ANALYSIS OF CHLOROPHENOLS, CHLOROCATECHOLS,

CHLORINATED METHOXYPHENOLS AND MONOTERPENES

IN COMMUNAL SEWAGE OF L
ODZ AND IN THE NER
RIVER IN 19992000

JAROMIR MICHA
LOWICZ and ROBERT OZADOWICZ WIRGILIUSZ DUDA

Department of Environmental Pollution Biophysics, University of
Lodz, 12/16 Banacha St.,
90-237
Lodz, Poland
( author for correspondence, e-mail: michalow@biol.uni.lodz.pl; Tel: +48-42-6354475;
Fax: +48-42-6354473)

(Received 24 June 2004; accepted 17 February 2005)

Abstract. The aim of the study was to determine phenol, chlorophenols, chlorocatechols, chlorinated
methoxyphenols and monoterpenes in communal sewage that was purified by Group Purification
Plant in
Lodz (Poland) and also in Ner River that is the receiver of purified sewage. The effectivity of
degradation (purification) of investigeted compounds was also analysed. The compounds were con-
centrated on octadecyl (C 18) layers in a Baker-Separex system. Obtained extract was separated using
gas chromatography (GC) and analysed by mass spectrometry (MS). In investigated samples phe-
nol, chlorophenols, chlorocatechols, chloroguaiacols, chlorosyringols, 3,4,5-trichloroveratrole, 5,6-
dichlorovaniline and several monoterpenes were determined. Performed analysis showed unsufficient
effectivity of degradation of investigated compounds, particulary chlorophenols and their chlorinated
derivatives. In some cases also appearance of some of the compounds (chlorinated catechols and
methoxyphenols) after biodegradation (purification) proccess was observed.

Keywords: chlorophenols, chlorocatechols, chlorinated methoxyphenols, monoterpenes, microbio-

logical purification

1. Introduction

Phenols and their derivatives are present in the environment with regard to use and
degradation of phenoxyherbicydes such as 2,4-dichlorophenoxyacetic acid (2,4-D)
(Mc Brain et al., 1996) or 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) (Daubaras
et al., 1996). Those compounds are also used such as phenolic biocydes including
2-chlorophenol (2-CP), 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP)
and 2,4,5-trichlorophenol (2,4,5-TCP) (Cernakowa and Zemanowicowa, 1998) or
penachlorophenol (PCP) (Laine and Jorgensen, 1996). The appearrance of phenols
in the environment and in sewages also results from industrial (Bruce et al.,
1987) and municipal activity. Catechols are also formed in a result of degradation
of pesticides (Rozanski, 1998), biphenyls, chlorobenzenes and chlorinated
phenoxyacetics (Sauret-Ignatzi et al., 1996). Chlorinated guaiacols and syringols
are mainly formed by paper industry during bleaching (chlorinating) of wood
Water, Air, and Soil Pollution (2005) 164: 205222 
C Springer 2005
206 J. MICHA
LOWICZ AND R. OZADOWICZ WIRGILIUSZ DUDA

pulp (Morales et al., 1992; Knuutinen, 1982). Methoxyphenols are also used in
pharmacy, medicine and stomatology (Shapiro and Guggenheim, 1998). Some of
described compounds have natural origin. Phenol is formed during decomposition
of organic matter, catechol is biosynthetized by plants (Weiss et al., 1997) and fungi
create chlorinated methoxyphenols. Monoterpenes are produced by coniferous
trees and herbaceous plants (Slimestad et al., 1996; Tomaszewicz-Matysikowa,
1954), and some of them such as pinenes and camphene reach the environment
due to the activity of chemical, tinctoral or pharmaceutical industry (Krupowicz
and Zachariewicz, 1959). Toxicity of phenols (Hoovield et al., 1998; Paintner and
Howard, 1982), catechol (Hagiwara et al., 2001; Wada et al., 1998; Tsutsui et al.
1997), chlorocatechols (Schweigert et al., 2000), guaiacol (Hamaguchi and Tsutsui,
2000), chloroguaiacols (Nimmaguda et al., 1995), syringol (Okada et al., 2000) and
some monoterpenes including their allergic, cytotoxic mutagenic and cancerogenic
properities is the reason to eliminate those compounds from the environment and
sewages. As it is known the methods of microbiological degradation in aerobic con-
dition (Watanabe et al., 1998; Kobayashi and Rittman, 1982) are at least as effective
as physico-chemical (Oturan et al., 2000) or enzymatic methods (Vasudevan and
Li, 1996). High effectivity of degradation is usually obtained in investigations in
which only one or several compounds are used. However effectivity of purification
may considerably be decreased while even several hundreds compounds are de-
graded in sewage in the same time. The aim of this study was to determine phenol,
chlorophenols, chlorinated catechols and chlorinated methoxyphenols and also
monoterpenes in sewages that are formed in the result of industrial and municipal
activity of
Lodz City. Moreover the compunds were analyzed in Ner River that
is a receiver of purified sewages. The samples were taken in spring, summer and
autumn. In work also the estimation of the microbiological degradation of those
compounds by Group Puryfication Plant in
Lodz was undertaken.

2. Collecting Samples

Group Purification Plant Smulsko is situated in
Lodz City in Central Poland. It

is a receiver of sewages throwing down from over one hundred fifty big and sev-
eral hundreds smaller pollution sources such as thermal-electric power stations,
production and industrial plants, petrol filling stations, car washes, leather manu-
factures, abattoris, markets, and hospitals situated within border of the City (raw
sewage). It uses mechanical and biological purification methods that employed
microorganisms such as Spirillum, Vitreoscilla, Sphaerotilus, Beggiatoa, Zooglea,
Vahlkampfia, Mayorella, Arcelal, Stentor, Paramecium and Vorticella.
The samples were collected from raw, purified and mixed sewages (mixture of
purified and raw sewage smaller part of raw sewage that is not purified because
of unfinished building of the plant) and also from Ner river situated in Poddebice
near
Lodz which is the receiver of the mixed sewage.
 ANALYSIS OF COMMUNAL SEWAGE OF
LODZ AND NER RIVER 207

3. Experimental Procedures

3.1. CHEMICALS

Chromatographic standards (purity: 98%99.9%): 1-hydroxybenzene (phenol),

2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,3,6-trichlorophenol, 2,4,5-
trichlorophenol, 2,4,6-trichlorophenol, 2,3,4,5-tetrachlorophenol, pentachlorophe-
nol, 4-methylphenol (p-cresole), 1,2-dihydroxybenzene (catechol), 4-chlorocat-
echol, 3,4,5-trichlorocatechol, tetrachlorocatechol, 2-methoxyphenol (guaiacol),
4,6-dichloroguaiacol, 4,5,6-trichloroguaiacol, tetrachloroguaiacol, 2,5-dimetho-
xyphenol (syringol), 3-chlorosyringol, trichlorosyringol, 1,2-dimethoxybenzene
(veratrole), 3,4,5-trichloroveratrole, 5,6-dichloro-4-hydroxy-3-methoxybenzald-
ehyde (5,6-dichlorovaniline), and monoterpenes -pinene, -pinene, -terpinene,
-terpinene, -terpineole, 2-carene, 3-carene, fenchol, fenchone, borneol, cumene,
camphene and limonen were all bought in Fluka AG, Germany. The solvents
(HPLC purity): methanol, acetone, diethyl ether, hexane and methylene chloride
were obtained from Baker J.T., USA.

3.2. E XPERIMENTAL

3.2.1. Preparation of Sample

Samples were collected in 1 L volumes in dull HD polyethylene bottles. To sam-
ples to inhibit biodegradation and oxidation proccesses 10 ml of methanol and
0.1 g of ascorbic acid were added. Then 10 g of sodium sulphite was added to
precipitate humus substances. Samples were shaken by 15 min and humus was
separated using tissue-paper filters. Next, the inner standard was added (1 g of
2,3,6-trichlorophenol in 1 ml of acetone) and samples were acidified to pH = 2
to decrease solubility of investigated compounds in water. Finally, samples were
mixed using electromagnetic stirrer (750 rts/min) in time of 30 min.

3.2.2. Solid-Phase Extraction on Octadecyl (C18) Filters

in a Baker-Separex System
Adsorption of phenols and their derivatives was performed on octadecyl filters
EMPORE Extraction Disks in a Baker Separex system. The system EMPORE
spe of extraction filters (disks) was equipped with its binding phase octadecyl C18,
diameter of 50 mm and layer thickness of 0.5 mm. The filters (disks) were used in
a special vacuum extraction apparatus Baker Separex made of borosilicate glass.
Octadecyl layer was conditioned using 10 ml volumes of diethyl ether, methylene
chloride, methanol and bidistilized water respectively and elution was done with
four 5 ml volumes of methylene chloride. Next, samples were evaporated, dissolved
in hexane and acethylated (derivatized). Finally samples were concentrated down
to a volume of 0.1 ml.
208 J. MICHA
LOWICZ AND R. OZADOWICZ WIRGILIUSZ DUDA

3.2.3. Gas Chromatography and Mass Spectrometry (GC-MS)

The chromatographic analysis was made using gas chromatograph (Hewlett-
Packard type 5890) connected with a quadruple mass spectrometer type 5972 (tem-
perature MS 152 C) equipped with capillary colum HP 5 (60 m 0.25 mm).
Chromatographic separations were leaded in programmed heating conditions in
the range of the temperature from 60 C which was keeping by 1 min after it was
increased to 160 C with the speed of 5 C/min and finally hightened to 280 C.
The temperature of injector was 260 C. Carrier gas was hellium (flow 1 ml/min).
Qualitative estimation was made in SCAN system (identification of individual com-
pounds by comparision with standards or spectra from spectras library type NBS
75KL) and quantitative estimation was done in SIM system (identification by com-
parision with calibrated standards).

4. Results

In collected samples phenol, 4-methylphenol, chlorophenols, chlorocat-

echols, guaiacol, chloroguaiacols, chlorosyringols, 3,4,5-trichloroveratrole,
5,6-dichlorowaniline and also several monoterpenes were determined. The ranges
of determined concentrations for individual chlorophenols and their derivatives
were of 0.010 g/l to 4.129 g/l in 1999 and of 0.010 g/l to 5.500 g/l in 2000
respectively. The concentrations of monoterpenes were of 0.010 g/l to 25.559 g/l
in 1999 and of 0.010 g/l to 5.435 g/l in 2000. The formation of some compounds,
particulary chlorocatechols and chlorinated methoxyphenols after proccees of mi-
crobiological degradation (purification) was also noted. In Ner river considerable
concentrations of some of chlorophenols and their derivatives were determined.
The comparision of means of total concentrations of determined compounds and
their deviations values in sewages and in Ner river in spring, summer and autumn
were shown in Tables IVI. Chromatogramms of standards of chlorophenols and
their derivatives were shown in Figures 1 and 2 and selected chromatogramms of
the compounds determined in sewage and in Ner river were shown in Figures 35.

5. Discussion of Results

In samples of sewages phenol, 4-methylphenol, chlorophenols, chlorocate-

chols and chlorinated methoxyphenols chloroguaiacols and chlorosyrigols,
3,4,5-trichloroveratrole, 5,6-dichlorovaniline and several monoterpenes were de-
termined. Generaly, the above compounds are synthetized and used by chemical,
cosmetic, edible or pharmaceutical industry that in
Lodz are represented by two
chemical and cosmetic manufactures and also several smaller plants throwing down
effluents to sewer pipe. For example phenol, some chlorophenols and chlorocate-
chols, guaiacol, vaniline and several monoterpenes are used such as precursors or
components of meal, synthetic camphore, fragrances, farmaceutics, dyes, varnishes
 TABLE I
Comparison of means (n = 3) of concentrations (g/l) and values of standard deviation (SD) of phenol, chlorophenols, chlorocatechols and chlorinated
methoxyphenols determined in raw, purified and mixed sewages in spring, summer and autumn of 1999
Spring 1999 Summer 1999 Autumn 1999

Raw sewage Purified sewage Mixed sewage Raw sewage Purified sewage Mixed sewage Raw sewage Purified sewage Mixed sewage

Name of compound Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD
Phenol 1.022 0.085 1.297 0.130 0.349 0.034 2.199 0.218 2.523 0.251 0.667 0.066 2.232 0.222 3.076 0.309 0.548 0.055
4-Methylphenol 0.576 0.058 0.102 0.011 0.187 0.019 1.401 0.142 0.139 0.012 0.224 0.022 0.867 0.087 0.145 0.014 0.199 0.019
4-Chlorophenol 0.603 0.060 0.191 0.019 0.222 0.022 0.172 0.015
2,4-Dichlorophenol 0.049 0.005 0.011 0.001 0.045 0.004 0.022 0.002 0.012 0.002 0.017 0.002
2,4,5-Trichlorophenol 0.119 0.011 0.099 0.009 0.159 0.015
2,4,6-Trichlorophenol 0.061 0.006 0.042 0.004 0.051 0.005 1.101 0.108 1.232 0.122
2,3,4,5-Tetrachlorophenol 0.088 0.008 0.027 0.004
Pentachlorophenol 0.048 0.005
4-Chlorokatechol 0.378 0.038 4.129 0.411 0.222 0.022 0.462 0.045 0.084 0.008 0.074 0.008
3,4,5-Trichlorocatechol 0.247 0.023 0.027 0.002 0.078 0.006
3,4,5,6-Tetrachlorocatechol 0.022 0.003 0.321 0.030 0.110 0.012 0.05 0.006 0.108 0.011 0.036 0.004
Guaiacol 0.344 0.034 0.105 0.010 0.503 0.049 0.037 0.004 0.351 0.036 0.012 0.002 0.147 0.015 0.029 0.003 0.131 0.013
4,6-Dichloroguaiacol 0.445 0.045 0.491 0.047
4,5,6-Trichloroguaiacol 0.022 0.002 0.013 0.002
3,4,5,6-Tetrachloroguaiacol 0.012 0.001 0.011 0.001 0.069 0.006
3-Chlorosyringol 0.237 0.022 0.011 0.001 0.125 0.011 0.138 0.014 0.718 0.071 0.287 0.029 0.010 0.000
3,4,5-Trichlorosyringol 0.071 0.007 0.043 0.004 0.055 0.006 0.022 0.002
ANALYSIS OF COMMUNAL SEWAGE OF
LODZ AND NER RIVER

3,4,5-Trichloroveratrol 0.799 0.081 1.022 0.103 1.487 0.144 0.799 0.079 1.017 0.101 1.479 0.148 0.025 0.003 0.899 0.089 0.037 0.004
5,6-Dichlorowanilina 0.021 0.002 0.011 0.001
Total 4.065 0.390 7.858 0.778 3.439 0.336 6.841 0.675 6.074 0.600 2.469 0.248 4.061 0.406 4.556 0.457 1.144 0.114

= none detected.
209
 210
TABLE II
Comparison of means (n = 3) of the concentrations (g/l) and values of standard deviation (SD) of phenol, chlorophenols, chlorocatechols and chlorinated
methoxyphenols determined in raw, purified and mixed sewages in spring, summer and autumn of 2000
Spring 2000 Summer 2000 Autumn 2000

Raw sewage Purified sewage Mixed sewage Raw sewage Purified sewage Mixed sewage Raw sewage Purified sewage Mixed sewage

Name of compound Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD
Phenol 0.250 0.026 0.080 0.008 2.104 0.208 2.468 0.246 0.653 0.064 2.310 0.234 3.129 0.317 0.563 0.057
4-Methylphenol 1.376 0.139 0.136 0.013 0.656 0.068 0.110 0.012 0.195 0.019
4-Chlorophenol 0.295 0.029
2,4-Dichlophenol 0.480 0.047 0.050 0.006 1.120 0.113
2,4,5-Trichlorophenol 0.010 0.000 0.010 0.000
2,4,6-Trichlorophenol 0.020 0.003 0.010 0.000 0.010 0.000 1.028 0.102 1.097 0.104 0.831 0.086
2,3,4,5-Tetrachlorophenol 0.020 0.003 0.010 0.000 0.102 0.011 0.093 0.010 0.247 0.024
Pentachlorophenol 0.030 0.004
4-Chlorocatechol 5.500 0.547 0.260 0.027
3,4,5-Trichlorocatechol 0.270 0.027 0.030 0.004
3,4,5,6-Tetrachlorocatechol 0.020 0.003 0.370 0.037
Guaiacol 0.500 0.051 0.100 0.011 0.800 0.079 0.347 0.034
4,6-Dichloroguaiacol 0.556 0.054 0.593 0.060 0.472 0.047
4,5,6-Trichloroguaiacol 0.020 0.003 0.010 0.000
3,4,5,6-Tetrachloroguaiacol 0.010 0.000
J. MICHA
LOWICZ AND R. OZADOWICZ WIRGILIUSZ DUDA

3-Chlorosyringol 0.300 0.030 0.010 0.000 0.425 0.040 0.442 0.043 0.817 0.081 0.334 0.034
3,4,5-Trichlorosyringol
3,4,5-Trichloroveratrol 0.819 0.084 1.026 0.103 1.506 0.152 1.076 0.108
5,6-Dichlorowaniline 0.020 0.020 0.010
Total 1.340 0.138 6.730 0.670 2.260 0.223 6.705 0.667 6.202 0.613 2.159 0.216 3.783 0.383 6.199 0.628 0.758 0.076
 TABLE III
Comparson of means (n = 3) of the concentrations (g/l) and values of standard deviation (SD) of monoterpenes determined in raw, purified and mixed
sewages in spring, summer and autumn of 1999
Spring 1999 Summer 1999 Autumn 1999

Raw sewage Purified sewage Mixed sewage Raw sewage Purified sewage Mixed sewage Raw sewage Purified sewage Mixed sewage

Name of compound Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD
-Pinene 1.429 0.144 0.524 0.051 0.059 0.006 0.061 0.006
-Pinene 6.081 0.608 2.397 0.239 17.16 1.716
-Terpinene 0.089 0.009 0.015 0.002 0.499 0.051 0.012 0.001
-Terpinene 3.761 0.377 1.827 0.182 2.373 0.237 0.051 0.006 0.059 0.006
-Terpineole
2-Carene
3-Carene 0.069 0.007 0.029 0.003 0.013 0.001
Camphene 7.379 0.739 4.909 0.490 25.56 2.554 0.939 0.094
Cumene 1.699 0.168 0.776 0.078 0.062 0.007 0.049 0.005 0.031 0.003 0.121 0.012
Fenchole 0.759 0.075 0.247 0.025 1.071 0.108
Borneol 2.132 0.214 0.132 0.014 2.168 0.217 0.072 0.007 0.116 0.012
Limonene
Fenchone 0.039 0.004 0.011 0.001 0.058 0.006 0.039 0.004 0.019 0.002 0.081 0.008 0.012 0.001
Total 15.99 1.599 5.930 0.592 23.45 2.348 7.659 0.768 4.988 0.498 25.95 2.593 1.024 0.102
ANALYSIS OF COMMUNAL SEWAGE OF
LODZ AND NER RIVER

= none detected.
211
 212

TABLE IV
Comparson of means (n = 3) of the concentrations (g/l) and values of standard deviation (SD) of monoterpenes determined in raw, purified and mixed
sewages in spring, summer and autumn of 2000
Spring 2000 Summer 2000 Autumn 2000

Raw sewage Purified sewage Mixed sewage Raw sewage Purified sewage Mixed sewage Raw sewage Purified sewage Mixed sewage

Name of compound Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD
-Pinene 0.010 0.000 0.019 0.002
-Pinene 0.050 0.006
-Terpinene 0.010 0.000 0.010 0.000 0.420 0.043
-Terpinene 0.010 0.000 0.010 0.000 0.077 0.009 0.258 0.027
-Terpineole 2.672 0.266 0.059 0.007 1.518 0.152 5.435 0.546 0.075 0.008 1.782 0.177
2-Carene 0.010 0.000
3-Carene 0.370 0.035
Camphene 0.030 0.004
Cumene 0.010 0.000 0.020 0.003
Fenchole 0.050 0.006 0.039 0.004 0.01 0.000 0.011 0.001 0.016 0.001
Borneol 0.050 0.005 1.204 0.120 0.139 0.013 0.483 0.048 0.390 0.039 0.175 0.018
Limonene 0.159 0.018 0.310 0.031 0.030 0.004
J. MICHA
LOWICZ AND R. OZADOWICZ WIRGILIUSZ DUDA

Total 0.110 0.011 0.070 0.004 0.490 0.049 4.151 0.417 0.208 0.020 2.989 0.299 5.871 0.590 0.075 0.008 1.957 0.195

= none detected.
 TABLE V
Comparsion of means (n = 3) of the concentrations (g/l) and values of standard deviation (SD) of phenol, chlorophenols, chlorocatechols and chlorinated
methoxyphenols determined in Ner River in 1999 and 2000
Spring 1999 Summer 1999 Autumn 1999 Spring 2000 Summer 2000 Autumn 2000

Number of compound Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD

Phenol 0.652 0.063 0.773 0.077 0.762 0.076 0.010 0.431 0.044 1.721 0.166
4-Metylophenol 0.067 0.007 0.062 0.006 0.064 0.007 0.050 0.006 0.071 0.008
4-Chlorophenol 0.072 0.007 0.077 0.008 0.078 0.008 0.038 0.004 0.084 0.008
2,4-Dichlorophenol 0.072 0.008 0.112 0.011 0.014 0.002 0.060 0.007 0.126 0.013
2,4,5-Trichlorophenol 0.021 0.002 0.134 0.013 0.121 0.011 0.020 0.002 0.156 0.016
2,4,6-Trichlorophenol 0.022 0.003 0.181 0.017 0.157 0.015 0.100 0.010 0.177 0.017 0.986 0.100
2,3,4,5-Tetrachlorophenol 0.044 0.005 0.100 0.011 0.047 0.005
Pentachlorophenol
4-Chlorocatechol 0.014 0.001 0.010 0.000 0.101 0.010
3,4,5-Trichlorocatechol 0.029 0.002
3,4,5,6-Tetrachlorocatechol 1.974 0.196 0.127 0.012 2.000 0.185
Guaiacol 0.042 0.004 0.024 0.003 0.088 0.009
4,6-Dichloroguaiacol 0.041 0.004 0.102 0.010
4,5,6-Trichloroguaiacol 0.273 0.027 0.300 0.029 0.071 0.007
3,4,5,6-Tetrachloroguaiacol 0.124 0.012
3-Chlorosyringol 0.033 0.002 0.052 0.005 0.031 0.004 0.059 0.006 0.044 0.005
3,4,5-Trichlorosyringol 0.096 0.008 0.039 0.005 0.400 0.038 0.041 0.004 0.052 0.006
ANALYSIS OF COMMUNAL SEWAGE OF
LODZ AND NER RIVER

3,4,5-Trichloroveratrole 0.083 0.008 0.169 0.016 0.700 0.067 0.170 0.016

5,6-Dichlorovaniline 0.077 0.009 0.024 0.002 0.080 0.008
Total 3.497 0.345 1.685 0.167 1.431 0.142 3.780 0.357 1.556 0.157 3.183 0.315
213

= none detected.
214 J. MICHA
LOWICZ AND R. OZADOWICZ WIRGILIUSZ DUDA

TABLE VI
Comparsion of means (n = 3) of the concentrations (g/l) and values of standard deviation (SD)
of monoterpenes determined in Ner River in 1999 and 2000
Spring 1999 Summer 1999 Autumn 1999 Spring 2000 Summer 2000 Autumn 2000
Number of
compound Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD

-Pinene 0.041 0.004 0.010 0.000 0.013 0.001 0.031 0.004

-Pinene 1.079 0.108 0.019 0.002 0.030 0.004
-Terpinene 17.551 1.755 0.039 0.004 0.280 0.026
-Terpinene 0.259 0.026 0.020 0.003
-Terpineole 0.273 0.031 0.079 0.008
2-Carene 0.011 0.001 0.012 0.001
3-Carene 0.012 0.001 0.017 0.001 0.041 0.005
Camphene 1.178 0.118 5.851 0.585 0.721 0.072 0.040 0.005
Cumene 0.026 0.003 0.059 0.006 0.010 0.000 0.013 0.001 0.047 0.005
Fenchole 0.171 0.018 0.020 0.003
Borneol 0.591 0.059 0.085 0.009
Limonene 0.029 0.004 0.053 0.006
Fenchone 0.013 0.002 0.041 0.004
Total 2.261 0.228 24.58 2.458 0.832 0.083 0.390 0.038 0.450 0.050 0.251 0.028

= none detected.

or solvents (Bruce et al., 1987; Krupowicz and Zachariewicz, 1959). The pres-
ence of these compounds may also result from the activity of two thermal-electric
power stations that use coal and fractions of crude natural oil with high contents
of phenols or their precursors. Determined compounds are also used such as disin-
fectants lisole (4-methylphenol) and eugenole (amino-methoxyphenol) (Shapiro
and Guggenheim, 1998; Bobranski, 1973) in hospitals and clinics. Some of the
compounds determined are used as the pesticides fungicydes and insectycydes
(pentachlorophenol) in disinfections and deratizations applications or as impreg-
nats (Indulski, 1992) in wood, leather or textiles manufactures that numerously
are present in the city. Described compounds also stem from petrol filling sta-
tions, car washes, abattoris and markets situated in
Lodz. Probably presence of
chlorophenols, their derivaties and monoterpenes produced by plants or fungi in
investigated system was minimal because of antropogenical character of pollutions
and no contact of sewer with external environment (covered channel). Phenols and
their derivatives may have been also formed in sewage during degradation or trans-
formation of other (indetermined in work) aromatic compounds such as benzenes,
toluenes, phenoxyacetics, cyclohexanes (Rozanski, 1998) or chlorinated biphenyls
and furans (Schmidt, 1998). Those transformations mainly leaded by bacteria and
fungi refer to hydroxylation (creation of phenols and catechols) (Oian et al., 1997;
Powlowski et al., 1996), dealkilation, O-methylation (formation of chlorinated
methoxyphenols) (Laine and Jorgensen, 1996; Jaspers et al., 2002) halogenation
 ANALYSIS OF COMMUNAL SEWAGE OF
LODZ AND NER RIVER 215

Figure 1. Chromatogram of standards of chlorophenols and chlorocatechols separated by GC-MS

method 1. phenol, 2. 4-metylphenol, 3. chlorophenol, 4. guaiacol, 6. dichlorophenol, 7. chlorocat-
echol, 8. tetrachlorophenol, 9. pentachlorophenol, 10. tetrachlorocatechol.

(creation of chloroaromatic compounds) (Vazquez-Dulhalt et al., 2001) or dehalo-

genation (Wieser et al., 1997) proccesses. The compounds such as phenol or p-
cresole may be also formed in result of natural transformations, in excrements or
during decomposition of organic matter situated on the bottom of the sewer pipe.
It is clear that in all of investigated seasons the quantitative and qualitative
differences depend on various amounts of carrying pollutions to sewage in a pe-
riod of time. This may be confirmed by increasing sums of the concentrations of
monoterpenes during year of 2000, very low in spring (0.110 g/l), high in sum-
mer (4.151 g/l) and the highest in autumn (5.871 g/l). Analysis of obtained
216 J. MICHA
LOWICZ AND R. OZADOWICZ WIRGILIUSZ DUDA

Figure 2. Chromatogram of standards of chlorophenols, chloroguaiacols, chlorosyringols and

trichloroveratrole separated by GC-MS method 11. 2,4,6-trichlorophenol, 12. 2,3,6-trichlorophenol,
13. 2,4,5-trichlorophenol, 14. dichloroguaiacol, 15. chlorosyringol, 16. trichloroveratrole, 17.
trichloroguaiacol, 18. tetrachloroguaiacol, 19. trichlorosyringol.

results show that only in some cases total biodegradation of determined com-
pounds occurred. Moreover, in all of the seasons the formation de novo of some
chlorophenols, chlorocatechols and chlorinated methoxyphenols was observed af-
ter purification proccess. Those concerns determined 2,3,4,5-tetrachlorophenol
0.088 g/l, 3,4,5-trichlorocatechol 0.247 g/l and 3-chlorosyringol 0.237 g/l
in 1999 and 4-chlorocatechol 5.500 g/L, 2,4,6-trichlorophenol 0.831 g/L or
trichloroveratrole 1.076 g/L in 2000. We suppose that formation of above men-
tioned compounds was caused by microorganisms that are employed in purification
 ANALYSIS OF COMMUNAL SEWAGE OF
LODZ AND NER RIVER 217

Figure 3. Chromatogram of cumene 1. 1.697 g/l, 2. -pinene 1.427 g/l 1. 3. -pinene

6.083 g/l, 4. -terpinene 0.089 g/l, 5. -terpinene 3.763 g/l, 6. fenchone 0.038 g/l, 7.
fenchole 0.761 g/l, 8. borneole 2.135 g/l determined in raw sewage in spring of 1999.

proccess and were capable to chlorinate, hydroxylate or O-methylate phenols, cate-

chols or their precursors that were present in raw sewage. Generally, total effectivity
of purification of sewages from investigated compounds is at a distance unsufficient
what may result from high diversity of aromatic and aliphatic (derived from rock-
oil substances) compounds (also indeterminated in work) that coexist with phenols
in raw sewage. Due to their toxic influence those compounds may inhibit degra-
dation proccess by decreaseing microbes activity (Rutgers et al., 1996; Sulisti
et al., 1996). The effectivity of degradation of individual chlorinated compound
218 J. MICHA
LOWICZ AND R. OZADOWICZ WIRGILIUSZ DUDA

Figure 4. Chromatogram of 1. guaiacol 0.099 g/l, 2. 2,4-dichlorophenol 0.048 g/l, 3. 2,4,6-

trichlorophenol 0.010 g/l, 4. internal standard 2,3,6-trichlorophenol, 5. 2,4,5-trichlorophenol
0.010 g/l, 6. 4-chlorocatechol 5.505 g/l, 7. 3-chlorosyringole 0.300 g/l, 8. pentachlorophenol
0.031 g/l, 9. 3,4,5-trichlorocatechol 0.269 g/l, 10. 3,4,5,6-tetrachloroguaiacol 0.010 g/l,
11. 3,4,5,6-tetrachlorocatechol 0.373 g/l determined in purified sewage in spring of 2000.

was often related with its concentration. For example, phenol and chlorinated
compounds that were determined in high concentration in raw sewage in sum-
mer of 2000 were biodegraded (excluding 4-methylphenol) with low effectivity.
Stronger ability of biodegradation and mineralisation was observed for monoter-
penes. This fact may be explained by stronger susceptibility for degradation of these
 ANALYSIS OF COMMUNAL SEWAGE OF
LODZ AND NER RIVER 219

Figure 5. Chromatogram of 1. 2,4,6-trichlorophenol 0.179 g/l, 2. internal standard 2,3,6-

trichlorophenol, 3. 2,4,5-trichlorophenol 0.155 g/l, 4. 4,6-dichloroguaiacol 0.104 g/l, 5. 3-
chlorosyringol 0.058 g/l, 6. 3,4,5-trichloroveratrole 0.172 g/l, 7. 4,5,6-trichloroguaiacol
0.069 g/l, 8. 3,4,5-trichlorosyringol 0.039 g/l determined in Ner river in summer of 2000.

compounds by bacteria in comparison to chloroaromatic compounds and lack of

precursors of monoterpenes in raw sewage. The appearrance of small amounts of
monoterpenes after sewage purification in spring may be explained by mutual con-
version of these compounds under the influence of oxygen, what was previously
observed by Krupowicz and Zachariewicz (1959). Ner River is strongly polluted by
waters (sewages) derived from GOS, nearby situated households, small factories
and leather manufactures. Some of the physico-chemical parameters repeatedly
exceeded admissible standards for its surface waters (WIOS, 1999). Determined
220 J. MICHA
LOWICZ AND R. OZADOWICZ WIRGILIUSZ DUDA

compounds were chemicaly similar to those estimated in samples of sewages and

considerable concentrations were noted for 3,4,5,6-tetrachlorocatechol 1.974
g/l, -terpinene 17.551 g/l or camphene 5.851 g/l in 1999 also phenol
1.721 g/l, 2,4,6-trichlorophenol 0.986 g/l and tetrachlorocatechol 2.000 g/l
in 2000. As it was explained above those compounds are produced by industry and
may be formed during degradation of phenolic pesticides and phenoxyherbicy-
des flowing down from the cultivated fields situated along the riverbanks. High
quantities of organic compounds (including phenols and their derivatives) are un-
doubtedly relased from sediments as the river has been strongly polluted in recent
years. Determined monoterpens are present in describing ecosystem with regard to
antropogenic pollution but also to the activity of plants that grow near to the bed of
the river. The concentrations of determined compounds point at considerable pol-
lution of investigated ecosystem. No observed seasonal changes may result from
variable contamination of rivers water with high amounts of different xenobiotics
for sum of the concentration of chlorophenols and their derivatives in individual
season may be responsible only one of them. For example in spring of 2000, the
concentration of tetrachlorocatechol was 2.000 g/L what constituted over 50% of
the sum of concentration of all determined compounds in this season.

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