in the colloidal phase

c o m p a r e d t o t h e fi lt e r e d s a m p le s' ( h is m a y b e e ; p la i n e d b y t h e s e n si ti & it y o f t h e a n al y

ti c al m et h o d' ( h e le ss di rt y s a m pl e s, i' e' w h er e p ar ti cl e s h a & e b e e n re m o & e d, s h o w a lo w er m at ri ; ef fe ct

, which leads to higher method sensi5 ti&ity and lower concentrations can be detected' (he phenomena may also be e;plained by inhomogeneo s samples as it is diffic lt to achie&e e8 al distrib tion of organic compo nds when samples are portioned into three s bsamples before chemical analysis' 2'4' Calc lations of 32,C >n addition to sorption onto particles in water samples, the organic poll tants can also partition to the colloid5 siHed particles 6Q"'1 X;m7' (o get an nderstanding of how the organic poll tants are distrib ted in water samples, three5phase partition models can be established 6$i et al', 2""!9 =adie et al', 199", 19927' >n these models the organic compo nds are distrib ted among the partic late, colloid and

dissol&ed pha5 ses, and the distrib tion is controlled by partition to the organic carbon content of both particles and colloids' (he partition coefficients determined sing empirical data can be correlated to the contaminants octanol:water coefficient, 3,*, and the contaminants water sol bility' (he partition coefficient, 32,C, 8 antifies the ratio of 2,C5 bo nd concentrations of poll tants, C2,C, to the free dissol&ed concentration of the poll tant, C2, and has in this st dy been calc lated as. 32,C Y C2,CY2,CUC2 9 inmlYg2,C

@ ' + e s lt s a n d d is c s si o n @ ' 1 ' * % % u r r e n % e a n d c o n c e n tr at i o n s o f o r g a n ic p

o ll ta n ts i n t o ta l s a m p le s ( h e r e s lt s f o r e a c h s p e c if i c s a m p l e a r e p r e s e n t e d i

n # pplementar y (able #2' Among the phenols, BPA was detected at the highest total concentrations , followed by 45t5BP and 45 0P 6(able 17' (he detection fre8 ency 6d'f'7 of the phenols ranged between A! and 1""K 6BPA & 450P Y 45t5PP & 45t5 ,P & 45t5BP7' Among the alkylphenol etho;ylates, only ,P1=, was detected in a maEority of samples 6d'f' A!K7, whereas the other etho;ylates showed a d'f' of @@K or less' =tho;ylates other than ,P1=, were fo nd only in the fo r stormwater samples 64B, #3, -1, /27' 4owe&er, 0P1=,O 0P6=, may be more ab ndant than meas red in this st dy as the detection limit is 1"" ng:l, in contrast to 1" ng:l for other in&estigated phenols' As a comparison, a maEority of the detected concentrations of octylphenolic

compo nds fall nder 1"" ng:l' (he 2>0P showed the highest detected concentration among the phthalates, followed by 2=4P and 2=P 6(able 17' (he highest detection fre8 ency was fo nd for 2=4P ( 2BP ( BBP ( 2=P Y 2>0P ( 2n,P' (he 2=4P, 2>0P and 2>2P may potentially be present in other samples as they were meas red with a detection limit of 1'" X ;g:l, in contrast to "'1 X;g:l for the rest of the phthalates' 0aphthalen e 60AP7 showed the highest detection fre8 ency and concentrations among the PA4s, followed by fl orene 6L$7, phenanthrene 6P4=7, fl oranthene 6L$S7 and acenaphthene 6AC=7 6(able 27' (he low molec lar weight 6$M*7 PA4s 6M* Q 2""7 were detected at ma;im m concentrations one magnit de

h i g h e r t h a n t h e h e a & i e r P A 4 s 6 M * P 2 2 1 7, w it h t h e e ; c e p ti o n o f a c e n a p h t h y l e n e

6 A C C 7, w h i c h w a s f o n d a t c o n c e n tr a ti o n s c l o s e r t o t h e h e a & i e r P A 4 s 6 ( a b l e 2 7' 4

owe&er, the median concentrations of all analyHed PA4s were &ery similar and considerably lower than the ma;im m concentrations ' Phenanthrene 6P4=7 showed the highest median concentration at "'11 X;g:l and se&en of the 1! PA4s showed a d'f' of less than !"K 6(able 27' (he median alkylphenol and phthalate concentrations meas red in this st dy are similar to concentrations reported for landfill leachates and stormwater in #weden 6(able 17' ,n the contrary, the #wedish screenings of r noff from waste5sorting s rfaces 6(able 27 show p to one order of magnit de higher median concentrations for P4=, L$S, PC+, BaA, C4C, BbkL and BaP and m ch higher detection fre8 encies for all the high molec lar

weight 64M*7 PA4s 6/ nestedt et al', 2""@7' Phenol concentrations reported for leachates from /apan are lower than le&els fo nd in this st dy. "'"!O"'"A X ;g:l for 450P and "'"4O "'@1 Xig:l for 45t5,P 6Asak ra et al', 2""479 Q"'""@O "'"14 6E'g:l 6median Q"'""@7 for 45 t5PP and Q"'""@O64 X ;g:l 6median "'1@! Xig:l7 for 45t5BP 63 rata et al', 2""17' (he detected concentrations of BPA in the c rrent st dy are lower or in the same magnit de as concentrations reported e'g' by 3 rata et al' 62""17 from @1 landfills in /apan 6"'""9 O@6"" ng:l, median 1'A X ;g:l7 and Camamoto et al' 62""17 from ten sites in /apan 61'@ O1A,2"" X ;g:l, median 269 ng:l7' #imilar to this st dy, Asak ra et al' 62""47 detected higher

1@22 water resear ch 47 (2013) 1317e 1328 c o n c e n tr at i o n s o f 2 = 4 P 6 9 ' 6 e 4 9 m g :l 7 t h a n o t h e r i n & e st i g at e d p h t h al at e s 6 B B P " ' A e A ' 1 m g :l 9 2 B P @ e 1 ! m g :l 9 2 = P 1 e 1 ' 4 m g :l 7 i n la n d fi ll le a c h at

es from /apan' >n landfill leachates 6n % A7 from Port gal, 4erbert et al' 62""67 fo nd 0AP, AC= and L$ le&els that were p to 16, 46 and 14 times higher, respecti&ely, than corresponding concentrations in this st dy' >n contrast, concentrations of PA4s in leachate from operating Linnish landfills 6n % 1"7, reported by Marttinen et al' 62""@7, were generally lower than concentration fo nd in the c rrent st dy and no PA4s were detected in leachate from closed landfills' >tis belie&ed that less hydrophobic s bstances tendtoel te easily from the landfill material and rapidly mo&e into the leachate compared to more hydrophobic s bstances 6Asak ra et al', 2""47' 4owe&er, no correlation between the phenol and phthalate occ rrence or concentrations in total samples and

the compo nds< hydrophobicit y 6log 3,*7 was fo nd in this st dy' (herefore, other factors, s ch as occ rrence of the compo nds in the landfilled material and on rban s rfaces, transport processes and their degradation patterns are likely to be more important' >n contrast, occ rrence and concen5 trations of PA4s followed the s bstances< water sol bility and log 3,* reasonably well 6d'f' 0AP Tlog 3,* % @'@U ( L$ Tlog 3,* % 4'2U ( P4= Tlog 3,* % 4'!U ( L$S Tlog 3,* % 4'9U ( AC= Tlog 3,* % 4'"U7' Ba er et al' 619917 fo nd that the presence of organic macromolec l es in leachate may enhance the migration of hydrophobic s bstances s ch as many 4M* phthalates and PA4s' (he moderately hydrophobic

4 5 t5 , P a n d t h e m o r e h y d r o p h il ic B P A w e r e p o si ti & el y c o rr el at e d t o t o ta l o r g a n ic c a r b o n

6 ( , C 7 le & el s, w h ic h m a y b e a n i n d ic at i o n o f t h ei r a d h e r e n c e t o ( , C 6 # p e a r m a n <s r % "' 6

9 and "'6@, respecti&ely, significant at the "'"! le&el7' #imilarly, Srase and Miyashita 62""@7 also obser&ed a slight positi&e correlation between BPA and (,C leachate concentrations ' 0o correlation to (,C was fo nd for other compo nds9 also monitoring of storm5water 8 ality in #weden showed no correlation between phthalates and alkylphenols and (,C or 2,C 6BEoFrkl nd et al', 2""97' (hese res lts s ggest that (,C cannot be sed as predictors of le&els of phthalate, PA4 and most phenols in landfill leachates and stormwater' According to a fate modelling performed by #ato et al' 62"117, the fate of PA4s in landfills is dominated by the presence of organic carbon' (he 4M* PA4s attach strongly to organic carbon and

will therefore ha&e a long residence time in the landfill' , r res lts confirm this hypothesis as both the detection fre8 ency and the concentrations of the 4M* PA4s was m ch lower than those for the $M* PA4s, s ggesting that the former are adsorbed to the organic material in the landfills' %olatile PA4s, s ch as 0AP, may e&aporate from the landfill material and, beca se of lower hydrophobicit y, are more likely to be el ted with leachate' (his ass mption was confirmed in this st dy, as 0AP was the only PA4 that was detected in all the samples' (he highest phenol concentrations were generally fo nd in (A2, leachate from landfilled sewage sl dge, and in B+1, the old landfill with mi;ed waste' Both sites were in operation 194"e191"' Ab ndance of phenols in

b o t h s o li d w a st e a n d w a st e w at e r sl d g e fr o m t h is p e ri o d il l st r at e s t h ei r w i d e s p r e a d s

e b e f o r e le g al r e st ri ct i o n s i n t h e 1 9 9 " s 6 e' g ' + e g l a ti o n s A 9 @ : 9 @ , 6 1 9 : 2 " " 1 a n d 2 ir

ecti&e 2""@:!@:=-7' (he so rce of

phenolic compo nds in B+1 and (A2 is most likely cons mer prod cts' (his ass mption is confirmed by the fact that leachate from an ind strial landfill 6#+7 operated d ring the same period contains considerably less phenols' Concentra5 tions of phenols in leachate from the ash landfill 6(A17 were low as the organic content of the waste has been comb sted and only smaller amo nts of sl dge are sed to stabiliHe the ash' >n L$, the newer ind strial landfill, phenol concentrations were below or close to the detection limit, therefore no partitioning analysis of this sample was performed' (he obser&ed detection fre8 encies and concentrations may also be a res lt of phenol degradation patterns' (he anaerobic conditions of co&ered landfills are

a s s m e d t o sl o w d o w n o r p r e & e n t t h e d e g r a d at i o n o f B P A 6 C a n et al ', 2 " " 2 9 = C B , 2 " 1

" 7, w h ic h m a y e ; p la i n t h e h i g h B P A c o n c e n tr at i o n s i n B + 1 a n d ( A 2, a s b o t h la n d fi ll s w e r

e co&ered in the 191"s' Biodegradatio n may e;plain the low occ rrence of especially longer etho;ylates 60P4e6=,s7 in landfill leachates in the c rrent st dy, as was seen in the st dy of Ba n et al' 62""47' >n contrast, stormwater from the waste5sorting sites 64B and #37 is still e;posed to materials possibly containing alkylphenol etho;ylates' Srban stormwater is constantly e;posed to emissions from &ehicles and rban s rfaces containing alkylphenol etho;ylates s ch as concrete and plastic materials, l bricants, tyre r bber and car care prod cts' 4ence, r noff samples are belie&ed to contain higher concentrations of alkylphenol etho;ylates than leachate samples, which was also the case in this st dy' >n rban r noff, obser&ed concentrations

of 2>0P 6A" and 21 mg:l7 were one magnit de higher than in the leachate samples 61'! and 2'1 mg:$7' (he opposite relationship was tr e for 2=4P, for which concentrations p to 2@ mg:l were fo nd in the leachate from an old landfill 6B+17, whereas meas red concentrations in rban stormwater were 2 e@ mg:l' (hese res lts &alidate the hypothesis that stormwater 8 ality reflects the recent se of chemicals whereas landfill leachate reflects the historical se' 4istorically, 2=4Pis one of the most e;tensi&ely sed phthalates worldwide' 4owe&er, following restrictions on the marketing and se of 2=4P 6e'g' 2irecti&es 2""@:@6:=C, 2""4:9@:=C and 2""!:14:=C7, the higher molec lar weight phthalates, incl ding for e;ample 2>0P

a n d 2 > 2 P, h a s i n c r e a si n g l y ta k e n o & e r t h e m a r k et ' S r b a n r n o ff h a s b e e n s h o w n t o b

e a n i m p o rt a n t si n k f o r p h t h al at e s, w h ic h a r e e m it te d fr o m P % C a p p li c at i o n s o n & e h ic le s, r

oofing and cladding materials, and sealants 6BEoFrkl nd, 2"1"7' At B+ landfill, all types of waste ha&e been deposited and it is likely that P%C is an important phthalate so rce at this site, as the maEor se of phthalates is as P%C plasticiHers 6=CP>, 2"1"7' (he high 2=4P le&els detected at B+1 s ggests that after more than @" years of possible degradation, 2=4P is still emitted at high le&els from this site' #imilarly, PA4s are still emitted at high le&els from this landfill, confirming their slow degradation process' PA4

le&els in other samples were considerably lower' Comb stion of organic materials, incl ding e'g' coal, petrole m prod cts, wood and waste prod cts, is the largest contrib tor to PA4s in the en&ironment 6Mostert et al', 2"1"7' >n the rban en&ironment, &ehicle e;ha sts, r bber tires and asphalt materials are probable emission so rces 60orin and #troFm&all, 2""47' (he PA4s may reach the landfill thro gh atmospheric deposition and &ia disposed material, s ch as

water research 47 (2013) 1317e1328

1@2@

Lig ' 1 e (h e mi ni m m and ma ;i m m, the low er, me dia n and pp er 8 a rtil e,

and possible o tliers of total, dissol&ed and colloid5bo nd concentrations of 450P, 45t5 ,P, 45t5BP, BPA, 2=P and 2=4P in landfill leachate and stormwater samples' (he n mber below the bo; denotes the detection fre8 ency, e;pressed as a percentage' tires, asphalt, sed oils and creosote treated wood' 0aphthalene, the most ab ndant PA4 in the c rrent st dy, is a significant component of creosote tar and reclaimed asphalt material' (he PA4s are fo nd as mi;t res of the different molec les,it is therefore diffic lttoident ify specific so rces of an identified PA4 pattern 6Mostert et al', 2"1"7' (ho gh, as a general r le, $M* PA4s are a res lt of low temperat re processes s ch as wood b rning, whereas high temperat re processes s ch as &ehicle emissions gi&e rise to 4M* PA4s' (his r le, howe&er, does not e;plain why high concentrations of 0AP are fo nd in the leachate samples' (he fact that 0AP is the most water sol ble PA4 is probably the go&erning factor for the obser&ed res lts' @'2' Compar ison with water 8 ality g idelin es

( h e = r o p e a n w at e r 8 al it y st a n d a r d s f o r B b k L a n d B P C $ > 0 P w e r e e ; c e e d e d i n al l s a m

p le s w h e r e t h e s b st a n c e s w e r e d et e ct e d 6 n % 6 a n d 4, r e s p e ct i & el y, s e e ( a b le 2 7' # i m il a rl

y, the Canadian water 8 ality g idelines were repeatedly e;ceeded for se&eral of the PA4s 6(able 27' (he infringements of the 8 ality standards imply that negati&e effects on a8 atic life from these anthropogenic stressors cannot be e;cl ded' (he st died landfill leachates are con&eyed to the sewage treatment plant, and the As seen in (able 1, detected le&els in the wastewater samples repeatedly e;ceeded the = ropean en&ironmental 8 ality standards for 2=4P 6n % 9 e;ceeding AA7, octylphenol 6n % 97 and nonylphenol 6n % !7 in s rface waters, and the Canadian freshwater 8 ality g ideline for 0P and its etho;ylates 6n % 47'

rban r noff is treated in sedimentation facilities prior to discharge into recei&ing waters' 4owe&er, the efficiency of the sedimentation facilities for the remo&al of st died poll tants is nknown and sho ld be in&estigated' (reatment by filtering is c rrently being installed at the waste5 sorting sites by the recommen5 dation of the a thors' @'@' 2istrib tio n between the total, dissol&ed and colloid5 bo nd phases Lor method &erification p rposes, the distrib tion of phenols between the total, dissol&ed and colloid5bo nd phases has

1@24 water resear ch 47 (2013) 1317e 1328

lower, median and pper 8 artile, and possible o tliers of total, dissol&ed and colloid5 bo nd concentrations of 0AP, P4=, L$S and BaP in landfill leachate and stormwater samples' (he n mber below the bo; denotes the detection fre8 ency, e;pressed as a percentage' been st died in spiked samples of tap water with and witho t addition of h mic colloids 62,C7' >n the total and filtered samples witho t 2,C addition, 44 and 1A |xg $(1 of 450P was detected, while no 450P was detected in the #P=5 and 24 |xg $Z1 450P was detected in the #P=5treated sample' +es lts for the #P=5treated samples confirmed that #P= disks remo&e tr ly dissol&ed compo nds while the colloid5bo nd compo nds are transported thro gh the disks' (he fact

Lig' 2 e (he minim m and ma;i m m, the

treated sample' >n the total and filtered samples with 2,C addition, AA and @2 |xg $(1 of 450P was detected

that a concentration twice as high was detected in the total sample with addition of 2,C as compared to

t h e s a m p le s w it h o t 2 , C a d d it i o n i n d ic at e s t h at 4 5 0 P b e c o m e s m o r e w at er 5 b o r n i n t h e

s a m p le s w it h 2 , C , a s 4 5 0 P a d h e r e s t o 2 , C i n st e a d o f t h e g la s s e 8 i p m e n t s rf a c e s' A

s the technical 0Ps standard was sed, not all the added 0Ps isomers were meas red' 4owe&er, 45t5 BP and 45t5PP were also detected and res lts were similar to those of 450P 6not presented7' @'@'1' Phenols (he concentrations of phenols in the dissol&ed and colloid5 bo nd fractions generally follow the order fo nd in total samples. 45t5BP ( BPA ( 45t5PP ( 45t5 ,P ( 450P 6Lig' 17' ,cc rrence in the dissol&ed and the colloidal phases generally decreased with increasing log 3,*, in contrast to total samples, where no correlation was fo nd to log3,*' (he least hydrophobic phenols, 45t5 BP and BPA, showed high detection fre8 encies in both the dissol&ed 61"" and 64K, respecti&ely7 and the colloidal phase 61""

and 1"K, respecti&ely7' Concen5 trations of the moderately sol ble 45t5PP and 45t5BP were mainly nchanged after filtration 6see # pplementar y (able #27, whereas the colloidal concentrations were lower

t h a n t o ta l a n d d is s o l & e d c o n c e n tr at i o n s 6 * il c o ; o n si g n e d r a n k te st , st at is ti c al l y si g n if

ic a n t at t h e "' " ! le & el 7' ( h e r e f o r e, m o st o f t h e 4 5 t5 P P a n d 4 5 t5 B P is li k el y t o b e p r e s e n t a s

tr ly dissol&ed while a smaller fraction is colloid5bo nd' 4owe&er, the difference in medians was not statistically significant for BPA between any of the fractions, which indicates that BPA is predominantly adsorbed to colloids 6as s ggested, 2,C7' Srase and Miyashita 62""@7 also fo nd that a maEor fraction of BPA in landfill leachates remained in the filtered samples' (he alkylphenol etho;ylates were infre8 ently detected in the dissol&ed and colloidal phase which s ggests them being mostly bo nd to particles P"'A mm9 no *ilco;on signed rank test was performed for these compo nds' (he least water sol ble of the in&estigated phenols, 45t5 ,P and 450P, showed only a slight decrease in median concentrations 6not statisti5

cally significant7 after filtration, b t were not detected in the colloidal phase' 2 e to their hydrophobic nat re, it is nlikely that 45t5,P and 45 0P are tr ly dissol&ed and therefore adsorbed to the #P=5disk material' >nstead, they may be adsorbed to the particles which are smaller than "'A mm b t larger than the #P=5disk pores 6"'""6 mm7 and are therefore sterically hindered and retained by the disk' @'@'2' Phthalates (he detection fre8 encies of phthalates in the dissol&ed fraction were generally lower than in the total samples, b t at similar le&els as in the colloid5bo nd fraction 6Lig' 17' (he median concentrations of 2=P, 2nBP, BBP and 2=4P decrease only slightly after filtration and #P=5 treatment' #tatistically significant

d if f e r e n c e s 6 * il c o ; o n si g n e d r a n k te st 7 b et w e e n t h e m e d ia n s i n d if f e r

e n t fr a ct i o n s w e r e n o t f o n d f o r a n y o f t h e p h t h al at e s 6 n o t s h o w n 7'

water research 47 (2013) 1317e1328

1@2!

(able @ e Partitio n coeffic ients to 2,C colloid s, log ) and ) , compar ed with the octanol :water partitio n coeffic ients, log ) , and water sol bili ty for selecte d phenoli c, phthali c and polycy clic aromat ic poll ta nts in landfill leachat es and stormw ater sample s' C L h sol bil press 3 m literat mg:l ml:g ' 4 h 6 !4 5 ' A
2,C

I I

2,C

,*

b 2,C

1 Bisp heno lA 6BP A7 1"5 "!5A m ^ y f Q .

m

!'@ x 1" @'4 4'! @2 x 1" 1'9 x 1"

@

' 2h i

! 9 "

6' ! x 1 "
2

4@1 'x 61"

@

' o @ 4' @ 2 2 x 1 " 2' 6 x 1 " O 1 9 x 1 "

@ @ @

2' ! @91 1" 1" !'9 1"

@ ! @

P 2'! x 2'! x A'A A4" x

2i 6 2 5 e t h y l h e ; y l7 p h t h a l a t e 6 2 = 4 P 7 1 1 A 5 1 1 5 A

L 9 ' 1 x 1 "
2

4 ' ! 4 ' 9 1 A x 1 "

@

1 9 x 1 "
@

O 2 " x 1 "
@

2 " 2 2' "

x 1" 6'A x 1" 4'9 !'" 1"" x 1" 94 x 1" O 99 x 1"

1 4 @ @ @

s o l b il it y 9 t h e h i g h e st d et e ct i o n fr e 8 e n ci e s w e r e o b s e r & e d f o r t h e m o st s o l b le P A

a =CB 62""1, 2"1"7, Co sins et al' 62""@7 and 0eilson 619917' b Calc lated from the analysis data in this st dy, for original data see s pporting material' c $i et al' 62""!7, Brown and Peake 62""@7 and $ee and 3 o 619997' d 0o data a&ailable'

(he 4M* phthalates are highly hydrophobic and are e;5 pected to adsorb strongly toparticles, hence can be remo&ed by filtration and sedimentation' 4owe&er, despite its hydrophobic character 6log 3 % A'A7, 2=4P was detected in the dissol&ed and the #P=5 treated samples as fre8 ently as was 2=P 6Lig' 17' (he same trend was seen for BBP 6log 3 % 4'A, not shown7' (his indicates that the partition coefficient to the partic late organic content 3 in the water samples of 2=4P and BBP are decreased by components of the sample
,*

matri;, for e;ample 2,C as s ggested by $ee and 3 o 619997' #imilarly, )heng et al' 62""A7 showed that most of 2BP and 2=4P in landfill leachate were sol ble 6"'A mm7 and highly associated with 2,C' @'@'@' Polycyclic aromatic hydrocarbons (he detection fre8 encies of PA4s in the filtered samples were similar to the total samples, slightly lower in the colloid5 bo nd fraction and correlated well with the PA4 water

4 s 6 L i g' 2 7' ( h e h e a & ie st P A 4 s e B a P, 2 B A , B P C a n d > 0 2 e w e r e d et e ct e d i n le s s t h a n 2 A K

,*

,C

of the filtered samples and in the colloid5 bo nd phase' Contrary to what can be e;pected from the high log 3 &al es, no statistically significant difference 6*ilco;on signed rank test7 in concentrations between phases was fo nd for the 4M* BaP 6log 3 6'17' (his s ggests that the partition to the organic content in particles 63 7 is decreased by the presence of 2,C' Lor the most water sol ble PA4,
,* ,*
,C

0AP, total and dissol&ed concentrations were not significantly different, while the colloid5bo nd concentrations were lower 6statistically significant at the "'"! le&el7 than the total concentrations ' (his s ggests a presence of a significant fraction of tr ly dissol&ed 0AP' Lor P4=, both the dissol&ed and the colloid5 bo nd concentrations were lower 6statistically significant at the "'"! le&el7 than the total concentrations , which indicates it

1@26 water resear ch 47 (2013) 1317e 1328 g 7 a n d l o g )

,*

tants in contaminated water 6landfill leachates and stormwater7, compared with data from determination of PA4s sorption on colloids in spiked fresh water'

L i g' @ e $ i n e a r r e g r e s si o n a n al y si s o f l o g )
2, C

6 m l:

f o r s el e ct e d p h e n o li c, p o l y c y cl ic a r o m at ic a n d p h t h al ic p o ll

being predominantly bo nd to particles' 0o *ilco;on signed rank test was performed for the remaining PA4s d e to low detection fre8 encies' @'@'4' >mportance of particles, 2,C and 3,* for the partitionin g of the organic poll tants (he hypothesis i7 that the PA4s, 450P, 45t5,P and the 4M* phthalates are adsorbedto particles, was in part confirmed for selected samples and only for P4= for all the samples' Partic late concentrations of 4M* PA4s, 2=4P and 2n,P were higher than dissol&ed concentrations for B+1 and

B+2' >n stormwater samples, 450P and nonylphenol etho;ylates< partic late concentrations were higher than dissol&ed concentrations ' (he ab ndance of organic poll tants, incl ding those of high hydrophobicit y, in the dissol&ed and colloid5bo nd fractions has confirmed the hypothesis of increased sol bility of organic compo nds in presence of colloids, s ch as2,C' >ndeed, the dissol&ed and colloid5bo nd fractions were shown to be e8 ally or more important than the partic late fraction for organic poll tants partitioning in rban waters' >n s ch a way, the mobility of organic poll tants is increased, as ill strated by the e;ample of the samples B+1, B+2 and B+@ taken at different stages of leachate treatment 6oil separator and sedimentation pond7' (he fact that

c o n c e n tr at i o n s o f o r g a n ic p o ll ta n ts d o n o t d e c r e a s e si g n if i5 c a n tl y b et w e e n t h e tr e at m

e n t st e p s i m p li e s t h at s e d i m e n t a ti o n f a ci li ti e s c rr e n tl y b ei n g a p p li e d f o r tr e at m e n t o

f stormwater and landfill leachates are not effecti&e in remo&ing organic poll tants, hence different techni8 es ha&e to be de&eloped' As no correlation was fo nd for occ rrence and concen5 tration of alkylphenols and phthalates with 3,* in total samples, the composition of landfilled waste and rban so rces are likely to be the go&erning factors' Bisphenol A showed moderate correlation with the (,C concentration' >n

addition, degradation patterns co ld e;plain occ rrence of se&eral of alkylphenols and phthalates' >n contrast, occ rrence and concentrations of PA4 in total samples followed their water sol bility reasonably well' -enerally for most of compo nds, a moderate correlation of 5"'6" was fo nd for the filtered and colloid5bo nd phases 6#pearman rank test, significant at the "'"1 le&el, 25tailed test7' (his potentially enables prediction of poll tants transport based on their physico5 chemical properties' @'@'!' Correlations of 32,C and 3,* Binding of organic poll tants in sediments is primarily controlled by physico5 chemical properties like 3,* and the organic carbon content of sediments

6 2 it o r o et al ', 1 9 9 1 9 # h e a, 1 9 1 1 7' ( h e h y d r o p h o b ic p a rt it i o n is t h e d o m i n a n t b i n d i n g m

e c h a n is m t o o r g a n ic c a r b o n i n s e d i m e n ts 9 it is t h e r e f o r e o f i n te r e st t o e & al at e if t h e

same relation is &alid for organic contaminants binding to the organic carbon in colloids' (he determined log 32,C for selected phenols, phthalates and PA4s, calc lated from the analysis data of landfill leachates and stormwater, are presented in (able @ and plotted against log 3,* in Lig' @' (he res lts 6Lig' @7 show a linear relationship between log 32,C and log 3,* for the selected PA4s, phenolic and phthalic compo nds' 4ence, the s ggested binding process of these contaminants to the 2,C is partitioning' (he compo nds with the lowest water sol bility, e'g' 45t5BP and 2=P, showed the lowest correlation 6(able @7' 2epending on the higher polarity these compo nds may interact with colloids thro gh other mechanisms

than hydrophobic partition or sorption to organic macromolec l es' (he res lts confirm that the 3,* &al es for organic poll tants co ld be sed to describe the organic poll tants binding process to 2,C colloids' >n Lig' @, the res lts from this st dy are compared with res lts from a st dy of specific PA4s binding to h mic acid colloids in spiked freshwater samples 6Brown and Peake, 2""@79 the organic poll tants are to a higher degree sorbed to the 2,C colloids in the landfill leachates and stormwater' (his may be e;plained by comple; matri; effects of other poll tants< occ rrence in contaminated water as stormwater and landfill leachates, b t also of effects from the m ch higher &ariation in 2,C concentrations 62O2@" mg:l7 sed in o r st dy' (he

2 , C i n t h e la n d fi ll le a c h at e s a n d st o r m w at e r m a y al s o h a & e a d if f e r e n t c h e m ic al c o m p o si ti

o n, e' g' m o r e a s p h al t5 a n d p et r o le m 5 r el at e d c o m p o n d s, t h a n t h e h m ic a ci d a d d e d t o t h e

freshwater samples' 4' Concl sions Alkylphenols, Bisphenol A, phthalates and PA4s were detec5tedin all the ntreated and mostofthefilter ed samples' 45 tert5 Pentylphenol was only detected in leachate samples whereas 2>0P was fo nd only in rban stormwater' Concentration s of phenols and PA4s in

rban stormwater were one order of magnit de lower than in landfill leachates and stormwater from waste5 sorting sites' (he phthalate concentrations were fo nd to be in the same range for all types of waters apart from 2>0P, for which rban stormwater le&els were one order of magnit de higher than the rest of the samples' (he median

water research 47 (2013) 1317e1328

1@2A c o n c e n tr at i o n s f o r m o st o f t h e p o ll ta n ts , 4 5 t5 , P a n d , P 1 = , b ei n g t h e o n l y e ; c e p ti o n s, w e r e i n t h e s a m e r a n g e a s e a rl ie r r e p o rt e d c o n c e n tr at i o n s f o r s e w a g e i

n #weden' (he = ropean en&ironmental 8 ality standards for s rface water were repeatedly e;ceeded for octylphenol, nonylphenol, 2=4P, BbkL and BPC $ >02' 4owe&er, all the st died waters are treated either locally or at the sewage treatment plant before discharge into recei&ing waters' A method for separation of colloid5 bo nd organic poll tants has been de&eloped, &erified and applied to the samples' Most of the st died compo nds were fre8 ently detected in the dissol&ed 6Q"'A mm7 and the colloid5bo nd phase, their occ rrence generally decreasing with increasing log 3 ' A *ilco;on signed rank test was performed to e&al ate the hypothesis that there isa differenceinm edians between total, dissol&ed and colloid5bo nd
,*

concentrations ' Lor most tested compo nds, the total concentration is higher than the concentration in the dissol&ed samples and similarly dissol&ed ( colloidal' 4owe&er, the difference in concentrations between total and dissol&ed phase is not significant at the "'"! le&el for any phenols or phthalates, b t for three of the tested PA4s9 naphthalene 6mostly dissol&ed7, phenan5threne and fl oranthene 6mostly particle bo nd7' (hese res lts indicate that organic compo nds are predominantly tr ly dissol&ed and:or attached to particles Q"'A mm in landfill leachates and stormwater' >t is s ggested that 2,C decreases the apparent 3 of the compo nds' (he linear relationship between log 3 and log 3 for the selected phenolic,
,* 2,C ,*

P A 4 s a n d p h t h al ic c o m p o n d s c o n fi r m e d t h at t h e b i n d i n g p r o c e s s o f t h e s e c o n ta m i

n a n ts t o t h e 2 , C is p a rt it i o n i n g' A c k n o w le d g e m e n ts ( h is p r o Ee ct w a s fi n a n ci al l y

s pported by +eno&a AB and 3retsloppskon toret in -othenb rg and by Ale M nicipality' *e are gratef l to the anonymo s re&iewers for their &al able comments on the man script' Appendi; A' # pplementar y material # pplementar y material associated with this article can be fo nd, in the online &ersion, at http.::d;'doi'or g:1"'1"16:E' watres'2"12'1 1'"!4' references Angelidaki, >', Mogensen, A'#', Ahring, B'3', 2"""' 2egradation of organic contaminant s fo nd in organic waste' Biodegradat ion 11, @AAe@1@' Asak ra, 4', Mats to, (', (anaka, 0', 2""4' Beha&ior of endocrine5 disr pting chemicals in leachate from M#* landfill sites in /apan'

*aste Managemen t 24, 61@e622' Ba er, M'/', 4errmann, +', Martin, A', )ellmann, 4', 1991' Chemodyna mics, transport beha&io r and treatment of phthalic acid esters in m nicipal landfill leachates' *ater #cience and (echnology @1, 11!e192'

Ba n, A ', $ e d i n, A ', + ei tH el , $ ' A ', B Ee r g, P' $ ', C h ri st e n s e n, ( ' 4 ', 2 " " 4' [ e n o b i o ti c o r g a n ic c o m p o n d s i n le a

c h at e s fr o m te n 2 a n is h M # * la n d fi ll s e c h e m ic al a n al y si s a n d t o ; ic it y te st s' * at e r + e s e a r c h @ 1, @ 1 4 ! e @

1!1' BEoFrkl nd, 3', 2"1"' # bstance flow analyses of phthalates and nonylphenol s in stormwater' *ater #cience \ (echnology 62, 11!4e116" ' BEoFrkl nd, 3', Palm Co sins, A', #troFm&all, A'5M', Malm8&ist, P'5A', 2""9' Phthalates and nonylphenol s in rban r noff. occ rrence, distrib tion and area emission factors' #cience of the (otal =n&ironmen t 4"A, 466!e46A2 ' BEoFrkl nd, 3', #troF m&all, A'5 M', Malm8&ist, P'5A', 2"11' #creening of organic contaminant s in rban snow' *ater #cience \ (echnology 64, 2"6e21@' Brown, /'0', Peake, B'M', 2""@' 2eterminati on of colloidally5 associated polycyclic aromatic hydrocarbo ns 6PA4s7 in fresh water sing C11 solid phase e;traction disks'

Analytica Chimica Acta 416, 1!9e169' CCM=, 2"11' >n. 6CCM=7, C'C'o'M'o't'=' 6=d'7, Canadian =n&ironmen tal R ality - idelines # mmary (able. *ater R ality - idelines for the Protection of A8 atic $ife' Canadian Co ncil of Ministers of the =n&ironmen t 6CCM=7' Cerne, ,', Allard, A'5 #', =k, M', / nestedt, C', #&enson, A', 2""A' St&aFrderin g a& behandlings metoder foFr lak&atten fra]n deponier. 3emisk karaktaFrise ring a& lak&atten foFre och efter olika behandlings steg pa] ett antal s&enska deponier 6=&al ation of (reatment Methods LoFr $andfill $eachates. Chemical Charaterisat ion of $eachate Before and After 2ifferent (reatment #teps at a 0 mber of #wedish $andfills7'

> % $ # w e d is h = n & ir o n m e n ta l + e s e a r c h > n st it C te ' h a n g , B ' % ' , C , C ' 4 ' , C a n , # ' C ' , 2 "

" 4 ' 2 e g r a d a t i o n o f n o n y l p h e n o l b y a n a e r o b i c m i c r o o r g a n i s m s f r o m r i & e r s e

diment' Chemos phere !!, 49@e!" "' Chin, C'P', -schwend, P'M', 1992' Partitioning of polycyclic aromatic hydrocarbo ns to marine porewater organic colloids' =n&ironmen tal #cience \ (echnology 26, 1621e1626 ' Co sins, >'(', Mackay, 2', Parkerton, ('L', 2""@' Physicalec hemical properties and e&al ati&e fate modelling of phthalate esters' >n. #taples, C'A' 6=d'7, (he 4andbook of =n&ironmen tal Chemistry. Phthalate =sters' #pringer, Berlin, pp' !Ae14' 2itoro, 2'M', )arba, C'#', 4ansen, 2'/', Berry, *'/', #wartH, +'C', Cowan, C'=', Pa&lo , #'P', Allen, 4'=', (homas, 0'A', Pa8 in, P'+', 1991' (echnical basis for establishing sediment 8 ality criteria for nonionic

organic5 chemicals sing e8 ilibri m partitioning' =n&ironmen tal (o;icology and Chemistry 1", 1!41e1!1@ ' =adie, B'/', Morehead, 0'+', $andr m, P'L', 199"' @5Phase partitioning of hydrophobi c organic5 compo nds in -reat5 $akes waters' Chemosphe re 2" 61e27, 161e1A1' =adie, B'/', Morehead, 0'+', %alkl mp, /', $andr m, P'L', 1992' 2istrib tion of hydrophobi c organic5 compo nds between dissol&ed and partic late organic5 matter in -reen Bay waters' /o rnal of -reat $akes +esearch 11 617, 91e9A' =CB, 2""1' +isk assessment report. bis625 ethylhe;yl7 phthalate 62=4P7, >n. = ropean Chemicals B rea , 6=d'7, = ropean Snion +isk Assessment +eport' ,ffice for ,fficial

P b li c at i o n s o f t h e = r o p e a n C o m m n it ie s, $ ; e m b o r g' =C B , 2 " 1 "' S p d at e d ri s k a s s e s s m e n t r e p o

rt . 4, 4 5 is o p r o p y li d e n e d i p h e n o l 6 b is p h e n o l5 A 7' > n . =
"

r o p e a n C h e m ic al s B r e a 6 = d' 7, = r o p e a n

Snion +isk Assessment +eport' ,ffice for ,fficial P blications of the = ropean Comm nitie s, $ ;embo r g, p' 69!' =CP>, 2"1"' Plasticisers >nformation Centre. Commodity Phthalate =sters' >n. = ropean Co ncil for Plasticisers and

>ntermediat es 6=d'7, Br ssels, Belgi m' =riksson, M', #odersten, =', C , )', 2alhammar, -', Mohn, *'*', 2""@' 2egradation of polycyclic aromatic hydrocarbo ns at low temperat re nder aerobic and nitrate5 red cing conditions in

1@21 water resear ch 47 (2013) 1317e 1328

enrichment c lt res from northern soils' Applied and =n&ironmental Microbiology 69, 2A!e214' Llorence, ('M', 1912' (he speciation of trace5 elements in waters' (alanta 29, @4!e@64' Lorstner, S', /acobs, P', %on der 3ammer, L', 2""1' >mpact of nat ral nanophases on hea&y5 metal retention in Heolite5s pported reacti&e filtration facilities for rban r n5off treatment' Lreseni s /o rnal of Analytical Chemistry @A1, 6!2e6!9' 4aitHer, M', 4oFss, #', (ra nsp rger, *', #teinberg, C', 1991' =ffects of dissol&ed organic matter 62,M7 on the bioconcentration of organic chemicals in a8 atic organisms e a re&iew' Chemosphere @A, 1@@!e1@62' 4erbert, P', #il&a, A', /oa^o, M', #antos, $', Al&es, A', 2""6' 2etermination of semi5&olatile priority poll tants in landfill leachates and sediments sing microwa&e5assisted headspace solid5 phase microe;traction' Analytical and Bioanalytical Chemistry @16, @24e@@1' >sobe, (', 0ishiyama, 4', 0akashima, A', (akada, 4', 2""1' 2istrib tion and beha&ior of nonylphenol, octylphenol, and nonylphenol monoetho;ylate in (okyo Metropolitan area. their association with a8 atic particles and sedimentary distrib tions' =n&ironmental #cience \ (echnology @!, 1"41e1"49' /aradat, A'R', Lowler, 3', -rimberg, #'/', 4olsen, ('M', 2""9' (ransport of colloids and associated hydrophobic organic chemicals thro gh a nat ral media filter' /o rnal of =n&ironmental =ngineering 1@!, @6e4!' / nestedt, C', =k, M', #olyom, P', Palm, A', ,F dman, C', 2""@' 3araktaFrinsering a& tslaFpp. /aFmfoF relse a& olika tslaFpp till &atten 6Characterisation of =missions. Comparison of 2ifferent =missions to *ater7, p' 14@' >%$ #wedish =n&ironmental +esearch >nstit te' 3almyko&a, C', +a ch, #', #troFm&all, A'M', Morrison, -', #tolpe, B', 4assello&, M', 2"1"' Colloid5facilitated transport of metals in peat filters' *ater =n&ironment +esearch 12, !"6e!11' 3an, A'(', (omson, M'B', 199"' -ro nd water transport of hydrophobic organic compo nds in the presence of dissol&ed organic matter' =n&ironmental (o;icology and Chemistry 9, 2!@e26@' 3Eeldsen, P', BarlaH, M'A', +ooker, A'P', Ba n, A', $edin, A', Christensen, ('4', 2""2' Present and long5term composition of M#* landfill leachate. a re&iew' Critical +e&iews in =n&ironmental #cience and (echnology @2, 29Ae@@6' 3 rata, C', ,no, C', ,no, C', 2""1' ,cc rrence of phenols in leachates from m nicipal solid waste landfill sites in /apan' /o rnal of Material Cycles and *aste Management 1", 144e1!2' $ee, C'$', 3 o, $'/', 1999' R antification of the dissol&ed organic matter effect on the sorption of hydrophobic organic poll tant. application of an o&erall mechanistic sorption model' Chemosphere @1, 1"Ae121' $i , +'[', *ilding, A', 4ibberd, A', )ho , /'$', 2""!' Partition of endocrine5disr pting

chemicals between colloids and dissol&ed phase as determined by cross5flow ltrafiltration' =n&ironmental #cience \ (echnology @9 617, 2A!@e2A61' Mackay, 2', Callcott, 2', 1991' Partitioning and physical chemical properties of PA4s' >n. 0eilson, A'4' 6=d'7, (he 4andbook of =n&ironmental Chemistry' PA4s and +elated Compo nds. Chemistry' #pringer, Berlin, pp' @2!e@46' Marttinen, #'3', 3ett nen, +'4', +intala, /'A', 2""@' ,cc rrence and remo&al of organic poll tants in sewages and landfill leachates' #cience of the (otal =n&ironment @"1, 1e12' Mostert, M'M'+', Ayoko, -'A', 3okot, #', 2"1"' Application of chemometrics to analysis of soil poll tants' (rAC (rends in Analytical Chemistry 29, 4@"e44!'

0eilson, A'4', 1991' PA4s and +elated Compo nds, (he 4andbook of =n&ironmental Chemistry' #pringer %erlag, Berlin: 4eidelberg, -ermany' 0orin, M', #troFm&all, A'M', 2""4' $eaching of organic contaminants from storage of reclaimed asphalt pa&ement' =n&ironmental (echnology 2!, @2@e@4"' ,F man, C'B', / nestedt, C', 2""1' Chemical characteriHation of landfill leachates e 4"" parameters and compo nds' *aste Management 21, 11A6e1191' #aGncheH5 A&ila, /', Bonet, /', %elasco, -', $acorte, #', 2""9' 2etermination and occ rrence of phthalates, alkylphenols, bisphenol A, PB2=s, PCBs and PA4s in an ind strial sewage grid discharging to a m nicipal wastewater treatment plant' #cience of the (otal =n&ironment 4"A, 41!Ae416A' #ato, M', (oEo, C', Mats o, (akay ki, Mats to, (oshihiko, 2"11' >n&estigation of polycyclic aromatic hydrocarbon 6PA4s7 content in bottom ashes from some /apanese waste incinerators and simple estimation of their fate in landfill' # stainable =n&ironment +esearch 21, 219e22A' #er&os, M'+', 1999' +e&iew of the a8 atic to;icity, estrogenic responses and bioacc m lation of alkylphenols and alkylphenol polyetho;ylates' *ater R ality +esearch /o rnal of Canada @4, 12@e1AA' #hea, 2', 1911' 2e&eloping national sediment 8 ality criteria' =n&ironmental #cience \ (echnology 22, 12!6e1261' #himiH , C', #ogabe, 4', (erashima, C', 1991' (he effects of colloidal h mic s bstances on the mo&ement of non5ionic hydrophobic organic contaminants in gro ndwater' *ater #cience and (echnology @1, 1!9e16A' #lack, +'/', -ronow, /'+', %o l&o lis, 0', 2""!' 4o sehold haHardo s waste in m nicipal landfills. contaminants in leachate' #cience of the (otal =n&ironment @@A, 119e1@A' #taples, C'A', Adams, *'/', Parkerton, ('L', -ors ch, /'*', Biddinger, -'+', +einert, 3'4', 199Aa' A8 atic to;icity of eighteen phthalate esters' =n&ironmental (o;icology and Chemistry 16, 1A!e191' #taples, C'A', Peterson, 2'+', Parkerton, ('L', Adams, *'/', 199Ab' (he en&ironmental fate of phthalate esters. a literat re re&iew' Chemosphere @!, 66AeA49' Srase, (', Miyashita, 3', 2""@' Lactors affecting the concentration of bisphenol A in leachates from solid waste disposal sites and

its fate in treatment processes' /o rnal of Material Cycles and *aste Management !, ""AAe""12' %ignati, 2'A'$', %alsecchi, #', Polesello, #', Patrolecco, $', 2ominik, /', 2""9' Poll tant partitioning for monitoring s rface waters' (rAC (rends in Analytical Chemistry 21, 1!9e169' %illholth, 3'-', 1999' Colloid characteriHation and colloidal phase partitioning of polycyclic aromatic hydrocarbons in two creosote5contaminated a8 ifers in 2enmark' =n&ironmental #cience \ (echnology @@, 691e699' Camamoto, (', Cas hara, A', #hiraishi, 4', 0akas gi, ,', 2""1' Bisphenol A in haHardo s waste landfill leachates' Chemosphere 42, 41!e411' Cing, -'5-', 3ookana, +'#', 2illon, P', 2""@' #orption and degradation of selected fi&e endocrine disr pting chemicals in a8 ifer material' *ater +esearch @A, @A1!e@A91' C an, #'C', $i , C', $iao, C'#', Chang, B'%', 2""2' ,cc rrence and microbial degradation of phthalate esters in (aiwan ri&er sediments' Chemosphere 49, 129!e1299' )gheib, #', Moilleron, +', #aad, M', Chebbo, -', 2"11' Partition of poll tion between dissol&ed and partic late phases. what abo t emerging s bstances in rban stormwater catchments_ *ater +esearch 4!, 91@e92!' )heng, )', 4e, P'5/', #hao, $'5M', $ee, 2'5/', 2""A' Phthalic acid esters in dissol&ed fractions of landfill leachates' *ater +esearch 41, 4696e4A"2'