GC-MS screening and PCB analysis

of sediment from central Kattegat

Emma Eriksson

Örebro University

2015-07-07

i

Abstract Five sediment samples were collected in Bua on the Swedish west coast, near two industries,

a paper mill, and a nuclear power plant. The two industries use water in their processes and

have long been associated with releases of different substances, such as PCBs, and other

chlorinated compounds. The environmental impact by the two industries is believed to be

significant. The aim of the project was to examine the sediments close to both the water intake

and water output to determine if these industrial activities have in any way changed the

composition of the sediments. The sediments were extracted by Soxhlet extraction, followed

by a deactivated silica and an acidic silica clean-up and then analysed by using a gas

chromatograph coupled to a mass spectrometer, (GC-MS) with electron ionization, EI+, mode

used in full scan mode. Each mass spectra were analysed by comparing them to the NIST

database from 1998. The results were inconclusive since the peaks were not properly

resolved, causing a poor correlation to the NIST database.

One batch was specifically analysed for polychlorinated biphenyls (PCB) by using an

atmospheric pressure gas chromatograph (APGC) coupled to a mass spectrometer (MS). The

PCB analysis provided accurate results, except for the Ringhals intake where the MS became

saturated due to the high levels. The river Viskan also showed high levels of PCB. The

congener pattern from PCBs found near Ringhals intake resembled an Aroclor pattern from

Aroclor 1248. Since the Aroclor pattern is only seen in Ringhals intake, the source is most

likely from the small harbour and not from either of the industries.

Key words: Paper mill, nuclear power plant, screening, GC-MS, PCB, APGC

ii

Table of Content Abstract ....................................................................................................................................... i

List of Figures ........................................................................................................................... iii

List of Tables ............................................................................................................................. iv

1. Introduction ............................................................................................................................ 1

1.1 Aim and objective ............................................................................................................. 1

2. Background and theory .......................................................................................................... 2

3. Material and Method .............................................................................................................. 4

3.1 Sampling ....................................................................................................................... 4

3.2 Soxhlet extraction ......................................................................................................... 4

3.3 Metallic copper clean-up .............................................................................................. 5

3.4 Silica clean-up .............................................................................................................. 6

4. Results and Discussion ......................................................................................................... 10

4.1 Ringhals .......................................................................................................................... 11

4.1.1 Indicative ions for chlorine and bromine ................................................................ 13

4.2 Södra Cell Värö .............................................................................................................. 15

4.3 Polychlorinated biphenyls .............................................................................................. 17

5. Conclusion ............................................................................................................................ 25

6. References ............................................................................................................................ 29

Appendix A- Batch 1, without minisilica ................................................................................. 31

Appendix B: Batch 1 with minisilica ....................................................................................... 35

Appendix C: Batch 2 ................................................................................................................ 37

Appendix D – NIST Database matches and analyses .............................................................. 39

Appendix E – APGC results ..................................................................................................... 56

iii

List of Figures Figure 1: Sampling locations, marked as circles, with the industries, marked as squares, and

actual intake and discharge, marked as diamonds (Google Maps 2015). .................................. 2

Figure 2: Silica columns ............................................................................................................. 7

Figure 3: Total ion chromatogram, TIC, of Ringhals input, batch 1 ........................................ 11

Figure 4: TIC of Ringhals output, batch 1 ............................................................................... 11

Figure 5: TIC of Ringhals intake, batch 2 ................................................................................ 12

Figure 6: TIC for Ringhals output, batch 2 .............................................................................. 12

Figure 11: Indicative ions for chlorine, m/z 35 and 37 ............................................................ 13

Figure 12: Indicative ions for bromine, m/z 79 and 81 ............................................................ 14

Figure 7: TIC of Södra Cell Värö intake, batch 1 .................................................................... 15

Figure 8: TIC of Södra Cell Värö output, batch 1 .................................................................... 15

Figure 9: TIC of Södra Cell Värö intake, batch 2 .................................................................... 16

Figure 10: TIC of Södra Cell Värö output, batch 2 .................................................................. 16

Figure 13: PCB levels in sediment samples from the different sites. The blue stars indicates

peaks with too high concentration of PCBs which saturated the MS. The red stars indicate

peaks with bad peak shape. ...................................................................................................... 17

Figure 14: PCB levels in sediment samples from the different sites, the blue stars indicate

saturation of the MS, and the red stars indicate peaks with bad peak shape. ........................... 18

Figure 15: Indicative ions for PCB with one chlorine substitution .......................................... 19

Figure 16: Indicative ions for PCB with two chlorine substitution .......................................... 20

Figure 17: Indicative ions for PCB with three chlorine substitution ........................................ 20

Figure 18: Indicative ions for PCB with four chlorine substitutions ....................................... 21

Figure 19: Indicative ions for PCBs with five chlorine substitutions ...................................... 21

Figure 20: Indicative ions for PCBs with six chlorine substitutions ........................................ 22

Figure 21: Indicative ions for PCBs with seven chlorine substitutions ................................... 22

Figure 22: Indicative ions for PCBs with eight chlorine substitutions .................................... 23

Figure 23: Indicative ions for PCBs with nine chlorine substitutions ...................................... 23

Figure 24: Indicative ions for PCBs with ten chlorine substitutions ........................................ 24

Figure 25: TIC from Toluene ................................................................................................... 31

Figure 26: TIC from Soxhlet blank .......................................................................................... 31

Figure 27: TIC from Ringhals input ......................................................................................... 32

Figure 28: TIC from Ringhals output ....................................................................................... 32

Figure 29: TIC from Södra Cell Värös input ........................................................................... 33

Figure 30: TIC from Södra Cell Värö output ........................................................................... 33

Figure 31: TIC of sample from the bay .................................................................................... 34

Figure 32: TIC of toluene blank ............................................................................................... 35

Figure 33: TIC of Soxhlet blank, after use of minisilica .......................................................... 35

Figure 34: TIC of sample from the bay, after the use of minisilica ......................................... 36

Figure 35: TIC of toluene ......................................................................................................... 37

Figure 36: TIC of Soxhlet blank from batch 2 ......................................................................... 37

Figure 37: TIC of sample taken in the bay from batch 2 ......................................................... 38

Figure 38: NIST database match for Ringhals batch 1, 6.258 min .......................................... 39

Figure 39: NIST database match for Ringhals batch 1, 15.378 min ........................................ 40

Figure 40: NIST database match for Ringhals batch 1, 18.291 min ........................................ 41

Figure 41: NIST database match for Ringhals batch 1, 29.686 min ........................................ 42

iv

Figure 42: NIST database match for Ringhals batch 2, 15.817 min ........................................ 43

Figure 43: NIST database match for Ringhals batch 2, 19.883 min ........................................ 44

Figure 44: NIST database match for Ringhals batch 2, 20.408 min ........................................ 45

Figure 45: NIST database match for Ringhals batch 2, 20.987 min ........................................ 46

Figure 46: NIST database match for Södra Cell Värö batch 1, 16.271 min ............................ 47

The molecule suggested by the NIST database for the peak at 16.27 min is 2,2’-diethyl-1,1’-

biphenyl (Fig. 46). The NIST reference spectra show several similarities, mainly the peaks at

m/z 181 and 165. There are two peaks from the reference spectra just above m/z 181, which

seems to be missing or have a very low intensity in the sample spectra. The ions at m/z ratio

of 181 and 165 seem to be very common for many polyaromatic hydrocarbons, since the first

four hits from the NIST database all display the same ions, m/z 181 and 165, at similar

intensities. The delta plot show some differences between the sample spectra and the NIST

reference spectra. The compound with retention time 16.27 minutes might be a biphenyl or

another polyaromatic hydrocarbon, but the functional groups have not been determined Figure

47: NIST database match for Södra Cell Värö batch 1, 18.442 min ........................................ 47

Figure 48: NIST database match for Södra Cell Värö batch 1, 18.520 min ............................ 49

Figure 49: NIST database match for Södra Cell Värö batch 1, 20.546 min ............................ 50

Figure 50: NIST database match for Södra Cell Värö batch 2, 5.939 min .............................. 51

Figure 51: NIST database match for Södra Cell Värö batch 2, 20.004 min ............................ 53

Figure 52: NIST database match for Södra Cell Värö batch 2, 21.515 min ............................ 54

Figure 53: NIST database match for Södra Cell Värö batch 2, 32.553 min ............................ 55

List of Tables Table 1: Sampling information .................................................................................................. 4

Table 2: Examples of Soxhlet extraction methods used in literature ......................................... 5

Table 3: Internal standard added to the samples. ....................................................................... 5

Table 4: GC-MS full scan conditions ......................................................................................... 8

Table 5: APGC conditions ......................................................................................................... 9

Table 6: Swedish EPA classifications of PCB contaminated sediments, µg/g dry weight of

sediment (Naturvårdsverket 1999) ........................................................................................... 24

Table 7: Comparison of levels with the Swedish EPA * indicates peaks too large to integrate

** indicate bad peaks ............................................................................................................... 24

Table 8: PCB levels from APGC analysis ............................................................................... 56

1

1. Introduction Paper mills have long been associated with the release of different environmental

contaminants, such as polychlorinated biphenyls (PCB) and polychlorinated dioxin and furans

(PCDD/F), especially when the chlorine bleaching method was used (Ratia & Oikari 2014).

Urban activities have been a source of contamination for the aquatic environment, and paper

mills have been considered to be the sixth largest source of contamination (Ali &

Sreekrishnan 2001). Chlorinated effluent from the pulp industry is an extensive toxic hazard

for the aquatic environment (Wulff et al. 1993). The pulp produced only contain around 40-

45% of the original raw material. The rest of the raw material is then released with the

effluent, mainly as organic matter. Some suggested by-products released with the effluent are

chlorinated products, fibres, fatty acids, lignin, sulphur containing compounds, chlorinated

lignin, resin acids, phenols, dioxins, and furans (Ali & Sreekrishnan 2001).

Since PCBs and PCDD/Fs are included in the Stockholm Convention on Persistent Organic

Pollutants (POP), they have been well monitored globally for the past 20 years (United

Nations 1995). A POP is a substance that remains in the environment for a long period of

time. It accumulates in adipose tissue, and are toxic to humans and all living organisms. A

majority of the known POPs have a low solubility in water, but they dissolve easily in adipose

tissue and therefore accumulate in any substance that display lipophilic properties (Secretariat

of the Stockholm Convention n.d.). Some POPs display different characteristics, such as poly

fluorinated compounds, that have a lower degree of hydrophobicity (Lau et al. 2007).

Since the beginning of the 1990s, the pulp industry have changed from chlorine bleaching to

chlorine-free bleaching methods, or elemental chlorine free bleaching. Decreasing levels of

PCBs and PCDD/Fs have been demonstrated, although they are still present as contaminants

in sediments surrounding paper mills (Ratia & Oikari 2014).

In another study fish from the unheated and heated area near a nuclear power plant was

compared, and found that perch showed significantly higher levels of PCBs. However, there

were no significant difference for another fish species (Edgren et al. 1981)

The cooling water from the nuclear power plant Ringhals, does normally only affect the

surface water. Surface water is considered water down to 7 meters depth. Under extreme

conditions during the winter, the sediments can be exposed to the heated water. The heat

increase will affect the uptake of PCBs and DDT. The first studies on the subject showed that

the uptake were twice as big in fish when the temperature increased from 5°C to 15°C. The

initial study was performed in a laboratory, and the effect was much less prominent in the

environment (Elforsk 2009).

1.1 Aim and objective The aim of this project was to compare the sediments from the inlet and outlet of the selected

industries. This approach was chosen to determine if the changed characteristics of the water

(such as heat increase and organic components) have affected the composition of the

sediments. This will be examined through a GC-MS screening where the chromatographic

pattern will be examined and through a specific PCB analysis of the sediments. The sediment

near the two industries was also compared to a sample from the nearby bay, to determine if

any potential contamination can be linked to either of the two industries. The PCB analysis is

2

also to be compared to known congener profiles of Aroclor to possibly link the PCBs to a

specific Aroclor.

2. Background and theory Bua is a village situated 20 km north of Varberg, on Värö peninsula. In the surrounding area

there are two larger industries, Södra Cell Värö, a paper mill, and Ringhals, a nuclear power

plant. Both industries use the sea and river water in their processes. Ringhals uses the water

from the sea as cooling water for the reactors. The water is only used for heat exchange and is

not a part of the nuclear fission itself. Södra Cell Värö uses water from Viskan, a larger river

that ends in Kattegatt, in its process. The water is after usage released into the sea from a 2 km

long pipeline. The pipeline is situated at near 20 meters depth and the release takes place

through 180 holes along the pipeline (Eriksson 2015).

Figure 1: Sampling locations, marked as circles, with the industries, marked as squares, and

actual intake and discharge, marked as diamonds (Google Maps 2015).

Södra Cell Värö was built in 1978. From the beginning until 1990, the bleaching used

chlorine, when they started the transition to chlorine free bleaching. In 1993, the bleaching

process at Södra Cell Värö was totally free of chlorine, being one of the first paper mills in the

wold to apply a chlorine free bleaching method. The chlorine bleaching was replaced with

oxygen bleaching. The oxygen bleaching is then followed by further bleaching with hydrogen

peroxide, oxygen and peracetic acid, if further beaching is requested. In 2002, Södra Cell

Värö installed a facility for biological cleaning of the waste water (Södra Cell Värö 2014). In

2010, Södra Cell Värö was the first paper mill in the world to be independent of fossil fuels in

their normal production (Södra Cell Värö 2015). Södra Cell Värö produces around 425 000

3

metric tonnes of paper pulp each year of witch about 90% is exported, mainly to Europe.

Södra Cell Värö mainly produce paper pulp, but in recent years they have also started

producing green electricity, biofuel, and long distance heating to the surrounding area (Södra

Cell Värö 2014).

Previous investigations have been conducted by Södra Cell Värö in 1989-1996, where they

analysed 2,3,7,8-tetrachlorodibenzodioxin (TCDD), 3,4,3’,4’-tetrachlordibenzofuran (TCDF),

1,2,3,7,8-pentachlorodibenzofuran (PeCDF), and extractable organic chlorine (EOCl). The

samples were taken from an affected point near the industry and included crabs and common

whelk, Buccinum undatum (Stibe 2015; Nationalencyklopedin n.d.). The samples were

compared to a reference site in Fladen. The study ended soon after Södra Cell Värö changed

bleaching process from the chlorine bleaching to oxygen bleaching since the levels from the

affected station approached the levels in the reference samples (Stibe 2015; Södra Cell Värö

2014).

Ringhals is situated on the northern side of Värö peninsula, and produces 20% of the

electricity consumed in Sweden today. The construction of the power plant started in 1969,

and in May 1975 the first reactor was put into operation. There are currently four reactors in

operation, Ringhals 1 through 4. In 2002, Ringhals became certified according to

Environmental Product Declaration (EPD), which means that they for each kWh produced can

calculate the environmental effects. The sea water is used as cooling water for the steam

produced in the reactors. When operating at full power, around 170 cubic meters of seawater

is used per second for the cooling of the reactors. (Vattenfall 2012a).

The cooling water leaves the reactor around 10°C warmer than the initial temperature.

Ringhals have constantly tried to minimize the different emissions to the environment, such as

regular and dangerous waste, chemicals, cooling water discharge water treatment and

radioactive emission. Ringhals has since 1990 been registered with Eco Management and

Audit Scheme (Emas) and since 1998 it is also certified according to ISO 14001 (Vattenfall

2012b). Their ammonia emission to water is less than one tenth of the natural amount found in

the sea. The boric acid release is near one hundredth of the natural content found in the sea.

Furthermore, chlorine is released at around 0.1 ppm per year (Vattenfall 2012b).

PCB are considered to be persistent and toxic in the environment. The PCBs have different

degrees of chlorination, from one to ten, where each chlorine is attached to a carbon in a

biphenyl backbone. PCB is a mixture of 209 different congeners. When producing PCBs, they

were sold under the trade name Aroclor. Commensally, there were nine different formulations

sold, all containing different weight percentage of chlorine. Aroclor were used in a vast

number of purposes, such as dielectric fluid, inks, and pesticide extenders (Murphy &

Morrison 2007).

4

3. Material and Method

3.1 Sampling

Duplicate samples for each site were acquired by using an Ekman sediment grab sampler. The

samples were collected from five different locations along the coastline. Each location was

chosen so that it could be compared to the other locations.

Table 1: Sampling information

Sample Sediment

type

Location

description

Coordinates Depth

(m)

Ringhals

intake

Clay Small harbour N57°16.069’

E012°06.511’

2

Ringhals

output

Sand Open water, near

coastline

N57°15.078’

E012°05.351.’

5

Södra Cell

intake

Clay Open water,

middle of river

N57°13.678’

E012°12.768’

N57°13.633’

E012°12.804’

3

Södra Cell

output

Clay Open water, near

coastline

N57°12.843’

E012°09.502’

4

Bay Sand Open water, near

coastline

N57°14.666’

E012°06.323’

3.5

The sample vials were filled to the best capacity in amber glass jars, 250 ml, and kept frozen

until the extraction took place. The sampling point from Södra Cell Värös intake, were

acquired from two different locations, from both sides of a delta at the end of the river.

3.2 Soxhlet extraction

Before extraction began, the samples were thawed and dried overnight. The sediments were

spread out on aluminium foil and left in room temperature in the fume hood until dryness.

There are several problems associated with the drying technique, mainly the loss of analyte.

Drying times of only 4 hours have been associated with 14 – 23 % loss of PCBs from

sediments. This, when the temperature was 20°C and the relative humidity was 25%. The

main part of the total PCB losses, up to 90%, occurred after the first 4 hours of drying. The

heat, air flow, water content and grain size are believed to affect the amount of PCBs in

sediments. The congener pattern found in the sediments may also be altered in the drying

process. The change in congener pattern are most distinct in sediments with PCB source from

lighter Aroclors (Chiarenzelli et al. 1996).

For the first batch, dryness was achieved after 12 hours and for batch 2 after 48 hours.

Different amounts of sediment were dried between the different batches and that can account

for the difference in drying time. The Soxhlet extraction chambers were cleaned by starting an

extraction with clean thimbels and toluene while the samples were drying. The Soxhlet blank,

which is a method blank were treated in the same way as the samples. The wash continued for

24 hours before the extractions were stopped at reflux and the toluene was discarded. The dry

sediments were then weighed, and 10 g of sediments were placed in each thimble. The

decision to use 10 g of sediments was based on previous studies which used similar amount

and method for extraction of sediments (Table 2).

5

Table 2: Examples of Soxhlet extraction methods used in literature

Amount of

sediment used

Solvent Time (h) Reference

5 g n-hexane:DCM 1:1 v/v 16 (Parera et al.

2004)

10 g Hexane, acetonitrile,

toluene/methanol, acetone:hexne

1:1, 2-propanol, cyclohexane, or

acetone:hexane

16 – 24 (US EPA 1996)

1 g Methanol 18 h (Jurado-Sánchez

et al. 2013)

2 g Chloromethyl: Acetone 18 h (Hawthorne et al.

2000)

Since the sediments contained varying amounts of water, the water present in the sediments

had to be estimated with the intent of having 10 g of sediment present for the analysis. For

batch 1, the sample representing Södra Cell Värös intake, only 8.17 g were used since the

amount of water in the sediment was underestimated. After the drying process were

completed, only 8.17 g of sediment were present and used for the analysis.

A PCB internal standard was added to the sediments, 25 µl was added (Table 3), and the

extraction started. The extraction was then discontinued after 24 hours and the toluene used

for the Soxhlet extraction was evaporated using a rotary evaporator until ~1 ml of extract

remained in the round bottom flask. The rotary evaporator was washed with hexane before

usage. The temperature of the water bath was 45°C, and the pressure was 1000 mbar for

hexane and 80 mbar for toluene.

Table 3: Internal standard added to the samples.

Compound Amount (pg µl-1) 13C PCB #70 30 13C PCB #101 30 13C PCB #118 30 13C PCB #105 30 13C PCB #153 30 13C PCB #138 30 13C PCB #156 30 13C PCB #180 30 13C PCB #170 30 13C PCB #194 30 13C PCB #206 30 13C PCB #209 30 13C PCB #47 3 13C OCDD 5

3.3 Metallic copper clean-up

If any of the samples at this stage had a yellow discolouration, metallic copper was added to

the eluate to react with sulphur that can disturb the analysis at higher levels. The copper was

added to the round bottom flask and allowed to react. The extract was then removed from the

6

round bottom flask and placed in a new flask. The copper was rinsed with hexane three times

to ensure that most of the analyte had been transferred to the new round bottom flask. The

new round bottom flask was evaporated until ~1 ml of the extract remained.

Batch 1 was at this point split, around half of the solvent was removed and stored in 8 ml

amber glass vials. The partition occurred in case the clean-up method were to be altered and

the extract would be needed for a second clean up.

3.4 Silica clean-up

The extract was then added to a 10% deactivated silica for purification. The deactivated silica

was prepared by weighing 70 g of silica, and adding 7 ml of MilliQ to the silica. The silica

was shaken for three hours on a shaker, and additionally shaken by hand every 15 minutes

under the three hours to ensure that the silica was homogenized. This method for the silica

preparation was used since there was no access to the rotary shaker at the time of the

experiment. The setup can be seen in fig. 2

To prepare the deactivated silica column, a piece of glass wool was placed at the bottom of a

column and rinsed with ethanol, hexane, and dichloromethane, DCM. To the column, 10 g of

silica was added, followed by a layer of anhydrous sodium sulphate to remove traces of water

from the organic solvents used.

The columns were then rinsed with 40 ml of hexane before the addition of the sample. The

eluates were collected after the samples were added to the column. After the samples were

added the round bottom flasks were rinsed three times with hexane and added to the silica.

The analytes were then eluted by addition of 100 ml hexane. The extract was then evaporated

using the rotary evaporator until ~ 1 ml of the extract remained.

For the first batch, the extracts were transferred to 8 ml amber glass vials, and the previous

vials washed with hexane three times. The extracts were then evaporated until near dryness

with nitrogen gas. The extracts were then transferred to GC vials and 25 µl of toluene was

added. The 8 ml amber glass vials were rinsed 3 times with hexane. The GC vials were then

placed under nitrogen gas.

7

Figure 2: Silica columns

The samples were then analysed using GC-MS. When evaluating the results, it was noticed

that the samples were too impure to provide useful mass spectra and chromatograms, see

Appendix A. The samples were after the GC-MS analysis further purified by using a

minisilica column.

The minisilica column were prepared in a Pasteur pipette, with glass wool acting as a plug at

the end. The pipette and the glass wool was initially rinsed with ethanol, hexane, and DCM.

The last drops of DCM were pushed out, the column was then packed. Around 2 cm of KOH

silica and 2 cm 40% H2SO4 silica were added to the pipette (Fig. 2). The silica was then

covered with sodium sulphate. The minisilica column was then rinsed with two pipettes of

hexane before the sample was added. The collection vials were placed under the pipettes as

soon as the samples were added. The analytes were eluted with 2 pipette volumes of hexane.

The eluate was collected in 8 ml amber glass vials and then evaporated until near dryness

before being transferred to the GC vial, in the same manner as stated previously.

The chromatograms were matched to the NIST library. The NIST database match comes in

four parts, one part gives the name of the suggested structure, denoted hit list, and a visual

representation of the first compound on the hit list. The third part is the mass spectra of the

sample and the first three hits on the hit list. The fourth part is a delta plot where the sample

spectra and the NIST reference spectra is compared to each other. For an ideal match, the

delta plot should show no peaks. On the y-axis, the positive side indicates a peak present in

the sample and negative side represents a peak present in the reference spectra.

8

Batch 2 was analysed in the same manner as the previous batch, the only difference was that

the GC-MS analysis only took place after the minisilica clean-up, not before and after.

Table 4: GC-MS full scan conditions

Inlet

Injection type Splitless

Volume 1 µl

Heater 250°C

Pressure 12.29 psi

Total flow 24.3 ml/min

Purge flow

Split vent 50.0 ml/min @ 2 min

Gas saver 20.0 ml/min @ 4.0 min

Column

Constant flow 14.40 psi

Flow 1.4 ml/min

Average velocity 44 cm/sek

Manufacturer specifications

Model number J & W 122-5032

Column DB-5

Capillary

30 m * 250 µm * 0.25 µm nominal

Oven settings

Oven ramp Temperature

increase °C/min

Next °C Hold

Initial 90 2 min

Ramp 1 7 320 5 min

Ramp 2 0

Run time 39.86 min

Solvent delay 4 min

GC-MS

Brand Hewlett & Packard

Model GC 6890 plus series

Model MS 5973

Ionization mode Positive Electron ionization (EI+)

Scanning range Batch 1: m/z 50-500

Batch 2: m/z 33-500

9

Batch 2 was also analysed for PCBs using atmospheric pressure gas chromatography, APGC.

Table 5: APGC conditions

Inlet

Injection type Splitless

Pulse time 1 min

Heater 280°C

Pulse pressure 450 kPA

Column

Constant pressure 14.40 psi

Flow 1.4 ml/min

Average velocity 44 cm/sek

Manufacturer specifications

Model number Cat #: 12623

Serial #: 941009

Column Rtx®-5MS

Capillary

30 m * 0.25 mmID * 0.25 µm no

Oven settings

Oven ramp Temperature

increase °C/min

Next °C Hold time

Initial 180

Ramp 1 3.50 260 0 min

Ramp 2 6.50 300 0 min

Run time 31.01 min

Solvent delay 3 min

Ion source

Transferline Temperature 280°C

Make up gas Nitrogen

Make up gas flow 370 ml/min

APGC

GC Agilent 7890

MS Waters XEVO TQS

10

4. Results and Discussion The results from the full scan experiment are presented as chromatograms that can be seen in

Appendix A, B and C. The NIST spectral database from 1998 was used to determine which

compounds were present in the sediments from the full scan experiment. Each match was of

varying quality since many of the mass spectra obtained did not match well with the

suggested spectra.

The chromatograms from the intake and output from the same industry and batch are

compared to each other to determine which peaks are present in the output but not in the

input. This, in order to determine which compounds might have been released from the two

industries, the chromatograms were examined, and attempts were made to identify peaks that

appears in the output but not in the input. The chromatographic pattern were examined and

each pair of chromatograms provided a varying number of peaks that can only be found in the

output. . This approach resulted in several peaks that were examined, and the peaks with the

highest probability of obtaining a good match were chosen from each sample. The

chromatograms are examined for peaks only present in the output and NIST matches are

generated for each peak. The NIST comparisons with the highest probability of providing and

accurate match have been presented in the thesis. The selection process is based on the delta

plot and if the main peaks, such as molecular ions or indicative ions, are present in the

spectra.

The chromatograms seen in Appendix A, batch 1 before the minisilica clean-up, have not

been matched to the NIST library, due to the poor peak resolution. Appendix B show the total

ion chromatogram, TIC, from batch 1 for toluene, the Soxhlet blank and the sample from the

bay. Appendix C show the TIC for toluene, the Soxhlet blank and the sample from the bay for

batch 2.

11

4.1 Ringhals When comparing the samples from Ringhals batch 1 (Fig. 3,4) some peaks appeared in the

output, but not in the input. Some of these peaks were suggested to be 2,3-dihydro-1,1,3-

trimethyl-1H-indene, chlorocycloheptane, 2,3,4,6-tetramethyl-bibenzyl and, erucylamide.

Figure 3: Total ion chromatogram, TIC, of Ringhals input, batch 1

Figure 4: TIC of Ringhals output, batch 1

The samples from Ringhals batch 2 (Fig. 5,6) were n-methyl-n-phenyl benzamine, 3-(1,1´-

biphenyl-4-YL)butanenitrile, 1H-indene, 2,3-dihydro-1,1,3-trimethyl-3-phenyl and, 1(2-

bromoethyl)-4-methoxy-benzene.

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150528_003 Scan EI+ TIC

3.26e7

27.2313.41

13.28

13.24

5.22

13.55

21.49

20.68

20.03

18.56

17.68

16.9514.45

16.17

18.67

27.08

21.6024.24

23.3824.26

25.45

28.07

28.15

28.21

28.4731.00

30.82 31.23

32.25

R2

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150528_004 Scan EI+ TIC

3.95e7

13.77

13.73

13.47

13.35

5.24 12.7410.84

8.4411.71

13.81

24.76

22.6919.9118.4715.29

16.05 18.29 21.39

24.04

25.6727.03

28.0228.7230.13

32.94

12

Figure 5: TIC of Ringhals intake, batch 2

Figure 6: TIC for Ringhals output, batch 2

The NIST database output can be seen in Appendix D together with an analysis of the spectra

(Fig. 38-45).

These substances are highly possible matches for some of the peaks found in the output of

Ringhals. Each match is of varying quality, and the peaks with the highest probability of

providing an accurate match have been included in the thesis.

Erucylamide is used as a slip and antiblocking agent for polyolefins (Fine Organics 2012).

Polyolefins is a polymer made from any simple alkene and is for example used in detergent to

strengthen the package (Fine Organics 2012; Vasile 2000). Erucylamide is also found in leaf

essential oil from Citrus medica. Since C. medica has its origin in Bangladesh (Bhuiyan et al.

2009), it is unlikely to be found in sediment in Kattegat from the C. medica plant.

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150613_003 Scan EI+ TIC

5.29e7

16.50

16.477.54

6.385.92

4.99

15.95

15.27

11.12

9.528.81

13.15

11.46

17.07

29.90

18.89

17.22

29.67

28.4926.42

25.99

24.27

20.5223.71

21.91

25.64

27.29

34.3831.89

30.40

32.61

36.22

36.91

R2

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150613_004 Scan EI+ TIC

5.67e7

18.58

18.52

17.91

17.6515.82

4.10

7.76

18.86

27.6618.97 26.97

21.02

19.58

21.09

26.0824.44

21.18

23.85

24.67

28.12

36.38

28.55

28.9130.39

34.8932.34 36.77

13

For the other compounds, no information on their uses or origin have been found. Since no

information have been obtained about the other substances, it is difficult to determine their

origin.

4.1.1 Indicative ions for chlorine and bromine

Indicative ions for chlorine and bromine have been examined from the sample from Ringhals

intake (Fig. 11). There are some peaks present in both chromatograms for chlorine, m/z 35,

and 37. This supports the presence of chlorine at several retention times, among them 5.92,

and 16.22 minutes. The noise levels are much higher in the chromatogram displaying m/z 35.

The signal for m/z 37 is nearly ten times higher than for m/z 35 for the main peak, this

suggests that the peak with retention time 16.07 and 16.45 is from an impurity. The other

peaks present, 5.92, 7.54, 24.25, 25.88, 26.68, and 27.92, seems to conform to the theoretical

distribution of chlorine. In conclusion, chlorine seems to be present in the sample, since

several peaks appear with similar retention times.

Figure 7: Indicative ions for chlorine, m/z 35 and 37

The indicative ions for bromine (Fig. 10), show some peaks with retention time between

15.27 and 19.55 minutes, since peaks are present in both chromatogram, it supports the theory

that bromine is present in the sample from Ringhals. The isotope ratios for bromine are

acceptable for some peaks, such as 15.27, where the isotope ratio are nearly ideal. For the

main peak, 16.83 min, the isotope ratio does not resemble bromine, the abundance for the

lighter isotope is 32.9%. This is far from the ideal value, suggesting that the peak at 16.82 min

does not contain bromine. In conclusion, there are evidence of bromine being present in the

sample from Ringhals.

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

LRH_150613_003 Scan EI+ 35

6.56e3

27.92

24.255.92

24.2416.22

16.215.95

16.037.54

22.5216.24

22.5120.5218.3317.11

25.88

26.68

27.96

28.5629.69

30.36 32.5335.5333.38

36.93

LRH_150613_003 Scan EI+ 37

8.09e4

16.45

16.36

16.32

16.19

16.07

16.51

16.94 24.2718.7322.53

25.88 27.9129.90 31.92 34.29

14

Figure 8: Indicative ions for bromine, m/z 79 and 81

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

LRH_150613_003 Scan EI+ 79

5.98e5

16.83

7.54

4.99 5.59

16.50

16.4615.27

9.979.52

11.11 13.15

16.98

30.4227.56

27.3417.4326.3224.30

19.55

28.4731.10

32.6233.75

36.91

LRH_150613_003 Scan EI+ 81

1.22e6

16.83

16.48

15.28

5.61

32.5431.4530.43

29.7028.1016.9826.45

33.1534.82

36.91

15

4.2 Södra Cell Värö When comparing the samples from Södra Cell Värö batch 1 (Fig. 7,8) some peaks appeared in

the output, but not in the input. Some of these peaks were suggested to be 2,2’-diethyl-1,1’-

biphenyl, (2-methylphenyl)-methyl-carbamic acid, 2,6,10,14-tetramethyl-nonadecane, and

2,6,10,14,18-pentamethyl-eicosane.

Figure 9: TIC of Södra Cell Värö intake, batch 1

Figure 10: TIC of Södra Cell Värö output, batch 1

The samples from Södra Cell Värö batch 2 (Fig. 9,10) were suggested to be 1-chloro-3-

methyl-benzene, (E)-stilbene, 3,4,5,6-tetramethyl-phenanthrene and, erucylamide.

VB1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150528_005 Scan EI+ TIC

4.37e7

13.76

13.66

13.43

13.23

5.27

12.70

11.24

8.46 9.86

13.89

21.71

21.63

21.31

20.67

20.57

27.03

27.0024.61

23.29

26.46

29.2327.17

28.38

31.24

31.18

31.11

33.07

31.27

37.22

34.78

VB2

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150528_006 Scan EI+ TIC

3.60e7

15.76

15.63

14.94

14.17

13.19

15.79

25.41

24.23

15.94

18.43

16.83

23.24

23.22

18.52

21.3818.64

32.43

25.5327.09

27.58

28.75 29.70

32.98

33.56

16

Figure 11: TIC of Södra Cell Värö intake, batch 2

Figure 12: TIC of Södra Cell Värö output, batch 2

The NIST database output can be seen in Appendix D together with an analysis of the spectra

(Fig. 46-53).

These substances are highly possible matches for some of the peaks found in the output of

Södra Cell Värö. Each match is of varying quality, and the peaks with the highest probability

of providing an accurate match have been included in the thesis. The substances may have its

origin from the paper mill, since the long carbon chains may be a component from the raw

material used in the process.

Since erucylamide is found near both Ringhals and Södra Cell Värö, either its source is of a

natural origin, or the chemical is released from either of the industries and is transported with

the currents in the sea.

For the other compounds, no information on their uses or origin have been found. Since no

information have been obtained about the other substances, it is difficult to determine their

origin.

VB1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150613_005 Scan EI+ TIC

5.49e7

17.07

16.85

15.96

7.54

7.36

4.11

6.425.97

5.05

12.53

7.75 8.849.99

13.64

31.9629.77

28.27

28.2420.97

17.37

17.9419.21

25.10

24.50

21.93

26.16 28.31

31.1734.44

33.01

35.29 36.25

VB2

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150613_006 Scan EI+ TIC

5.52e7

19.46

18.0815.80

4.09

10.05

20.05 27.7826.92

21.3126.22

26.1224.46

24.19

22.32

28.41

28.69 36.60

29.00

35.5335.0533.34

30.4332.56 34.03

17

4.3 Polychlorinated biphenyls The results from the APGC can be seen in Table 8, appendix E. The results from the PCB

analysis (Fig. 13), are shown below. The peaks representing Ringhals intake saturated the

detector, and only the base of the peaks were present. Therefore the peaks were not integrated.

There were no attempts made to integrate the peaks since the levels were believed to be

completely misguided if prefrormed. The peaks from all samples are also shown in graphical

form below in Fig. 14, which is a cropped axis of Fig. 13.

In table 5 in appendix E, it can be seen that the blank contain high levels of the analysed

PCBs. This might be due to contaminations that occurred in the sample preparation. The

samples may contain additional analytes than the PCB that may interfere with the PCB

analysis, this is seen in the large shift in retention time which could be up to 0.5 minutes. This

problem should also affect the samples, and should be kept in mind when examining the

results. Due to the high levels found in the blank, the levels are only indicative.

Figure 13: PCB levels in sediment samples from the different sites. The blue stars indicates

peaks with too high concentration of PCBs which saturated the MS. The red stars indicate

peaks with bad peak shape.

0

2000

4000

6000

8000

10000

12000

PCB 28 PCB 52 PCB 101 PCB 118 PCB 153 PCB138 PCB 180

pg/

g d

.w. s

edim

ent

Ringhals intake Ringhals output Södra Cell Värö intake Södra Cell Värö output Bay

18

Figure 14: PCB levels in sediment samples from the different sites, the blue stars indicate

saturation of the MS, and the red stars indicate peaks with bad peak shape.

The sample from Ringhals intake, PCB #101, #118, #153 and #138 saturated the detector,

since only the base of the peaks were seen in the chromatograms. PCB #180 from Ringhals

intake is several times larger than the other sites, supporting the saturation theory. The intake

of both industries seems to contain higher levels of PCBs. Although, this may be a biased

statement, both intake points come from places believed to contain higher levels of

contaminants. Ringhals intake comes from a small harbour near the intake where the extra

activity associated with the harbour might increase the PCB levels. This is due to a sampling

error, since the sediments were too well packed to obtain samples closer to the actual input.

The only sediment that were obtained from Ringhals intake were from the harbour, initially

the effect of the harbour was unknown.

The intake for Södra Cell Värö was taken from the river Viskan, which passes through Borås,

a town associated with the textile industry. Kattegat can therefore receive contaminants from

Viskan, as it absorbs pollutants from the nearby land and industries as it passes through

Sweden, and deposits them in the sea (Forsman & Edlund n.d.). Since the intake is situated in

the river Viskan, no other sampling point was available for the intake from Södra Cell Värö.

PCB #118 showed signs of co-elution in Ringhals output and Södra Cell Värös output, and

they were therefore not integrated in those samples. In general, the peaks had a poor peak

shape and the co-elution is most likely from several PCBs, so obtaining any useful

information is hard.

In another report from Swedish EPA, the levels of several congeners of PCBs (PCB #28, #69,

#73, #52, #84, #89, #90, #101, #106, #118, #153, #138, #164, #163, and #180) show a

maximum level of 25000 for the PCBs previously mentioned in pg g-1 d.w in the Baltic

Proper region in 1990 (Wiberg et al. 2013). The PCB 180 levels from Ringhals intake for

alone account for around 40% of the concentration in the highest level found in the study.

0

100

200

300

400

500

600

700

800

900

1000

PCB 28 PCB 52 PCB 101 PCB 118 PCB 153 PCB138 PCB 180

pg/

g d

.w. s

edim

ent

Ringhals intake Ringhals output Södra Cell Värö intake Södra Cell Värö output Bay

19

A study showed that the mean concentration along the Baltic Sea were for PCB #101 210 pg

g-1 d.w., PCB #118 was 130pg g-1 d.w., PCB #153 was 400 pg g-1 d.w., PCB #138 was 110 pg

g-1 d.w and for PCB #180 it was 220 pg g-1 d.w. in 1985 (Sobek et al. 2015).

For PCB #101 the levels are all lower than the mean.

For PCB #118 all sampling sites were lower than the levels from the Baltic Sea coast.

For PCB #153, all but Södra Cell Värös intake were lower than the mean. The intake from

Södra Cell Värö had around 700 pg g-1 d.w, the highest level at a sampling site in the Baltic

Sea was 13 000 pg g-1 d.w.

For PCB #180 the levels were lower than the mean from the Baltic Sea, except for Södra Cell

Värös intake and Ringhals intake. The levels near Södra Cell Värö are close to the mean value

from the study. The levels near Ringhals intake are much higher than the mean level for PCB

#180, but the highest level measured in the study was 17000 pg g-1 d.w. from one of the

sampling sites. Ringhals intake are much lower than the highest level measured. The PCB

levels from Ringhals intake are believed to be the sampling point with the highest

concentration of PCBs. The levels from Ringhals intake saturates the detector causing the top

of the peak to be removed in some cases the base were nearly invisible. No attempt at

integrating the levels of those PCBs have been made.

Since Ringhals intake showed high levels, 11071 pg/g sediment of PCB #180, the remaining

PCBs were believed to be seen in the chromatograms from the GC-MS screening.

The indicator ions for PCBs with one chlorine substitution can be seen fig. 15. The two ions

displayed are m/z 188 and 190, these are the two ions with the highest and second highest

intensity. Since the peaks displayed in either chromatogram are not present in the other

chromatogram, the single chlorine substituted PCBs are most likely found in levels below the

GC-MS limit of detection, (LOD).

Figure 15: Indicative ions for PCB with one chlorine substitution

In fig. 16 the indicative ions for PCBs with two chlorine substitutions. Some peaks are visible

in both chromatograms, such as 22.53. There is a large peak disturbing the chromatogram

displaying m/z 224, suggesting that the chromatogram suffers from impurities. Since this peak

is visible in the GC-MS full scan experiment, the levels are believed to be quiet high.

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

LRH_150613_003 Scan EI+ 188

5.80e5

16.9815.28

14.78

16.91

16.83

17.02

17.12

36.1133.30 34.15

LRH_150613_003 Scan EI+ 190

8.61e4

22.30

22.08

12.0620.2119.03

12.91

31.45

31.4328.4527.6326.27

23.97

23.78

33.2833.75

36.9134.17

20

Figure 16: Indicative ions for PCB with two chlorine substitution

In fig. 17 the indicative ions for PCBs with three chlorine substitution can be seen. Several

peaks can be seen in both chromatograms, especially peaks around retention time 24.26 and

27.32 minutes. Since the peaks can be seen with the GC-MS full scan, it indicates high levels,

supporting the saturation theory from the PCB analysis with the APGC. Since the standards

for the APGC analysis are not visible in the samples when using the GC-MS approach, the

peaks cannot be matched to a specific PCB.

Figure 17: Indicative ions for PCB with three chlorine substitution

Fig. 18 show the two largest ions for PCBs with four chlorine substitutions. They show a

similar pattern in both chromatogram, suggesting that PCBs with three chlorine atoms are

present in high levels. Peaks with retention time of 22.53, 24.27, 27.25, 27.92, 29.18, 29.34

minutes are possible PCBs.

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

LRH_150613_003 Scan EI+ 222

2.19e5

22.53

20.2119.03

16.4720.40

36.22

24.27

24.34

27.9327.24 29.67 32.7930.23 33.73

LRH_150613_003 Scan EI+ 224

9.88e4

34.3722.53

19.96

19.21

18.6117.0515.05

22.44

22.00

23.9031.8924.03

24.3229.3728.57

24.38 29.68

30.77

32.8134.44

34.53 35.87

36.96

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

LRH_150613_003 Scan EI+ 256

7.36e5

24.26

23.70

24.96 25.88

26.68

27.32

31.9431.1027.92

LRH_150613_003 Scan EI+ 258

2.43e5

24.26

24.16

23.3221.56

20.24

31.1024.96

25.8830.42

26.68 30.22

27.3228.69

32.13 33.09

33.75 35.43

21

Figure 18: Indicative ions for PCB with four chlorine substitutions

Fig. 19 show the two largest indicative ions for PCBs with five chlorine substitutions. Many

peaks are present in both chromatograms, such as the peaks with retention time 24.27, 24.96,

25.88, 26.68, and 27.32 minutes. Those peaks are suggested to be PCBs with four chlorine

substitutions.

Figure 19: Indicative ions for PCBs with five chlorine substitutions

Fig 20 show the two largest indicative ions for PCBs with six chlorine substitutions. Several

peaks are present in both chromatograms, among them the peaks with retention time 25.73,

26.50, 27.25, 27.92, and 28.58 minutes.

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

LRH_150613_003 Scan EI+ 292

4.08e5

24.2822.53

27.9227.25

25.73

29.18

29.34

LRH_150613_003 Scan EI+ 294

2.03e5

24.28

22.53

22.32

27.9227.25

24.77

34.3831.89

29.68 32.5635.84

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

LRH_150613_003 Scan EI+ 326

1.14e6

25.88

24.9624.2726.68

27.32

28.36

33.1829.69

LRH_150613_003 Scan EI+ 328

7.27e5

25.88

24.9624.2626.68

27.32

29.6728.29 33.1930.40

22

Figure 20: Indicative ions for PCBs with six chlorine substitutions

Fig. 21 show the two main indicative ions for PCBs with seven chlorine substitutions. Peaks

with retention time 27.47, 28.29, 28.87, 29.69, and 30.37 minutes, among other are suggested

to be PCB with six chlorine substitutions.

Figure 21: Indicative ions for PCBs with seven chlorine substitutions

Fig. 22, 23 and 24 show indicative ions for PCBs with eight, nine and ten chlorine

substitutions. All six chromatogram show noise at the end of the chromatogram, and the

levels of PCBs are believed to be below LOD for the GC-MS screening.

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

LRH_150613_003 Scan EI+ 360

7.38e5

27.92

27.25

26.50

25.73

28.57

30.37 31.66

LRH_150613_003 Scan EI+ 362

5.83e5

27.92

27.25

26.50

25.73

28.58

31.5830.22 32.06 34.07

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

LRH_150613_003 Scan EI+ 394

8.87e4

29.69

28.8728.29

27.47

32.99

30.37

32.80

32.04

33.00

35.4234.26

35.49

35.83

LRH_150613_003 Scan EI+ 396

8.57e4

29.69

28.8828.29

27.48

25.49

30.37

32.9532.22

31.9534.45

35.66

36.16

36.84

23

Figure 22: Indicative ions for PCBs with eight chlorine substitutions

Figure 23: Indicative ions for PCBs with nine chlorine substitutions

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

LRH_150613_003 Scan EI+ 430

2.50e4

35.5134.58

34.19

33.84

32.67

31.9830.72

36.72

36.99

LRH_150613_003 Scan EI+ 428

3.98e4

35.51

35.3733.85

33.79

33.27

32.41

36.78

36.95

36.97

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

LRH_150613_003 Scan EI+ 464

5.60e3

36.2335.63

34.72

33.92

33.76

32.71

36.99

LRH_150613_003 Scan EI+ 461

1.02e4

36.66

36.61

35.10

34.42

33.80

33.54

36.86

36.95

24

Figure 24: Indicative ions for PCBs with ten chlorine substitutions

Swedish EPA have proposed five levels of PCB concentrations, which is no levels, low levels,

average levels, high levels and very high levels. Ringhals intake is 5 times higher than the

level characterised as very high levels for PCB #180. The saturated peaks are most likely of

higher concentrations than PCB #180 and are therefore most likely placed in the very high

levels category.

Table 6: Swedish EPA classifications of PCB contaminated sediments, µg/g dry weight of

sediment (Naturvårdsverket 1999)

PCB congener No levels Low levels Average

levels

High levels Very High

levels

#101 0 0 – 0.16 0.16 – 0.60 0.60 – 2.0 >2.0

#118 0 0 – 0.15 0.15 – 0.60 0.60 – 2.0 >2.0

#153 0 0 – 0.030 0.030 – 0.30 0.30 – 3.5 >3.5

#138 0 0 – 0.30 0.30 – 1.2 1.2 – 4.1 >4.1

#180 0 0 – 0.10 0.10 – 0.40 0.40 – 1.9 >1.9

Table 7: Comparison of levels with the Swedish EPA * indicates peaks too large to integrate

** indicate bad peaks

PCB

congener

Ringhals

intake

Ringhals

output

Södra Cell

Värö intake

Södra Cell

Värö output

Bay

#101 * Low Low Low Low

#118 * ** Low ** Low

#153 * Average High Average Average

#138 * Low Average Low Low

#180 Very high Low Low Average Low

Comparing the results obtained to the data from Swedish EPA, the values are shown as levels

instead of numerical values (Table 7). The result indicates that there are PCBs present in the

sediments, in high levels at some of the sampling sites, Södra Cell Värö intake, and at very

high levels in some samples, Ringhals intake. The industries seem to have no effect on the

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00

%

0

100

LRH_150613_003 Scan EI+ 498

2.13e3

36.9035.87

35.41

35.0733.46

33.0231.33

29.4728.2922.0816.724.72

11.449.596.38 16.23 21.5619.0124.56 26.79

36.98

36.99

LRH_150613_003 Scan EI+ 500

1.15e3

36.73

36.49

35.1334.43

31.97

31.6024.13

16.4215.8410.406.255.79 7.99 9.09 10.8612.13 14.69

16.87 18.59

17.8319.87

22.58

30.2829.0727.3525.90

33.74

33.72

36.96

36.99

25

PCB concentration in sediments surrounding the two industries since the levels are lower in

the output than the input. The levels from Ringhals intake indicates very high levels of PCBs,

since peaks are visible in the GC-MS experiment. PCB #180 is believed to have the lowest

concentration of all the PCBs measured. PCB #180 is according to the Swedish EPA very

high suggesting that the levels for the other PCBs indicative very high levels.

The levels indicated with an asterisk, probably falls in the category of very high levels, since

they have a higher concentration than PCB #180 in the GC-MS screening, and PCB #180 falls

under the category of very high levels.

The levels proposed by the Swedish EPA have in recent years been out dated, but it is still

applied routinely.

The pattern of the congeners may by lined to a specific Aroclor. The conclusion that PCB

#180 which was the only peak small enough to integrate, is supported since PCB #180 is a

heptachlor, shown in fig. 21, and only noise is visible, suggesting that the levels of the other

PCBs with two, three, four, five, and six chlorine substitutions are higher than the PCB #180

levels from the APGC.

For the patter determination, the chromatograms from the GC-MS indicative ions were used.

The chromatogram with the highest intensity belonged to the heptachlorobiphenyls. The

second highest intensity was hexachlorobiphenyls, followed by trichlorobiphenyls and tetra

chlorobiphenyls. The highest intensity is plotted, and the other peaks are plotted by their

relative intensity, providing a plot used to match against the congener patterns from EPA.

When examining the PCB congeners, the highest peaks belong to heptachlorobiphenyls, PCB

#40 – PCB #81. The Aroclor patterns from EPA show higher levels of PCBs with other

degrees of chlorination, such as Aroclor 1016 and 1242, where the maximum concentration is

between PCB #15 and PCB #30. Aroclor 1254a and 1254g have a maximum between PCB

#110 and #120. Aroclor 1260 have its maximum around PCB #180. Neither of those match

the pattern from the sample collected from Ringhals intake. The Aroclors that match these

high levels of heptaklorobifenyls, is Aroclor 1248a and 1248g from EPA. Aroclor 1248a and

1248g display a very similar pattern, and since the specific PCB congener cannot be

determined from the GC-MS, the Aroclor cannot be differentiated between Aroclor 1248a and

1248g (US EPA n.d.)

5. Conclusion The aim of this study was to determine if there were any differences between the intake and

output of the two industries and if potential contaminants linked to either industry can be

found in the bay. This was done by applying a full scan approach. With this approach,

numerous errors were encountered. Many of the peaks were not sufficiently resolved to

provide reliable results, and most of the results cannot give any conclusive information

regarding the presence of contaminants in the samples. Often, the type of compound group

present can be matched with the reference library, but the specific compound cannot be

determined. The samples from Ringhals generally contained longer carbon chains, whereas

Ringhals generally contained more PAHs.

The high levels found in the Soxhlet blank may be due to the fact that the sample was

analysed late in a sequence, causing a memory effect. This may explain the high levels found

26

in the Soxhlet blank. The levels in the Soxhlet blank are higher than the levels in some

samples, so any levels below that of the Soxhlet blank may be used as indicative levels of the

PCB concentration.

Since the study is performed by using a screening method, identification of analytes may not

be feasible due to the co-elution of different analytes with similar retention time. Some

compounds will co-elute and overlapping chromatogram and mass spectra will most likely be

obtained. Overlapping mass spectra will then be much harder to match to databases since the

mixed mass spectra will generate a different spectra and the possible matches will not fit the

mass spectra suggested by the database. Not only will the purity of mass spectra be of issue,

many compounds have several congeners, often with similar mass spectra and they cannot be

differentiated by only using the mass spectra. For this kind of study, it is impossible to acquire

standards for all compounds analysed, and therefore each match to the database is a tentative

identification. There are other indications that can be used for the confirmation of the

compound than the mass spectra and retention time. If possible, a MS/MS spectra, and 13C

standards for important ions can be used to further strengthen the conclusion. With the

MS/MS approach, the limits of detection, LOD, are lowered, but all other analytes are lost in

the process. The MS/MS approach does lower the LOD, but the risk of overcharging the

detector increases with higher levels. The spectra from the full scan, all follow the criteria

from the mass spectra, and the retention time in many cases seems plausible.

The screening method provided some good matches for each chromatogram. The

chromatogram do indicate differences in the sediments from the five locations. Each

chromatogram show different peaks, suggesting that the industries have affected the

composition of the sediments. Since the peaks have not been identified, to maintain within the

scope of the thesis, only differences in the pattern have been examined.

The main part of the thesis was to determine what substances have been released by the

industries, and that was proven to be difficult. The industries could not be linked to any

compounds found in the sediments. But the general difference in chromatographic pattern

suggests that there is a difference in the sediments. The differences in the sediments might be

worth additional studies with another approach. There appear to be less extractable material in

the outtake of the two industries, suggesting that they have not affected the superficial

environment surrounding Värö peninsula. Since the samples acquired for the intakes are from

sites believed to show additional contamination, such as a harbour for Ringhals intake, and

the fabric industry for Södra Cell Värö intake. Again, the intake for Ringhals should have

been acquired closer to the actual intake and not in the harbour, but due to sampling errors,

this was unavailable. The sediments were packed too hard for the Ekman sediment grabber to

acquire a sample. The results show a general decrease in the intensity in the chromatogram

from the Ringhals comparison, but the decrease might be from the additional elements added

by the harbour. The same problem may arise with the water from Södra Cell Värö, the

contamination from the previous releases in Viskan.

Several of compounds suggested by the NIST library, any information on the origin of the

compound were unattainable. In many instances medical safety data sheets (MSDS) have

been found, and they do not provide information on the sources of the compounds.

To maintain within the scope of the thesis, the sampling was limited to five locations.

Preferably a reference point should have been obtained, further out from the coast. There is a

27

small river that flows into the bay in the middle of the peninsula, which should have been

investigated as well.

When running the APGC, there are some limitations with the standards, as the standard added

only contains a few different congeners of PCBs, and the analysis is thereby limited to those

PCBs alone. The large time shift that appeared in retention time due to the high content in the

samples made the identification via retention time nearly impossible. The samples were

analysed in the end of a long sequence, causing several of the peaks to tail. The samples were

also highly contaminated, since no further clean-up took place between the GC-MS screening

and the APGC analysis, causing the retention time to shift. This shift in retention time makes

the identification of PCB congeners hard. Since the retention time from the PCB standard

does not match the retention times in the samples.

The industries seems to not affect the levels of PCB in the sediments, since they should be

elevated at the output sites, and that is not the case. The PCB levels are much lower in the

output locations suggesting that the industries do not affect the levels of PCBs in the

sediments. Ringhals output, Södra Cell Värös output and the bay seem to contain similar

levels of PCBs, suggesting that the sites are exposed to similar sources.

Since an Aroclor pattern can be determined from the GC-MS analysis, the levels of PCB

#101, PCB #118, PCB #153, and PCB #138, are most likely higher than the levels found for

PCB # 180. The Aroclor found near Ringhals intake probably have its origin in the activity

associated with the harbour, not the neighbouring industries. This since the elevated levels are

only found near Ringhals intake, and all other points display lower levels.

The initial intention was to compare the samples taken in the bay to the findings in the other

samples; this was proven to be difficult, it has been excluded as a part of the experiment. Sop

for further investigations, the bay should be more extensively compared to the two industries

to determine if any releases takes place and affects the industries. Another possibility is to

widen the search and examine more than the indicator PCBs. This may be done by using

principal component analysis to determine the source of the PCB congeners. It would also be

helpful in the Aroclor pattern recognition, since the levels in this thesis is only based on the

peak height from the GC-MS screening.

To continue the studies, several additional sample should be examined for PCBs, which seems

to be present at quite high levels in some of the sample locations. Preferably, a clean-up

adapted for the analysis of PCBs should be used. Another possibility is to examine the

exposure to seals, fish, crabs, or clams to determine the impact on wildlife. Preferably crabs

and clams, since they live in the sediments. Water samples is another possibility to continue

the study.

The results are inconclusive, so further studies are needed to achieve reliable results. The

sampling should have taken place at another location than the harbour for the Ringhals intake.

Since this location most likely do not represent what can be found closer to the intake, further

from the harbour. The harbour near Ringhals intake is in a small bay, probably with limited

water exchange, causing the levels released by the boats to increase. If sediment samples are

to be acquired again, the Ringhals intake should not be taken from the small harbour but

closer to the actual intake, on open water. The congener profile found in the harbour is

probably due to the activity in the harbour. This since a similar profile is present in all sites

28

except for Ringhals intake, suggesting that the release of Aroclor is due to the activity in the

harbour.

29

6. References

Ali, M. & Sreekrishnan, T.R., 2001. Aquatic toxicity from pulp and paper mill effluents: A

review. Advances in Environmental Research, 5(2), pp.175–196.

Bhuiyan, M.N.I. et al., 2009. Constituents of Peel and Leaf Essential Oils of Citrus Medica L.

Journal of Scientific Research, 1(2), pp.6–11.

Chiarenzelli, J. et al., 1996. Volatilization of polychlorinated biphenyls from sediement

drying at ambient conditions. Chemosphere, 33(5), pp.899–911.

Edgren, M., Olsson, M. & Reutergårdh, L., 1981. A one year study of the seasonal variations

of sDDT and PCB levels in fish from heated and unheated areas near a nuclear power

plant. Chemosphere, 10(5), pp.447 – 452.

Elforsk, 2009. Miljöeffecter av stora kylvattenutsläpp - Erfarenheter från de svenska

kärnkraftverken,

Eriksson, S.G., 2015. Personal communication.

Fine Organics, 2012. Material safety data sheet - Erucamide. , pp.1–8.

Forsman, A. & Edlund, L.-E., Viskan. Available at:

http://www.ne.se/uppslagsverk/encyklopedi/l%C3%A5ng/viskan [Accessed July 1,

2015].

Google Maps, 2015. Google maps.

Hawthorne, S.B. et al., 2000. Comparisons of Soxhlet extraction, pressurized liquid

extraction, supercritical fluid extraction and subcritical water extraction for

environmental solids: Recovery, selectivity and effects on sample matrix. Journal of

Chromatography A, 892(1-2), pp.421–433.

Jurado-Sánchez, B., Ballesteros, E. & Gallego, M., 2013. Comparison of microwave assisted,

ultrasonic assisted and Soxhlet extractions of N-nitrosamines and aromatic amines in

sewage sludge, soils and sediments. Science of the Total Environment, 463-464, pp.293–

301. Available at: http://dx.doi.org/10.1016/j.scitotenv.2013.06.002.

Lau, C. et al., 2007. Perfluoroalkyl acids: A review of monitoring and toxicological findings.

Toxicological Sciences, 99(2), pp.366–394.

Murphy, B.L. & Morrison, R.D., 2007. Introduction to environmental forensics 2nd ed.,

Elsevir Inc.

Nationalencyklopedin, Valthornssnäcka. Nationalencyklopedin. Available at:

http://www.ne.se/uppslagsverk/encyklopedi/l%C3%A5ng/valthornssn%C3%A4cka

[Accessed June 21, 2015].

Naturvårdsverket, 1999. Rapport 4919: Bedömningsgrunder för miljökvalitet – Kust och hav,

30

Parera, J., Santos, F.J. & Galceran, M.T., 2004. Microwave-assisted extraction versus Soxhlet

extraction for the analysis of short-chain chlorinated alkanes in sediments. Journal of

Chromatography A, 1046(1-2), pp.19–26.

Ratia, H. & Oikari, a., 2014. Vertical distribution of AhR-activating compounds in sediments

contaminated by modernized pulp and paper industry. Water Research, 50, pp.27–34.

Available at: http://linkinghub.elsevier.com/retrieve/pii/S004313541300986X.

Secretariat of the Stockholm Convention, What are POPs?

Sobek, A. et al., 2015. Baltic Sea sediment records: Unlikely near-future declines in PCBs and

HCB. Science of The Total Environment, 518-519, pp.8–15. Available at:

http://linkinghub.elsevier.com/retrieve/pii/S0048969715002466.

Stibe, L., 2015. Email, personal communication.

Södra Cell Värö, 2015. Massafabrik i ständig utveckling. Available at:

http://www.sodra.com/sv/Massa/Vara-massabruk/Sodra-Cell-Varo/ [Accessed June 20,

2015].

Södra Cell Värö, 2014. Välkommen till Södra Cell Värö - En av världens största och mest

moderna massaindustrier,

United Nations, 1995. Stockholm convention.

US EPA, Aroclor plot EPA. Available at:

http://www.epa.gov/osw/hazard/tsd/pcbs/pubs/aroclor.htm [Accessed July 30, 2015].

US EPA, 1996. EPA method 3540c. , pp.1–8.

Vasile, C., 2000. Handbook of Polyolefins (2nd Edition) 2nd ed., New York: CRC Press.

Vattenfall, 2012a. Ringhals – The largest Nordic power plant,

Vattenfall, 2012b. Technical information on Ringhals,

Wiberg, K. et al., 2013. Managing the Dioxin Problem in the Baltic Region With Focus on

Sources To Air and Edible Fish,

Wulff, F. et al., 1993. A Mass-Balance Model of Chlorinated Organic Matter for the Baltic

Sea: A Challenge for Ecotoxicology. AMBIO, 22(1), pp.27–31. Available at:

http://www.jstor.org/stable/4314033?seq=1#page_scan_tab_contents.

31

Appendix A- Batch 1, without minisilica

Figure 25: TIC from Toluene

Figure 26: TIC from Soxhlet blank

Toluen

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150527_008 Scan EI+ TIC

6.53e6

4.41

39.1036.9335.70

34.7534.34

33.67

37.18 39.45

39.65

Blank

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150527_009 Scan EI+ TIC

5.11e7

4.29

4.37

14.9914.18

13.994.46

4.54 13.57 15.2426.8526.13

25.0522.7021.79

20.86

30.1128.13

30.28

31.54 33.25

32

Figure 27: TIC from Ringhals input

Figure 28: TIC from Ringhals output

R1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150527_010 Scan EI+ TIC

2.71e7

21.7313.37

13.20

13.16

18.3913.55

18.27

18.17

18.16

18.07

21.66

21.51

20.64

20.26

20.19

21.95

22.06

22.2925.7724.35 27.08

29.1329.80 31.41

34.5232.48 35.15

R2

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150527_011 Scan EI+ TIC

2.80e7

13.69

13.64

13.30

13.23

13.20

13.194.30

13.14

4.3113.13

14.17

28.1827.24

27.2021.80

21.66

21.6318.32

18.28

21.6018.35

27.13

27.11

24.16

22.8924.49

25.47

28.30

30.4328.37

34.6834.0730.83

33.9435.31 37.34

35.55 37.38

33

Figure 29: TIC from Södra Cell Värös input

Figure 30: TIC from Södra Cell Värö output

VB1

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150527_012 Scan EI+ TIC

3.35e7

13.88

13.52

13.28

13.22

13.19

13.16

13.145.45

5.37 5.61

13.99

18.16

16.54

16.52

16.50

16.48

18.13

18.12

17.92

18.3321.84

21.1618.36

20.72

20.66

18.57

23.9230.65

28.5224.25

27.0924.72

24.74

26.20

30.62

29.3232.58

31.35

34.43

VB2

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150527_013 Scan EI+ TIC

3.19e7

4.314.62

17.3816.0715.634.72

14.57

14.31

17.95

17.96

24.48

24.4718.5721.79

21.72

21.65

21.62

21.60

24.12

24.11

24.08

25.31 31.13

30.72

30.70

30.60

27.1131.16

34

Figure 31: TIC of sample from the bay

F

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150527_014 Scan EI+ TIC

3.54e7

4.50

4.95

5.02

16.805.03

16.2314.97

13.42

17.41

18.0024.46

18.04

18.1921.66

21.62

24.09

22.81

25.35

30.70

30.67

30.64

30.95

35

Appendix B: Batch 1 with minisilica

Figure 32: TIC of toluene blank

Figure 33: TIC of Soxhlet blank, after use of minisilica

Toluen

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150528_001 Scan EI+ TIC

2.33e6

36.98

36.84

36.46

36.31

36.20

35.23

35.18

4.45 34.82

34.74

37.57

37.81

38.39

38.74

39.83

Blank

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150528_002 Scan EI+ TIC

3.65e7

14.82

13.98

13.58

13.44

13.29

27.3514.83

27.2324.6223.92

22.85

22.41

27.44

28.01

28.19

28.38

28.44

28.52

36

Figure 34: TIC of sample from the bay, after the use of minisilica

F

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150528_007 Scan EI+ TIC

3.63e7

15.99

14.26

14.08

13.44

13.26

13.12

12.66

11.44

11.33

16.06

25.4024.2116.14

24.05

23.2422.74

18.4216.92

18.4921.35

32.43

25.51

27.02

29.68

32.96

33.54

37

Appendix C: Batch 2

Figure 35: TIC of toluene

Figure 36: TIC of Soxhlet blank from batch 2

Toluene

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150613_001 Scan EI+ TIC

2.31e7

4.12

4.15

6.55

4.34

5.24

Blank

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150613_002 Scan EI+ TIC

4.93e7

18.24

18.20

18.10

17.58

16.79

15.85

4.20

7.64

6.01 11.58

27.68

26.9618.52

18.83

21.02

19.7926.01

25.52

21.1324.74

28.55

36.56

35.00

28.8934.00

32.53

31.81

36.89

38

Figure 37: TIC of sample taken in the bay from batch 2

F

Time5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50

%

0

100

LRH_150613_007 Scan EI+ TIC

6.07e7

4.10 17.77

17.65

17.56

17.4415.93

4.327.60

7.406.078.88 13.66

27.7117.84 26.94

21.0119.37

17.93

21.11

26.33

26.1424.47

22.29

29.95

35.01

30.48

33.45

31.75

35.55

39

Appendix D – NIST Database matches and analyses

The NIST database suggested 2,3-dihydro-1,1,3-trimethyl-1H-indene for the mass spectra

generated at 6.26 min (Fig. 38). The spectra from the NIST library resembled the spectra

obtained, but there were small variations between the reference and the sample spectra. The

other hits from the NIST library were also resembling the mass spectra from the sample,

therefore an identification was not possible. The conclusion that can be drawn was that the

structure most likely have an indene, or an aromatic structure. Many of the suggested matches

from the NIST library all contain indene, benzene, or naphthalene as the suggested backbone

for the structure. The proposed analyte most likely have an aromatic structure, with a methyl

substitution.

Figure 38: NIST database match for Ringhals batch 1, 6.258 min

40

Figure 39: NIST database match for Ringhals batch 1, 15.378 min

The suggested molecule for the mass spectra at 15.37 minutes is chlorocycloheptane (Fig. 39).

Many of the peaks in the mass spectra are again not matching, there are additional peaks in

both the reference spectra and in the sample spectra. The suggested match by the NIST library

seemed poor and it could not be used to determine the structure of the compound. The series

of m/z 55, 69, 83, 97, 111 suggest an alkene, cycloalkane, alkenyl-, cycloalkyl carbonyl,

cyclic alcohol, ethers, or cyanides. The presence of chlorine seems to be unlikely since no

clorine clusters are present in the samples. The peak at 83 should be more prominent if the

structure suggested by NIST is true. In this spectra, the settings of the MS should have been

different. If the scanning range included m/z 35 and 37, the presence of chlorine would have

been apparent and the analysis of the spectra would have been simplified. The suggested

analyte is most likely an alkene, possibly with a cyclo configuration.

41

Figure 40: NIST database match for Ringhals batch 1, 18.291 min

The NIST database suggestion for the peak at 18.29 minutes was 2,3,4,6-tetramethyl-bibenzyl

(Fig. 40). The peak at m/z 91 confirms the possible presence of a benzene structure in the

molecule. The first two matches from the NIST library are of two bibenzyl and the third and

fourth match consists of a benzene structure. When examining the delta plot, there are some

differences indicating that the suggested molecule may not be the best possible match. The

sample spectra have a possible molecular ion at m/z 238, but there is an additional peak at m/z

223. The additional peak at m/z ratio 223 may indicate the loss of a methyl group, this could

be possible with either of the structures, since there are methyl groups on the first four spectra

matches from the hit list. The analyte is probably bibenzyle, with unknown functional groups.

The structure probably contains at least one benzene ring.

42

Figure 41: NIST database match for Ringhals batch 1, 29.686 min

The peak with retention time 29.69 min is suggested to be erucylamide (Fig. 41). The delta

plot show some discrepancies between the sample and the NIST reference spectra. The

differences are minimal for large parts of the delta plot, but some key peaks are missing from

the sample spectra, such as the peak between m/z 80 and 90, where around 60 % of the peak

is unaccounted for. The main peaks present in the sample are m/z 55, 83, 69, 97, and 112, this

suggests an alkene, cycloalkane, alkyl, cycloalkyl carbonyl, cyclic alcohol, or an ether. The

delta plot shows too large differences between the spectra. The peak with m/z 72 and 126 is

not a part of the sample spectra. The erucylamide is a tentative identification, but the

uncertainty of the match is too high to provide any reliable results.

43

Figure 42: NIST database match for Ringhals batch 2, 15.817 min

For the peak with retention time 15.82 min, the mass spectra from 15.817 min have been used

for comparison to the NIST database (Fig. 42). The NIST library’s best match is an n-methyl-

n-phenyl benzamine. When comparing the sample spectra and the reference spectra to each

other, some differences become apparent. The match is of poor quality with many additional

peaks near the lower m/z ratios, but nearly all of the main peaks are present, and it is possible

that the peak suffers from impurities can account for the additional peaks. The sample spectra

obtained have many peaks that is not present in the NIST reference spectra, and therefore it is

possible that the additional peaks are due to a contaminant that co-eluted with the analyte.

Since the mass spectra displays characteristic ions such as m/z 91, and 182, it is highly

possible that it is an aromatic compound even with the exact structure is not known.

44

Figure 43: NIST database match for Ringhals batch 2, 19.883 min

The structure proposed by the NIST database for the peak with retention time 19.88 minutes

is a 3-(1,1´-biphenyl-4-YL)butanenitrile (Fig. 43). The structure seems plausible, the spectra

closely resembles the reference spectra with minor differences. The same conclusion can be

drawn from the delta plot, where there are minor difference, the biggest differences is under

20% in the delta plot. It is worth noting that the spectra is not a perfect match. Since there are

no standards to analyse with the GC-MS, the conclusion is not definite. To make a definite

match, the retention time needs to be compared to the retention time of a standard.

45

Figure 44: NIST database match for Ringhals batch 2, 20.408 min

The NIST database suggested that the structure is a 1H-indene, 2,3-dihydro-1,1,3-trimethyl-3-

phenyl (Fig. 44). The first five matches are the same compound. The spectra obtained from

the sample show some additional peaks compared to the NIST reference spectra. The match

suggested seems plausible, but the additional peaks present may be due to impurities or the

sample spectra might originate from a different compound. The sample spectra does display

the characteristics of benzene like structure due to the peak present at m/z 91 and 128. Since

The first five matches are the same compound, it is highly possible that the compound is the

match suggested by the NIST database.

46

Figure 45: NIST database match for Ringhals batch 2, 20.987 min

The suggested match by the NIST library for the peak at 21.02 minutes is suggested to be 1(2-

bromoethyl)-4-methoxy-benzene (Fig. 45). The delta plot show major differences between the

two spectra. There are few peaks that strengthen the fact that bromine is a part of the

molecule. The possible molecular ion, m/z 236, show weak indications of a bromine cluster,

at m/z 236 and 238. The peak representing the heavier isotope is of lower intensity than the

theoretical value. The presence of the M+2 peak, is most likely due to another compound than

bromine. Other than that peak at m/z 236 and 238 there are no indications of a bromine

present in the spectra. The suggested match by the NIST library is most likely not the analyte.

The presence of a benzene may not be accurate either, since the m/z ratio of 91 is not very

prominent in the spectra. The benzene ring is usually a very stable molecule, not prone to

brakeage, so the peak should show a peak of higher intensity, if it was present in the sample.

The molecule probably consists of a benzene ring, possibly containing a bromine atom,

although the configuration is unknown.

47

Figure 46: NIST database match for Södra Cell Värö batch 1, 16.271 min

The molecule suggested by the NIST database for the peak at 16.27 min is 2,2’-diethyl-1,1’-

biphenyl (Fig. 46). The NIST reference spectra show several similarities, mainly the peaks at

m/z 181 and 165. There are two peaks from the reference spectra just above m/z 181, which

seems to be missing or have a very low intensity in the sample spectra. The ions at m/z ratio

of 181 and 165 seem to be very common for many polyaromatic hydrocarbons, since the first

four hits from the NIST database all display the same ions, m/z 181 and 165, at similar

intensities. The delta plot show some differences between the sample spectra and the NIST

reference spectra. The compound with retention time 16.27 minutes might be a biphenyl or

another polyaromatic hydrocarbon, but the functional groups have not been determined

48

Figure 47: NIST database match for Södra Cell Värö batch 1, 18.442 min

The suggested NIST database match for the peak at 18.43 minutes is suggested to be (2-

methylphenyl)-methyl-carbamic acid, (Fig. 47). The NIST suggested database match show

several discrepancies between the two spectra. What appears to be the molecular ion in the

NIST database, m/z 165, appears much smaller and does not appear to be the molecular ion in

the sample spectra. The presence of m/z 77, and 105 suggests a phenylalkyl, or chloroalkyl.

The peaks at m/z ratio of 51 and 65 may indicate a nitrogen heterocyclic compound. The delta

plot show too large differences to confirm the NIST match as the analyte, even when the

statement is supported by the peaks at m/z 77 and 105. The analyte does probably contain an

aromatic structure, with an alkyl chain substitution.

49

Figure 48: NIST database match for Södra Cell Värö batch 1, 18.520 min

The match suggested by the NIST library for the peak at 18.52 min is 2,6,10,14-tetramethyl-

nonadecane, (Fig. 48). When comparing the reference spectra with the sample spectra, there

are some differences between them, namely the decreasing series in the reference spectra. The

sample spectra show the first peak with the highest intensity, and then a constant intensity, the

NIST reference peak show a slight decrease between all peaks. This suggests another

congener than the suggested analyte. When examining the delta plot, the differences become

more apparent. The alignment between the two spectra is not sufficient to confirm a match.

The pattern in the sample spectra still indicates an alkyl, of unknown length and possibly with

more branching of the chain, to achieve the pattern of the sample spectra.

50

Figure 49: NIST database match for Södra Cell Värö batch 1, 20.546 min

The NIST database suggests a 3,4,5,6-tetramethyl-phenanthrene for the peak with retention

time 21.52 minutes (Fig. 49). The same general pattern with several differences is displayed

in both the sample spectra and the reference spectra. The delta plot again show many peaks

that are different between the sample spectra and the NIST reference spectra. There is a

cluster arround m/z 100, which is much smaller in the NIST spectra, this is an indication that

the NIST suggested match is not the analyte. The delta plot indicate several peaks that are

unaccounted for in both spectra, and the suggested match is most likely not the analyte. Since

there are some similarities between the two spectra, it is possible that the same backbone is

present in the analyte. The analyte is probably a PAH, most likely a phenanthrene, with

unknown functional groups.

51

Figure 50: NIST database match for Södra Cell Värö batch 2, 5.939 min

The peak at 5.94 minutes is suggested to be 1-chloro-3-methyl-benzene by the NIST database

(Fig. 50). All of the 20 matches from the NIST database contain one chlorine atom. The

spectra show good alignment between the reference spectra and the sample spectra. The delta

plot show some differences, but they are minor except for one peak, m/z 60-70. The suggested

structure seems highly possible. The right isomer cannot be determined, so the functional

groups are in either ortho, para or meta position.

52

53

Figure 51: NIST database match for Södra Cell Värö batch 2, 20.004 min

The peak with retention time 20.05 is suggested to be (E)-stilbene (Fig. 51). When examining

the spectra, the sample spectrum show extremely small differences between the spectra. The

reference spectrum show several additional peaks. The reference spectrum do display several

additional peaks, suggesting that the analyte may not be the NIST suggested match. Since

there still are differences between the two spectra, there might be a chance that the (E)-

stilbene is not the analyte. The reference spectrum seems to account for all peaks in the

sample spectra. The analyte does most likely contain a minimum of one benzene ring and the

suggested match from the NIST is a highly possible match.

54

Figure 52: NIST database match for Södra Cell Värö batch 2, 21.515 min

The NIST database suggests a 3,4,5,6-tetramethyl-phenanthrene for the peak with retention

time 21.52 minutes (Fig. 52). The same general pattern with several differences is displayed

in both the sample spectra and the reference spectra. The delta plot again show many peaks

that are different between the sample spectra and the NIST reference spectra. There is a

cluster arround m/z 100, which is much smaller in the NIST spectra, this is an indication that

the NIST suggested match is not the analyte. The delta plot indicate several peaks that are

unaccounted for in both spectra, and the suggested match is most likely not the analyte. Since

there are some similarities between the two spectra, it is possible that the same backbone is

present in the analyte. The analyte is probably a PAH, most likely a phenanthrene, with

unknown functional groups.

55

Figure 53: NIST database match for Södra Cell Värö batch 2, 32.553 min

The molecules suggested to be the match for the peak with retention time 32.56 minutes is

suggested to be erucylamide (Fig. 53). The sample spectra display the same general patter that

can be seen in the NIST reference spectra. Although, the intensity of some peaks differ, the

same ions seems to be present. The delta plot show several differences between the two

spectra. The suggested molecule seems plausible, but the delta plot show to major differences

to allow the mass spectra to be used as the sole identification.

56

Appendix E – APGC results Table 8: PCB levels from APGC analysis

Amount

(pg)

Standard Soxhlet

Blank

R1 R2 VB1 VB2 F Standard

PCB 28 2577 2422.6

PCB 52 2978 2022.1

PCB 101 3156 1096.7 589.3 1128 244.7 326 1844.1

PCB 118 3077 1063 145.3 1923.1

PCB 153 2654 2177.6 1493.5 6219.8 849.3 959.3 2346.1

PCB 138 2706 1667.6 1087.6 6824.4 792.8 631.0 2294.2

PCB 180 2610 333.3 110715 208.5 2031.1 162.6 126.8 2389.6

Amount (pg g-1 sample)

PCB 28

PCB 52

PCB 101 58,93 112,8 24,4676 32,5674

PCB 118 106,3 14,5155

PCB 153 149,35 621,98 84,9215 95,8342

PCB138 108,76 682,44 79,2721 63,037

PCB 180 11071,5 20,85 203,11 16,2584 12,6673