Occurrence, distribution and behavior of hydrophilic ethers in the aquatic environment

162 Pages·2014·3.98 MB·German

Occurrence, distribution and behavior
of hydrophilic ethers in the aquatic environment

Dissertation
for attaining the PhD degree
of Natural Sciences

submitted to the Faculty
of the Johann Wolfgang Goethe-University
in Frankfurt am Main

by
Daria Katarzyna Demers-Stępień
from Gdynia

Frankfurt (2013)
(D 30)
accepted as a dissertation

by the Faculty of Geoscience/Geology

of the Johann Wolfgang Goethe University

Dean: Prof. Dr. Andreas Junge

Expert assessors: Prof. Dr. Wilhelm Pütmann
Prof. Dr. Ruprecht Schleyer
Prof. Dr. Christoph Schüth
Prof. Dr. Peter Cornel

Date of the disputation: February 4th, 2014
Table of contents
Table of Contents

List of Tables .................................................................................................................................. 6
List of Figures ................................................................................................................................ 8
Abstract ........................................................................................................................................ 10
Zusammenfassung ....................................................................................................................... 14
Acknowledgements ...................................................................................................................... 21
Acronyms ...................................................................................................................................... 23
Chapter 1 Introduction .................................................................................................................. 25
1.1 Target analytes ................................................................................................................. 25
1.2 Toxicity ............................................................................................................................ 29
1.3 Formation of 1,4-dioxane as a by-product ....................................................................... 30
1.4 Focus of the research ....................................................................................................... 32
Chapter 2 Simultaneous determination of six hydrophilic ethers at trace levels using coconut
charcoal adsorbent and gas chromatography/mass spectrometry .................................................. 34
2.1 Abstract ................................................................................................................................ 34
2.2 Introduction .......................................................................................................................... 35
2.3 Experimental ........................................................................................................................ 37
2.3.1 Chemical standards and reagents .................................................................................. 37
2.3.2 Sample collection .......................................................................................................... 38
2.3.3 Extraction procedure ..................................................................................................... 40
2.3.4 GC/MS analytical conditions ........................................................................................ 40
2.3.5 Quantification and quality control ................................................................................ 41
2.4 Results and discussion ......................................................................................................... 43
2.4.1 Optimization of the extraction method ......................................................................... 43
2.4.2 Precision and accuracy study ........................................................................................ 43
2.4.3 Detection and quantification limits ............................................................................... 45
2.4.4 Stability study ................................................................................................................ 46
2.4.5 Application to environmental water samples ................................................................ 49
2.5 Conclusions .......................................................................................................................... 51
Chapter 3 Behavior of organophosphates and hydrophilic ethers during bank filtration and their
potential application as organic tracers. A field study from the Oderbruch, Germany. ................ 52
3.1 Abstract ................................................................................................................................ 52
3.2 Introduction .......................................................................................................................... 53
3.3 Area description and methods .............................................................................................. 56
3.3.1 Site description .............................................................................................................. 56
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3.3.2 Analytical methods ........................................................................................................ 59
3.3.3 Quality assurance .......................................................................................................... 61
3.4 Results and discussion ......................................................................................................... 62
3.4.1 Hydrochemistry ............................................................................................................. 62
3.4.2 Infiltration of OPs and ethers into the main drainage ditch .......................................... 64
3.4.3 Occurrence of OPs and ethers in the aquifer ................................................................. 66
3.4.4 Factors influencing OP and ether concentrations .......................................................... 67
3.4.5 Attenuation of OPs and ethers during bank filtration ................................................... 70
3.4.6 Organic pollutants as hydrological tracers .................................................................... 72
3.5 Conclusions .......................................................................................................................... 74
Chapter 4 Fate of 1,4-dioxane in the aquatic environment: from sewage to drinking water ........ 75
4.1 Abstract ................................................................................................................................ 75
4.2. Introduction ......................................................................................................................... 76
4.3. Materials and methods ........................................................................................................ 78
4.3.1. Chemicals and reagents ................................................................................................ 78
4.3.2 Analytical methods ........................................................................................................ 79
4.3.3. Quality assurance ......................................................................................................... 80
4.5. Site description and sampling methods .............................................................................. 81
4.5.1. Sewage treatment plants ............................................................................................... 81
4.5.2. Surface waters .............................................................................................................. 82
4.5.3. Bank filtration and drinking water treatment ............................................................... 83
4.6. Results and discussion ........................................................................................................ 86
4.6.1. 1,4-dioxane in municipal sewage treatment plants ...................................................... 86
4.6.2. Temporal and spatial distribution of 1,4-dioxane in surface waters ............................ 89
4.6.3. Occurrence of 1,4-dioxane in bank filtration and drinking water ................................ 97
4.7 Conclusions ........................................................................................................................ 101
Chapter 5 Source identification of high glyme concentrations in the Oder River ...................... 103
5.1. Abstract ............................................................................................................................. 103
5.2. Introduction ....................................................................................................................... 103
5.3. Materials and methods ...................................................................................................... 106
5.3.1. Chemicals and reagents .............................................................................................. 107
5.3.2. Analytical methods ..................................................................................................... 108
5.3.3. Quality assurance ....................................................................................................... 109
5.4. Site description and sampling methods ............................................................................ 109
5.4.1. Description of the study area ...................................................................................... 109
5.4.2. Surface water sampling .............................................................................................. 109
5.4.3. Wastewater sampling ................................................................................................. 113
5.5. Results and discussion ...................................................................................................... 113
5.5.1. Occurrence of glymes in the Oder River .................................................................... 113
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5.5.2. Occurrence of glymes in tributaries ........................................................................... 119
5.5.3. Glymes in the investigated industrial wastewater ...................................................... 121
5.5.4. Gas desulphurization as a source of glyme pollution ................................................. 122
5.6. Conclusions ....................................................................................................................... 123
Chapter 6 Summary, conclusions and outlook .......................................................................... 125
6.1. Summary ........................................................................................................................... 125
6.2. Conclusions ....................................................................................................................... 127
6.3. Outlook ............................................................................................................................. 131
References................................................................................................................................... 133
Appendix .................................................................................................................................... 147
Publications ................................................................................................................................ 161
Curriculum Vitae ....................................................................................................................... 162
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List of tables
List of Tables
TABLE 1.1 Reported concentrations of ETBE, 1,4-dioxane and glymes in the aquatic
environment in Europe. ........................................................................................................ 28
TABLE 2.1 CAS numbers, molecular weight, and relevant physiochemical properties of ETBE,
monoglyme, 1,4-dioxane, diglyme, triglyme, and tetraglyme. ............................................ 37
TABLE 2.2 Locations of river samplings in Germany. ............................................................... 39
TABLE 2.3 GC/MS in time scheduled selected ion monitoring (SIM) acquisition program ..... 42
TABLE 2.4 Precision and accuracy of the method analytes fortified at 1.0 µg L–1 and 10.0 µg L–1
in ultrapure water. ................................................................................................................ 44
TABLE 2.5 Method detection limit (MDL) and limit of quantiation (LOQ) in micrograms per
liter for ultrapure water samples and environmental samples (Main River) ........................ 45
TABLE 2.6 Average, minimum, and maximum (in parenthesis) concentrations of ether
compounds (in micrograms per liter) in the surface water bodies in Germany ................... 50
TABLE 3.1 Physicochemical properties of the analyzed OPs and ethers. ................................... 56
TABLE 3.2 ID codes of the monitoring wells, grid values, sampling depth, distance to the Oder
River and groundwater age (apparent 3H/3He age) at Oderbruch polder, Germany. ........... 59
TABLE 3.3 Concentrations of OPs and ethers (ng L−1) in the Oder River, adjacent main drainage
ditch as well as shallow (F) and deep (T) groundwater sampling wells. ............................. 65

TABLE 4.1 Physicochemical properties and the structure of 1,4-dioxane. ................................. 77
TABLE 4.2 Sampling events and characteristics of the four sewage treatment plants sampled. 82
TABLE 4.3 Sampling locations, sample ID, river water level (cm), and discharge (m3 s-1) during
surface water collection from the Oder, Rhine, and Main River. ........................................ 84
TABLE 4.4 Amount of methanol (MeOH) used for postanoxic denitrification (in Liters per d) at
STP C ,effluent discharge in m3 d-1, amount of 1,4-dioxane detected (kg d-1) in the effluent
in this study, amount of 1,4-dioxane as an impurity (kg d-1) calculated based on the detected
concentration in the methanol (1650 µg mL−1) used for denitrification, and percent
difference between results. ................................................................................................... 89
TABLE 4.5 Summary of 1,4-dioxane concentrations (in ng L–1) in the three rivers investigated.
.............................................................................................................................................. 92

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List of tables
TABLE 5.1 Physicochemical properties and applications of glymes ........................................ 105
TABLE 5.2 Locations, date, and conditions during surface water sampling. ........................... 111
TABLE 5.3 Average, minimum and maximum concentrations of diglyme, triglyme, and
tetraglyme, in µg L−1, on the left and right riverbank, during four sampling campaigns. . 114
Table 5.4 Concentration (μg L−1) and load (kg d−1) of diglyme, triglyme and tetraglyme in the
three wastewater (WW) samples from the WW treatment plant treating effluents from a
Solinox process…………………………………………………………………………...122

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List of figures
List of Figures
FIGURE 1.1 Chemical structures of target analytes: EtBe, 1,4-dioxane, 4-chlorotetrahydropyran,
monoglyme, diglyme, triglyme, and tetraglyme .................................................................. 26
FIGURE 1.2 Dimerization of ethylene oxide to 1,4-dioxane. ...................................................... 30
FIGURE 1.3 Sulfonation of ethoxylated alcohols to alcohol ether sulfates ................................ 31
FIGURE 1.4 Formation of 1,4-dioxane during PET production .................................................. 31
FIGURE 2.1 Stability of ethers in a) ultrapure water (n = 5) and b) Main River samples (n = 2)
with percent difference in the concentration between days 0 and 9. .................................. 47
FIGURE 2.2 Stability of ethers in dichloromethane extracts over 13-day period (n = 7).. ........ 48
FIGURE 3.1 Location of the Oderbruch polder northeast of Berlin and a simplified geological
cross section of the sampling site ......................................................................................... 58
FIGURE 3.2 Concentration of redox relevant parameters in the Oder River (n = 1) and six deep
groundwater wells (n = 3): redox potential (Eh), dissolved organic carbon (DOC), pH,
conductivity (K), oxygen (O ), nitrate (NO -), ferrous iron (Fe(II)) and sulfate (SO 2-). .... 63
2 3 4
FIGURE 3.3 Average monthly water level (cm) and mean flow (discharge, m3 s−1) of the Oder
River between January 2006 and May 2012 ........................................................................ 68
FIGURE 3.4 Variations of OP and ether concentrations (ng L−1) with discharge (m3 s−1) of the
Oder River during four sampling campaigns. ...................................................................... 69
FIGURE 3.5 Relations between chloride (mg L−1), 1,4-dioxane, and tetraglyme (ng L−1)
concentrations in the Oder River and deep groundwater wells during four sampling
campaigns ............................................................................................................................. 73
FIGURE 4.1 Map of surface water sampling sites in Germany and Poland, including major
tributaries. Sample IDs reflect the locations listed in Table 4-3. ......................................... 85
FIGURE 4.2 Average concentration (ng L-1) and a standard deviation of 1,4-dioxane in influent
samples, after primary and secondary treatment, and in effluent water samples in four
municipal sewage treatment plants (STP) investigated. ...................................................... 87
FIGURE 4.3 a) Concentration profile of 1,4-dioxane (ng L-1) on the left (MWL1) and on the
right (MWL4) side of the Rhine River during a two week study at the Rhine Water Control
Station Worms, Germany with the river discharge values (m3 s-1). b) Monthly concentration
of 1,4-dioxane in 2012 at the monitoring station Lobith, Germany with the discharge
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List of figures
values. On 11.01.12 concentration of 1,4-dioxane was below detection limit (< 500 ng L-1).
.............................................................................................................................................. 91
FIGURE 4.4 Spatial distribution of 1,4-dioxane in the Oder, Rhine, and Main River ............... 93
FIGURE 4.5 Load of 1,4-dioxane (kg d-1) in the three rivers sampled. ...................................... 95
FIGURE 4.6 Loads of 1,4-dioxane (kg d−1) at locations sampled on two different occasions. .. 96
FIGURE 4.7 Hydrological cross section through the Rhine River and the bank filtration site. 98
FIGURE 4.8 Concentration of 1,4-dioxane (ng L−1) in the raw water after bank filtration and in
the drinking water after water purification........................................................................... 99

FIGURE 5.1 Map of sampling points along the Oder River with sample IDs. .......................... 112
FIGURE 5.2 Concentration of triglyme and tetraglyme, in μg L−1, on the left and right side of
the Oder River during the sampling campaigns conducted in August 2012 and April 2013.
............................................................................................................................................ 116
FIGURE 5.3 Load of diglyme, triglyme, and tetraglyme (in kg d−1) in the Oder River. ........... 118
FIGURE 5.4 Concentrations of glymes (μg L−1) in the Oder River (OD), Czarna Woda
stream (CW) and Kaczawa River (KW) during April 2013 sampling campaign. ... 120
FIGURE A.1 Consumption of E5, E10, ETBE, and E85 in Germany during 2007 and 2011 .. 155
FIGURE A.2 Historical concentrations of a) ETBE, b) diglyme, c) triglyme, and d) tetraglyme in
the Rhine River at the measuring station Lobith ............................................................... 159
FIGURE A.3 GC/MS chromatogram of the target analytes: ETBE, monoglyme 1,4-dioxane, 1,4-
dioxane-d (Surrogate), 4-chlorotetrahydropyran (Internal Standard), diglyme, triglyme and
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tetraglyme in total ion chromatogram (TIC) and selected ion monitoring (SIM). ............. 160
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Abstract
Abstract
The objective of the present doctoral thesis was to investigate the occurrence, distribution,
and behaviour of six hydrophilic ethers: ethyl tert-butyl ether (ETBE), 1,4-dioxane, ethylene
glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), triethylene
glycol dimethyl ether (triglyme), and tetraethylene glycol dimethyl ether (tetraglyme) in surface-,
waste-, ground- and drinking water samples. Solid phase extraction and gas
chromatography/mass spectrometry were used to analyze the six hydrophilic ethers. Altogether
more than 150 surface water samples, almost 100 of each groundwater and wastewater samples,
and 10 raw and drinking water samples were analyzed during the research project.
Initially, the method was validated in order to simultaneously determine the analytes of
interest in various aquatic environments. A solid phase extraction method that uses coconut
charcoal (Resprep® activated coconut charcoal, Restek) or carbon molecular sieve material
(SupelcleanTM Envi-CarbTM Plus, Supelco) for analyte absorption were found suitable for
determination of ETBE, 1,4-dioxane, and glymes in surface-, drinking-, ground- and wastewater
samples. Precision and accuracy of both methods was demonstrated for all analytes of interest.
The recovery of target compounds from the ultrapure water spiked at 1.0 µg L−1 was between
86.8 % and 98.2 %, with relative standard deviation below 6 %. The samples spiked at 10.0 µg
L−1 gave slightly higher recovery of 90.6 % to 112.2 % with a relative standard deviation below
3.4 % for each analyte. Detection and quantification limits in ultrapure water and surface waters
were furthermore established. The limit of quantitation (LOQ) in ultrapure water ranged between
0.024 µg L−1 to 0.057 µg L−1 using Restek cartridges, and 0.030 µg L−1 to 0.069 µg L−1 using
Supelco cartridges. In the surface water samples the calculated LOQ was 0.032 µg L−1 to 0.067µg
L−1 using coconut charcoal material and 0.032 µg L−1 to 0.052 µg L−1 using the carbon molecular
sieve material. Moreover, stability of the unpreserved and preserved water samples as well as the
extracts was determined. Preservation of samples with sodium bisulfate (at 1 gram per Liter)
resulted in much better stability of the ethers in water samples. Subsequently, 27 samples
obtained from seven surface water bodies in Germany (Rivers Rhine, Lippe, Main, Oder, Rur,
Schwarzbach and Wesel-Datteln Canal) were analyzed for the six hydrophilic ethers. ETBE was
present in only two surface waters (Rhine River and Wesel-Datteln Canal) with concentrations
close to the LOQ (up to 0.065 µg L−1). 1,4-Dioxane was detected in all of the water samples at
concentrations reaching 1.93 µg L–1. Monoglyme was identified only in the Main and Rhine
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