In si u calib a ion o a ube passi e sample in was ewa e
1
e luen wi h adjus able olume ic low o assessmen o
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mic o-pollu an s wi h luc ua ing concen a ions
3
Tobias Hensela, Jö g-Helge Heinb, Tho s en Reem smac, Alexande Spe licha,
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Regina Gni ßa, F ede ik Zie zschmanna*
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aBe line Wasse be iebe, Neue Jüdens aße 1, 10179 Be lin, Ge many
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bGCI GmbH, Bahnho s aße 19, 15711 Königs Wus e hausen, Ge many
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cHelmhol z-Cen e o En i onmen al Resea ch (UFZ), Depa men o Analy ical
8
Chemis y, Pe mose s asse 15, 04318 Leipzig, Ge many
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*[email p o ec ed]
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This documen is he unedi ed Au ho ’s e sion o a Submi ed Wo k ha was
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subsequen ly accep ed o publica ion in ES&T Wa e , copy igh © 2024 The Au ho s.
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Published by Ame ican Chemical Socie y a e pee e iew. To access he inal edi ed
13
and published wo k see h ps://doi.o g/10.1021/acses wa e .4c00348.
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15
Abs ac
16
We p esen a e sa ile low- h ough ube passi e sampling de ice (TPS), wi h
17
con ollable eed wa e olume ic low, ha can be calib a ed in si u agains he eed
18
wa e load o o ganic mic o-pollu an s (OMPs). This semi-passi e app oach has he
19
ad an age o a de e minable wa e load eeding he sampling de ice. The design o
20
he TPS allows o new sampling scena ios in closed piping while p o iding s able and
21
con olled sampling condi ions. The calib a ion e e encing an OMP’s eed wa e load
22
can desc ibe he up ake beha io om was ewa e ea men plan e luen wi h
23
po en ially highly luc ua ing OMP concen a ions. The TPS and i s load-dependen
24
calib a ion unde ealis ic en i onmen al condi ions p o es possible o a a ie y o
25
o ganic ace subs ances in a challenging ma ix. Nine o he 20 moni o ed
26
ep esen a i e OMPs could be calib a ed load-dependen ly, leading o a good
27
ag eemen be ween he calcula ed concen a ion om he TPS and he a e age
28
concen a ion o co esponding di ec measu emen s. Due o he simple measu ing
29
p inciple and he memb ane-less discs, many in luencing ac o s such as di usion,
30
u bulence and lag ime phenomena can be neglec ed. The TPS could suppo he
31
exis ing online measu emen analy ics in a (p ocess-) wa e ea men plan by
32
deli e ing in eg a ed wa e concen a ions o discha ge moni o ing.
33
Keywo ds
34
passi e sampling, load dependen calib a ion, was ewa e , o ganic con aminan s,
35
luc ua ing concen a ions, o ganic mic o-pollu an s, low- h ough.
36
Synopsis
37
The s udy in oduces a e sa ile ube passi e sampling de ice ha allows con olled
38
low and in si u calib a ion o moni o ing o ganic mic o-pollu an s in was ewa e ,
39
demons a ing e ec i e load-dependen calib a ion unde luc ua ing condi ions.
40
Con ibu ion
41
T. Hensel: me hodology, in es iga ion, so wa e and w i ing o iginal d a , J.-H. Hein:
42
me hodology, in es iga ion and so wa e, T. Reem sma: w i ing - e iew, A. Spe lich:
43
p ojec adminis a ion, R. Gni ß: unding acquisi ion, F. Zie zschmann: me hodology,
44
supe ision, e iew & edi ing.
45
1 In oduc ion
46
O ganic mic o-pollu an s (OMP) play a cen al ole in he quali y assessmen o a ious
47
compa men s o he wa e cycle; was ewa e in pa icula accoun s o a high
48
p opo ion o he in oduc ion o OMPs in o wa e bodies1. Pa icula ly in highly
49
u banised a eas, i is necessa y o conside no only he concen a ion o hese
50
subs ances bu also he associa ed load which he aqua ic en i onmen is con on ed
51
wi h2–5.
52
Se e al op ions o was ewa e ea men plan (WWTP) e luen moni o ing exis :
53
• G ab samples which p o ide accu a e snapsho s o moni o ing bu lack any
54
in o ma ion ou side he indi idual sampled poin in ime6,
55
• composi e samples which p o ide a e age da a o e he chosen ime pe iod bu
56
equi e cos ly and labo ious con inuous main enance and su eillance,
57
• passi e sample s (PS) which p o ide cheap and eadily a ailable quali a i e ime-
58
in eg a i e da a o e he applica ion pe iod bu end o loose accu acy i OMP
59
concen a ions a y subs an ially7,8.
60
The p inciple o PS is he en ichmen o analy es om a dono phase ( ypically liquids
61
like aqueous phases; o gases9) on o a so ben and subsequen analysis o he
62
so ben o so bed analy es a e a ce ain pe iod. PS-en iched OMP o subsequen
63
analysis should be nei he deg adable no ola ile. The e is a a ie y o passi e
64
sample ypes o aqueous use, specializing in he ype o con aminan s hey a e
65
a ge ing, like he well-desc ibed memb ane-encapsula ed sample “pola o ganic
66
chemical in eg a i e sample ” (POCIS)10 o he o ganic-di usi e g adien s in hin- ilms
67
(o-DGT)11 ha a e a ge ing pola o ganic compounds. The e a e also app oaches ha
68
assess i uses12, use di e en ma e ials like silicone ubbe 13, apply ube shaped
69
de ices14, o y mo e complex de ices wi h a o ced low h ough15,16. To da e, he
70
passi e sample s desc ibed in he li e a u e a e limi ed wi h espec o possible poin s
71
o uses. Fo example, passi e sample -based moni o ing o was ewa e s eams
72
equi es non-p essu ized, ee- lowing, accessible sampling loca ions17,18 like ponds,
73
basins, s eams e c. In addi ion, many app oaches use labo a o y-based calib a ion,
74
hus po en ially missing impo an en i onmen al ac o s19. In d inking and g ound
75
wa e (wi h ela i ely s able OMP concen a ions), he concen a ion s a emen s o pe -
76
and poly lou oalkyl subs ances (PFAS) om POCIS wi h labo a o y low- h ough
77
calib a ion led o a good ag eemen o he accompanied composi e samples20. In
78
su ace wa e , quan i a i e applica ions o labo a o y-calib a ed PS appea
79
con o e sial, leading o only quali a i e s a emen s21. Applica ions in was ewa e
80
in oduce an ex emely inhomogeneous and challenging ma ix22 compa ed o
81
d inking, g ound, o su ace wa e . Labo a o y PS calib a ion unde con olled
82
condi ions canno p o ide su icien eliabili y o such highly complex wa e ma ices
83
o s ong composi ional luc ua ions. Known impac s on he OMP-up ake like salini y,
84
empe a u e23, pH alue, and he concen a ion o dissol ed o ganic ma e (DOC)24,
85
all o which can change apidly, a e mos ly neglec ed. Fo hese easons, in si u
86
calib a ion is much mo e accu a e25 and leads o good quan i a i e s a emen s in
87
was ewa e wi h passi e sample applica ions ( o OMPs wi h non- luc ua ing
88
concen a ions)8. Howe e mos passi e sampling de ices a e calib a ed in i o in
89
hei kine ic up ake phase26.
90
To compensa e o changing pe iphe al pa ame e s ( empe a u e, u bulence, e c.),
91
iso ope-labelled pe o mance e e ence compounds (PRC) can be used27. The use o
92
PRCs hough has i s limi a ions (e.g. di e en elease beha iou o PRC as compa ed
93
o up ake beha iou o a ge OMP)28,29.
94
Many au ho s commonly a oid he use o PRCs and ely on in si u calib a ion30–32,
95
ob ia ing he need o PRCs, whe eas all in luences on he up ake a e p esen .33,34
96
The p esen s udy compa es an in si u ime-dependen calib a ion wi h a load-
97
dependen app oach which ela es he up ake o analy es in o he so ben o he eed
98
wa e load o a subs ance o he PS. Wi h his new calib a ion app oach he goals o
99
his s udy a e:
100
• In oduce a con olled low- h ough sampling de ice ( ube passi e sample ,
101
TPS) ha has an adjus able eed wa e low,
102
• p esen a quan i a i e load-dependen calib a ion app oach o 20 o ganic mic o
103
pollu an s (OMPs) om WWTP e luen ,
104
• compa e he concen a ion esul s o 11 OMPs de i ed by he p esen ed TPS
105
o OMP concen a ions om con en ional composi e sampling in a WWTP
106
e luen .
107
2 Ma e ials and Me hods
108
2.1 Design o he Tube Passi e Sample
109
The design o he TPS (c . Fig. 1) aims a highly con ollable and ep oducible so p ion
110
o OMPs on o PS discs, sup essing in luences like u bulence27, low eloci ies35,
111
addi ional memb anes10, and a oiding PRCs36. The TPS can access open wa e
112
su aces by use o a gea pump. The design also allows o con enien ly sample in
113
p essu ised lines by enclosing he so p ion discs in a special designed pipe (Fig. 1C),
114
hus in any moni o ing se up ha uses sligh o e p essu e as ound in ea men
115
plan s, p ocess ubing, o pumping s a ions; in such scena ios, an ac i e pump is no
116
necessa y.
117
118
Fig. 1: A: Schema ic c oss-sec ion and zig-zag- low diag am o he minia u ised TPS. Ci cles wi h do s acing
119
owa ds, ci cles wi h c osses acing away. B: Pho og aph o he TPS. C: In eg a ion in o a p ocess wa e sys em.
120
Wi hin he TPS, a cons an sample wa e low passes la e ally along he passi e
121
sampling discs (Fig. 1A and Fig. S6A, including TPS & housing dimensions). A mass
122
low con olle (MFC) se s he olume low o each expe imen . The de ice consis s
123
o s ainless s eel and was designed and cons uc ed by GCI GmbH Königs
124
Wus e hausen (GER), pa en DE 10 2016 003 8430, 2017. Fou di e en comme cially
125
a ailable and unmodi ied 47 mm-discs we e used o e alua ion (A lan ic® HLB
126
(Bio age), A lan ic® DVB (Bio age), A lan ic® C18 (Bio age) and Resp ep-C18
127
(Res ek)). All discs came wi h glass ib e laye s applied by he manu ac u e s. The
128
s ainless s eel disc e aine i s he diame e o he discs as well as he hickness
129
(5 mm) o he discs exac ly and holds he discs wi h a s ainless s eel mesh-pla e (mesh
130
diame e ca. 7 mm) on bo h exposed sides ( o mo e de ails see Fig. S6B), lea ing
131
1735 mm2 disc a ea pe side exposed o he sample wa e .
132
2.2 Calcula ion o he load-dependen calib a ion o he ube passi e sample
133
Ou TPS calib a ion bases on he classical ime-dependen calib a ion app oach
134
discussed in de ail by Booij e al.26, c . equa ion (1) below, and applied in a a ie y o
135
s udies8,16, wi h cons an concen a ions. This app oach p o ed only spa sely
136
applicable on OMPs wi h s ongly luc ua ing concen a ions8,26. I uses a ime-
137
weigh ed a e age concen a ion (cw, wa) and ollows equa ion (1).
138
𝑀𝐷,𝑡𝑖𝑚𝑒(𝑡)=𝑅𝑆∗∫𝑐𝑊𝑑𝑡
(1)
MD, ime (g) is he amoun o analy e on he disc a e he exposu e ime (d), 𝑅𝑆
139
ep esen s he sampling a e in he dimension o (𝐿∗𝑑−1), ∫ cw d = * cw,TWA.
140
To di e en ia e be ween he ime-dependen and he load-dependen calib a ion we
141
in oduce he collec ion a io (𝑅𝐶, dimensionless), ela ed o he sampling a e h ough
142
equa ion (2)
143
𝑅𝑆=𝑅𝐶∗𝑄
(2)
wi h 𝑄 being he (adjus able) ixed wa e low h ough he sample .
144
This di e ence allows he calcula ion o he TPS’s eed wa e load 𝑀𝑊,𝑐𝑢𝑚 ia equa ion
145
(3).
146
𝑀𝑊,𝑐𝑢𝑚(𝑡)=𝑄∗∫𝑐𝑊 𝑑𝑡
(3)
Using equa ions (2) and (3) in equa ion (1) leads o equa ion (4) o calcula e he
147
compound-speci ic collec ion a io 𝑅𝐶.
148
𝑅𝐶=𝑀𝐷(𝑡)
𝑀𝑊,𝑐𝑢𝑚(𝑡)
(4)
To calcula e he ime weigh ed a e age concen a ion 𝑐𝑊,𝑇𝑊𝐴 om he sampling a io
149
𝑅𝐶, equa ions (1) and (2) can be combined o equa ion (5).
150
𝑐𝑊,𝑇𝑊𝐴 =𝑀𝐷(𝑡)
𝑅𝐶∗𝑡∗𝑄
(5)
2.3 Expe imen al design
151
E alua ion and in si u calib a ion o he TPS ook place in a WWTP ea ing domes ic
152
was ewa e wi h some indus ial was ewa e sha es in Be lin, Ge many. The WWTP
153
has a capaci y o 42 500 m³ pe day which is equi alen o a popula ion equi alen o
154
~350 000. The TPS was placed inside he p ocess moni o ing s a ion a he WWTP
155
ou le channel. B anching om a p essu ized e luen pipe wi h con inuous low inside
156
he s a ion, wo o e low con aine s we e ed wi h mode a e o e p essu e (~1.2 ba ),
157
o he se up see Fig. S2. Fo he calib a ion expe imen s, an au oma ic wa e sample
158
WS Po i 24T (Wa e Sam GmbH, Balingen, Ge many) was placed jus ou side he
159
moni o ing s a ion. The sample insed i s hose au oma ically be o e i ook
160
consecu i e 8 hou composi e samples (20 mL/6 min) o he e luen h oughou each
161
comple e expe imen . The samples we e cooled a 4 °C un il ans e o he labo a o y.
162
All passi e sampling expe imen s ook place consecu i ely one a e ano he , all
163
accompanied wi h hei indi idual composi e samples. Fo he o de and du a ion o
164
he TPS expe imen s, see Fig. S7.
165
2.4 P epa a ion o he so p ion discs
166
Disc condi ioning in ol ed ca e ul placemen o he DVB and HLB so p ion discs in a
167
solid phase ex ac ion (SPE) disc mani old, ollowed by insing wi h LC-MS-g ade
168
solu ions o 5 mL me hanol wi h 1 % ( / ) o mic acid, 5 mL me hanol, 5 mL o me hanol
169
wi h 1 % ( / ) ammonia and 20 mL ul a-pu e wa e be o e s o age in ul a-pu e wa e
170
un il usage. Moun ing o he discs wi hin he TPS comp ised ca e ul ixa ion in o he
171
disc e aine , inse ion o he disc e aine in o he TPS, and closing o he lids. The
172
mass low con olle o he elec onic con ol uni yielded a s eady olume ic wa e
173
low h ough he TPS. A e he expe imen , sho insing wi h ul a-pu e wa e emo ed
174
deposi s and pa icles on he discs (while inside he e aine ), ollowed by
175
disassemblage o he e aine s and ans e o he discs in o a polyp opylene box lined
176
wi h a shee o aluminium oil o anspo a ion. In he labo a o y, he discs d ied unde
177
a gen le ai low in a ume hood o 2 days. The discs we e hen ans e ed in an SPE
178
disc mani old and we e insed consecu i ely wi h 5 mL o me hanol wi h 1 % ( / )
179
o mic acid, 5 mL me hanol, 5 mL o me hanol wi h 1 % ( / ) ammonia collec ing all
180
h ee il a es o one disc in one ial. The combined il a es we e concen a ed o 0.5
181
mL in a wa e ba h unde a cons an ni ogen low, ans e ed in a 1.5 mL- ial and
182
econs i u ed wi h me hanol o 1 mL. The ials we e s o ed a -25 °C. Each disc
183
ep esen ed an indi idual sample.
184
2.5 Analysis
185
Elua es we e measu ed in aqueous dilu ions o 1:500 and 1:50.000, wa e samples in
186
aqueous dilu ions o 1:5 and 1:100, espec i ely. The compounds we e analysed using
187
an Exac i e+ O bi ap sys em wi h Dionex eluen pumps om The mo Fishe Scien i ic
188
(Wal ham, USA). The injec ion olume on o he online SPE column (The mo Fishe
189
Scien i ic Hype sil GOLD aQ 2.1x20 mm) was 1 mL. The analy ical column was an
190
Acqui y UPLC HSS T3 (2.1x50 mm, 1.8 µm, Wa e s Co p., Mil o d USA). Compound
191
sepa a ion esul ed om a cons an low o 0.6 mL pe minu e, using a bina y eluen
192
g adien o ul a-pu e wa e (1 % ( / ) me hanol, 0.1 % ( / ) o mic acid) (A) and
193
me hanol (0.1 % ( / ) o mic acid) (B) wi h a g adien elu ion om 1 % B amping
194
linea ly o 95 % B a 7 minu es. Column insing uses 99 % B o 2.5 minu es, ollowed
195
by a econs i u ion s ep on s a ing condi ions a 1 % B o 3 minu es. Ionisa ion was
196
achie ed using an elec on sp ay ionisa ion (ESI) in posi i e and nega i e mode. The
197
cons an concen a ion o e ime like me op olol, he load alues show a simila x-axis
328
dis ibu ion compa ed o he ime-dependen g aph, despi e di e en axis uni s (a ows
329
om A o C). None heless, e en small di e ences in concen a ion among he
330
consecu i ely conduc ed expe imen s o he same exposu e ime lead o di e en
331
loads, hus small shi s on he x-axis (Fig. 4C). When conside ing a compound wi h
332
highly a iable concen a ions, like olyl iazole, he load-dependen calib a ion (Fig.
333
4D) demons a es p onounced di e ences as compa ed o he ime-dependen
334
calib a ion (Fig. 4B): The 4 a ows o he le o he g aph ( om Fig. 4 B o D) depic
335
he spli ing o each o he wo consecu i e expe imen s wi h 2 and 7 days exposu e.
336
The concen a ion a ia ions o olyl iazole esul in di e en eed wa e loads in
337
expe imen s ha had he same du a ion (2 days o 7 days) bu we e conduc ed a
338
di e en imes (i.e. a di e en eed wa e concen a ions). This obse a ion also
339
occu s o he o he obse ed OMPs’ calib a ion cu es, see Fig. S8.
340
Wi hin Fig. 4, panels B & D, he wo igh mos a ows indica e a lowe olyl iazole disc
341
up ake du ing he 21 days expe imen compa ed o he 14 days expe imen . While he
342
ime-dependen calib a ion leads o he conclusion ha he 14 day expe imen ma ks
343
he maximum allowable exposu e ime (co esponding o he highes OMP disc
344
up ake), he eed wa e load-dependen calib a ion demons a es ha longe exposu e
345
imes a e possible – wi h almos linea inc eases o he disc up ake up un il he 21s
346
day (despi e no in eg a ed in he calib a ion due o ou conse a i e 2/3 h eshold
347
app oach). This beha io applies o o he subs ances whose concen a ions luc ua e,
348
like indus ial chemical benzo iazole (da a no shown). Compounds ha ha e a mos ly
349
cons an concen a ion o e ime (e.g. me op olol) show no compa able change in da a
350
poin sequence (on he x-axis) when plo ed o e he load, al hough a sp eading o
351
x-axis alues occu s in he load-dependen plo (c . o he calib a ion plo s, e.g. AMPH
352
and DEET in Fig. S8). The plo ing o disc-load/cW,TWA8,26 s. ime, ea anges he da a
353
poin s on he y-axis depending on hei speci ic cW,TWA alues, which in luences he
354
linea eg ession, c . Fig S10. The load-dependen ep esen a ion p o ides a
355
esolu ion o each indi idual expe imen acco ding o i s speci ic measu ed load.
356
The eed wa e load-dependen calib a ion is powe ul in scena ios o la gely a ying
357
OMP concen a ions – such as WWTP e luen s wi h hou ly, daily, weekly, mon hly e c.
358
pa e ns o indus ial/household chemicals o pha maceu ical agen s (Fig. 2; and
359
weekly a ia ion o x- ay con as media38,39). In cases o subs an ially luc ua ing OMP
360
concen a ions, he disc up ake migh occu apidly (high OMP concen a ions, c .
361
olyl iazole 14 d expe imen in Fig. 4) o slowly (low OMP concen a ions, c .
362
olyl iazole 21 d expe imen ). No e ha he 14 d expe imen and he 21 d expe imen
363
we e no execu ed in pa allel bu consecu i ely. Hence, no he exposu e ime is
364
gene ally he limi ing a iable, bu he maximum disc up ake is he limi ing a iable.
365
Resul ing om de ined ime alues in ime-dependen calib a ion app oaches, he
366
co esponding models include ewe x-axis alues han he eed wa e load-dependen
367
app oach (c . di e en ia ion o da a poin s when changing om op g aphs o bo om
368
g aphs in Fig. 4). Passi e sample s o “classical” designs – hus lacking he highly
369
con olled cha ac e is ics o he he e-p esen ed TPS – addi ionally su e om
370
unce ain ies induced by ei he unknown o luc ua ing olume ic lows. Such cases
371
occu when deploying passi e sample s eely in o wa e s eams in ponds/basins e c.
372
Fo some OMPs (acesul ame, p opyphenazone, 4-dime hylaminoan ipy ine, iomep ol,
373
ibu ylphospha e, is-(2-chlo oisop opyl)-phospha e, iphenylphospha e), an
374
e alua ion was no possible due o a lack o da a om he wa e samples. Fo alsa an
375
acid howe e , a special beha io occu s: This OMP occu s con inuously in all aqueous
376
samples and also on all PS discs bu he applica ion o bo h he ime-dependen and
377
he load-dependen calib a ion ails, see Fig. S9. This beha io could esul om
378
(mic obial) ans o ma ion o alsa an and o he sa ans in o alsa an acid,
379
accumula ing no only om he eed wa e bu also being o med di ec ly in he passi e
380
sample om p ecu so s40,41. Uns able and/o po en ially deg adable subs ances a e
381
he e o e no sui able o assessmen s ia passi e sampling. Fo
382
2-me hyl hiobenzo hiazole (MTBT), no calib a ion was possible, po en ially due o he
383
ola ili y o his hioe he and long dwell ime on he sampling disc.
384
The classical sampling a e (RS in L/d) and he e-in oduced collec ion a io (RC wi h no
385
dimension) o all e aluable OMPs a e summa ized in Tab. 1 unde “la ge p o o ype”.
386
The sampling a es (RS) and collec ion a ios (RC) esul om he slope o he
387
espec i e linea eg ession and o RS he mean concen a ion o e all expe imen s
388
included in he linea eg ession co esponding o Fig. 4. The uni s o RC allow o
389
di ec in e ence o he amoun o an OMP collec ed om he eed wa e low o he
390
TPS. Since he coe icien o de e mina ion will no gi e an adequa e in e p e a ion on
391
he e o o he used no-in e cep eg essions used o de e mine RS and RC42, we use
392
he absolu e esidual e o (ARE, in mg) o he disc up ake (y- alues) o in e p e he
393
quali y o i , see also Sec ion S3. Fo he la ge p o o ype, 7 o he 11 OMPs ARE a e
394
compa able i no be e o he load-dependen calib a ion han o ime-dependen
395
one (highligh ed in g een). No e ha bo h he ime-dependen and he load-dependen
396
calib a ion use he bene i s o he TPS ( low- h ough de ice, s eady low condi ions,
397
cons an empe a u e). Fu he mo e, we used consecu i e expe imen s, which di e s
398
om o he s udies ha s a di e en expe imen s a he same ime and only a y he
399
exposu e leng h8. Fu u e s udies should assess he TPS’ bene i s (load-dependen
400
calib a ion, ime-dependen calib a ion) agains classical passi e sampling wi hou
401
olume ic low con ol (e.g., POCIS, o-DGT) wi h co esponding ime-dependen
402
calib a ion.
403
Tab. 1: Pe o mance pa ame e s (sampling a e 𝑅𝑆 and collec ion a io 𝑅𝐶) o he in si u calib a ion o he wo TPS,
404
be e pe o ming calib a ion acco ding o absolu e esidual e o highligh ed in g een; ARE: Absolu e esidual e o
405
(ARE compa es modelled and measu ed disc up ake da a poin s, see sec ion S3).
406
La ge p o o ype
Minia u ised p o o ype
Time-Dependen
Load-
Dependen
Time-Dependen
Load-
Dependen
Compound
RS
(mL/d)
ARE
(mg)
Rc
(ng/µg)
ARE
(mg)
RS
(mL/d)
ARE
(mg)
RC
(ng/µg)
ARE
(mg)
Phenazone
29
0.017
0.035
0.01
38
0.058
0.094
0.053
AAA
13
0.21
0.014
0.18
37
0.33
0.075
0.25
AMPH
19
0.028
0.016
0.031
30
0.069
0.077
0.069
FAA
27
0.28
0.026
0.38
35
1.10
0.075
0.99
Diclo enac
40
0.045
0.039
0.054
46
0.36
0.097
0.44
Me op olol
43
0.063
0.043
0.044
33
0.11
0.071
0.15
Iomep ol
21
0.33
0.014
0.24
Valsa an
37
1.1
0.023
0.39
DEET
39
0.008
0.047
0.006
32
0.017
0.082
0.011
Benzo iazole
13
1.70
0.023
0.92
15
0.58
0.037
0.48
Tolyl iazole
34
0.18
0.037
0.23
44
1.0
0.104
0.88
407
3.3 Minia u isa ion and in eg a ion in online measu emen
408
One o he goals o his s udy was o minia u ize he TPS in a way ha i could be used
409
pe manen ly side-by-side exis ing moni o ing equipmen in WWTPs, whils educing
410
he numbe o deployable passi e sample discs o wo. We conduc ed consecu i e
411
expe imen s wi h he minia u ized TPS p o o ype a exposu e imes o 3, 4, 5, 7, 8 and
412
14 days, now ecei ing WWTP e luen as eed wa e di ec ly om a p essu ized
413
bypass o he online measu emen de ices in he moni o ing s a ion o he examined
414
WWTP. The expe imen s las ed ≤14 d due o he insigh o he p e ious expe imen s
415
ha 2/3 o he maximum disc up ake gene ally occu ed du ing ha ime. Again, he
416
subsequen calib a ion calcula ions only used da a poin s below he 2/3 h eshold o
417
he obse ed maximum disc up ake.
418
The in si u ime-dependen ( op) and load-dependen (bo om) calib a ion plo s o he
419
minia u ized TPS (mini TPS) a e shown in Fig. 5. The compa ison o he ime-
420
dependen and he load-dependen calib a ions o me op olol (Fig. 5 A and C) shows
421
no pa icula change in o de on he x-axis, as indica ed by he a ows. In con as , he
422
olyl iazole da a (Fig. 5 B and D) ea ange on he x-axis upon plo ing load-
423
dependen ly (Fig. 5 B) opposed o ime-dependen (Fig. 5 B). This beha io is simila
424
o he plo s o olyl iazole in he la ge TPS (Fig. 4 B and D). Such beha io also applies
425
o he calib a ion plo s o diclo enac, benzo iazole, and AMPH, see Fig. S5, which also
426
con ains he da a o he o he es ed OMPs. When plo ing disc-load/cW,TWA s. ime,
427
a da a poin shi is obse ed on he y-axis, see Fig. S11. The e-a angemen o disc-
428
up ake da a poin s demons a es he impo ance o conside ing po en ially a iable
429
OMP concen a ions. E en i a gi en OMP ypically exhibi s ela i ely cons an
430
concen a ions, po en ial a ia ions may s ill occu , necessi a ing in si u calib a ion wi h
431
con inuous moni o ing o he OMP concen a ion. The 𝑅𝐶 as well as he 𝑅𝑆 esul s o
432
he co esponding calib a ions a e summa ized in Tab. 1 unde “minia u ized
433
p o o ype”.
434
435
Fig. 5: Top: Me op olol (A) and olyl iazole (B) amoun s on disc o he minia u ized TPS o e exposu e ime in
436
expe imen s o a iable du a ions (3, 4, 5, 7, 8, 14 days) and bo om: Same amoun s on disc o e me op olol (C)
437
and olyl iazole (D) eed wa e loads (as ob ained om con inuous 24 h composi e samples) h ough he mini-TPS
438
du ing he co esponding expe imen al un imes; eg essions only including alues below h eshold; ed a ows
439
linking same alues in he di e en g aphs. Da a poin s esul om means o duplica es.
440
3.4 Valida ion o he ube passi e sample
441
In o de o es he load-dependen calib a ion (Fig. 5 C and D), we ca ied ou an
442
addi ional 7-day es (we chose his expe imen al un ime so ha he disc up ake
443
would likely no exceed he h eshold and hus lie wi hin he calib a ion ange). We
444
used he measu ed disc up ake om his expe imen o calcula e he eed wa e load
445
esul ing om he linea eg ession equa ion in Fig. 5. Accompanying con inuous
446
composi e samples p o ided he necessa y in o ma ion on he ac ual concen a ions
447
in he eed wa e du ing he expe imen as a e e ence. The calcula ion esul s using
448
𝑅𝐶 along wi h equa ion (5), he esul s using 𝑅𝑆 and he esul s om he composi e
449
samples a e compa ed in Tab. 2. Fo MTBT no concen a ion esul ed om he TPS.
450
Tab. 2: OMP a e age concen a ions (cW) ob ained o a 7 day expe imen o he mini-TPS in WWTP e luen
451
calcula ed om ime-dependen and load-dependen TPS calib a ion compa ed o mean concen a ions om 7 day
452
composi e wa e samples.
453
CW in µg/L
Compound
ime-dependen a
load-dependen a
au osample b
Phenazone
0.23
±
0.01
0.21
±
0.01
0.33
±
0.01
AAA
2.8
±
0.2
2.8
±
0.2
3.0
±
0.2
AMPH
0.19
±
0.01
0.19
±
0.01
0.35
±
0.01
FAA
9.5
±
0.7
9.4
±
0.7
11.6
±
0.9
Diclo enac
3.8
±
0.3
3.8
±
0.3
4.0
±
0.3
Me op olol
2.0
±
0.1
1.9
±
0.1
1.7
±
0.1
DEET
0.12
±
0.01
0.11
±
0.01
0.13
±
0.01
Benzo iazole
42.8
±
1
35.5
±
0.9
16.6
±
0.4
Tolyl iazole
11.5
±
0.1
10.1
±
0.1
7.9
±
0.1
a Calcula ed alue ± absolu e e o , based on he indi idual e o ,
454
b Mean alue ± absolu e e o , based on he indi idual e o .
455
The OMP concen a ions calcula ed ia he load-dependen and ime-dependen TPS
456
calib a ion a e anging in wo o de s o magni ude om 0.11 µg/L, 0.12 µg/L,
457
espec i ely o DEET and 35.5 µg/L, 42.8 µg/L, espec i ely o benzo iazole and a e
458
in simila anges as concen a ions ob ained om au o-sampling. The alues
459
gene a ed om he PS a e mos ly in good ag eemen wi h hose om he au osample ,
460
e.g. 3.8 µg/L (load-dependen TPS) and 4.0 µg/L (au osample ) o diclo enac.
461
De ia ions >30% occu o AMPH and benzo iazole, ye he TPS s ill allows o ough
462
quan i a i e assessmen s o such OMPs. We u he assume ha mo e calib a ion
463
da a poin s and mo e ou ine in deploymen o he mini-TPS will allow o inc eased
464
accu acy. The concen a ions de i ed om he ime-dependen and he
465
load-dependen calib a ions a e compa able, while bo h app oaches likely p o i om
466
he o e all highly cons an condi ions acili a ed by he TPS. The TPS is a aluable
467
asse o long- e m moni o ing o WWTP e luen s whe e au osampling is o en e y
468
ime- and esou ce-consuming. Ano he ad an age o he TPS compa ed o
469
au osample s is i s small size, allowing o deploymen in moni o ing boo hs o unning
470
p ocess lines. This ea u e also means ha empe a u es below eezing impac he
471
TPS much less han au osample s which mal unc ion easily due o eezing wa e in
472
in e mi en ly ponding supply ubes; he cons an ly unning wa e low in he TPS
473
a oids mal unc ion by eezing. Due o i s e sa ili y o using any comme cial 47 mm
474
SPE disc ma e ial, he TPS opens up many possibili ies o moni o ing chemically
475
a iable a ge compounds while being in eg a ed in o he exis ing analy ical
476
equipmen .
477
4 Conclusion
478
This s udy es ed a semi-passi e sample concep wi h p ecisely adjus able olume ic
479
low, con aining s anda d 47 mm SPE discs, o moni o o ganic mic o-pollu an s in
480
WWTP e luen . A minia u ized design wi h wo passi e sample discs was
481
implemen ed in p essu ized lines o a WWTP moni o ing s a ion. A e a load-
482
dependen calib a ion o he sys em, an addi ional es un showed applicable and
483
de e mined a e age WWTP e luen concen a ions o a a ie y o OMPs, which we e
484
highly simila o concen a ions ob ained om measu ed composi e samples. Gi en
485
he s aigh o wa d handling once ins alled, and – mo e impo an ly – he
486
good/accu a e quan i a i e esul s, his semi-passi e sys em is, o ou knowledge, he
487
i s o calib a e passi e sample discs wi h exac eed wa e loads o po en ially
488
s ongly luc ua ing concen a ions, combined wi h he possibili y o ope a e in
489
p essu ized lines. The load-dependen calib a ion and he ime-dependen calib a ion
490
bo h ag eed well wi h co esponding composi e samples. Fu he expe imen s should
491
compa e he load-dependen and ime-dependen calib a ions wi hin he TPS wi h
492
“classical” passi e sampling wi hou olume ic low con ol. Many use-cases appea
493
easible o he TPS, like quan i a i e con inuous moni o ing which spa es – once he
494
TPS is calib a ed – he need o ex ensi e and labo ious au o-sampling. Due o he
495
e sa ili y o he TPS, u he applica ion could esul om con inuous moni o ing o
496
indus ial discha ges by ei he he indus y hemsel es o au ho i ies43,44.
497
Suppo ing In o ma ion
498
Addi ional expe imen al de ails, ma e ials, and me hods, including pho og aphs o
499
expe imen al se up
500
5 Acknowledgemen s
501
This s udy was pa ially ounded by he Eu opean Union’s P ojec Ho izon 2020
502
esea ch and inno a ion p og amme “PROMISCES” unde he g and ag eemen No.
503
101036449. Addi ional in-house unding om Be line Wasse be iebe is also
504
g a e ully acknowledged. The design and cons uc ion o he TPS is p ope y o GCI
505
GmbH (pa en No. DE 10 2016 003 8430, 2017) and was kindly made a ailable o he
506
expe imen s. We hank M . Robe Bloch, M . Paul Simmons and he eam o Be line
507
Wasse be iebe’s WWPTs labo a o ies o aluable discussions and analy ical
508
assis ance. We also like o hank he e iewe s o hei e ealing insigh s.
509
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510
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