passive sampling in monitoring of nonylphenol ethoxylates and nonylphenol in aquatic environments

110 Pages·2012·2.99 MB·English

by  Heidi Ahkola

DEPARTMENT OF CHEMISTRY, UNIVERSITY OF JYVÄSKYLÄ
RESEARCH REPORT No. 152
PASSIVE SAMPLING IN MONITORING
OF NONYLPHENOL ETHOXYLATES AND NONYLPHENOL
IN AQUATIC ENVIRONMENTS
BY
HEIDI AHKOLA
Academic Dissertation for the Degree of
Doctor of Philosophy
To be presented, by permission of the Faculty of Mathematics and Science of the
University of Jyväskylä, for public examination in Auditorium KEM4, on March 23rd,
2012 at 12 noon.
�
Copyright ©, 2012
University of Jyväskylä
Jyväskylä, Finland
ISBN 978-951-39-4658-6 (nid.)

ISSN 0357-346X

ISBN 978-951-39-4699-9 (PDF)
URN:ISBN:978-951-39-4699-9
i
ABSTRACT
The present practices for determining the concentration levels of various
pollutants are in many respect s insufficient and for this reason, there is an
urgent need especially to develop more cost-effective sampling methods. In this
study, a novel passi ve sampling tool (the C hemcatcher®) for monitoring
nonylphenol ethoxylates (NPEOs) and nonylphenol (NP) in aqueous media was
tested. These environmentally harmful substances have been widely used in
different household and industrial applications and they affect aquatic
ecosystems, for example, by acting as endocrine disrupting compounds.
The highest accumulation of NPEOs and NP in laboratory-scale tests was
obtained when using an SDB-XC (standard styrene-divinyl benzene) Empore
disk as a receiving phase (adsorbent) of the passive sampler. The accumulation
of these compounds was then field tested by this technique for two or four
weeks at two sampling sites which had received effluents from e.g. the pulp and
paper industry for decades. In addition, the samplers were exposed in seawater
conditions, although in these cases the results were, mainly due to a too long
sampling time period, only approximate.
In all cases, NPEOs and NP w ere analysed by high-performance liquid
chromatography coupled with an electrospray ionisation mass spectrometry
(HPLC/ESI-MS). These compounds were also separated f rom water samples
using solid phase extract ion (SPE) pretreatment which showed to be a useful
tool for this purpose. It co uld be conclu ded that passive sampling with
Chemcatcher® offers an effective technique suitable for monitoring NPEOs and
NP in watercourses. However, more accurat e data (e.g., obtained by LC/MS-
MS) on various contaminants are still needed for further method development.
Keywords: alkylphenol ethoxylates, C hemcatcher®, passive sampli ng,
high-performance liquid chromatography, non-ionic surfactants, nonylphenol,
nonylphenol ethoxylates, solid phase extraction
ii
Author’s address Heidi Ahkola
Research and Innovations
Laboratories
Finnish Environment Institute (SYKE)
P.O. Box 35
FI-40014 University of Jyväskylä
Finland
[email protected]
Supervisors Professor Juha Knuutinen
Department of Chemistry
University of Jyväskylä
Finland
Research Professor Sirpa Herve
Research and Innovations
Laboratories
Finnish Environment Institute (SYKE)
Finland
Reviewers Professor Tadeusz Górecki
Department of Chemistry
University of Waterloo
Ontario
Canada
Dr. Juha Hyötyläinen
Kemira Oyj
Espoo
Finland
Opponent Professor Mika Sillanpää
Department of Environmental Engineering
Lappeenranta University of Technology
Finland
iii
PREFACE
This research was ca rried out in cooperation between the University of
Jyväskylä, Laboratory of Applied Chemistry, and the Finnish Environment
Institute during the years 2006-2011.
I would like to express my warmest gratitude to my supervisors, Professor
Juha Knuutinen and Research Professor Sirpa Herve, for their encouragement
and guidance during my studies. I am deeply grateful to the personnel of
Central Finland Regional Environment Centre and the So utheast Finland
Regional Environment Centre for their pr ecious help with practical details
concerning the field trials. My sincere thanks go to Dr. Jaana Koistinen for
organising the laboratory trials at Tvärminne Zoological Station and Dr. Kari
Lehtonen from the Marine Research Cent re of the Finni sh Environment
Institute for arrangi ng the deployment of Chemcatchers® in the Balti c Sea.
Warm thanks to the personnel of the Institute for Environmental Research of
University of Jyväskylä for enjoyable coffee breaks duri ng these years. I am
deeply grateful to my col league M.Sc. Juha Keränen f or valuable discussions
and encouragement.
I am also very grateful to the perso nnel of the Laboratory of Applied
Chemistry for creating a ple asant working atmosphere, and especially to
Mrs. Arja Mäkelä and Mrs. Marja Salo for a ll their help and positive attitude. I
also would like to thank my co-workers at SYKE in Jyväskylä for support and
encouragement.
Special thanks to all my friends who have always been there for me. My
parents deserve the warmest thanks for all the support they have given to me.
Finally, I express my deepest grati tude to Jarno for his pati ence and support
during this process.
I gratefully acknowledge the financial support of the Magnus Ehrnrooth
Foundation, Finnish Cultural Foundation, Olvi Foundation and Maa- ja
vesitekniikan tuki ry.
v
CONTENTS
ABSTRACT ...................................................................................................................... i
PREFACE ....................................................................................................................... iii
ABBREVIATIONS ........................................................................................................ vii
1 INTRODUCTION...................................................................................................... 1
2 PASSIVE SAMPLING ............................................................................................... 3
2.1 Theory ....................................................................................................... 3
2.2 Development of passive sampling ......................................................... 5
2.2.1 Semi-permeable membrane devices ........................................... 6
2.2.2 Chemcatcher® ............................................................................... 7
2.2.3 Other techniques ........................................................................ 11
2.3 Passive sampling vs. biological incubation ......................................... 12
2.4 Effect of humic substances .................................................................... 14
3 NONYLPHENOL ETHOXYLATES (NPEOS) AND
NONYLPHENOL (NP) ........................................................................................... 15
3.1 Chemical structure and properties....................................................... 15
3.2 Calculation of the Poisson distributions (Wt%) of NPEOs ................ 16
3.3 Manufacturing and use of NP and NPEOs ......................................... 17
3.4 Degradation and biological effects of NPEOs ..................................... 18
3.4.1 Biological degradation ............................................................... 19
3.4.2 Photodegradation ....................................................................... 20
3.4.3 Removal of NPEOs from sewage water ................................... 20
3.5 Determination of NP and NPEOs from water samples ..................... 22
3.5.1 Sampling ..................................................................................... 22
3.5.2 Determination of NP and NPEOs from water
samples using SPE ..................................................................... 23
3.6 Determination of NP, NPEO and NPEO in water using
1 2
multi-capillary trap extraction. ............................................................. 26
3.7 Determination of NP and NPEOs in biological matrices
(sample pretreatment) ........................................................................... 27
3.8 GC determination of NP and NPEOs .................................................. 29
3.9 HPLC/MS determination of NPEOs ................................................... 29
3.9.1 HPLC eluents .............................................................................. 30
3.9.2 Ionisation techniques: APCI and ESI ........................................ 31
4 EXPERIMENTAL .................................................................................................... 32
4.1 Materials and methods .......................................................................... 32
4.2 HPLC analysis........................................................................................ 33
4.2.1 Apparatus ................................................................................... 33
4.2.2 Optimization of the HPLC/MS operating conditions ............ 33
4.2.3 Standards .................................................................................... 36
4.3 Pre-test of solid phase extraction (SPE) ............................................... 37
4.4 Sampler design ...................................................................................... 39
4.5 Preparation of the sampler ................................................................... 39
vi
4.5.1 C-18 Empore disk ....................................................................... 39
4.5.2 SDB-RPS and SDB-XC Empore disks ....................................... 39
4.6 Recovery tests of Empore disk extraction procedure ......................... 40
4.7 Laboratory tests and field trials ............................................................ 42
4.7.1 Exposure of passive samplers, UHQ water ............................. 42
4.7.2 Exposure of passive samplers, brackish water ........................ 43
4.7.3 Exposure of passive samplers without
flow-through conditions ............................................................ 44
4.7.4 Field deployment of passive samplers ..................................... 44
4.8 Extraction method for the C-18, SDB-RPS and SDB-XC receiving
phases ..................................................................................................... 46
4.9 Extraction of analytes from water samples ......................................... 46
5 RESULTS AND DISCUSSION ............................................................................... 47
5.1 Pre-test of SPE ........................................................................................ 47
5.2 Pre-test of Empore disk extraction ....................................................... 48
5.3 Laboratory trials of passive samplers with and without a
diffusion-limiting membrane ................................................................ 51
5.3.1 Accumulation of NPEO .......................................................... 52
1-3
5.3.2 Accumulation of NPEO ........................................................... 53
10
5.3.3 Accumulation of NP .................................................................. 53
5.4 Laboratory exposure of passive samplers ........................................... 54
5.4.1 Accumulation of NPEO .......................................................... 54
1-3
5.4.2 Accumulation of NPEO ........................................................... 57
10
5.4.3 Accumulation of NP .................................................................. 59
5.5 Laboratory trial of passive samplers in brackish water ..................... 62
5.6 Laboratory test without flow-through conditions .............................. 63
5.7 Waterflow and temperature during the field trials of
Chemcatchers® ....................................................................................... 64
5.7.1 In 2007 ......................................................................................... 66
5.7.2 In 2008 ......................................................................................... 67
5.7.3 In 2009 ......................................................................................... 68
5.7.4 In 2010 ......................................................................................... 70
5.7.5 Gulf of Finland ........................................................................... 70
5.7.6 Gulf of Bothnia ........................................................................... 71
5.8 Inaccuracy of the analysis ..................................................................... 72
6 CONCLUSIONS ...................................................................................................... 74
REFERENCES ............................................................................................................... 75
vii
ABBREVIATIONS
ACN Acetonitrile
AEs Alkyl ethoxylate
AO Alcohol ethoxylate
AP Alkylphenol
APCI Atmospheric pressure chemical ionisation
APEC Alkylphenoxy carboxylate
APEO Alkylphenol ethoxylate
ASE Accelerated solvent extraction
BDE-153 Hexabrominated diphenyl ether
BDE-47 Tetrabrominated diphenyl ether
BSI British Standards Institution
C-18 Octadecyl silica phase; Empore disk with octadecyl silica
adsorbent
CNPEC Nonylphenol dicarboxylate
C EO Decanol polyethoxylate
10 6
DCM Dichloromethane
DDD Dichlorodiphenyldichloroethane
DDE Dichlorodiphenyldichloroethylene
DDT Dichlorodiphenyltrichloroethane
DOC Dissolved organic carbon
DOM Dissolved organic matter
EC European Commission
ECD Electron capture detector
EI Electron ionization detector
ELY Centres for Economic Development, Transport and
the Environment
ESI Electrospray ionisation
FIA Flow injection analysis
FID Flame ionisation detector
GC Gas chromatography
GCB Graphitised carbon black
HFA Hexafluoroacetone
HPLC High-performance liquid chromatography
ISO International Organization for Standardization
LC Liquid chromatography
LDPE Low-density polyethylene
LLE Liquid-liquid extraction
LOD Limit of detection
LogK Log octanol/water partition coefficient
OW
LOQ Limit of quantification
MESCO Membrane-enclosed sorptive coating sampler
MS Mass spectrometry
viii
MSD Mass spectrometric detection, mass-selective detection,
mass selective detector
MS-MS Tandem mass spectrometry
MSPD Matrix solid-phase dispersion
MTBE Methyl tert-butyl ether
m/z Mass-to-charge ratio
NaAc Sodium acetate
NH Ac Ammonium acetate
4
NP Nonylphenol
NPEC Nonylphenol carboxylate
NPEC Nonylphenol ethoxy acetic acid
2
NPEO Nonylphenol ethoxylate
NPEO Mixture of nonylphenol mono-, di and triethoxylate
1-3
NPEO Nonylphenol ethoxylate mixture, the average length of
n
ethoxylate chain is n units
NP-HPLC Normal-phase HPLC
OP Octylphenol
OPEC Octylphenol carboxylate
OPEO Octylphenol ethoxylate
p.a. pro analysis
PAH Polyaromatic hydrocarbon
PCB Polychlorinated biphenyl
PDMS Poly(dimethylsiloxane)
PE Polyethylene
PEG Polyethylene glycol
PES Polyethersulphone
PFB-Br Pentafluorobenzyl bromide
PFOA Perfluorooctanoate
PFOS Perfluorooctanesulphonate
POCIS Polar organic chemical integrative sampler
PRC Performance reference compound
PS Polysulphone
PTFE Poly(tetrafluoroethylene)
REC Regional Environment Centre
RP-HPLC Reversed-phase HPLC
SBSE Stir bar sorptive extraction
SDB-RPS Styrene-divinylbenzene Empore disk with sulphonic acid
functionality
SDB-XC Standard styrene-divinylbenzene Empore disk
SEC Size-exclusion chromatography
SIM Selected ion monitoring
SPE Solid phase extraction
SPMD Semipermeable membrane device
ix
STAMPS Standardized aquatic monitoring of priority pollutants
by passive sampling
TMAOH Tetramethylammonium hydroxide
TWA Time weighted average
UBL Unstirred boundary layer
UHQ Ultra high quality
UV Ultraviolet
WFD Water framework directive
1
1 INTRODUCTION
The European Union Water Framework Directive (2000/60/EC) (WFD) is
an important piece of e nvironmental legislation that pro tects rivers, lakes,
coastal waters and groundwaters [EC, 2000]. Its objective is that by 2015 al l the
European surface waters have a ‘good status’, which means both ‘good
ecological status’ and ‘good chemical status’. The WFD classification for water
quality consists of five status categories: high, good, moderate, poor and bad.
The implementation of WFD requires extensive monitoring of the concentration
levels of priority substances in waters, which would be time consuming using
traditional sampling methods. T he list of the priority pollutants includes 33
substances or substan ce groups, which hav e been ind icated to be of major
concern in European waters. Nonylphenol ethoxylates (NPEOs) are harmful
substances at a national level in Finland and nonylphenol (NP) is one of the
priority pollutants at the community level.
The only legally a ccepted sampling method for monitoring levels of
pollutants in water is spot sampling, in which the water is taken in bottles and
the chemicals of concern are analysed [ Allan et al., 2006]. This method gives
only a snapshot of the concentration levels at the time of sampling and, since
the levels of many pollutants can fluctuate over a tidal cycle or with times of
sporadic discharges of i ndustrial or domestic effluents, spot samples can give
misleading information on water quality . The implementation of the WFD
requires the establishment and use of novel and low-cost m onitoring
programmes, which apply to all member st ates. Several methods hav e been
developed to make the sampling process more representative compared to spot
sampling, e.g., on-line continuous monitoring, biomonitoring or passive
sampling [Södergren, 1987; Huckins et al., 1993; Koester et al., 2003; Vrana et al.,
2006a].
National water quality monitoring in Finland is organised by the
environmental authorities [Niemi and Heinonen, 2003]. It started in 1962 for
river waters, in 1965 for lake depths and i n 1963 for biological monitoring. The
water samples are taken r egularly at the same sampling sites to analyse
physical and chemical water quality determinands using standardised methods.
The local pollution control monitoring based on environmental legislation
introduced the ‘polluter pays’ principle, which still applies. The monitoring
plan is tailored for each polluter, such as fish farms, landfills and waste water
treatment plants, and is accepted by the environmental authorities. The
intensity of the sampli ng plan depends on the quality and quantity of wast e
water and the st ate of the receiving wat ers. The regional water quality
monitoring, which completes national and local pollution control, was
organised by the Regional Environment C entres (RECs). Since 2010, after th e