Environmental Toxicology and Chemistry, Vol. 33, No. 4, pp. 761–767, 2014
# 2013 SETAC
Printed in the USA
OCCURRENCE AND DISSIPATION OF BENZOTRIAZOLES AND BENZOTRIAZOLE
ULTRAVIOLET STABILIZERS IN BIOSOLID-AMENDED SOILS
HUA-JIE LAI,y GUANG-GUO YING,*y YI-BING MA,z ZHI-FENG CHEN,y FENG CHEN,y and YOU-SHENG LIUy
yState Key Laboratory of Organic Geochemistry, CAS Centre for Pearl River Delta Environmental Pollution and Control Research, Guangzhou Institute of
Geochemistry, Chinese Academy of Sciences, Guangzhou, China
zMinistry of Agriculture Key Laboratory of Plant Nutrition and Nutrient Cycling, Institute of Agricultural Resources and Regional Planning, Chinese
Academy of Agricultural Sciences, Beijing, China
(Submitted 27 August 2013; Returned for Revision 2 October 2013; Accepted 5 December 2013)
Abstract: Benzotriazoles (BTs) and benzotriazole ultraviolet (UV) stabilizers (BUVSs) are commonly used industrial and household
chemicals, but little is known about their dissipation behavior in the soil environment associated with biosolid application. The authors
investigated the occurrence and dissipation of 4 BTs (BT, 5-methyl-1H-benzotriazole [5-TT], 5-chloro-1H-benzotriazole [CBT], and
5,6-dimethyl-1H-benzotriazole [XT]) and 5 BUVSs (UV-326, UV-327, UV-328, UV-329, and UV-P) in biosolid-amended soil of 3 trial
sites (Zhejiang, Hunan, and Shandong) in China following 2 treatments (treatment 1: a single application of biosolid; treatment 2: repeated
application of biosolid). The results showed that except for CBT and XT, the other 7 compounds could be detected in most of the biosolid
and biosolid-amended soils at levels of a few to tens of nanograms per gram and that the concentrations of the 7 compounds for treatment 2
were obviously higher than those for treatment 1. In the 1-yr monitoring of the Shandong site, 2 BTs (BT and 5-TT) and 5 BUVSs
(UV-326, UV-327, UV-328, UV-329, and UV-P) were significantly dissipated in the biosolid-amended soils. The field half-lives of BT
and 5-TT ranged from 217 d to 345 d, while those for the BUVSs ranged between 75 d and 218 d. The field half-lives of target compounds
in soil were found to be comparable to the modeling results. The results suggest the persistence of BTs and BUVSs in soil environments
with quite slow dissipation rates. Environ Toxicol Chem 2014;33:761–767. # 2013 SETAC
Keywords: Benzotriazole
Ultraviolet stabilizer
Biosolid application
Soil
Dissipation
be fully assessed [13]. A gender-related difference in the toxicity
of UV-327 was found in neonatal rats, which is likely to be
linked to alterations in sex hormones [9]. This suggests potential
toxic biological effects of BUVSs, although these compounds
did not exhibit estrogenic activities in in vitro studies [16].
Because of their wide presence and potential adverse impacts,
BTs and BUVSs have been regarded as emerging contaminants.
Benzotriazoles and BUVSs could enter the environment
either via direct use in fields during various activities or via
indirect discharge of sludge and effluent of wastewater-treatment
plants (WWTPs). Benzotriazoles have been detected at relatively
high concentrations (up to milligrams per liter) in effluents
of WWTPs [17,18]. Most of the BUVSs are hydrophobic
substances; therefore, these compounds have low concentrations
in effluent and tend to absorb into sludge [19,20]. For example,
BT and 5-TT were found in biosolid (sludge) at concentrations
ranging between 68 3 ng/g and 120 18 ng/g, and UV-326
and UV-329 were also detected at 88 12 ng/g and 27 0.1 ng/
g, respectively [18]. One pathway for these chemicals to enter the
environment is via the application of biosolid as fertilizer in
agricultural land [21,22]. To date, information about the
dissipation of BTs and BUVSs in soil is very limited.
The aims of the present study were to examine the occurrence
and fate of 4 BTs (BT, 5-TT, 5,6-dimethyl-1H-benzotriazole
[XT] and 5-chloro-1H-benzotriazole [CBT]) and 5 BUVSs (UV326, UV-327, 2-[2-hydroxy-3,5-dipenryl-phenyl] benzotriazole
[UV-328], UV-329, and 20 -hydroxy-5mg-methylphenyl benzotriazole [UV-P]) in biosolid-amended soils of 3 trial sites
(Zhejiang, Hunan, and Shandong) in China following 2 different
treatments (treatment 1: a single application of biosolid;
treatment 2: repeated application of biosolid).
INTRODUCTION
Benzotriazoles (BTs) are commonly used as corrosion
inhibitors in dishwasher detergents and de-icer fluids, ultraviolet
(UV) light stabilizers in plastics, and antifogging agents in
photography and airports [1,2]. Benzotriazole UV stabilizers
(BUVSs), which have a phenolic group attached to a
benzotriazole structure, have excellent absorption capacity
with a full spectrum [3]. Benzotriazole UV stabilizers are
widely used in commodities, skin care products, and industrial
products to reduce harm to skin, improve the stability of
industrial products, and prevent light-induced degradation
reactions and yellowing caused by UV radiation from
sunlight [4]. In recent years, the occurrence of BTs such as 5methyl-1H-benzotriazole (5-TT) and BUVSs such as 2-(3-tbutyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole (UV326), 2-(20 -hydroxy-30 ,50 -di-tert-butylphenyl)-5-chlorobenzotriazole (UV-327), and 2-(20 -hydroxy-50 -octylphenyl) benzotriazole (UV-329) has been reported in surface water [5–7],
sediment [8–10], and fish [4,9,11]. From the limited acute
toxicity data available in the literature, BTs and BUVSs have
relatively low acute toxicity [12–14]. However, in vitro assays
indicate that BTs possess antiestrogenic properties [15].
Benzotriazole UV stabilizers have significant bioaccumulative
characteristics, and their potentially toxic effects on biota need to
All Supplemental Data may be found in the online version of this article.
* Address correspondence to guangguo.ying@gmail.com or guang-guo.
ying@gig.ac.cn.
Published online 24 December 2013 in Wiley Online Library
(wileyonlinelibrary.com).
DOI: 10.1002/etc.2498
761
762
Environ Toxicol Chem 33, 2014
H.-J. Lai et al.
Benzotriazole (99%) was purchased from Tokyo Chemical
Industry, and 5-TT (98%), XT (99%), CBT (99%), and a
surrogate standard benzyl cinnamate (99%) were purchased
from Acros Organics. The following were purchased from J&K
Chemical: UV-P (99%), UV-326 (98%), UV-327 (98%),
UV-328 (98%), and UV-329 (98%). Two internal standards,
thiabendozole NH D6 (100%) and chrysene-d12 (100%), were
purchased from Dr. Ehrenstorfer and Supelco, respectively. The
physicochemical properties of the target compounds are shown
in Supplemental Data, Table S1. High-performance liquid
chromatography (HPLC)–grade methanol and dichloromethane
were purchased from Merck and CNW Technologies, respectively. Cellulose filters (30 mm) were purchased from Dionex.
Silica gel (80–100 mesh; Haiyang Chemical) and silica sand
(Qiangsheng Chemical) were successively hand-washed with
methanol and dichloromethane 3 times and baked at 400 8C for
4 h prior to use.
Stock solutions (100 mg/L) of BT, 5-TT, XT, and thiabendozole NH D6 were prepared in methanol and stored at 18 8C
until use. Stock solutions (100 mg/L) of UV-326, UV-327,
UV-328, UV-329, UV-P, chrysene-d12, and benzyl cinnamate
were prepared in dichloromethane and stored at 18 8C until
use. Working standard solutions were prepared weekly. All
glassware was hand-washed with tap water, rinsed with Milli-Q
water, and baked at 400 8C for at least 4 h before use.
to incorporate the biosolids. Only 1 application was carried out
for treatment 1, while repeat applications were carried out for
treatment 2 on 5 October every year until 2010.
Sampling was carried out from the beginning of October 2010
to October 2011, though the field trials started in May 2007
because initial field trials focused on inorganic contaminants in
the biosolid-amended soils [22] but not organic contaminants.
Each composite sample was comprised of 5 subsamples taken
from 5 points of each plot at the same soil depth of 0 cm to 20 cm.
Four replicate samples (1 composite sample for each plot) were
collected from the 4 replicate plots. The first sampling was taken
at the 3 trial sites on 5 October 2010 prior to the reapplication of
biosolid. After the first sampling, the Zhejiang and Hunan trial
sites were closed down as a result of the logistical problems in
the transport of biosolid because the 2 sites were far away from
Beijing. Moreover, sampling in Shandong was carried out on
day 5 of each month from December 2010 to October 2011.
Because of the frost period in Shandong, however, no soil
samples were collected in January and February 2011. The
collected samples were freeze-dried, then sieved through a
0.90-mm mesh standard screen, and stored in the dark at 4 8C
before extraction.
Information about the 3 field trial sites is shown in Table 1.
Soil pH was measured with 0.01 M CaCl2 (soil to solution ratio
of 1:5) using a pH meter. Total organic carbon (TOC) content
was determined by a LECO carbon and nitrogen analyzer, while
soil particle size distribution was analyzed using the pipette
method [23].
Field trials
Chemical analysis
Field trials of biosolid application on agricultural land were
carried out at 3 sites (Zhejiang, Hunan, and Shandong) in China.
The trials included 3 treatments: control (without application of
biosolid), treatment 1 (a single application of biosolid), and
treatment 2 (repeated application of biosolid). Each treatment
had 4 replicate plots (3 m 2 m, each). The biosolid for
application in the trials was dewatered sludge from a WWTP
in Beijing collected in May 2006. The dried sludge was stored in
a warehouse before use, and these biosolids were always applied
in the trails at 3 sites. Biosolid samples were collected from
a warehouse every year during 2007 to 2010 and stored in a
refrigerator at 20 8C for chemical analysis in 2010. The
biosolid was first applied at 3 sites on 31 May 2007 at a rate of 60
t/ha. All plots were then cultivated with a hoe to a depth of 20 cm
Extraction. Freeze-dried soil (5.0 g each) and sludge (1.0 g
each with 4.0 g silica sand mixed evenly) samples were extracted
using a pressurized liquid extractor, ASE 300 accelerated
solvent extraction system (Dionex), equipped with 34-mL–
capacity stainless-steel cells. A cellulose filter was placed at the
bottom of the stainless-steel cell, followed by 2.0 g silica gel as
an in-cell clean-up sorbent. Samples were loaded individually,
and then 100 mL 1 mg/L internal standard (thiabendozole NH
D6) and surrogate standard (benzyl cinnamate) mixed solution
was added. After adding 5.0 g silica sand, another cellulose filter
was placed on the top. The extraction solvent was methanol/
dichloromethane (50:50, v/v). The operating conditions were as
follows: 120 8C extraction temperature, 5 min extraction time,
and 2 cycles. Each extract was evaporated to dryness under a
MATERIALS AND METHODS
Chemicals and materials
Table 1. Information on the field trial sites and treatments
Treatment
Zhejiang
Control
Treatment
Treatment
Hunan
Control
Treatment
Treatment
Shandong
Control
Treatment
Treatment
Crops
Annual
average
temperature
(8C)
Annual
total
rainfall
(mm)
Soil type/texture
1
2
Rice and rape
Rice and rape
Rice and rape
15.9
15.9
15.9
1168
1168
1168
Paddy soil/silt loam
Paddy soil/silt loam
Paddy soil/silt loam
1
2
Wheat and maize
Wheat and maize
Wheat and maize
19.1
19.1
19.1
1360
1360
1360
Red soil/loam
Red soil/loam
Red soil/loam
1
2
Wheat and maize
Wheat and maize
Wheat and maize
12.9
12.9
12.9
522
522
522
Fluvo-aquic soil/clay loam
Fluvo-aquic soil/clay loam
Fluvo-aquic soil/clay loam
a
Mean standard deviation (%) (n ¼ 3).
TOC ¼ total organic carbon.
Soil
moisture
(%)
TOC (%)
Clay
(<0.002 mm)
(%)a
Biosolid
application
(kg/m2)
pH
100
100
100
6.3 0.5
6.8 0.2
7.1 0.1
1.4 0.4
2.1 0.6
1.2 0.2
9.7 9.2
11.2 6.8
9.7 1.0
0
6, once
6, every year
24–25
24–25
24–25
4.3 0.1
5.6 0.1
7.0 0.2
1.0 0.1
1.3 0.1
2.4 0.2
10.3 1.7
9.6 1.0
7.4 3.5
0
6, once
6, every year
23
23
23
7.6 0.2
7.6 0.1
7.5 0.1
0.6 0.0
1.0 0.1
1.4 0.3
21.7 4.2
21.9 1.5
26.0 0.8
0
6, once
6, every year
Dissipation of benzotriazole ultraviolet stabilizers
rotary evaporator (Buchi), redissolved in 1 mL methanol, and
then filtered through a 0.22-mm membrane filter (Anple) into a
2-mL amber glass vial (Agilent). The final extract (100 mL) was
added into a 250-mL glass insert (Agilent) and solventexchanged into 100 mL of dichloromethane spiked with 10 ng
of internal standard (chrysene-d12) for analysis by gas
chromatography-mass spectrometry (GC-MS). The rest of
the extract was used for analysis by HPLC tandem mass
spectrometry (LC-MS/MS).
GC-MS. The BUVSs (UV-P, UV-326, UV-327, UV-328, and
UV-329) were analyzed by GC-MS (Agilent 6890N/5975B). The
target compounds were separated on an Agilent DB-5MS column
(30.0 m 250 mm, 0.25 mm thickness) with helium as the carrier
gas at a flow rate of 1.0 mL/min. The GC oven temperature was
programmed from 80 8C (held 1 min) to 230 8C (25 8C/min, held
1 min), then increased to 260 8C (15 8C/min, held 1 min), and
finally increased to 310 8C (20 8C/min, held 8 min). Post-run was
8 min at 300 8C. The injection port, ionization source, mass
analyzer, and transfer line temperatures were set at 280 8C, 250
8C, 150 8C, and 280 8C, respectively. The injection volume was
2.0 mL. The injection was performed in splitless mode, and the
splitless time and split flow were set at 1 min and 100 mL/min,
respectively. The MS was operated in electron impact mode at
70 eV and in the selected ion monitoring mode for quantification
purposes. Retention times and ions monitored for each
compound are summarized in Supplemental Data, Table S2.
LC-MS/MS. Benzotriazole, 5-TT, CBT and XT were analyzed by high-performance LC-MS/MS with electrospray
ionization in positive ionization mode. The chromatographic
column was an Agilent Zorbax SB-C18 (3.0 mm 100 mm,
1.8 mm particle size) with its corresponding precolumn filter
(2.1 mm, 0.2 mm) at 40 8C as the column temperature. The
mobile phase was Milli-Q water containing 0.01% (v/v) formic
acid (A) and methanol (B). The gradient elution started with 40%
B at a flow rate of 0.30 mL/min, increased to 90% B at 4 min,
then increased flow rate to 0.35 mL/min at 5 min, and kept 90%
B and 0.35 mL/min for 7 min. The injection volume was 5.0 mL.
The MS parameters including fragmentor voltage, collision
energy, precursor ion, and product ions for each compound were
optimized by Optimizer (Agilent) in electrospray ionization (þ)
mode. The following optimized parameters were selected:
drying gas temperature 300 8C, drying gas flow rate 3 mL/min,
capillary voltage 3500 V, nebulizing gas pressure 30 psi, sheath
gas temperature 250 8C, and sheath gas flow rate 11 mL/min.
Nitrogen was used as the nebulizer, drying, curtain, and collision
gas. The system was reequilibrated for 8 min between runs.
Quantification of each target compound in the samples was
performed in multiple reaction monitoring mode. More detailed
MS operating conditions and retention times for each compound
are summarized in Supplemental Data, Table S3.
Quality control
The target compounds were identified by comparing the
retention times and the ratios of the 2 selected ions for LC-MS/
MS and 3 selected ions for GC-MS with those of the standards.
Quantification of the target compounds was obtained using the
internal standard method. Good linearity was achieved, with
correlation coefficients >0.995 at concentrations from 1 mg/L to
900 mg/L in GC-MS (for UV-P, UV-326, UV-327, UV-328, and
UV-329) and from 1 mg/L to 200 mg/L in LC-MS/MS (for BT, 5TT, CBT and XT). The recoveries, matrix effects, limits of
detection (LODs), and limits of quantitation (LOQs) are given in
Supplemental Data, Table S4.
Environ Toxicol Chem 33, 2014
763
The recovery test was performed for all target compounds in
matrix-spiked samples of soil (20 ng/g) and biosolid (200 ng/g).
The matrix effect for each compound was determined by
comparing extracts from matrix spiked with chemical standards
with the standard solution in mobile phase. For soil samples, the
recoveries of target compounds ranged between 74.7% and
117%. For biosolid samples, the recoveries of target compounds
ranged between 70.9% and 112%.
The LOD and LOQ for each target compound were calculated
based on the signal-to-noise ratio near the target peak. The LOD
was defined as 3 times the signal-to-noise ratio, and the LOQ was
10 times the signal-to-noise ratio. The LOQs of most targets for
soil samples were less than 1 ng/g, and the highest LOQ was
1.57 ng/g for UV-P. The LOQs of targets for biosolid samples
ranged between 2.45 ng/g and 11.6 ng/g.
All data obtained from the analysis were subjected to strict
quality-control procedures. For each batch of samples to be
analyzed, a solvent blank, a standard solution (100 mg/L), and a
method blank were run in sequence to check for background
contamination and instrument performance. The recoveries of
the surrogate standard benzyl cinnamate in all samples ranged
between 86.4% and 129%.
Data analysis
Statistical analysis and dynamic curve fitting were performed
using the software SPSS 19.0 and Sigma Plot 10.0, respectively.
A one-way analysis of variance and Duncan’s multiple range
tests were performed to determine significant differences
(p < 0.05) among the concentration data of the target compounds
at the 3 different sites. Prior to all nonlinear regression fitting, the
concentration data from the Shandong site were converted to a
normalized concentration as a ratio of the initial concentration
(C/C0). The term C0 represented the average concentration of
each compound in the biosolid-amended soils in October 2010.
A standard first-order exponential decay model with 2
parameters was applied to fit the concentration data (C/C0)
and the time t (days). The time to dissipate 50% of a chemical
(DT50; half-life, days) was calculated based on the first-order
reaction kinetic model.
RESULTS
BTs and UV filters in biosolid and biosolid-amended soils from the
3 trial sites
For BTs in the biosolid applied in the field, BT and 5-TT were
detected at concentrations of 147 7.3 ng/g and 141 3.9 ng/g
(n ¼ 4), but CBT and XT were found below the LOQs. For
BUVSs, UV-329 had the highest concentration at 389 13.7 ng/g,
followed by UV-328 and UV-P with concentrations of
108 2.6 ng/g and 102 1.5 ng/g, respectively; and the lowest
concentrations were found for UV-326 and UV-327 at
47.0 0.2 ng/g and 28.3 1.2 ng/g, respectively.
The concentrations of BTs and BUVSs in biosolid-amended
soil samples collected from the 3 sites (Hunan, Zhejiang, and
Shandong) in October 2010 are summarized in Figure 1 and
Supplemental Data, Table S5. Only trace concentrations (<LOQ
to 1.8 ng/g) of BT, 5-TT, and UV-327 were detected in the soil
samples from the control plots without the amendment of
biosolid (control), and the rest of the target compounds were not
detected.
In the biosolid-treated plots of the 3 sites, the highest
concentrations for the 4 BTs were detected for 5-TT (Figure 1).
The concentrations for 5-TT ranged from 3.9 ng/g to 9.2 ng/g for
treatment 1 and from 7.0 ng/g to 22.6 ng/g for treatment 2,
764
Environ Toxicol Chem 33, 2014
H.-J. Lai et al.
Field dissipation of the BTs and UV filters in soil
The dissipation of 2 BTs (BT and 5-TT) and 5 BUVSs (UV326, UV-327, UV-328, UV-329, and UV-P) in soil was assessed
at the Shandong site from October 2010 to October 2011
(Figures 2 and 3). Because of limited concentration data
available, CBT and XT were not included in the assessment of
dissipation. For the 7 chemicals assessed for their field
dissipation, considerable variations in their concentrations
were observed during the 1-yr monitoring period, with the
concentrations of each compound increasing slowly from
October 2010 and reaching a maximum in March 2011 after
the frost period. The phenomenon may be mainly the result of
difficulties in obtaining a homogeneous sample and the
degradation of samples during storage until extraction [21,24].
Therefore, dynamic curve fitting was performed for the
concentration data obtained for the period March 2011 to
October 2011.
Significant dissipation (p < 0.05) was found for the 7
chemicals under both treatments (Figures 2 and 3). Based on
the first-order reaction model, dissipation kinetic parameters for
each chemical were obtained and are given in Table 2. Under
both treatments, BT had the highest DT50 values (345 d for
treatment 1 and 268 d for treatment 2). Among the 5 BUVSs,
UV-327 and UV-328 showed higher DT50 values than the rest
of the compounds (Table 2). For BT and 5-TT, higher DT50
values were found for treatment 1 than treatment 2, while for the
5 BUVSs, similar DT50 values were observed between the 2
treatments (Table 2).
DISCUSSION
Figure 1. Concentrations of benzotriazoles and benzotriazole ultraviolet
stabilizers in the soils collected from the 3 trial sites in October 2010. Letters (a
and b) indicate the significant difference of concentration data by Duncan’s
multiple range test, p < 0.05. Top panel shows concentrations under treatment 1
(T1), a single biosolid application; bottom panel shows concentrations under
treatment 2 (T2), biosolid application every year. BT ¼ benzotriazole; 5TT ¼ 5-methyl-1H-benzotriazole; CBT ¼ 5-chloro-1H-benzotriazole; XT
¼ 5,6-dimethyl-1H-benzotriazole; UV-326 ¼ 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole; UV-327 ¼ 2-(20 -hydroxy-30 ,50 -di-tert-butylphenyl)-5-chlorobenzotriazole; UV-328 ¼ 2-(2-hydroxy-3,5-dipenryl-phenyl)
benzotriazole; UV-329 ¼ 2-(20 -hydroxy-50 -octylphenyl) benzotriazole; UVP ¼ 20 -hydroxy-5mg-methylphenyl benzotriazole.
whereas the concentrations for BT varied from 2.8 ng/g to
6.8 ng/g for treatment 1 and from 6.1 ng/g to 15.5 ng/g for
treatment 2 (Supplemental Data, Table S5). Both CBT and XT
were either not detected or found at very low concentrations. The
5 BUVSs (UV-326, UV-327, UV-328, UV-329, and UV-P)
were detected in all biosolid-amended soil samples from the 3
trial sites (Figure 1). The stabilizer UV-329 showed significantly
higher concentrations than the other UV filters, with the
following decreasing order: UV-329, UV-328, UV-P, UV-327,
and UV-326. The highest concentrations for UV-329 in the
biosolid-amended soils were found up to 10.3 3.1 ng/g for
treatment 1 (Shandong) and 33.3 7.3 for treatment 2
(Shandong; Supplemental Data, Table S5). Among the 3 trial
sites, the concentrations of BT and 5-TT at the Hunan site were
significantly higher than those at the other 2 sites (Zhejiang and
Shandong) for both treatments (Figure 1). For most BUVSs, the
Shandong site had the highest chemical concentrations for
treatment 1; for treatment 2, however, the Shandong site showed
similar concentrations to the Hunan site and higher concentrations than the Zhejiang site (Figure 1).
The field trials at the 3 sites (Hunan, Shandong, and Zhejiang)
clearly showed the presence of 2 BTs and 5 BUVSs in the soils
applied with biosolid. No detection or trace detection of these
compounds in the control soils without biosolid application
suggests they were from biosolid application. In fact, these UV
filters have been reported to be detected in biosolid (or sludge) in
the present study and previous studies [8,18]. For treatment 1,
only 1 application was carried out, in May 2007, while repeat
applications were carried out for treatment 2 on 5 October every
year from 2007 until 2010. Higher soil concentrations were
observed for treatment 2 than for treatment 1 (Figure 1). This
indicates that these chemicals could be persistent and accumulated in agricultural soils following repeated biosolid application.
Further 1-yr monitoring at the Shandong site demonstrated the
persistence of 2 BTs and 5 BUVSs in soil, with their DT50 values
ranging from 75 d to 346 d (Table 2). The 2 BTs (BT and 5-TT)
showed generally higher persistence than the 5 BUVSs. This
suggests that addition of more functional groups such as phenolic
groups onto the benzotriazole structure increased the degradability
of UV filters. The dissipation of BT and 5-TT in the environment
is mainly via biodegradation [25]. Laboratory biodegradation
studies [25] found the half-lives of BT (114–315 d) and 5-TT (14–
128 d) to be lower than those (BT: 268–345 d; 5-TT: 217–265 d)
in the present study. The dissipation rates of BT and 5-TT for
treatment 2 were faster than those for treatment 1, which suggests
that the repeated application of biosolid could promote their
dissipation in biosolid-amended soils. This may be owing to the
addition of more nutrients through biosolid application that can
increase microbial activities. However, no consistent differences
were found for the 5 BUVSs between the 2 treatments (Table 2),
suggesting their different degradation behaviors.
The stabilizers UV-326, UV-327, UV-328, UV-329, and
UV-P are derivatives of 2-hydroxyphenyl benzotriazole and
Dissipation of benzotriazole ultraviolet stabilizers
Environ Toxicol Chem 33, 2014
765
Figure 2. Field dissipation of the selected compounds for treatment 1 (T1) at the Shandong site within 1 yr (October 2010–October 2011). Data points with empty
symbols were treated as outliers during data fitting because the points are not included between the 95% prediction bands. The nonlinear regression fits for the firstorder kinetic model, 95% confidence band, and 95% prediction band are represented by the solid line, dashed line, and dotted line, respectively. See Figure 1
caption for definition of abbreviations.
have similar molecular structures, which only differ by the
different substituents (Figure 4). Their biodegradation potentials
can also be perceived to be quite similar [20]. Ruan et al. [20]
applied the US Environmental Protection Agency EPI Suite
V4.1, the University of Minnesota Pathway Prediction System,
and the Organisation for Economic Co-operation and Development’s overall persistence and long-range transport potential
fugacity screening tool (Pov-LRTP tool) to predict potential
transformation pathways and total persistence of these BUVSs
compounds in a multimedia evaluative environment. The
predicted half-lives of the 5 BUVSs in soil calculated by EPI
Suite V4.1 ranged between 75 d and 120 d, while those predicted
by the Pov-LRTP tool were between 108 d and 173 d (Table 3).
These predicted results were in general comparable with those
obtained from the field trials in the present study.
The present study showed different degradation patterns
among the 5 BUVSs (UV-326, UV-327, UV-328, UV-329, and
UV-P). Two of these, UV-329 and UV-P, showed faster
dissipation in the soils with repeated application of biosolid
(treatment 2) than with a single application of biosolid; UV-326,
UV-327, and UV-328 had the opposite results, however, with
repeated application of biosolid slowing their dissipation. This is
linked to their different chemical structures and subsequent
environmental behaviors. This can be explained by the
University of Minnesota Pathway Prediction System, which is
a well-established microbial catabolic reaction database that
recognizes the substructure of a chemical and predicts
transformation products by matching biotransformation rules.
The results predicted by the University of Minnesota Pathway
Prediction System showed that the 5 BUVSs with different
Figure 3. Field dissipation of the settled compounds for treatment 2 (T2) at the Shandong site within 1 yr (October 2010–October 2011). Data points with empty
symbols were treated as outliers during data fitting since the points are not included between the two 95% prediction bands. The nonlinear regression fits for the
first-order kinetic model, 95% confidence band, and 95% prediction band are represented by the solid line, dashed line, and dotted line, respectively. See Figure 1
caption for definition of abbreviations.
766
Environ Toxicol Chem 33, 2014
H.-J. Lai et al.
Table 2. Summary of the dissipation information in biosolid-amended soils based on the first-order model for benzotriazoles and ultraviolet filters at the Shandong
site
Compound
BT
5-TT
UV-326
UV-327
UV-328
UV-329
UV-P
Calculation
Treatment 1
Treatment 2
Fitting formula
R2a
p valueb
k (error)c
DT50 (error)d
Fitting formula
R2
p value
k (error)
DT50 (error)
Fitting formula
R2
p value
k (error)
DT50 (error)
Fitting formula
r2
p value
k (error)
DT50 (error)
Fitting formula
r2
p value
k (error)
DT50 (error)
Fitting formula
r2
p value
k (error)
DT50 (error)
Fitting formula
r2
p value
k (error)
DT50 (error)
Y ¼ 1.9477 exp(0.0602 X)
0.1901
0.0126
0.0602 (0.0237)
345 (161)
Y ¼ 2.0719 exp(0.0786 X)
0.2967
0.0015
0.0786 (0.0227)
265 (83)
Y ¼ 3.7259 exp(0.1995 X)
0.8128
<0.0001
0.1995 (0.0187)
104 (10)
Y ¼ 2.5512 exp(0.1380 X)
0.6912
<0.0001
0.1380 (0.0170)
151 (19)
Y ¼ 2.4303 exp(0.1159 X)
0.6107
<0.0001
0.1159 (0.0171)
179 (27)
Y ¼ 6.1681 exp(0.1614 X)
0.5133
<0.0001
0.1614 (0.0332)
129 (28)
Y ¼ 7.0246 exp(0.1837 X)
0.3429
0.0013
0.1837 (0.0524)
113 (35)
Y ¼ 2.8020 exp(0.0776 X)
0.3415
0.0004
0.0776 (0.0207)
268 (77)
Y ¼ 3.4018 exp(0.0954 X)
0.4112
<0.0001
0.0954 (0.0218)
217 (53)
Y ¼ 5.0355 exp(0.1476 X)
0.7476
<0.0001
0.1476 (0.0171)
141 (17)
Y ¼ 3.3293 exp(0.1085 X)
0.6468
<0.0001
0.1085 (0.0155)
192 (28)
Y ¼ 3.9249 exp(0.0952 X)
0.5188
<0.0001
0.0952 (0.0178)
218 (42)
Y ¼ 21.2728 exp(0.2127 X)
0.6486
<0.0001
0.2127 (0.0344)
98 (16)
Y ¼ 28.0073 exp(0.2768 X)
0.6069
<0.0001
0.2768 (0.0485)
75 (14)
The correlation coefficient of the first-order reaction kinetic model.
Significance of the first-order reaction kinetic model.
Rate constant of the first-order reaction kinetic model.
d
The dissipation half-life (days) determined using the first-order reaction kinetic model under the 2 treatments.
BT ¼ benzotriazole; 5-TT ¼ 5-methyl-1H-benzotriazole; UV ¼ ultraviolet; DT50 ¼ 50% dissipation time; UV-326 ¼ 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5chlorobenzotriazole; UV-327 ¼ 2-(20 -hydroxy-30 ,50 -di-tert-butylphenyl)-5-chlorobenzotriazole; UV-328 ¼ 2-(2-hydroxy-3,5-dipenryl-phenyl) benzotriazole;
UV-329 ¼ 2-(20 -hydroxy-50 -octylphenyl) benzotriazole; UV-P ¼ 20 -hydroxy-5mg-methylphenyl benzotriazole.
a
b
c
Table 3. Comparison of the predicted and measured half-lives (d) of
benzotriazole ultraviolet stabilizers in biosolid-amended soils from the
Shandong site
Predicted
EPI Suitea
Pov-LRTP Toob
Measured
Treatment 1
Treatment 2
a
Figure 4. Predicted biotransformation routes for the 5 benzotriazole
ultraviolet stabilizers (BUVSs) by the University of Minnesota Pathway
Prediction System. UV-326 ¼ 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5chlorobenzotriazole; UV-327 ¼ 2-(20 -hydroxy-30 ,50 -di-tert-butylphenyl)-5chlorobenzotriazole; UV-328 ¼ 2-(2-hydroxy-3,5-dipenryl-phenyl) benzotriazole; UV-329 ¼ 2-(20 -hydroxy-50 -octylphenyl) benzotriazole; UV-P ¼
20 -hydroxy-5mg-methylphenyl benzotriazole.
UV-326
UV-327
UV-328
UV-329
UV-P
120
173
120
173
120
173
120
173
75
108
104
141
151
192
179
218
129
98
113
75
The half-lives of the 5 benzotriazole ultraviolet stabilizers in soil calculated
by the US Environmental Protection Agency EPI Suite Ver. 4.1 [20].
b
The overall persistent half-lives predicted by the Organisation for Economic
Co-operation and Development’s overall persistence and long-range
transport potential fugacity screening (Pov-LRTP) tool [20].
UV-326 ¼ 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole;
UV-327 ¼ 2-(20 -hydroxy-30 ,50 -di-tert-butylphenyl)-5-chlorobenzotriazole;
UV-328 ¼ 2-(2-hydroxy-3,5-dipenryl-phenyl) benzotriazole; UV-329 ¼
2-(20 -hydroxy-50 -octylphenyl) benzotriazole; UV-P ¼ 20 -hydroxy-5mgmethylphenyl benzotriazole.
Dissipation of benzotriazole ultraviolet stabilizers
branched-chain substituents displayed distinct plausible transformation pathways in aerobic conditions (Figure 4). Hydrolysis
could occur for the 5 BUVSs as the first step of the
transformation, but it might take place at different positions
for different compounds. For UV-329 and UV-P with 1 aliphatic
branched-chain substituent, a hydrolytic process might occur at
the phenol subgroup. For UV-328 with 2 aliphatic substituents, a
hydrolytic process might occur at the branched-chain substituents. For UV-326 and UV-327 with a chlorine-containing
substituent, hydrolysis might occur at the benzotriazole
subgroup. Therefore, UV-329 and UV-P showed similar
dissipation behaviors in the biosolid-amended soils but were
different from UV-326, UV-327, and UV-328.
Environ Toxicol Chem 33, 2014
7.
8.
9.
10.
11.
CONCLUSIONS
The present study demonstrated the accumulation and
persistence of the selected BTs and BUVSs in biosolid-amended
soils of the 3 field trials. But 1-yr monitoring also showed
significant dissipation of BT, 5-TT, UV-326, UV-327, UV-328,
UV-329, and UV-P in the field soils, with half-lives of 76 d to
345 d. Higher persistence in the biosolid-amended soils was
found for BT and 5-TT than the 5 BUVSs. Repeated application
of biosolid promoted the dissipation of UV-329 and UV-P but
slowed the dissipation of UV-326, UV-327, and UV-328. This
phenomenon could be explained by their different chemical
structures, which can affect their transformation pathways in the
soil environment.
12.
13.
14.
15.
16.
SUPPLEMENTAL DATA
Tables S1–S7.
Figures S1 and S2. (725 KB DOC).
Acknowledgment—We acknowledge financial support from the CAS Key
Projects (KZCX2-EW-108, KZZD-EW-09, and KZCX2-YW-JC105) and
the Natural Science Foundation of China (NSFC U1133005 and 41121063).
We thank Y.B. Zuo at the Dezhou Agriculture Experimental Station for his
help in field trials. This is a contribution no. 1815 from GIG CAS.
17.
18.
19.
20.
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