Organic pollutants in paper-recycling process water discharge areas: First detection and emission in aquatic environment

Article abstract of DOI:10.1016/j.envpol.2007.03.012

In this study, eight compounds have been identified and quantified from the samples collected from paper-recycling process water discharge areas. In particular, five aryl hydrocarbons, including a novel chlorinated aryl ether, were identified for the first time as environmental pollutants. In the effluent stream, concentration levels of up to 1600 μg L^-1 and 190 μg g^-1 were detected in the surface water and surface sediment, respectively. The results of this study have raised concerns regarding the organic chemicals used in thermal paper and the environmental consequences of their release.

Full text of DOI:10.1016/j.envpol.2007.03.012

Available online at www.sciencedirect.com
Environmental Pollution 151 (2008) 53e59
www.elsevier.com/locate/envpol
Organic pollutants in paper-recycling process water discharge areas:
First detection and emission in aquatic environment
b
a
a
Masanori Terasaki a, , Hitoshi Fukazawa , Yukinori Tani , Masakazu Makino
*
a Institute for Environmental Sciences, University of Shizuoka, Yada 52-1, Suruga-ku, Shizuoka 422-8526, Japan
b Shizuoka Institute of Environment and Hygiene, Kita-Ando 4-27-2, Aoi-ku, Shizuoka 420-8637, Japan
Received 7 November 2006; received in revised form 26 February 2007; accepted 12 March 2007
This study reports the first detection of aryl hydrocarbons used in thermal paper in the environment.
Abstract
In this study, eight compounds have been identified and quantified from the samples collected from paper-recycling process water discharge
areas. In particular, five aryl hydrocarbons, including a novel chlorinated aryl ether, were identified for the first time as environmental pollutants.
In the effluent stream, concentration levels of up to 1600 mg Lꢀ1 and 190 mg gꢀ1 were detected in the surface water and surface sediment,
respectively. The results of this study have raised concerns regarding the organic chemicals used in thermal paper and the environmental con-
sequences of their release.
Ó 2007 Elsevier Ltd. All rights reserved.
Keywords: Aryl hydrocarbons; Surface sediment; Synthesis; Thermal paper; Paper-recycling process water
1. Introduction
aromatic hydrocarbons (PAHs) and biphenyls. However, the
environmental occurrence of these organic pollutants, which
were not considered for a long time, is due to an increase in
the production of thermal paper over the last decade.
The effluents and process waters from paper-recycling in-
dustries are complex matrices containing several compounds
that may affect vertebrate physiology and reproductive func-
Thermal paper has been widely used in an increasing num-
ber of applications such as point-of-sale receipts, admission
tokens, ticket vending machines, medical records, baggage
tags, fax papers, and food delivery in point-of-sale systems
(Minami et al., 1991; Zeira and Ellett, 2000). In Japan, the an-
nual production of special paper including thermal paper is ap-
proximately 132,000 tons (Japan Paper Association, 2005). In
thermal paper manufacturing, large amounts of chemicals are
used to achieve a higher recording sensitivity or to improve the
preservability of recorded images (Iida and Tsuchida, 1999).
Many of these chemicals are hydrophobic organic compounds
such as aryl hydrocarbons and ethers (Kiritani et al., 1974; Jin
tions (Mellanen et al., 1996; Merilainen et al., 2006; Orrego
´
¨
et al., 2005; Rigol et al., 2004; Sepulveda et al., 2003). For
example, pulp and paper mill effluent was shown to exhibit
significant estrogen and aryl hydrocarbon receptor (AhR) me-
diated activity in vivo when extracted with methanol (Parks
et al., 2001; Zacharewski et al., 1995). In this study, however,
AhR ligands were not identified by chemical analysis because
of the lack of appropriate standards.
et al., 2006; Mitsuo and Iwasaki, 2004; Norback et al., 1988).
¨
Moreover, most of these compounds are considered potentially
persistent because of their structural analogy to polycyclic
Therefore, the objective of this study was to identify a gas
chromatography-mass spectrometry (GC-MS) method and
authentic synthetic standards by using fractionation by gel per-
meation chromatography (GPC). This study reports on the first
detection of aryl hydrocarbons and ethers in the surface water
and surface sediment collected from paper-recycling process
* Corresponding author. Tel./fax: þ81 54 264 5783.
E-mail address: terasaki@u-shizuoka-ken.ac.jp (M. Terasaki).
0269-7491/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2007.03.012

54
M. Terasaki et al. / Environmental Pollution 151 (2008) 53e59
acetate. The organic solution was washed with brine and dried over sodium
sulfate. After the removal of the solvent under a reduced pressure, the obtained
residue was chromatographed on a silica gel column (500 ꢂ 30 mm) and
eluted with hexane/dichloromethane (7/3, v/v). Fractions containing com-
pound (7) were collected and the solvent was evaporated to yield a white pow-
der (0.17 g). 1H NMR (CDCl3): d 2.34 (d, 6H, 2 ꢂ CH3), 4.28 (d, 4H,
2 ꢂ CH2), 6.71e6.83 (m, 5H, Ar-H), 7.17 (t, 1H, J ¼ 8.00 Hz, Ar-H), 7.22
(d, 1H, J ¼ 8.60 Hz, Ar-H); HR FAB MS þve mode (Mþ): 276.0856 (Int.
100%) (calcd. for 276.0888; C16H17O325Cl), 278.0901 (Int. 42%) (calcd. for
278.0918; C16H17O327Cl).
water discharge areas. In addition, the proposed authentic syn-
thetic standards would facilitate further analytical and toxico-
logical studies of this environment.
2. Materials and methods
2.1. Chemicals
1,10-Ditolylmethane (1) and m-terphenyl (5) were purchased from Wako
Pure Chemical Industries, Osaka, Japan; 2,6-diisopropylnaphthalene (3) and
4-benzylbiphenyl (8), from Tokyo Chemical Industry, Tokyo, Japan; Metha-
nol-d4, from Cambridge Isotope Laboratories, Maryland, USA; chloroform-d,
from Acros Organics, Tokyo, Japan; pyrene-d10, from Kanto Chemicals, Tokyo,
Japan; silica gel 60 (0.040e0.063 mm, for column chromatography), from
Merck, Darmstadt, Germany; and SephadexÔ LH-20, from Amersham Biosci-
ences, Tokyo, Japan. The solvents used were HPLC grade and were not purified
further.
2.3. Sampling locations, sample collection, and
physicochemical characterization
There are 85 pulp and paper mill and recycling paper mill industries in Fuji
city, Shizuoka Prefecture, which is the largest paper mill industry area in Ja-
pan. The port is also a commercial ship harbor with a total traffic of 3700 ships
in 2005 (Port of TAGONOURA Administration Office). The process water
from these industries is discharged via an outfall into the port; the average
daily flow is 570,000 m3 dꢀ1. Previous research has revealed that the chlori-
nated derivatives of bisphenol A originating from the wastepaper recycling
plants were found in the effluents discharged into this outfall (Fukazawa
et al., 2001).
2.2. Synthesis and characterization
1,10-Ditolylethane (2), 1,2-bis(3-methylphenoxy)ethane (4), benzyl 2-naph-
thyl ether (6), and 1-(4-chloro-3-methylphenoxy)-2-(3-methylphenoxy)ethane
(7) were synthesized and characterized by proton nuclear magnetic resonance
spectrometry (1H NMR) spectroscopy at 500 MHz (JEOL ECA-500 spectrom-
eter, JEOL, Tokyo, Japan), GC (HP6890A GC system, Agilent Technologies,
Tokyo, Japan)-MS (JMS-AMSUN200, JEOL, Tokyo, Japan), and high-resolu-
tion fast atom bombardment (FABþ) MS (JMS-700 instrument, JEOL, Tokyo,
Japan).
The samples were collected in two monthsdNovember 2005 and August
2006dfrom the outfall (site 1), upstream (site 2), mouth of the port (site 3),
and two tributaries (sites 4 and 5) from which the rivers discharge into the Pa-
cific Ocean (Fig. 1). Sediment samples (500 g) were collected from the sedi-
ment surface (depth: 5 cm) using an Ekman-Birge bottom sampler, and water
samples (1 L) were collected from the surface water (depth: 10 cm) between 8
am and 10 am. The samples were collected in glass bottles with aluminum-
lined stoppers, transported to the laboratory in cold boxes with ice, and stored
at 4 ꢁC until analysis (within 10 days). The physicochemical characterizations
of the samples are listed in Table 1. The temperature and pH values were mea-
sured using a pH meter (PICCOLOþ, HANNA instruments, Tokyo, Japan).
The salinity was obtained by converting the conductivity values to salinity us-
ing an electrical conductivity meter (CM-14P, TOA Electronics, Tokyo, Ja-
pan). The total organic carbon (TOC) was measured using a TOC analyzer
Compound (2) was obtained by coupling toluene and acetaldehyde with sul-
furic acid as the catalyst (Innes and Occelli, 1985). Toluene (4.1 mL) in concen-
trated sulfuric acid (1.5 mL) was cooled in an ice bath, and acetaldehyde
(0.6 mL) was added over a period of 30 min. This mixture was stirred for 3 h
at 5 ꢁC, poured into ice-water, and extracted using ethyl acetate. The organic
solution was washed with brine and dried over sodium sulfate. After the re-
moval of the solvent under reduced pressure, the residue was chromatographed
on a silica gel column (500 ꢂ 30 mm) and eluted with hexane/ethyl acetate (8/
2, v/v). Fractions containing compound (2) were collected and the solvent was
evaporated to yield a colorless liquid (70 mg). 1H NMR (CDCl3): d 1.60 (d, 3H,
CH3), 2.29 (s, 6H, 2 ꢂ CH3), 4.07 (q, 1H, CH), 7.07 (d, 4H, J ¼ 7.45 Hz, Ar-
H), 7.09 (d, 4H, J ¼ 7.45 Hz, Ar-H); MS: 210 (Mþ).
Compound (4) was obtained by reacting m-cresol in the presence of 50%
aqueous sodium hydroxide. Fifty percent aqueous sodium hydroxide (10 mL)
was added to a solution of m-cresol (50 g) in 1,2-dichloroethane (20 mL) over
a period of 60 min at 105 ꢁC, and the mixture was then refluxed for 7 h. After
cooling, the reaction mixture was extracted with ether. The organic layer was
washed with brine and dried over sodium sulfate. The solvent was evaporated
to yield compound (4) (15 g), which was crystallized from ethanol; the mp of
the compound was 96e97 ꢁC (lit. 98 ꢁC, Satomura et al., 1986). 1H NMR
(CDCl3): d 2.33 (s, 6H, 2 ꢂ CH3), 4.30 (s, 4H, 2 ꢂ CH2), 6.74e6.80 (m,
6H, Ar-H), 7.17 (t, 2H, J ¼ 8.05 Hz, Ar-H); MS: 242 (Mþ).
Pacific Ocean
N
Compound (6) was obtained by ether synthesis of 2-naphthol and benzyl
bromide. The mixture of benzyl bromide that was prepared from toluene
(9.2 g) and bromine (15 g) under light irradiation, 2-naphthol (11.5 g), potas-
sium carbonate (11 g), and acetone (150 mL) was refluxed for 24 h. Water
(100 mL) was added to this mixture and it was extracted with ether. The ex-
tract was washed with 10% aqueous sodium hydroxide after washing with
brine and dried over sodium sulfate. The solvent was evaporated to yield com-
pound (6) (6.1 g), which was crystallized from ether; the mp of the compound
was 98e100 ꢁC (lit. 99e100 ꢁC, Kornblum et al., 1963). 1H NMR (CDCl3):
d 5.19 (s, 2H, CH2), 7.23 (s, 1H, Ar-H), 7.25 (d, 1H, J ¼ 2.30 Hz, Ar-H),
7.33e7.46 (m, 5H, Ar-H), 7.50 (d, 2H, J ¼ 7.45 Hz, Ar-H), 7.73 (d, 1H,
J ¼ 8.60 Hz, Ar-H), 7.76 (d, 1H, J ¼ 8.60 Hz, Ar-H), 7.78 (d, 1H,
J ¼ 7.45 Hz, Ar-H); MS: 234 (Mþ).
5
4
Outfall
1
2
3
500 m
Compound (7) was obtained by reacting compound (4) (0.24 g) with chlo-
ramine T (2.8 g) in a refluxing 50% aqueous dioxane solution (10 mL) for 4 h.
Water (10 mL) was added to this mixture and it was extracted with ethyl
Fig. 1. Location of the sampling sites and the outfall in Shizuoka Prefecture.
The arrows indicate the direction of water flow in the area.

M. Terasaki et al. / Environmental Pollution 151 (2008) 53e59
55
Table 1
Physicochemical characterizations of the samples obtained from the study area
Surface water
Surface sediment
Site 1 Site 3
Site 1
Site 2
Site 3
Site 4
Site 5
Blank
Temperature/ꢁC
pH
24
24
26
24
20
16
n.a.a
n.a.
n.a.
21
n.a.
n.a.
n.a.
12
7.1
0.05
n.a.
7.6
0.02
n.a.
7.2
0.30
n.a.
7.8
<0.01
n.a.
7.9
<0.01
n.a.
8.0
<0.01
n.a.
Salinity/%
TOCb/%
a
Not analyzed.
Total organic carbon.
b
(TOC-5000A, Shimadzu, Kyoto, Japan) combined with an electric furnace
(SSM-5000A, Shimadzu, Kyoto, Japan) after pretreatment with 1 M hydro-
chloric acid.
was then programmed to approach 280 ꢁC at a rate of 10 ꢁC minꢀ1 with a final
hold time of 7 min. Helium was used as the carrier gas with a flow rate of
1.0 mL minꢀ1, and the column head pressure was maintained at 8.0 psi. The
injector temperature was maintained at 250 ꢁC and the injection volume was
1.0 mL in the splitless mode. The electron multiplier voltage for MS was
1988 V, and the interface temperature was maintained at 280 ꢁC. Mass spectra
were obtained by electron impact ionization at a voltage of 70 eV and scanned
in a range of m/z 50 to 550 a.m.u. at a rate of 1.5 scans sꢀ1; the ion source tem-
perature was maintained at 250 ꢁC. The chemicals in the samples were iden-
tified by comparing their gas chromatographic retention times and mass
spectra with those of the authentic standards. These compounds were quanti-
fied by correlating the ratio of the peak area of the compound of interest to that
of the internal standard (pyrene-d10) to the calibration curve of the standard
solution. The standard calibration solution containing compounds
(1e8) was prepared in dichloromethane.
2.4. Extraction and fractionation
The freeze-dried sediment samples (10 g) were extracted by ultrasonic ex-
traction using methanol (10 mL ꢂ 4). After the removal of the solvent under
reduced pressure, the residues dissolved in the methanol (5 mL) and samples
(1 mL) were subjected to gel permeation chromatography on a SephadexÔ
LH-20/methanol column (300 ꢂ 30 mm) and 18 mL fractions were collected
using a fraction collector (FR50N, Yamazen, Osaka, Japan). The methanol
was removed separately from each fraction by using a stream of nitrogen.
The fractions were pipetted along with methanol into a GC-MS vial and dried
in a stream of nitrogen. The extracted samples were reconstituted into
dichloromethane (0.1 mL) containing 2 mg mLꢀ1 of the internal standard
(pyrene-d10) and examined by GC-MS.
Water samples (100 mL) were filtered (GF/A glass microfiber filters,
Whatman Japan K.K, Tokyo, Japan) and extracted in dichloromethane
(25 mL ꢂ 2) by using a shaker (Recipro Shaker SR-2s, TAITEC, Saitama, Ja-
pan) at 265 rpm for 10 min. After the removal of the solvent under reduced
pressure, the residue was treated in the same manner as the sediment samples
for the GC-MS examination.
2.6. Quality assurance and quality control
Data are expressed as means of two separate experiments performed in du-
plicate. The characteristics of the method and chemicals used in this study are
listed in Table 2. The partition coefficients for octanol and water have been
calculated using the LogKow program (Syracuse Research Corporation,
2007). The relative standard deviations of these results were within 13%
and 24% for the recoveries and samples, respectively. The recoveries were de-
termined by using distillated water and pre-ignited sand spiked at 5 mg Lꢀ1
and 1 mg gꢀ1, respectively. The recoveries varied between 89% and 109%,
and all standards exhibited linearity from 0.7 mg Lꢀ1 up to 64 mg Lꢀ1. The co-
efficient of determination (R2) ranged from 0.98 to 0.99 for five concentration
levels. The concentration of the lowest calibration standard was operationally
defined as the limit of quantification (LOQ). Blank samples (surface water
2.5. Analytical methods
The standard and sample extracts were analyzed by employing GC (HP
6890 Series, Palo Alto, CA, USA)-MS (HP 6890 Series mass selective detec-
tor, Palo Alto, CA, USA) on a HP-5 fused silica capillary column
(30 m ꢂ 0.32 mm i.d., 0.25 mm film, J&W Scientific, Folsom, CA, USA).
The column temperature was initially maintained at 60 ꢁC for 1 min and it
Table 2
Characteristics of the method and chemicals
Compound
Rta
MS Ions
Recovery %
Water
LOQb
mg Lꢀ1
R2c
LogKowd
Min
Quante m/z
Conff m/z
Sand
1
2
3
4
5
6
7
4,40-Dimethyldiphenylmethane
13.4
14.0
14.2
16.9
18.4
18.5
18.8
181
195
197
242
230
234
276
196
210
212
134
115
91
107
108
108
100
97
104
106
109
96
2.7
2.2
0.8
0.6
0.8
0.9
0.7
0.99
0.99
0.99
0.98
0.99
0.99
0.99
5.11
5.24
6.08
4.90
5.52
4.96
5.16
1,1-Di(4-methylphenyl)ethane
2,6-Diisopropylnaphthalene
1,2-Bis(3-methylphenoxy)ethane
m-Terphenyl
102
96
Benzyl 2-naphthyl ether
1-(4-Chloro-3-methylphenoxy)-
2-(3-methylphenoxy)ethane
4-Benzylbiphenyl
105
89
168
95
8
19.1
244
165
96
97
1.2
0.99
5.78
a
b
c
d
e
f
Retention time.
Limits of quantification.
Coefficient of determination.
Calculated using SRC’s LogKow (KowWIN) Program.
For quantification.
For confirmatory purposes.

56
M. Terasaki et al. / Environmental Pollution 151 (2008) 53e59
from the Kusanagi river, E138ꢁ2702400, N34ꢁ5902800) were routinely analyzed
and no contamination of solvents or equipment was detected.
´
naphthalene (3) (Garcıa et al., 2006; Jin et al., 2006; Kiritani
et al., 1974). Fig. 2a reveals that the fragmentation patterns
of the spectra of all three peaks, including peak 2, on the total
ion chromatogram were similar to that of an authentic sample
of compound (2) and were therefore as its constitutional iso-
mers. For similar reasons, all four peaks, including peak 3,
on the total ion chromatogram were also characterized as the
constitutional isomers of diisopropylnaphthalene (3). Fraction
14 contained an aryl ether (4), its chloro-derivative (7), and
a non-fused tricyclic compound (8). Fraction 15 contained
compound (5) and naphthyl ether (6) (Fig. 2b,c). Compounds
(4)e(6) and (8) are widely employed as color sensitizers
during the manufacture of thermal paper and carbonless
copy paper (Iida and Tsuchida, 1999; Iwasaki et al., 2005;
Makitalo and Mattila, 2006).
3. Results and discussion
The typical chromatograms of the extracts from a surface
sediment sample (site 3) that were fractionated by GPC on
a SephadexÔ LH-20 are shown in Fig. 2. The MS data of
the identified compounds in the sample and their standards
are shown in Fig. 3. Four compounds identified as contami-
nants in the samples were synthesized and characterized (1H
NMR spectroscopy and mass spectrometry). Fractions 12e
13 contained solvents used in the manufacture of thermal
paper, such as diarylalkanes (1 and 2) and alkyl-substituted
Table 3 summarizes the concentrations of the aryl hydro-
carbons and ethers present in the samples obtained from the
study area. Higher concentrations were observed in site 1
because it is close to the outfall area of the industrial process
water. Site 3, which is the mouth of the port, receives a combi-
nation of the waters from the outfall (site 4) and site 5. These
compounds were also found in site 3, whereas they were not
detected upstream (site 2) of the outfall and in the other two
tributaries (sites 4 and 5). Therefore, the compounds detected
at sites 1 and 3 suggest that the chemicals detected in the pa-
per-recycling process water originated from thermal paper.
The concentration levels in site 1 ranged from 1.2 to
1600 mg Lꢀ1 and LOQ to 190 mg gꢀ1 for the water and sedi-
ment samples, respectively. At the downstream site of the out-
fall, the concentration levels ranged from LOQ to 8.9 mg Lꢀ1
and LOQ to 53 mg gꢀ1 for the water and sediment samples, re-
spectively. In particular, compounds (2), (4), and (6)e(8) were
detected for the first time as environmental pollutants. Com-
pound (2) was the most abundant in the samples investigated;
its maximum measured concentration was comparable to that
of alkylbenzenesulfonate found in paper-recycling process wa-
ters, as reported previously (5000 mg Lꢀ1, Rigol et al., 2002).
The concentrations of compounds (1) and (3) in the water near
the outfall were 500 and 260 mg Lꢀ1, respectively; these
values are equal to those of bisphenol A found in process
waters during papermaking (187 mg Lꢀ1, Rigol et al., 2004).
Compounds (4) and (6), which are aryl ethers, were found at
levels of up to 10 and 23 mg Lꢀ1, respectively. These con-
centration levels were similar to those stated in the literature
data on nonylphenol in paper-recycling process waters (1e
10 mg Lꢀ1, Lacorte et al., 2003).
a
a
2
b
3
1
13
14
15
4
b
I.S.
8
7
17
18
19
6
c
I.S.
5
Several of the identified compounds are known as anthro-
pogenic pollutants and are consequently reported in some en-
vironmental studies. Compound (1) has been observed in air
particulates as soot originating from fuel (Jones et al., 2004).
Compounds (3) and (5) were reported to be present in sedi-
ments as contaminants resulting from the emissions from bio-
mass fuel combustion as well as manufacturing plants (Kawata
et al., 2005). On the other hand, this study reports the presence
of compounds (2), (4), (6), (7), and (8) in the aquatic environ-
ment. The emission of these compounds into the aquatic envi-
ronment has not been reported thus far. Moreover, no data
16
17
18
Retention time / min
Fig. 2. Typical total ion chromatograms of fractionated extractsd(a) fraction
12; (b) fraction 14; and (c) fraction 15dfrom the surface sediment (site 3) that
were obtained by gel permeation chromatography on a SephadexÔ LH-20.
aThe chromatogram of 1,1-di(4-methylphenyl)ethane isomers consists of three
peaks. bThe chromatogram of the diisopropylnaphthalene isomers consists of
four peaks. I.S. ¼ Internal standard.

M. Terasaki et al. / Environmental Pollution 151 (2008) 53e59
57
A
B
181
181
1
Me
Me
196
196
165
165
104
77
152
89
96
77
89
51
65
115
152
115
103
51
128
63
141
128
141
189
195
173 189
195
207
Me
2
Me
Me
210
210
165
165
180
180
89
89
77
115
103 115
77
103
51
65
152
152
65
133
141
51
128
139
125
i-Pr
197
197
3
i-Pr
212
212
155
165
155
135
141
169
91
121
107
55
77
83
128
98 107 119
182
181
55
63 75
65
221
221
236
91
91
O
Me
Me
134
O
4
134
242
242
119
65 77
119
77
65
107
107
51
51
147
218
163
190
181 202
258
230
230
5
115
115
101
152
101
202 215
152
202
189
165 176
215
51
76
63
89
91
128
51
88
76
128
139
176 189
63
165
91
O
6
234
234
65
65
115
115
51
218
203
77
101
127
143 156
51
77
202 215
165 178189
157 177
127 143
101
186
243
166
Cl
Me
276
135
91
91
O
Me
135
O
7
276
77
77
168
107
119
168
107
119
65
65
51
51
153
197
181
165
229
244
244
8
165
57
91
152
71
228
91
115
152
187
177
229
115
133
142
82
103
202
212
215
202
51 65
77
141
128
101
189
178
Fig. 3. Mass spectra of compounds (1e8) (A) in the surface sediment (site 3) and (B) of the authentic standards. Numbers refer to the peak numbers of Fig. 2.

58
M. Terasaki et al. / Environmental Pollution 151 (2008) 53e59
Table 3
Concentrations of organic pollutants in the samples collected from the paper-recycling process water discharge areas
Compound
Outfall watershed
Site 4
Site 5
Adjacent area, site 1
Upstream, site 2
Downstream, site 3
Water
mg Lꢀ1
Water
mg Lꢀ1
Water
mg Lꢀ1
Sediment
mg gꢀ1
Water
mg Lꢀ1
Water
mg Lꢀ1
Sediment
mg gꢀ1
1
2
3
4
5
6
7
8
1,10-Ditolylmethane
500
1600
260
10
38
<LOQa
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
4.1
8.9
5.9
53
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
<LOQ
1,10-Ditolylethane
190
16
2,6-Diisopropylnaphthalene
1,2-Bis(3-methylphenoxy)ethane
m-Terphenyl
1.5
1.4
2.9
0.7
2.2
1.5
8.3
23
1.2
1.7
<LOQ
1.2
Benzyl 2-naphthyl ether
1-(4-Chloro-3-methylphenoxy)-2-(3-methylphenoxy)ethane
4-Benzylbiphenyl
3.7
<LOQ
1.6
1.2
5.8
<LOQ
1.9
<LOQ
<1.2
a
LOQ ¼ limits of quantification.
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The GC-MS analyses revealed the presence of eight aryl
hydrocarbons and ethers in the water and sediment samples
collected from paper-recycling process water discharge
areas. In particular, 1,10-ditolylethane (2), 1,2-bis(3-methyl-
phenoxy)ethane (4), benzyl 2-naphthyl ether (6), 1-(4-
chloro-3-methylphenoxy)-2-(3-methylphenoxy)ethane (7), and
4-benzylbiphenyl (8) were identified for the first time as
environmental pollutants. Concentration levels of up to
1600 mg Lꢀ1 and 190 mg gꢀ1 were detected for the surface wa-
ter and surface sediment samples, respectively. Compound (2)
was the most abundant in the investigated samples; its concen-
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in paper-recycling process waters, as reported previously. The
authentic synthetic standards and analytical studies reported in
this study will further investigations regarding the environ-
mental consequences of the release of the abovementioned
pollutants.
´
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