Quantifying PPCP interaction with dissolved organic matter in aqueous solution: Combined use of fluorescence quenching and tandem mass spectrometry Selene Hernandez-Ruiz a , Leif Abrell b , Samanthi Wickramasekara b , Benny Chefetz c , Jon Chorover a,b, * a Department of Soil, Water and Environmental Science, University of Arizona, 1177 E 4th St, Tucson, AZ 85721, USA b Arizona Laboratory for Emerging Contaminants, University of Arizona, 1040 East 4th St, Tucson, AZ 85721, USA c Department of Soil and Water Sciences, The Hebrew University of Jerusalem, P.O. Box 12, Rehovot 76100, Israel article info Article history: Received 17 August 2011 Received in revised form 11 November 2011 Accepted 20 November 2011 Available online 26 November 2011 Keywords: DOM IHSS Wastewater Pharmaceuticals LC-MS/MS Fluorescence Interaction abstract The documented presence of pharmaceuticals and personal care products (PPCPs) in water sources has prompted a global interest in understanding their environmental fate. Dissolved organic matter (DOM) can potentially alter the fate of these contaminants in aqueous systems by forming contaminant-DOM complexes. In-situ measurements were made to assess the interactions between three common PPCP contaminants and two distinct DOM sources: a wastewater treatment plant (WWOM) and the Suwannee River, GA (SROM). Aqueous DOM solutions (8.0 mg L 1 C, pH 7.4) were spiked with a range of concentrations of bisphenol-A, carbamazepine and ibuprofen to assess the DOM fluo- rophores quenched by PPCP interaction in excitationeemission matrices (EEM). Interac- tion effects on target analyte (PPCP) concentrations were also quantified using direct aqueous injection ultra high performance liquid chromatography tandem mass spec- trometry (LC-MS/MS). At low bisphenol-A concentration, WWOM fluorescence was quenched in an EEM region attributed to microbial byproduct-like and humic acid-like DOM components, whereas carbamazepine and ibuprofen quenched fulvic acid-like flu- orophores. Fluorescence quenching of SROM by bisphenol-A and carbamazepine was centered on humic acid-like components, whereas ibuprofen quenched the fulvic acid- like fluorophores. Nearly complete LC-MS/MS recovery of all three contaminants was obtained, irrespective of analyte structure and DOM source, indicating relatively weak PPCP-DOM bonding interactions. The results suggest that presence of DOM at environmentally-relevant concentration can give rise to PPCP interactions that could potentially affect their environmental transport, but these DOM-contaminant interac- tions do not suppress the accurate assessment of target analyte concentrations by aqueous injection LC-MS/MSMS. ª 2011 Elsevier Ltd. All rights reserved. * Corresponding author. Department of Soil, Water and Environmental Science, University of Arizona, 1177 E 4th St, Tucson, AZ 85721, USA. Tel.: þ1 520 626 5635; fax: þ1 520 621 1647. E-mail addresses: [email protected](S. Hernandez-Ruiz), [email protected](L. Abrell), samanthw@email. arizona.edu (S. Wickramasekara), [email protected](B. Chefetz), [email protected](J. Chorover). Available online at www.sciencedirect.com journal homepage: www.elsevier.com/locate/watres water research 46 (2012) 943 e954 0043-1354/$ e see front matter ª 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.watres.2011.11.061
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wat e r r e s e a r c h 4 6 ( 2 0 1 2 ) 9 4 3e9 5 4
Available online at w
journal homepage: www.elsevier .com/locate/watres
Quantifying PPCP interaction with dissolved organic matterin aqueous solution: Combined use of fluorescence quenchingand tandem mass spectrometry
Selene Hernandez-Ruiz a, Leif Abrell b, Samanthi Wickramasekara b, Benny Chefetz c,Jon Chorover a,b,*aDepartment of Soil, Water and Environmental Science, University of Arizona, 1177 E 4th St, Tucson, AZ 85721, USAbArizona Laboratory for Emerging Contaminants, University of Arizona, 1040 East 4th St, Tucson, AZ 85721, USAcDepartment of Soil and Water Sciences, The Hebrew University of Jerusalem, P.O. Box 12, Rehovot 76100, Israel
a r t i c l e i n f o
Article history:
Received 17 August 2011
Received in revised form
11 November 2011
Accepted 20 November 2011
Available online 26 November 2011
Keywords:
DOM
IHSS
Wastewater
Pharmaceuticals
LC-MS/MS
Fluorescence
Interaction
* Corresponding author. Department of Soil,USA. Tel.: þ1 520 626 5635; fax: þ1 520 621 1
E-mail addresses: [email protected] (S. Wickramasekara), chefetz0043-1354/$ e see front matter ª 2011 Elsevdoi:10.1016/j.watres.2011.11.061
a b s t r a c t
The documented presence of pharmaceuticals and personal care products (PPCPs) in
water sources has prompted a global interest in understanding their environmental fate.
Dissolved organic matter (DOM) can potentially alter the fate of these contaminants in
aqueous systems by forming contaminant-DOM complexes. In-situ measurements were
made to assess the interactions between three common PPCP contaminants and two
distinct DOM sources: a wastewater treatment plant (WWOM) and the Suwannee River,
GA (SROM). Aqueous DOM solutions (8.0 mg L�1 C, pH 7.4) were spiked with a range of
concentrations of bisphenol-A, carbamazepine and ibuprofen to assess the DOM fluo-
rophores quenched by PPCP interaction in excitationeemission matrices (EEM). Interac-
tion effects on target analyte (PPCP) concentrations were also quantified using direct
aqueous injection ultra high performance liquid chromatography tandem mass spec-
trometry (LC-MS/MS). At low bisphenol-A concentration, WWOM fluorescence was
quenched in an EEM region attributed to microbial byproduct-like and humic acid-like
DOM components, whereas carbamazepine and ibuprofen quenched fulvic acid-like flu-
orophores. Fluorescence quenching of SROM by bisphenol-A and carbamazepine was
centered on humic acid-like components, whereas ibuprofen quenched the fulvic acid-
like fluorophores. Nearly complete LC-MS/MS recovery of all three contaminants was
obtained, irrespective of analyte structure and DOM source, indicating relatively weak
PPCP-DOM bonding interactions. The results suggest that presence of DOM at
environmentally-relevant concentration can give rise to PPCP interactions that could
potentially affect their environmental transport, but these DOM-contaminant interac-
tions do not suppress the accurate assessment of target analyte concentrations by
aqueous injection LC-MS/MSMS.
ª 2011 Elsevier Ltd. All rights reserved.
Water and Environmental Science, University of Arizona, 1177 E 4th St, Tucson, AZ 85721,647.gmail.com (S. Hernandez-Ruiz), [email protected] (L. Abrell), samanthw@[email protected] (B. Chefetz), [email protected] (J. Chorover).ier Ltd. All rights reserved.
wat e r r e s e a r c h 4 6 ( 2 0 1 2 ) 9 4 3e9 5 4952
indeed more aromatic as a result of lignin-based precursors
than is DOM formed as a result of microbial processing that
occurs during wastewater treatment (Chen et al., 2003;
Leenheer and Croue, 2003; Leenheer, 2004). However, even
for such terrestrial sources, assessment of DOM-PPCP affinity
on the basis of Kow value does not account for polar inter-
actions that may be important to intermolecular association
(Tolls, 2001).
4.3. LC-MS/MS recovery
Tandemmass spectrometry has been previously used to aid in
understanding of complex formation in biological molecules,
and we assert that such an approach is profitably transferable
to PPCPs as well. Prior work has focused on non-covalent
bonding between known proteins and ligands wherein
complexation reduces the signal intensity detected by the LC-
MS/MS compared to that of a control investigated under the
same solution chemistry (Bolbach, 2005; Loo, 2000; Daniel
et al., 2002). Such a signal decrease can occur due to interac-
tion forces that prevent chromatographic or gas phase sepa-
ration of the complex. The strength and stability of
interactions can vary. For example, as shown by Loo (2000),
protein subunits can be associated via hydrophobic interac-
tion or hydrogen bonding, both of which are more fragile and
thus labile in the gas phase relative to electrostatic attractions
such as those between a cationic and anionic organic species.
Thus a reduction in LC-MS/MS signal compared to that of the
control signals potential strong ionic and/or covalent
interactions.
Table 3 e LC-MSMS Mean percent recovery and standarddeviations of spiked IBU, BPA and CBZ in WWOM andSROM solutions (DOC[ 8 mg LL1) and positive controls(DC) from 10e1000 mg LL1 in 24 mM NH4HCO3 electrolyteat pH 7.4.
PPCP (mg L�1) WWOM mean% recovery
SROM mean% recovery
IBU 10 95� 6 109� 8
þC 10 97� 3 97� 3
20 102� 2 107� 3
þC 20 99� 3 99� 3
200 98� 0 97� 1
þC 200 100� 2 100� 2
1000 93� 2 96� 2
þC 1000 100� 3 104� 6
BPA 200 101� 11 107� 5
þ C 200 96� 14 96� 14
1000 93� 9 86� 11
þC 1000 95� 5 95� 10
CBZ 10 103� 22 103� 3
þC 10 100� 5 100� 5
20 105� 18 100� 2
þC 20 100� 1 100� 1
200 106� 5 110� 2
þC 200 96� 4 96� 4
1000 108� 13 96� 3
þC 1000 101� 3 106� 10
The use of aqueous injection LC-MS/MS to measure PPCP
recovery in the presence of the two DOM sources with
different physico-chemical properties indicates that the
interactions giving rise to fluorescence quenching were not
strong enough to prevent chromatographic separation,
ionization, fragmentation and detection of the target analy-
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