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Photochemical fate of atorvastatin (lipitor) in simulated

natural waters

Behnaz Razavi a, Sihem Ben Abdelmelek a, Weihua Song a, Kevin E. O’Shea b,

William J. Cooper a,*
a
Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, CA 92697-2175, USA
b
Department of Chemistry and Biochemistry, Florida International University, Miami, FL 33199, USA

article info abstract

Article history: Cholesterol-lowering statin drugs are among the most frequently prescribed for reducing
Received 9 May 2010 human blood cholesterol and they have been detected as contaminants in natural waters. In
Received in revised form this study the photochemical behavior of atorvastatin (lipitor) was investigated at two
4 August 2010 different concentrations of 35.8 mM (20 mg L 1) and 35.8 nM (20 mg L 1) using a solar simulator
Accepted 10 August 2010 and a UV reactor. Photochemical fate in natural waters can be described in most cases by the
Available online 17 August 2010 sum of the loss due to hydrolysis, direct photolysis, and, reaction with hydroxyl radical (OH),
singlet oxygen (1O2) (or O2 (1D)), and excited state dissolved organic matter (DOM). The
Keywords: absolute bimolecular reaction rate constant with OH was measured, using pulsed radiolysis,
Atorvastatin (1.19  0.04)  1010 M 1
s 1. The reaction rate constant of 1O2 was determined to be
8 1 1
Photodegradation (3.1  0.2)  10 M s . Under the experimental conditions used, at high atorvastatin
Solar simulator concentration (35.8 mM) the contribution of singlet oxygen (1O2) to the photodegradation of
Singlet oxygen atorvastatin in natural waters was higher than that of hydroxyl radical, and accounted for up
Hydroxyl radical to 23% of the loss in aqueous solutions. Whereas, at a concentration of 35.8 nM, 1O2 (and OH)
Dissolved organic matter both played a minor role in the removal of this compound. Lastly, it also appears that ator-
vastatin reacts with 3DOM* contributing to its loss in simulated natural waters.
ª 2010 Elsevier Ltd. All rights reserved.

1. Introduction Snyder, 2006). Although the concentrations of these PhACs

In recent years, the environmental occurrence of pharmaceu-
tically active compounds (PhACs), human and veterinary
medication, has been a source of growing concern. Once these
compounds are in aquatic systems, it has been shown that they
can adversely affect both aquatic and non aquatic organisms
and thus the ecosystem (Bendz et al., 2005; Brain et al., 2006;
Dussault et al., 2008; Khetan and Collins, 2007; Kostich and
Lazorchak, 2008; Lam et al., 2004; Liu and Williams, 2007; Liu
et al., 2009). Current water and wastewater treatment
systems in most cases do not completely remove low concen-
trations of PhACs (Doll and Frimmel, 2005; Huber et al., 2005;
Lam and Mabury, 2005; Ternes et al., 2003; Vanderford and
are well below the medical dose (Wong and MacLeod, 2009;
Pomati et al., 2006), there are concerns that the presence of
mixtures of pharmaceuticals in drinking water may have long
term consequences to human health especially to children,
women of child bearing age, elderly and people with compro-
mised immune systems (Brody et al., 2006).
Statins have been reported to adversely affect a plant Lemna
gibba, also known as duckweed (Brain et al., 2006). Exposure to
environmentally relevant concentrations has also produced
effects in fish, resembling pathology observed in wild pop-
ulations of similar species (Kostich and Lazorchak, 2008;
Ramirez et al., 2007). Recent studies have found that low
concentrations of pharmaceuticals in drinking water, including

* Corresponding author. Tel.: þ1 949 824 5620.

E-mail addresses: brazavi@uci.edu (B. Razavi), sbenabdelmelek@gmail.com (S. Ben Abdelmelek), wsong@uci.edu (W. Song), osheak@
fiu.edu (K.E. O’Shea), wcooper@uci.edu (W.J. Cooper).
0043-1354/$ e see front matter ª 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2010.08.012
626 w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 6 2 5 e6 3 1

statins, affected human embryonic kidney cells (Pomati et al.,

2006; Wesierska-Gadek, 2006), human blood cells (de Voogt
et al., 2009; Cunningham et al., 2009) and human breast
cancer cells (Brody et al., 2006). NH
The focus of this study was atorvastatin, widely used for the
treatment of hypercholesterolemia (Prueksaritanont et al.,
O OH
2002). Atorvastatin was chosen due to its large production N
OH
volume and widespread use. Atorvastatin has been detected in
untreated sewage samples at 76 ng L 1, in treated sewage O

samples at 32 ng L 1, and in surface water samples in the ng L 1

range (Vanderford and Snyder, 2006; Miao and Metcalfe, 2003).
OH
Sunlight mediated photodegradation may occur via direct
or indirect reactions and may play an important role in the
fate of these compounds in natural waters (Khetan and
Collins, 2007; Lam and Mabury, 2005; Cermola et al., 2006; F
Montanaro et al., 2009). Direct photolysis requires that the Atorvastatin (MW 558)
compound absorb light at above 300 nm and this has been
reported to occur with atorvastatin (Lam et al., 2004; Lam and Fig. 1 e Chemical structure of atorvastatin [CAS 134523-00-
Mabury, 2005). In natural waters, reactions involving indirect 5]. IUPAC name, (3R,5R)-7-[2-(4-fluorophenyl)-3-phenyl-4-
photolysis, mainly resulting from photolysis of dissolved (phenylcarbamoyl)-5-(propan-2-yl)- 1H-pyrrol-1-yl]-3,5-
organic matter in surface waters with atorvastatin, have not dihydroxyheptanoic acid.
been studied in detail.
Indirect photochemical pathways include reaction with
a 1O2 scavenger. Studies were also conducted in D2O. Singlet
singlet oxygen (1O2), hydroxyl radical (OH), and photoexcited
oxygen has a significantly longer half-live in D2O (when
organic matter (1DOM* and/or 3DOM*). In this study the photo-
compared to H2O) and therefore, the steady-state concentration
chemical behavior of atorvastatin in simulated natural waters
is higher, and if 1O2 is involved then the rate of loss of the
was investigated. The bimolecular reaction rate constants for
compound would increase. Solutions were transferred to 47 mL
the reaction with 1O2 and OH were evaluated. Experiments
glass vials and the photolysis was conducted in a Luzchem Solar
were performed in a solar simulator and a UV (300e400 nm)
Simulator equipped with a 300 W ceramic xenon lamp (Luz-
reactor. Studies suggesting that at least 3DOM* is involved in the
chem Research Inc.). Similar experiments were conducted in
loss of atorvastatin were also conducted. The percent contri-
borosilicate test tubes on a turn-table apparatus inside a Rayo-
bution of hydroxyl radical and singlet oxygen to the photo-
net photochemical reactor equipped with sixteen 350-nm bulbs
degradation of atorvastatin was determined from the data.
(Southern New England Ultraviolet Co. RPR-3500 A).

2.3. Molar absorption coefficient spectra of atorvastatin

2. Materials and methods
2.1. Materials
The pharmaceutical compound atorvastatin (Fig. 1) was
purchased from Shanghai FWD Chemicals Limited in China.
Atorvastatin was shown to be 99% pure by high performance
liquid chromatography (HPLC). Suwannee River Fulvic Acid
standard (SRFA) (1S101F) was obtained from the International
Humic Substance Society (IHSS, 1991 Upper Buford Circle, St.
Paul, MN 55108, U.S.A.) and used as received. Furfuryl alcohol
(FFA), sorbic acid, sodium azide (NaN3), Rose Bengal and dipo-
tassium phosphate were purchased from Sigma Aldrich and
the deuterium oxide (D2O) was purchased from Cambridge
Isotope Laboratories, Inc. The 2-hydroxyl terephthalic acid
(2OHTA), used for calibration, was synthesized (Mason et al.,
1994) as described in the supporting information (Text S1).
2.2. Photolysis of atorvastatin
For this study, solutions were prepared with 35.8 mM (20 mg L 1)
and 35.8 nM (20 mg L 1) atorvastatin concentrations. These
solutions, buffered at pH ¼ 7 with a 5.0 mM phosphate buffer,
were prepared with the addition of SRFA (20 mg L 1), to simulate
waters with dissolved organic matter, and NaN3 (20 mg L 1), as
A Cary 100 Bio UV/visible, dual beam spectrometer was used
to obtain the absorption spectra of atorvastatin as shown in
supporting information, Fig. S1. The details are described in
the supporting information, Text S2.
2.4. Steady-state concentration of singlet oxygen (1O2)
To determine the reaction rate of 1O2 with atorvastatin, it was
first necessary to determine the steady state concentration of
1
O2 under the reaction conditions. A solution containing
200 mM FFA and 20 mg L 1 SRFA were prepared and photo-
lyzed. Aliquots were removed at various time points and
analyzed by HPLC. The steady-state concentration of singlet
oxygen was determined by dividing the observed FFA degra-
dation rate by the FFA reaction rate constant with 1O2
(krxn ¼ 8.3  107 M 1 s 1) (Latch et al., 2003).
2.5. Bimolecular reaction rate constant of singlet oxygen
(1O2)
Samples containing 100 mM atorvastatin, 100 mM furfuryl
alcohol (FFA), and 40 mM Rose Bengal (RB) were prepared and
transferred to glass vials (Boreen et al., 2008). The solution was
 w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 6 2 5 e6 3 1
photolyzed in the solar simulator with a UV filtered
(a commercial photographic UV filter was used) light source to
reduce the irradiance. Aliquots of the solutions were removed
at various time points and analyzed by HPLC. The loss of the
atorvastatin was recorded in the presence and absence of FFA,
and the reaction rate constant of atorvastatin with 1O2 was
obtained as shown in equation (1).
½FFAŠt krxn;FFA ½atorvastatinŠt
ln ¼ ln
½FFAŠ0 krxn;atorvastatin ½atorvastatinŠ0
2.6. Bimolecular reaction rate of hydroxyl radical (OH)
and solvated electron (eaq )
Electron pulse radiolysis was used to measure the absolute
bimolecular reaction rate of hydroxyl radical and the solvated
electron with atorvastatin as shown in supporting informa-
tion, Text S3.
2.7. Concentration of hydroxyl radical (OH)
To determine the contribution of hydroxyl radicals to the loss
of atorvastatin, the steady state concentration of OH in solu-
tions of SRFA was determined. A solution containing 600 mM
(99.7 mg L 1) terephthalic acid (TA) and 20 mg L 1 SRFA was
prepared and photolyzed, as above. Aliquots were removed at
various time points and analyzed by HPLC using a fluorescence
detector (lexcitation ¼ 315 nm; lemission ¼ 425 nm). The observed
formation rate of 2-hydroxy terephthalic acid (2OHTA) was
converted to OH concentration by dividing TA concentration
and its hydroxyl radical reaction rate (krxn ¼ 4.94  109 M 1 s 1,
this reaction rate has also been measured using electron pulse
radiolysis, and experimental results are shown in Fig. S2,
supporting information). The method of initial rates was used
to obtain the steady state concentration of OH as the direct
photolysis of the 2OHTA occurs at wavelength above 360 nm
(Page et al., in press).
2.8. HPLC and LC-MS-MS analysis
Atorvastatin was analyzed using an Agilent 1200 series HPLC,
equipped with Quaternary Gradient, Autosampler, UV/Vis and
fluorescence detectors, under the following conditions:
column, Phenomenex Gemini C18 250  4.6 mm i.d.; the mobile
phase consisted of isocratic mixtures varying between 2 and
50% CH3OH and 98e50% 10 mM phosphate buffer solution (pH
3.0). The detector was operated at wavelengths of 241 nm for
atorvastatin. The LC-MS-MS system used in this experiment
was a Waters Acquity UPLC system equipped with an Acquity
BEH C18 1.7 mm column (2.1  50 mm). The mobile phases A
(water supplemented with 2% acetonitrile and 0.2% acetic
Acid) and B (acetonitrile acidified with 0.2% acetic acid) were
used at a rate of 0.3 mL min 1. The gradient began at 90% A
with a linear increase to 90% of B in 1 min, where it was held
for 1 min followed by a return to 90% A in 0.05 min and held for
0.95 min. The total cycle time was 3 min. The column oven
temperature was set at 50  C. An injection volume of 10 mL was
used for all analyses. The UPLC system was coupled to
a Waters Quattro Premier XE triple quadrupole mass spec-
trometer (MS). The samples were run in positive ionization
627
MSeMS mode. Experimental conditions for the mass spec-
trometer were the following: desolvation and ESI source block
temperatures, 400  C and 125  C, respectively; capillary
voltage: 3.3 kV; argon collision gas 7  10 3 mbar. Nitrogen
was used as both the nebulization and desolvation (800 L/h)
gas. The cone voltage and collision energy were optimized for
atorvastatin using MassLynx 4.1 QuanOptimize software. For
quantitative analysis the MS was operated in multiple-reac-
(1) tion monitoring (MRM) mode. One transition between the
precursor ion and the most abundant fragment ion was
recorded (559 / 440).
3. Results and discussion
3.1. Photodegradation of atorvastatin (35.8 mM)
The results of the photolysis of 35.8 mM atorvastatin in the
solar simulator are summarized in Fig. 2. Photolysis in
distilled water under our experimental conditions
(k ¼ 9.55  10 6 s 1) suggested that direct photodegradation
was very slow (Lam and Mabury, 2005). The results of indirect
photolysis, atorvastatin and SRFA (20 mg L 1), gave a pseudo-
first order rate constant of 2.34  10 4 s 1 or a half-life under
those conditions of 4.89  103 s. The addition of NaN3,
0.308 mM, (k ¼ 5.6  108 M 1 s 1 for reaction with 1O2) reduced
the loss rate constant to 1.41  10 4 s 1 suggesting that 1O2
was involved in the indirect photolysis (Latch et al., 2003). To
further confirm this, solutions of SRFA and atorvastatin were
prepared in D2O and photolyzed. The rate constant for the
disappearance of atorvastatin in D2O was 1.10  10 3 s 1,
significantly faster than in H2O, suggesting that indeed, 1O2
was involved in the loss of the compound due to its increased
lifetime in D2O as compared to that in H2O (Boreen et al., 2008).
To further understand the impact of UV-A and UV-B on the
degradation of atorvastatin, a similar series of solutions were
photolyzed in a second photochemical reactor, where the
central wavelength of the light source was 350 nm which
tailed off on both sides in the range 300e400 nm. The results
0.0
Ln([atorvastatin]t /[atorvastatin]0)
-0.6
-1.2
-1.8
-2.4
-3.0
-3.6
0 1000 2000 3000
Time (sec)
Fig. 2 e Photodegradation of 35.8 mM atorvastatin in
various solutions in the solar simulator. The lines
represent the photodegradation of atorvastatin in distilled
water (-), and, in water to which were added, SRFA (C),
SRFA and NaN3 (:), and, SRFA in D2O (;).
628 w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 6 2 5 e6 3 1

from these experiments are summarized in the supporting 0.0

information, Text S4 and are shown in Fig. S3, Supporting
information.
-0.1

Ln([FFA]t /[FFA]0)
1
3.2. Stead state concentration of O2
-0.2
1
The steady state concentration of singlet oxygen, [ O2]ss, in
solutions of 20 mg L 1 SRFA, was determined in the photo- -0.3
chemical reactor and solar simulator to be 8.7  10 13 M and
1.8  10 13 M, respectively. Fig. 3 summarizes the results -0.4
obtained in the solar simulator for determining the [1O2]ss.

3.3. Reaction rate constant of 1O2
The steady state photolysis of the sensitizer Rose Bengal, as
a source of 1O2, was used to determine the reaction rate constant
of 1O2 and atorvastatin. The conditions employed were opti-
mized to promote the reaction with 1O2, using shorter exposure
times and a UV filtered light source to reduce the irradiance.
Fig. 4 summarizes the data used to calculate the rate constant
for the reaction of atorvastatin with 1O2, (3.1  0.2)  108 M 1 s 1.
This value is in close agreement with that determined by others,
(1.5  0.2)  108 M 1 s 1 (Montanaro et al., 2009).
3.4. Steady state concentration of OH
The steady state concentration of hydroxyl radical, [OH]ss, for
20 mg L 1 solutions of SRFA was determined in the photo-
chemical reactor and solar simulator (Fig. 5) to be 9.6  10 17 M
and 2.9  10 17 M, respectively. The initial rate of formation of
2OHTA was used to calculate the [OH]ss (Page et al., in press).
The fluorescence of the 2OHTA allowed quantification of the
cumulative concentration of OH and from that the steady state
concentration was derived. The reaction is shown in Scheme 1.
3.5. Kinetic measurements for OH radical and eaq
To determine the absolute bimolecular reaction rate of OH
with atorvastatin a transient absorption spectra was obtained
-0.5
-1.6 -1.2 -0.8 -0.4 0.0
Ln([atorvastatin]t /[atorvastatin]0)
Fig. 4 e Competitive 1O2 degradation of atorvastatin and
furfuryl alcohol in pH 5.0 buffered H2O with RB using as
sensitizer. krxn values were determined by multiplying the
slope obtained from these plots (0.269) by the krxn of FFA.
(Fig. S4, Supporting information). The maximum absorbance
at 330 nm was used for the rate determination. The absorption
coefficient, 11,600 M 1 cm 1 was calculated using a hydroxyl
radical G value of 0.59 mmol J 1, based upon the intraspur
scavenging model calculations of LaVerne and Pimblott (1993).
(The G value is the efficiency with which radicals are formed
in the radiolysis of water.)
The absolute hydroxyl radical reaction rate constant was
measured by fitting exponential curves to the pseudo-first-
order growth kinetics (Fig. S5a, Supporting information) and
then plotting these values as a function of the concentration
of atorvastatin (Fig. S5b, Supporting information). The bimo-
lecular rate constant for the reaction between OH and ator-
vastatin was determined to be (1.19  0.04)  1010 M 1 s 1,
which is consistent with a previously reported value of
(1.9  0.5)  1010 M 1 s 1 (Lam and Mabury, 2005). The absolute
bimolecular reaction rate of atorvastatin with the solvated

0.00
0.35
-0.02
Ln ([FFA]t /[FFA]0)

0.30
-0.04
[2OHTA] (µΜ)

0.25
-0.06

0.20
-0.08

0.15
-0.10

0 1000 2000 3000 4000 5000 6000 7000 0 2000 4000 6000 8000 10000
Time (sec) Time (sec)
1
Fig. 3 e The concentration of O2, in solar simulator, was Fig. 5 e The steady state concentration of OH, in the solar
determined by the loss of furfuryl alcohol. By dividing the simulator was calculated by dividing the initial slope of the
slope of the line (1.48 3 10L5 sL1) by the reaction rate of graph (3.38 3 10L5 M sL1) by the hydroxyl radical reaction
furfuryl alcohol with 1O2, the steady state concentration of rate of terephthalic acid and its concentration used in the
1
O2 in the reactor was determined. experiment.
 w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 6 2 5 e6 3 1 629

O OH O OH O OH
O OH

H OH OH
OH
OH H O2 H HO2
+
O
O

O OH O OH O OH
O OH
TA 2OHTA

Scheme 1.

electron (eaq ) was determined to be (1.42  0.02)  109 M 1 s 1
using the transient absorption of the eaq at 700 nm (Fig. S6,
Supporting information).
3.6. Photodegradation of atorvastatin near
environmental concentrations (35.8 nM)
Atorvastatin has been observed in the environment at rela-
tively low concentrations. Therefore, a series of experiments
were performed in the solar simulator using 35.8 nM ator-
vastatin solutions, and the results are summarized in Fig. 6.
The disappearance rates for atorvastatin were 4.02  10 4,
2.73  10 4 and 2.28  10 3 s 1, for the solutions with only
SRFA, SRFA and sodium azide, and in D2O with SRFA,
respectively. For each treatment the loss rate for the disap-
pearance of atorvastatin was faster than at the higher
concentration (see above, Fig. 2). The absolute concentration
of SRFA and sodium azide was the same in both studies, and
the only variable was the concentration of the atorvastatin.
The ratio of the reaction rates between the solution with only
SRFA in it and the one with SRFA and sodium azide were
comparable, suggesting that the contribution of 1O2 to the loss
of atorvastatin in both solutions was similar. However, the
degradation rate for the loss of the atorvastatin in the solution
containing 35.8 nM, was 58% faster. This suggested that
another reactive species accounted for a substantial portion of
the loss of the atorvastatin.
Although it was initially thought that the solvated electron
(eaq ) was produced in surface waters via sunlight meditated
photolysis of natural organic matter (Fischer et al., 1985, 1987;
Zepp et al., 1987a), later it was shown in three independent
studies that, at least for the reduction of dioxygen to super-
oxide anion radical (as the precursor to H2O2 in natural waters),
eaq is apparently not formed under normal sunlight irradiation
conditions (Cooper et al., 1994; Sturzenegger, 1989; Thomas-
Smith and Blough, 2001). Therefore, even though the absolute
bimolecular reaction rate of atorvastatin with the solvated
electron (eaq ) was determined to be at (1.42  0.02)  109 M 1 s 1,
however it is not likely to be involved in the loss of the phar-
maceutical in natural waters.
From studies probing the reduction of dioxygen in natural
waters it has been suggested that a direct reaction between
the triplet excited state of the DOM (3DOM*) and ground state
triplet dioxygen (Cooper et al., 1994) was a possible mecha-
nism. The data summarized in Fig. 2, suggest that a significant
loss of atorvastatin is not accounted for by reaction with 1O2 or
OH or e
aq . Therefore, a direct reaction of the atorvastatin with
excited state DOM is proposed. As these solutions were made
in high purity water there is no possibility of NO3 involvement
(Zepp et al., 1987b) suggesting that the major reactant with
atorvastatin is an excited state of DOM with atorvastatin.

0.0
0
Ln([atorvastatin]t /[atorvastatin]0)

-0.5
Ln([atorvastatin]t /[atorvastatin]0)

-1 -1.0

-1.5
-2 -2.0

-2.5
-3
-3.0

-3.5
-4
0 750 1500 2250 3000 3750
0 2000 4000 6000 8000 10000 Time (sec)
Time (sec)
Fig. 7 e Comparison study of indirect photodegradation of
Fig. 6 e Indirect photodegradation of 35.8 nM atorvastatin 35.8 mM atorvastatin in various solutions in the solar
in various solutions in the solar simulator. The solid lines simulator. The solid lines represent the photodegradation
represent the photodegradation of atorvastatin in D.I. H2O of atorvastatin in water to which were added SRFA (-),
(-), in SRFA (C), in SRFA and NaN3 (:), and in SRFA and SRFA in saturated O2 (C), SRFA in saturated N2 (:), and,
D2O (;). SRFA and sorbic acid (;).
630 w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 6 2 5 e6 3 1
To study this hypothesis solutions of 35.8 mM atorvastatin
were prepared with the addition of 1 mM sorbic acid, a known
triplet state quencher (Conceicao et al., 2000; Mateus et al.,
1994), 20 ppm SRFA, and by supersaturating the solution with
O2 and removing O2 by vigorous bubbling of N2. The solutions
were photolyzed in the solar simulator and aliquots were
removed at various time points and analyzed by HPLC. The
results are summarized in Fig. 7. The addition of sorbic acid
slowed the loss of atorvastatin, suggesting that 3DOM* was
responsible for a portion of the observed loss. The addition of
O2 resulted in a marked increase in the removal of atorvastatin,
likely as a result of an increase in 1O2, while at the same time
quenching the 3DOM*. The removal of oxygen by bubbling N2
into the solution increased the loss rate, suggesting that the
3
DOM* was indeed reacting directly with atorvastatin.
4. Conclusion
The indirect photodegradation using a solar simulator, of both
35.8 mM and 35.8 nM atorvastatin in the presence of SRFA, was
investigated. The results showed that 1O2 contributed to the
loss of atorvastatin, in 35.8 mM and 35.8 nM solutions, 23% and
14%, respectively. The OH contributed 0.15% and 0.085%, to
the degradation of atorvastatin in the 35.8 mM and 35.8 nM
solutions, respectively (Table S1). From the results it can be
concluded that at high atorvastatin concentration (35.8 mM)
nearly 23% of atorvastatin is photodegraded through reaction
with 1O2; and OH has very little role in photochemical
removal of this compound from natural compounds. It is
proposed that the other 77% of the indirect photodegradation
of atorvastatin in natural waters is due to the reaction of this
compound with excited state dissolved organic matter either
1
DOM* or 3DOM*. Quenching of the 3DOM* clearly showed
a reduced loss rate while enhancing 3DOM* (by saturating the
solution with N2) enhanced the loss. It is not possible to
determine the intermediacy of 1DOM* with these experi-
ments; however, we speculate that because of the short life-
time of the singlet state the reaction with the 3DOM* may be
the dominant pathway.
The results that were obtained for atorvastatin at the more
environmentally representative concentration (35.8 nM of
atorvastatin solution) suggest that at low atorvastatin
concentration, almost all of this compound is sorbed to
natural organic matter, and therefore both 1O2 and OH have
a minor little role in the removal of this compound. An
alternative hypothesis is that the sorbed atorvastatin reacts
directly with 1O2 in the “microenvironment” in the dissolved
organic matter, as suggested by Latch and McNeill (2006).
Further studies are required to elucidate the details of these
alternative mechanisms.
From the data presented it is likely that photodegradation
of atorvastatin is a major mechanism in determining its
overall environmental fate. The extent to which any photo-
chemical reaction occurs in natural waters will depend on
many variables. These variables include the amount of DOM,
latitude, flow (laminar vs turbulent) regimes, time of day and
year. i.e. the higher the concentration of DOM the less pene-
tration in a natural water. However, in many streams there are
areas of turbulent flow and these areas mix the water column
resulting in a redistribution of the pollutant. The data pre-
sented provide a more detailed assessment of the underlying
photochemistry of atorvastatin in natural waters and they
would need to be coupled with a hydraulic model to assess the
extent of degradation in a particular water system. The one
reaction rate constant that was not evaluated was that of
3
DOM* with Atorvastatin. The methodology for that
measurement is not straightforward and is the subject of on-
going studies.
Acknowledgments
Work performed at the Radiation Laboratory, University of
Notre Dame, is supported by the Office of Basic Energy
Sciences, U.S. Department of Energy. We thank The Newkirk
Center at the University of California, Irvine for partial support
of this study. This is contribution 57 from the University of
California, Irvine, Urban Water Research Center.
Appendix. Supplementary data
Supplementary data associated with this article can be found
in online version at doi:10.1016/j.watres.2010.08.012.
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