Study of estrogenic compounds in water using POCISOver the past two decades passive sampling methods as Semipermeable membrane devices (SPMDs) and more recently the Polar Organic Chemical

2014

International Summer Water Resources Research School

Dept. of Water Resources Engineering, Lund University

Study of estrogenic compounds in water using

POCIS

By

Cajsa-Lisa Ivarsson

The 8th Ling Feng Summer Research School

Xiamen University 2014

1

Abstract

Different passive measuring methods have been generated during the last decades in order to develop

the ways of water sampling beyond grab sampling. One of these is the Polar Organic Chemical

Integrative Sampler (POCIS). A POCIS contains an absorbent which in water will absorb a time weighted

average of the concentration of different types of polar compounds over that time span. This study

focus on measurements of estrogenic compounds with POCIS. The concentration of estrogenic

compounds are increasing in our environment and has been shown to have a negative effect on living

species. The reproduction system seems to be affected and especially the one of male fishes.

The study contains the uptake dynamics of estrogenic compounds using POCIS, an analyze of the

sampling rate of the different estrogenic compounds and finally a comparison of the sampling rate for

each estrogenic compound under different concentrations exposure.

15 POCIS device were left in water of 1 µg/L concentration of estrogenic compounds for 1, 3, 5, 7, and

10 days. 3 plates were gathered for each time scale. 3 plates additional POCIS were placed in water of 2

µ/L concentration of estrogenic compounds for 10 days to see if the concentration of the water will

affect the sampling rate. The samples were then washed and processed in a High performance liquid

chromatography mass spectrometer, HPLC-MS.

The result showed that the estrogenic compounds have a linear uptake in 10 days exposure. The

estrogenic compound E3 had been absorbed in the highest concentration after 10 days, had the highest

sampling rate. The sampling rate of estrogenic compounds is not affected by the exposure

concentration and they seems well fit to be measured with this kind of equipment.

Keywords: POCIS, Estrogenic compounds, water samples, HPLC-MS

Supervisor Yue Yun, me and my fellow students Huiping Zhang and Dan Lin outside the Department of Environmental Science



2

Table of content

Abstract ........................................................................................................................................................ 1

Table of content ........................................................................................................................................... 2

1. Introduction .......................................................................................................................................... 3

2. Objectives ............................................................................................................................................. 3

3. Background and theory ........................................................................................................................ 4

3.1 POCIS .................................................................................................................................................. 4

3.1.1 Function ....................................................................................................................................... 4

3.1.2 Performance Referent Compound (PRC) .................................................................................... 5

3.1.3 Calculations ................................................................................................................................. 6

3.2 Estrogens ............................................................................................................................................ 7

4. Method and material ........................................................................................................................... 8

4.1 Material .............................................................................................................................................. 8

4.2 Preparing of POCIS device and monitoring procedure ...................................................................... 9

4.3 Pretreatment of POCIS samples ....................................................................................................... 10

4.3 Analyze of absorption ....................................................................................................................... 11

5. Results ................................................................................................................................................ 12

5.1 Time series uptake data ................................................................................................................... 12

5.2 Calculation of the sampling rate, RS ................................................................................................. 14

5.3 Compare RS after 10 days with different concentrations ................................................................. 14

6. Discussion ........................................................................................................................................... 14

7. Sources of errors ................................................................................................................................ 15

8. Conclusions ......................................................................................................................................... 15

9. Acknowledgments .............................................................................................................................. 16

10. References ...................................................................................................................................... 17

11. Appendix ............................................................................................................................................... 18



3

1. Introduction

The study of water has always been of interest and different aquatic system surround us in our everyday

life as rivers, lakes, ponds and so on. If a pollutant reaches an aquatic system it will spread wildly and

quick. Most aquatic studies used to be based on grab sampling which contains of collecting bottle

samples to bring back to the lab or a 24 hours average of water at a given time. The use of grab sampling

are sometimes not convenient in the study of pollutants since these are mostly found as trace amounts

and the concentration usually vary over time. This conclude that with grab samples pollutants can easily

be overlooked or wrongly estimated in concentration (Grabic, Jurcikova, Tomejova, Ocelka, & Halirova,

2009).

Over the past two decades passive sampling methods as Semipermeable membrane devices (SPMDs)

and more recently the Polar Organic Chemical Integrative Sampler (POCIS) has been developed to

overcome some of these difficulties. These passive samplers will produce a time weight average (TWA)

of the concentration of lipophilic and hydrophilic chemicals, respectively. After positioned for a time in

contaminated water, they will obtain the same concentration of the waterborne contaminants, on ultra-

trace detection level (Mazzella, o.a., 2009). Estrogen is a pollutant which is increasing in our

environment and can be hazardous in smaller amounts than what can be revealed by grab sampling.

Detection of estrogens in the environment has raised concerns in recent years because of their potential

to affect both wildlife and humans (Caldwell, o.a., 2009). Among other things they are most likely to

affect the endocrine system of living species. This study will focus on the procedure and preciseness of

measurements of estrogens compounds in water using the passive sampler POCIS.

2. Objectives

The main objectives for this study was to investigate how the concentration in water of estrogenic

compounds, BPA, DES, HEX, E1, E2, E3 and EE2, can be measured with POCIS. This was followed through

with three criteria:

1. To study the uptake dynamics of estrogenic compounds using POCIS. That is carried through by

plotting the absorbed concentration of the different estrogenic compounds after the chosen

time spans of 1, 3, 5, 7 and 10 days in water with a concentration of 1 µg/L estrogenic

compounds.

2. To analyze the sampling rate (RS) for each estrogenic compounds in quite water with a

concentration of 1µg/L estrogenic compounds. The sampling rate is the rate of the volumes of

water that are purified per units of time (L/days) which also corresponds with the absorption

time for the different compounds.

3. To compare the sampling rate for the estrogenic compounds under different concentration

exposures. This is undertaken to see if the concentration effects the sampling rate.



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3. Background and theory

3.1 POCIS

3.1.1 Function The Polar Organic Chemical Integrative Sampler (POCIS) were developed by researchers with the United

States Geological Society (USGS) in Columbia, Missouri. It is used in water sampling to monitor

hydrophilic compounds such as medical drugs, surfactants (nonylphenols), triazines and caffeine

(Miége, o.a., 2011). There foremost quality is to present a time weighted average of pollutant in

contrast to grab sampling which are only showing the pollutant which existed in that blink of an eye

when the sample is gathered. With this passive sampler is also possible to detect smaller amounts of a

matter than what is possible to find with grab samples.

The actual monitoring system consists of two stainless steel plates, two isolation silicon plates, two

membrane and a powder for absorption of the pollutants is placed in the middle (Figure 1).

Figure 1. The different parts of the POCIS (Miége, o.a., 2011)

The type of absorbent can vary depending on which matter that is to be traced. It is beneficial to use an

absorbent with relatively high surface area (>∼300 m2/g) to get a linear uptake (Mazzella, o.a., 2009).

For this study the absorbent Oasis-HLB where used which has a surface area of around 800 m2/g and is

common to use for measurements of estrogen.

The POCIS are to be submerged in an aquatic environment. When in water the hydrophilic membrane

acts as a filter and the absorbent as an accumulator of the contaminants. The process of accumulation in

the POCIS is essentially adsorption into the internal adsorbent after contaminants passively diffuse

through the membrane. The sampling rate differs between contaminants and is also effected by the

sampler design and environmental conditions which are described further down. The time for the

absorption to receive the same concentration of a matter as the surrounding water can take from hours

to days. Figure 2 shows the faces that take place as the absorbent reaches the equilibrium regime. This



5

study is not made during enough time to reach the equilibrium regime and will only show the

integrative kinetic regime in the first part of the graph.

Figure 2. How the sample reaches the same concentration as the surrounding water (Miége, o.a., 2011)

3.1.2 Performance Referent Compound (PRC)

POCIS can be used for measurements both in quiet water; in-lab, as in moving water i.e. a river or lake,

so called in situ. Detection of trace levels from polar compounds in surface water and wastewater has

been proved to give reliable results (Miége, o.a., 2011). When using these devices for measurements in

situ is it important to bear in mind the effects of environmental factors such as flow and temperature,

why these should be measured at regular intervals (Harman, Reid, & Thomas, 2011). Furthermore, the

main physico-chemical parameters of the target water should be measured (i.e., dissolved organic

carbon, conductivity, pH, particulate suspended matter) as they can trace water quality changes over

time and also might influence the POCIS-available fraction (Miége, o.a., 2011).

An approach to calculate the effect from these outsider sources is to use of Performance Referent

Compound (PRC) the dissipation of which is equally affected by changes in deployment conditions

(Harman, Reid, & Thomas, 2011). A PRC is a compound which is added to the POCIS during construction

and are gradually lost to the surrounding water over time. Determination of the lost amount of PRC

provides an environmental adjustment factor to correct laboratory-derived sampling rates RS for the

site-specific environmental factors. Initial studies indicate careful selection of PRC. The absorbent is also

used to allow measureable loss of chemicals. This study aimed to include PRC but there was not enough

time to carry that through.



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3.1.3 Calculations When the exposure time is over the adsorbents are collected from the POCIS and the volumes of

absorbed compounds are extracted and detected. The mean contaminant concentration of the water is

then calculated as described in equation (1):

𝐶𝑤𝑎𝑡𝑒𝑟 =𝐶𝑃𝑂𝐶𝐼𝑆 𝑀𝑃𝑂𝐶𝐼𝑆

𝑅𝑆 𝑡 (1)

Cwater – mean contaminant concentration (over the sampling period) in the ambient water (ng/L)

CPOCIS – concentration in the POCIS (ng/g)

MPOCIS – mass of absorbent phase in the POCIS (g)

RS – sampling rate (L/d) which corresponds to the volume of water purified per unit of time

t – total exposure time (days)

The PRC samples are used to correct the RS value calculated in equation (1). RS corrected is calculated by

equation (2) and (3):

First the elimination constant, ke for both in lab and in situ is calculated:

𝑙𝑛𝑚𝑡

𝑚𝑜= 𝑘𝑒𝑡 (2)

mt – mass of PRC after time t (ng)

m0 – mass of PRC at time t = 0 (ng)

ke – elimination constant

t – total exposure time (days)

The different between ke in lab and in situ gives the corrected RS:

𝑅𝑆 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑒𝑑 =𝑘𝑒 𝑖𝑛 𝑠𝑖𝑡𝑢

𝑘𝑒 𝑖𝑛 𝑙𝑎𝑏𝑏∗ 𝑅𝑆 (3)

ke in lab – elimination constant calculated in the lab

ke in situ – elimination constant calculated in the field

RS – sampling rate (L/d), calculated in equation (1)

Finally, Rs corrected value is substituted for Rs in equation (1) in order to obtain the corresponding time-

weighted average Cwater.



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3.2 Estrogens

The female sex hormone estrogen is found naturally in humans and animals. It is primarily to affect the

development, maturation and function of the female reproduction system but in recent years it has

been showing up more frequently all over the environment. The two major natural occurring of these

hormone steroids are estrone (E1) and estradiol (E2). There are today also a lot of man-mad estrogens

such as 17a-ethynylestradiol (EE2), diethylstilbestrol (DES) etc. which are used in drugs like birth control

pills or to ease troubles with menopause and also in industrial products like plasticizers and surfactants,

and in agriculture (University of Wisconsin Aquatic Sciences Center, 2007). A major part of the steroids

are used in livestock to estrous cycle, treat reproductive disorders and induce abortion and will follow

the livestock urine to water (Kralchevska, Milanova, Hristova, & Todorovsky, 2013).

Figure 3. Molecular structures of 17β-estradiol (E2, a), 17α-ethynylestradiol (EE2, b), estrone (E1, c) and estriol (E3, d) (Kralchevska, Milanova, Hristova, & Todorovsky, 2013)

Estrogens are included among the Endocrine Disrupting Compounds (EDC), which has received

considerable attention the past decades since they in 1994 were first detected to affect the fishes by a

wastewater treatment plant in the UK. EDCs are defined as exogenous substances or mixtures that alter

functions of the endocrine system and consequently cause adverse health effects in an intact organism,

its offspring, or (sub)populations (Grabic, Jurcikova, Tomejova, Ocelka, & Halirova, 2009).

Both natural and synthetic EDCs that end up in the environment have been proved to produce harmful

effects in aquatic organisms, such as feminization of the males and hermaphroditism causing

reproductive disturbance to humans and wildlife. Especially the reproduction system of male fishes

seems to be affected. These compounds can be extremely potent even at low concentrations; for

instance, less than 1 ng/l EE2 can induce vitellogenin (egg yolk protein usually associated with adult

females) production in male rainbow trout and 4 ng/l caused male fathead minnows to fail to develop

normal secondary sexual characteristics (Kralchevska, Milanova, Hristova, & Todorovsky, 2013).



8

There are ways of cleaning the wastewater from most of the EDCs, for example with sand infiltration

aerobic pretreatment (University of Wisconsin Aquatic Sciences Center, 2007). The amounts of these

matters differs a lot over the world is also known to vary significantly over time. As a consequence it is

difficult to acquire an accurate picture of how much estrogen the environment accumulate over a longer

time-period (Vermeisster, Burkhardt-Holm, Körner, Schönenberger, & Suter, 2005). There is there for of

most important to find an easy and reliable way to measure these concentrations to find leakage in

early stage so that quick action can be taken to protect our ecosystems.

4. Method and material

4.1 Material

The following material was used in the study:

21 POCIS plates á diameter? Each consisting of 2 stainless steel plates and two isolating silicon

plates, and 3 screws with mutts

Membrane with diameter of 4.7 cm and poor size of 0.1µm. 2 á POCIS

HLB absorbent, á 100 mg/POCIS

Solution of estrogens 1 ppm of BPA, DES, HEX, E1, E2, E3 and EE2, which was diluted to a

concentration of 1 µg/L and 2 g/L

Methanol (CH3OH) for cleaning of the equipment, activation of the absorbent and solvent

Chemical regent, NaN3, to prevent bacterial growth in the beakers

Beakers to store the POCIS plates with the solvent of estrogen

Nonylphenol for internal standard

An injector and acetate, hexane and dichloromethane to clean the injector

Ultrasonic cleaner

Rotary evaporator

Pear shaped bottles

0.22 μm membrane to remove any left of the absorbent when transferring to bottles

High performance Liquid Chromatography Mass Spectrometer, HPLC-MS



9

4.2 Preparing of POCIS device and monitoring procedure

Each part of the POCIS device was first cleaned with an Ultrasonic cleaner and there after wiped with

methanol to dissolve any trace of estrogens that could be there from us humans for instant. They were

put together and 100 mg of the HLB absorbent was scaled and placed in the center of each between the

membranes. The membranes had different surfaces, and the shine side where to be placed facing out.

The two plates where finally tightly screwed together. 18 plates where produced and placed for 10

minutes in methanol to activate the absorbent.

When the POCIS devises where finish they were places in totally 4 beakers and the solution of dissolved

estrogen was added. One beaker would contain 3 plates and the solution with a concentration of 2 µg/L

of each estrogenic compound. The rest of the plates where spread out in the remaining beakers and the

1 µg/L solution was poured in until the plates where fully covered. The chemical regent NaN3 which will

prevent bacterial growth was added to all of the beakers, and the containers were covered with

aluminum foil. At last they were put in a dark space to prevent any estrogen being destroyed by the

sunlight.

Since the POCIS will absorb the estrogens by diffusion the solution needed to be changed daily to keep a

steady estrogen concentration at 1 µg/L. Three plates at a time were removed after 1, 3, 5, 7 and 10

days. The three plates in the 2 µg/L PRC container were removed after 10 days.

After a weak there were recognized that no PRC had been prepared. 4 more samples were produced

with PRC which contained of E2- d4, EE2- d3 and BPA – d10, and sorbent (HLB). These matter were

chosen since they represent the three different types of estrogens (natural, most common man-made

and others). Since the PRC were put in so late, they will not be used in this study.

Figure 4. The material for making POCIS Figure 5. Finish POCIS in exposure



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4.3 Pretreatment of POCIS samples

When all the plates had been taken out they were dried and then

opened so that the absorbent between the membranes could be

removed and placed in sampling tubes. The pretreatment was

preformed to separate the estrogenic compounds from the

absorbent.

To detect how much of the compounds that is lost during the

pretreatment, an internal standard is added. For this project

Nonylphenol was used which is a type of estrogenic compound

that is not inncluded in this study. The internal standards is

added in a known amount and afterward detected to get a value

of how much is lost during the pretreatment. The internal

standard were added with an injector which was washed with

ethyl acetate, hexane and dichloromethane in between each

matter.

10 mL methanol was added to each sampling tube and they were

placed in an Ultrasonic cleaner for 15 minutes, Figure 6. The estrogenic compounds from each sample

were to dissolve in the methanol which was now pipetted over to a pear-shaped bottle. This procedure

was repeated with 5 mL and 5 mL methanol respectively.

A rotary evaporator was used to remove the methanol. Each pear-shaped bottle now contained only the

gathered estrogenic compounds. 1 mL methanol were added to it dissolve the estrogenic compounds

and a 1 ml pipette was used to collect it all. The solution was the transferred to a small bottle while

filtration through 0.22 μm membrane to remove any left of the absorbent, Figure 7.

The samples were then refrigerated to await determination.

Figure 7. Samples of estrogenic compounds

Figure 6. Samples in Ultrasonic cleaner



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4.3 Analyze of absorption

The measurements of the amounts of estrogenic compounds in the samples were made in a High

performance Liquid Chromatography Mass Spectrometer, HPLC-MS. Where the HPLC separates the

estrogens and the MS detect them. 6 more bottles with known concentrations of estrogenic compounds

had also been prepared to determine if the machine measured correctly. The concentration of the

estrogenic compounds in these bottles were 1 ppb, 10 ppb, 100 ppb, 200 ppb, 500 ppb and 1 ppm.

The collected data from the MS was sorted in the program Agilient MassHunter Quantative Analyzis.

This program corrected the samples after the added amount of internal standard. It presented the data

of the average concentration of each estrogenic compound absorbed by the sorption after 1, 3, 5, 7, and

10 days (Table 2 page 10) and the data from the 6 bottles that were made to see the accuracy of the

total measurement. The data was then analyzed with Excel.

Figure 8. The samples are being processed in the HPLC-MS



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5. Results

The data from the measurements of the 6 bottles of known concentration is shown in Table 1. These

were used to see how well the machine preformed. If the samples would have been made by perfection

and the HPLC-MS would measure with absolute accuracy - the number for each standard concentration

would equal the number for each estrogenic compound.

Table 1. The measurements of the known standard concentrations

Standard

conc. (ppb)

BPA

(ppb)

HEX

(ppb)

E1

(ppb)

E2

(ppb)

E3

(ppb)

EE2

(ppb)

DES

(ppb)

1 2,6 2,0 3,0 - - 14,3 2,0

10 15,6 14,2 20,4 11,4 - 20,6 14,2

100 95,4 95,5 97,5 101,3 94,9 95,4 95,5

200 182,3 189,1 192,1 193,1 232,2 193,3 189,1

500 502,5 505,2 472,5 506,0 589,2 471,3 505,2

1000 1002,7 - 1015,5 998,2 949,8 1016,0 -

The data from the comparing samples where plotted to see if they were linear and there for would

indicate a trustworthy measurement from the machine. The R2 from these graphs are presented in Table

2 and their graphs are in appendix.

Table 2. R2 values of the corresponding estrogen concentrations are all close to 1 wich indicate a good correlation between measured an known value.

BPA HEX E1 E2 E3 EE2 DES

R2 0,999 0,999 0,999 0,999 0,985 0,998 0,999

5.1 Time series uptake data The measured amount of the different estrogenic compounds that had been absorbed during the test

period of totally 10 days is presented in Table 3. As can be seen the estrogenic compound E3 was not

absorbed at all in measurable amounts in the start but had the highest concentration after 10 days.



13

Table 3. Concentration of the different estrogenic compounds that had been absorbed after 1, 3, 5, 7, and 10 days.

Days from start: BPA

(ppb)

DES

(ppb)

HEX

(ppb)

E1

(ppb)

E2

(ppb)

E3

(ppb)

EE2

(ppb)

1 4,2 6,3 5,7 6,2 2,2 - 10,6

3 7,6 6,6 6,0 14,6 7,6 - 15,2

5 11,9 6,9 6,7 21,0 17,9 24,8 20,3

7 17,7 7,1 7,5 27,4 30,2 76,9 26,2

10 22,5 7,6 8,5 41,3 52,1 145,0 36,9

The data was plotted to get the time series uptake data of POCIS for the different estrogenic

compounds, Figure 9. As can be seen in Figure 9 when looking at the R2 values the concentration of

estrogenic compounds found in the sample follow an almost linear increase during the first ten days.

Figure 9. Time series uptake for each estrogenic compound. As can be seen the E3 has the fastest increase.

R² = 0,9907

R² = 0,9877R² = 0,9877

R² = 0,9741

R² = 0,9986

R² = 0,9909

-100

-50

0

50

100

150

200

0 2 4 6 8 10 12

Co

nce

ntr

atio

n (

pp

b)

Days

Time series uptake data of POCIS for Estrogenic compounds

BPA 结果 DES 结果 HEX 结果 E1 结果 E2 结果 E3 结果 EE2 结果



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5.2 Calculation of the sampling rate, RS

The sampling rate for each estrogenic compound was calculated as described in equation (1) page 6.

Following data were used for the calculations:

Cwater = 1 µg/L

CPOCIS = see Table 1, page 10

MPOCIS = 0, 01 g

t = total exposure time in days

Table 4. The sampling rate (RS) for each estrogenic compound. Described in average value and mean distribution.

RS BPA DES HEX E1 E2 E3 EE2

Median

distribution (L/d)

0,0033

±0,001

0,0034

±0,003

0,0031

±0,003

0,0051

±0,001

0,0037

±0,002

0,0097

±0,005

0,0071

±0,007

Average (L/d) 0,0028 0,0023 0,0022 0,0047 0,0036 0,0101 0,0054

The result is presented in Table 4. Both mean and median distribution is shown and they match fairly

well except for EE2.

5.3 Compare RS after 10 days with different concentrations

Table 5. Sampling rate (days/L) for each estrogenic compound after 10 days in 1 µg/L in compare to 2 µg/L

RS (d/L) BPA DES HEX E1 E2 E3 EE2

1 µg/L 0,0023 0,0008 0,0008 0,0041 0,0052 0,0145 0,0037

2 µg/L 0,0023 0,0004 0,0005 0,0041 0,0052 0,0141 0,0036

As can be seen in Table 5 the sampling rate is the about same in both concentrations except for DES and

HEX where the values are around the double.

6. Discussion

The R2 values from the 6 samples with known concentrations were close to 1 so the graphs are

considered to be linear and the equation were approaching x=y. This indicates that the measurements



15

from the machine are very close to the known values, and instrument seamed therefore to have been

working correct and the result should be considered credible.

After 10 days of exposure to water, none of the compounds hade reach their equilibrium stage, where

they will not continue to increase in concentration. E3 had been absorbed in the highest concentration

after and it make sense that it also had the highest sampling rate of 0, 0097 or 0, 0101 L/day. During the

first 3 days no E3 at all was traced in the absorbents. This was the same in the 6 bottles with known

concentrations (Table 1) which indicates that E3 is difficult to measure at low levels. EE2 is the

compound that varies the most in sampling rate which can be seen by the large span of values (±0,007)

and it also differs the most between mean and median value.

The concentration had increased for DES and HEX but not in reverse correlation with increased

concentration of the water. For the other compounds no such increase was detected. From earlier

studies it is concluded that the absorption of estrogenic compounds is not concentration dependent. It

should be very hard to measure a concentration dependent compound in situ since that would make it

impossible to produce a standard data for that compound. Since we detected so low concentration it

seems possible that the increase is just due to wrong measurements.

7. Sources of errors

There is possible to believe that some errors could be exciting due to mistake during the making of the

samples. There were a lot of different small measurements that had to be taken and the solutions were

transferred many times to different containers which could result in losses. To reduce this kind of

influence 3 plates were used for every time span but unfortunately a lot of the membrane were broken

during the drying and which resulted in samples that could not be used.

Since data from the 6 samples of known concentration were close to linear it is likely to believe that the

amount measured with the machine were accurate.

8. Conclusions

The estrogenic compounds, BPA, DES, HEX, E1, E2, E3 and EE2, have a linear uptake in 10 days exposure.

It take more than 10 days for the estrogenic compounds to reach their equilibrium stage. E3 had been

absorbed in the highest concentration after 10 days, had the highest sampling rate and is most likely to

reach equilibrium stage in the shortest time. The measurements of the bottles with known

concentration gave a content result and showed that the HPLC-MS seams to measure with good

accuracy. The sampling rate of estrogenic compounds shown not to be concentration dependent and

seems well fit to be measured with this kind of equipment. For further knowledge the study would

preferably be made until all compounds reaches their equilibrium stage.



16

9. Acknowledgments

Firstly I would like to thank my Chinese supervisor Yue Yun, for being so kind and for the excellent

support she gave me throughout this project. I want to give my best wishes you to my fellow Chinese

students Huiping Zhang and Dan Lin who’ve been great partners during the laboratory work and to

Professor Xinhong Wang for taking initiative for this study. I would also like to thank all the Chinese

students who made me feel at home in Xiamen and have been helping out so much. I want to send a

special thought to the eight Swedish students for sharing this experience and especially to Josefin

Lindström who never cease making my day. A great thanks to my Swedish professor Linus Zhang and

Lund University who made it possible for me to attend this course. I’m also very grateful to all the staff

at Xiamen University for taking care of us during our stay, especially the guards, and the staff at CEE Café

whom have been offering a wonderful place to study. And finally, I would like to thank Thyréns and

Sweco who made it possible for us to travel to China with their foundations.

All the Swedish students of Ling Feng Swedish Summer Research School 2014. From left; Beatrice Nordlöf, Tove Juhl Andersen, Ida Arvidsson, Josefin Lindström, Sofia Akhlaghi, Cajsa-Lisa Ivarsson (me), Karin Lindberg and Erik Sönegård



17

10. References

Caldwell, D. J., Mastrocco, F., Nowak, E., Johnston, J., Yekel, H., Pfeiffer, D., . . . Anderson, P. D. (2009).

An Assessment of Potential Exposure and Risk from Estrogens in Drinking Water. Environ Health

Perspect. Mar 2010; 118(3), 338–344.

Grabic, R., Jurcikova, J., Tomejova, S., Ocelka, T., & Halirova, J. (2009). Passive sampling methods for

monitoring edocrine distruption in the Svartka and Svitava rivers in the Czech Republic. Environmental

Toxicology and Chemistry, Vol. 29, No. 3, 550–555.

Harman, C., Reid, M., & Thomas, K. V. (2011). In Situ Calibration of a Passive Sampling Device for

Selected Illicit Drugs and Their Metabolites in Wastewater, And Subsequent Year-Long Assessment of

Community Drug Usage. Environ. Sci. Technol. 2011, 45, 5676–5682.

Kralchevska, R. P., Milanova, M. M., Hristova, I. L., & Todorovsky, D. S. (2013). Some endocrine

disrupting compounds in the environment and possibilities for their removal / degradation. Bulgarian

Chemical Communications, Volume 45, Number 2, 131 – 143.

Mazzella, N., Lissalde, S., Moreira, S., Delmas, F., Mazellier, P., & Huckins, J. N. (2009). Evaluation of the

Use of Performance Reference Compounds in an Oasis-HLB Adsorbent Based Passive Sampler for

Improving Water Concentration Estimates of Polar Herbicides in Freshwater. Environ. Sci. Technol. 2010,

14, 1713–1719.

Miége, C., Budzinski, H., Jacquet, R., Soulier, C., Peltec, T., & Coquerya, M. (2011). Polar organic

chemical integrative sampler (POCIS): application for monitoring organic micropollutants in wastewater

effluent and surface water. J. Environ. Monit., 2012, 14, 626–635.

University of Wisconsin Aquatic Sciences Center. (2007, spring). Care for a glass of H2O? Aquatic

Sciences Chronicle, p. 3.

Vermeisster, E., Burkhardt-Holm, P., Körner, O., Schönenberger, R., & Suter, M. (2005). Characterization

of Environmental Estrogens in River Water Using a Three Pronged Approach: Active and Passive Water

Sampling and the Analysis of Accumulated Estrogens in the Bile of Caged Fish”,. ENVIRONMENTAL

SCIENCE & TECHNOLOGY, 39, 21, 8191-8198.



18

11. Appendix

The graphs from the bottles of know concentration measured with the HPLC-MS.

y = xR² = 0,9999

0

500

1000

1500

0 200 400 600 800 1000 1200Mea

sure

d c

on

c.

Supposed concentration

E2

Linjär ()

y = 1,004x - 2,8718R² = 0,9985

-500

0

500

1000

1500

0 500 1000 1500Mea

sure

d c

on

c.


E1

Serie1

Linjär (Serie1)

y = 0,9782x + 15,77R² = 0,9853

0

500

1000

1500

0 500 1000 1500

Mea

sure

d c

on

c.


E3

Serie1

Linjär (Serie1)



19

y = 1,0048x - 1,7756R² = 0,999

-200

0

200

400

600

0 200 400 600Mea

sure

d c

on

c.


DES

Serie1

Linjär (Serie1)

y = 1,0048x - 1,7756R² = 0,999

-200

0

200

400

600

0 200 400 600Mea

sure

d c

on

c.


HEX

Serie1

Linjär (Serie1)

y = 1,004x - 2,8718R² = 0,9995

-500

0

500

1000

1500

0 5 0 0 1 0 0 0 1 5 0 0MEA

SUR

ED C

ON

C.

SUPPOSED CONCENTRATION

BPA

BPA 结果

Linjär (BPA 结果)

y = x - 1E-13R² = 0,9981

0

500

1000

1500

0 500 1000 1500Mea

sure

d c

on

c.


EE2

Serie1

Linjär (Serie1)

Documents

Study of estrogenic compounds in water using POCISOver the past two decades passive sampling methods as Semipermeable membrane devices (SPMDs) and more recently the Polar Organic Chemical