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Screening for pharmaceuticals, phthalates and polycyclic aromatic hydrocarbons (PAHs) in bivalves sampled along the Swedish coast Screening av läkemedel, ftalater och polyaromatiska kolväten (PAH:er) i musslor insamlade längs Sveriges kust Caroline Ek, Kerstin Winkens Pütz, Sara Danielsson, Suzanne Faxneld Överenskommelse: 213-18-013 Swedish Museum of Natural History Department of Environmental Research and Monitoring P.O. Box 50 007 104 05 Stockholm Sweden Report nr 1:2019
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Page 1: Screening for pharmaceuticals, phthalates and polycyclic ...naturvardsverket.diva-portal.org/smash/get/diva2:... · Screening for pharmaceuticals, phthalates and polycyclic aromatic

Screening for pharmaceuticals, phthalates and polycyclic aromatic hydrocarbons (PAHs) in bivalves

sampled along the Swedish coast

Screening av läkemedel, ftalater och polyaromatiska kolväten (PAH:er) i musslor insamlade längs Sveriges kust

Caroline Ek, Kerstin Winkens Pütz, Sara Danielsson, Suzanne Faxneld

Överenskommelse: 213-18-013

Swedish Museum of Natural History Department of Environmental Research and Monitoring P.O. Box 50 007 104 05 Stockholm Sweden

Report nr 1:2019

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2019-04-12

Preparation of samples and biological parameters: Swedish Museum of Natural History Sara Bernhardtz

Chemical analysis:

Pharmaceuticals:

Department of Chemistry, Umeå University, Sweden

Responsible: Jerker Fick

Phthalates and PAHs:

ALS Scandinavia, Stockholm, Sweden

Please cite as:

Ek, C., Winkens Pütz K., Danielsson, S., Faxneld, S., 2019. Screening for pharmaceuticals, phthalates and

polycyclic aromatic hydrocarbons (PAHs) in bivalves sampled along the Swedish coast, Report 1:2019. Swedish

Museum of Natural History, Stockholm, Sweden.

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NATIONAL

ENVIRONMENTAL

MONITORING

COMMISSIONED BY

THE SWEDISH EPA

FILE NO.

CONTRACT NO.

PROGRAMME AREA

SUBPROGRAMME

NV-04495-18

213-18-013

Miljögifter akvatiskt

Utveckling och

analys

Screening for phthalates, pharmaceuticals and polycyclic

aromatic hydrocarbons (PAHs) in bivalves sampled along

the Swedish coast

Report authors Caroline Ek, Kerstin Winkens Pütz, Sara Danielsson, Suzanne Faxneld

The Department of Environmental Research and Monitoring, Swedish Museum of Natural History

Responsible publisher Swedish Museum of Natural History

Postal address Naturhistoriska riksmuseet

Box 50007

104 05 Stockholm

Telephone +46(0)8-519 540 00

Report title and subtitle Screening av läkemedel, ftalater och polyaromatiska kolväten (PAH:er) i musslor insamlade längs Sveriges kust

Screening for pharmaceuticals, phthalates and polycyclic aromatic hydrocarbons (PAHs) in bivalves sampled along the Swedish coast

Purchaser Swedish Environmental Protection Agency, Environmental Monitoring Unit SE-106 48 Stockholm, Sweden

Funding National environmental monitoring

Keywords for location (specify in Swedish) Kas-Ängsfjärden, Långvinds-Skärsåfjärden, Gaviksfjärden, Norrbyn-Örefjärden, Östergarnsholm, Simpnäsklubb, Dragviksfjärden, Högby fyr, Utlängan, Abbekås, Landskrona, Kullen, Glommen, Kvädöfjärden, Fjällbacka, Nidingen

Keywords for subject (specify in Swedish) Blåmussla, Östersjömussla, PAH, Benso(a)pyren, ftalater, DEHP, läkemedel, Risperidone

Period in which underlying data were collected 2015-2017

Summary

Within the Swedish National Monitoring Programme for Contaminants in marine biota, a selection of the

wide array of contaminants that can be found in the environment is analysed. Analysing the samples for

all possible contaminants would hardly be feasible, however, screening for different substance groups is

a way to investigate if and where new substances arise and may pose a threat to wildlife and humans. In

this report, data from a spatial screening study is presented, which aimed to densify the ongoing

Swedish National Monitoring Programme for Contaminants in marine biota with regard to

pharmaceuticals, phthalates and polycyclic aromatic hydrocarbons (PAHs). The study includes 16

sampling sites along the Swedish coast, from where two different species of bivalves, Limecola balthica

and Mytilus edulis, were collected. All applied sampling material in this screening study originates from

the Swedish Environmental Specimen Bank of the Swedish Museum of Natural History. The screening

included a total of 100 pharmaceuticals, out of which 17 were detected and quantified in at least one

sampling site. Risperidone was the pharmaceutical detected at most sites (10 of 13). The only detected

phthalate was di(2-ethylhexyl) phthalate (DEHP), which was found in the samples from 3 of 13 sampling

sites. Among the PAHs, Benzo(a)pyrene was the substance quantified at most sites (14 out of 16). No

geographical patterns could be identified for the detected contaminants, besides for the PAHs. However,

this pattern could also be due to a difference in species rather than due to location. PAHs could be

detected in the Bothnian Sea and the Sea of Åland, where to date no mussel sampling sites exist within

the Swedish National Monitoring Programme for Contaminants in marine biota. The Baltic clam might be

a good additional monitoring species besides the Blue mussel, due to their difference in feeding strategy

and the potential higher PAH uptake from contaminated sediments rather than the water phase.

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1

Screening for pharmaceuticals, phthalates and polycyclic

aromatic hydrocarbons (PAHs) in bivalves sampled along

the Swedish coast

1 Summary

Within the Swedish National Monitoring Programme for Contaminants in marine biota, a selection of

the wide array of contaminants that can be found in the environment is analysed. Analysing the

samples for all possible contaminants would hardly be feasible, however, screening for different

substance groups is a way to investigate if and where new substances arise and may pose a threat to

wildlife and humans. In this report, we present data from a spatial screening study aimed to densify the

ongoing Swedish National Monitoring Programme for Contaminants in marine biota with regard to

phthalates, pharmaceuticals and polycyclic aromatic hydrocarbons (PAHs). The study includes 13

sampling sites along the Swedish coast, from where two different species of bivalves, Baltic clam and

Blue mussel were collected. All applied sampling material in this screening study originates from the

Swedish Environmental Specimen Bank of the Swedish Museum of Natural History. The screening

included a total of 100 pharmaceuticals, out of which 17 were detected and quantified in at least one

sampling site. Risperidone was the pharmaceutical detected at most sites (10 of 13). The only detected

phthalate was di(2-ethylhexyl) phthalate (DEHP), which was found in the samples from 3 of 13

sampling sites. Among the PAHs, Benzo(a)pyrene was the substance quantified at most sites (14 out

of 16). No geographical patterns could be identified for the detected contaminants, besides for the

PAHs. However, this pattern can also be due to a difference in species rather than due to location.

2 Background

Chemicals are applied in nearly all possible materials and products we come in contact with on a daily

basis. In fact, the global production of chemicals has increased from 1 million tonne in 1930 to several

million tonnes per year nowadays (ECHA 2019). It is uncertain how many chemicals exist on the

market, but new chemicals are constantly introduced. Chemicals can be released into the environment

during the entire lifetime of a product (i.e. from its production and usage to after its disposal).

Therefore, the existence of a wide array of chemicals in the environment is inevitable.

To monitor all these chemicals over time is not feasible; however, a method to investigate if any

substance group may pose a threat to biota and/or humans is screening for different substances. In this

report, a spatial screening study for pharmaceuticals, phthalates and polycyclic aromatic hydrocarbons

(PAHs) in bivalves (Baltic clam and Blue mussel) from a total of 13 different sites along the Swedish

coast is summarised. Pharmaceuticals and phthalates are not included into the Swedish National

Monitoring Programme for Contaminants in marine biota, whereas PAHs are monitored in Blue

mussel sampled annually from three different sites. Therefore, the PAHs analysed in this study are

aimed to densify the ongoing monitoring programme.

Pharmaceuticals is a group of substances designed to be biologically active in living organisms. The

mode of action of a drug connects specific molecular and metabolic interactions to a response.

Therefore, the potency of a pharmaceutical for non-target organisms is dependent on whether a drug

target is conserved (Gunnarsson et al. 2008). When administrated, only a small portion of the active

substance is taken up/metabolized in the body whereas the majority is excreted and will end up in the

sewage treatment plants (STP), where the removal is inefficient. Furthermore, veterinary

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pharmaceuticals applied in mass stocks penetrate the soil, until they may reach ground water or run-off

into surface water bodies. For this reason, organisms inhabiting STP recipient water bodies or close to

fields with regular manure application can be continuously exposed to pharmaceuticals although the

individual substances are not persistent in the environment.

Phthalates are synthesised mainly for the production of different forms of plastics. Commonly, they

are used as plasticizers in the production of polyvinyl chloride (PVC) and for the production of bottles

for carbonated drinks (Liang et al. 2008). They are even used as dissolvent agents and in vinyl flooring

as well as personal-care products. On a global scale, the production of phthalates has increased from 2

to 5.5 million tonnes within 20 years (1980-2000) (Liang et al. 2008).

PAHs, are a group of persistent organic compounds, which are known to accumulate in invertebrates,

such as bivalve molluscs (Burgess et al. 2003). PAHs are naturally occurring in fossil fuels and are

released into the environment during incomplete combustion of fossil fuels and other organic materials

as well as during the production, transport and use of petroleum (Burgess et al. 2003).

3 Sampling, methods and data treatment

3.1 Monitoring species, sampling sites and sample preparation

Bivalves of the species Baltic clam (Limecola balthica, previously Macoma balthica) and Blue mussel

(Mytilus edulis) were analysed in this study.

The Baltic clam is a facultative deposit- and suspension-feeder, with the main food sources being

organic material in sediment or phytoplankton, depending on the feeding strategy (Olafsson 1986).

Moreover, the Baltic clam is one of the most abundant macrobenthic animals in the Baltic Proper and

therefore plays an important role in the food webs at the benthic-pelagic interface (Aarnio and

Bonsdorff 1997). The Blue mussel, on the other hand, is an obligate suspension feeder, with

phytoplankton and suspended particulate matter as the main food sources. Blue mussel is an important

keystone species in the Baltic coastal areas, as its mussel beds create structures that are beneficial for

several other species (Norling and Kautsky 2007). Blue mussels are among the ‘first choice species’

recommended for monitoring within the Joint Assessment and Monitoring Programme (JAMP) within

the Oslo-Paris Convention (OSPAR).

The specimens were sampled at several sites along the Swedish coast between 2015 and 2017 (see

Figure 1, each site was only sampled for one year and for one species, see Appendix for detailed

information) and stored in the Environmental Specimen Bank in laminated plastic bags at -20C, prior

to sample preparation and analysis. In the laboratory, individual specimens were thawed and carefully

opened using a metallic scalpel for sample preparation. The soft tissue (not including the adductor

muscle) was removed and placed in a glass beaker. One pooled sample (n=10-159 individuals,

depending on size) was prepared for each site and homogenised using an IKA T25 digital ULTRA

TURRAX homogenizer, which was split into different aliquots for the analysis of the different

substance groups.

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Figure 1. Overview of the sampling sites included in this spatial screening study: 13 sampling sites and the 3

sites from the Swedish National Monitoring Programme of Contaminants in marine biota (7 – Kvädöfjärden, 15

– Nidingen and 16 – Fjällbacka). Specimens of the species Baltic clam were sampled from site number 1-4

whereas Blue mussel was sampled from the other sites (5-16).

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3.2 Analytical methods

The analysis of pharmaceuticals was done by the Department of Chemistry at Umeå University,

whereas the analysis for phthalates and PAHs was done by ALS Scandinavia.

The analysed pharmaceuticals were selected based on their potencies and predicted ability to

bioconcentrate (Fick et al. 2010). The pre-treatment of the biota samples have been described

previously (McCallum et al. 2017). In short, biota samples (1 g) were extracted sequentially after the

addition of 50 ng of internal and surrogate standards; all internal and surrogate standards used have

been presented in a previous publication (Grabic et al. 2012). Extraction of tissue samples were done

with 1.5 ml acetonitrile, repeated twice. Samples were homogenized for four minutes at 42 000

oscillations per minute, using a Mini Beadbeater (Biospec. Bartlesville, USA) with zirconium beads

and then centrifuged at 17 500 g for 10 minutes (Beckman Coulter Microfuge 22R Centrifuge). This

protocol was followed for both eluent mixtures individually and the supernatants were combined,

evaporated to 20 μl and reconstituted in 100 μl methanol. Samples were analyzed using a system with

a triple-stage quadrupole mass spectrometer (Quantum Ultra EMR (Thermo Fisher Scientific, San

Jose, CA) coupled with a liquid chromatographic pump (Accela, Thermo Fisher Scientific) and an

autosampler (PAL HTC, CTC Analytics AG, Zwingen, Switzerland). Heated electrospray (HESI),

krypton 10.6 eV, in positive ion mode were used for ionization of the pharmaceuticals. Specific details

related to the determination of the pharmaceuticals including HESI ionizations, polarities,

precursor/product ions, collision energies, tube lens values, etc. have been described in detail

elsewhere (Grabic et al. 2012, Lindberg et al. 2014).

Phthalates were analysed according to the order package OB-4A (ALS Scandinavia) and determined

using a GC-MS. For PAHs, order package OB-1 (ALS Scandinavia) was selected and measurements

were done using a GC-MS. For detailed information on the analytical methods behind these chemical

analysis packages, contact ALS Stockholm and refer to either §64 LFGB L 00.00-34:2010-09 (PAHs)

or DIN 19742:2014-08 (phthalates) for information on how to purchase the information.

3.3 Data treatment and statistical analysis

In the present study, only samples with quantifiable concentrations are shown in the figures as many

of the substances were below the limit of quantification (LOQ) for all or most of the samples. For the

13 sites that were originally included into this screening study, only one observation exists per

substance. However, for PAHs analysed within the National Monitoring Programme for

Contaminants, a geometric mean based on the years 2015-2017 (n=3) is calculated for each PAH. If

any of the three values was below the LOQ, this value was divided by the square root of 2 before the

geometric mean was calculated.

No statistical analyses were performed, due to the nature of the data included in this spatial screening

study.

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4 Results

4.1 Pharmaceuticals

In this study, 17 pharmaceuticals out of 100 analysed were detected and quantified. For most of the

detected pharmaceuticals, it was only possible to quantify the concentrations in a few (5 or less)

samples, whereas for risperidone, it was possible to quantify concentrations in 10 out of 13 samples

(Figure 2).

Figure 2. Bar chart showing the 17 quantified pharmaceuticals (out of 100 possible) in this study and their

quantification frequency (100 %=13 samples).

Risperidone is a physcoleptic drug commonly used as an antipsychotic to treat e.g. schizophrenia,

bipolar disorder, Alzheimer’s disease and irritability disorder associated with autism (FASS 2019).

The observed concentrations ranged between 1.2 and 0.1 ng risperidone/g ww (at Abbekås and Kas-

Ängsfjärden, respectively), with a mean concentration of 0.61 ng/g ww (Figure 3). No geographical

pattern could be found among the samples for which risperidone could be detected. At the three most

northern sites, no risperidone could be quantified (Figure 3). This pattern is also consistent with

findings from a screening study by Björlenius et al. (Björlenius et al. 2018), in which they screened for

pharmaceutical residues in water samples from the Baltic Sea coast and off shore sites. Similar to our

study, Björlenius et al. failed to quantify risperidone in any water samples from the Bothnian Bay or

the Bothnian Sea, however, in water samples from the northern Baltic Proper, this substance could be

detected. Risperidone was also one of the most frequently detected pharmaceuticals in otter analysed

for pharmaceuticals in Sweden (Roos et al. 2017).

The second most frequently measured pharmaceutical was orphenadrine (quantified in 5 out of 13

samples), a substance acting as a central muscle relaxant, which is used e.g. in the treatment of

Parkinson’s disease and related conditions (FASS 2019). The highest concentration for orphenadrine

was found in Blue mussel sampled at Abbekås (0.18 ng/g ww) and the lowest concentration in Blue

mussel sampled at Högby fyr (0.12 ng/g ww) (Figure 3). Contrary to risperidone, this substance was

detected in one sample from the Bothnian Sea, which is also consistent with previously published

findings for orphenadrine in water samples in the Baltic Sea (Björlenius et al. 2018).

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Figure 3. An overview of the sites where risperidone (left) and orphenadrine (right) could be quantified in

bivalves. The legend shows the 5th

, 25 th

, 50 th

, 75 th

and 95 th

percentile if the compound was quantified in more

than 5 samples, if the compounds was quantified in 5 or less samples were, the specific values are given in the

legend.

4.2 Phthalates

In this study, the samples were analysed for 13 phthalates out of which only one substance could be

quantified, di(2-ethylhexyl) phthalate (DEHP) in three samples: in Baltic clam from Kas-Ängsfjärden

and Långvinds-Skärsåfjärden, as well as in Blue mussel from Glommen (Figure 4). The highest

concentration was detected in Baltic clam sampled at Kas-Ängsfjärden (0.14 g/g ww) and the lowest

concentration in the Blue mussel sampled at Glommen (0.067 g/g ww) (Figure 4).

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Figure 4. Overview of the sites where DEHP could be quantified in mussels. The legend shows the specific

values.

4.3 Polycyclic Aromatic Hydrocarbons (PAHs)

In this study, 16 different PAHs were analysed and the calculated PAHs (16 US EPA PAHs) is

presented. In Figure 5, the quantified PAHs in this spatial screening are shown in their quantification

frequency in the samples (including the 3 additional sites from the contaminant monitoring

programme).

For PAHs, which can be considered as a measure of the total contaminant load of PAHs that were

analysed in this study, the highest concentration was found in Blue mussel sampled at Fjällbacka

(22 ng/g ww) compared to the second highest concentration observed in Baltic clam from Norrbyn-

Örefjärden (14 ng/g ww) (Figure 6). The higher concentration (1.5 times higher) for Fjällbacka

compared to the concentration at Norrbyn-Örefjärden, could be explained by the extremely high

reported values for PAHs in Blue mussel sampled at Fjällbacka in 2016. The reason for these elevated

concentrations during that year is still unknown. In 2017, the concentrations were back to the levels

from before 2016, but still higher compared to other sampling sites in this screening study. Only at

two sites, Kas-Ängsfjärden and Simpnäsklubb, no PAHs could be quantified in the bivalves.

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Figure 5. Bar chart showing the 9 quantified PAHs (out of 16 analysed) and their quantification frequency

(100 %=16 samples).

Benzo(a)pyrene was the substance quantified in most samples (14 out of 16) for the entire screening

study and all the way from sites in the Bothnian Sea to Skagerrak on the Swedish west coast

(Figure 6). No geographical pattern could be detected for the concentration of benzo(a)pyrene. The

highest concentration was found in Baltic clam from Långvinds-Skärsåfjärden although concentrations

measured in Baltic clam from Norrbyn-Örefjärden and Blue mussel from Nidingen and Fjällbacka

were in the same range (Figure 6). For fluoranthene, excluding Fjällbacka, the three highest

concentrations were measured in Baltic clam sampled in the Bothnian Sea and the Sea of Åland

(Figure 7). Similarly for pyrene, and again excluding Fjällbacka, the four highest concentrations were

observed in Baltic clam sampled in the Bothnian Sea and the Sea of Åland.

It is however, important to point out the possibility that the seemingly observed geographical pattern

can instead be the result of different species, as the Baltic clam was sampled at the four most northern

sampling sites instead of the Blue mussel. The feeding strategies of the Baltic clam and the Blue

mussel are different. The Baltic clam is a facultative deposit- and suspension feeder, i.e. this species

feeds and dwells in sediments (if the feed is favourable), which may increase the exposure for PAHs in

the case of contaminated sediments compared to the suspension-feeding Blue mussel, mostly found

attached to rocks on hard sea bottoms.

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Figure 6. An overview of the sites where PAHs (left) and Benzo(a)pyrene (right) could be quantified in

bivalves. The legend shows the 5th, 25 th, 50 th, 75 th and 95 th percentile, as the compounds could be

quantified in more than 5 samples.

Figure 7. Overview of the sites where fluoranthene (left) and pyrene (right) could be quantified in bivalves. The

legend shows the 5th

, 25 th

, 50 th

, 75 th

and 95 th

percentile, as the compounds could be quantified in more than 5

samples.

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5 Discussion

From this study we can conclude that it is possible to detect both pharmaceuticals and phthalates in

bivalves sampled along the Swedish coast, although for phthalates only one of the measured

substances could be quantified in the bivalves. Both pharmaceuticals and phthalates are manmade and

should be considered as potentially problematic from an environmental risk perspective.

Pharmaceuticals are, as previously stated, designed to be biologically active and also likely to have

effects on non-target organisms due to the conservation of drug targets during evolution. Phthalates

are known endocrine disruptors and can therefore potentially affect the physiology, especially when

hormonal regulation is critical such as during developmental stages.

This study also supplements the Swedish National Monitoring Programme with regard to PAH

monitoring in bivalves. The main conclusions from this part are 1) that PAHs also occur in the

Bothnian Sea and Sea of Åland, where today’s monitoring programme has no sampling sites for

bivalves and 2) that the Baltic clam might be a valuable additional bivalve species besides the Blue

mussel. The densified sampling regime indicate that PAHs are present in the Gulf of Bothnia, an area

not covered by the existing monitoring programme when it comes to sampling of bivalves for PAH

analyses. To extend the sampling to also this area could be of importance considering that the highest

concentrations were almost exclusively found in this region. However, the fact that we have analysed a

different species in this area compared to the Baltic Sea and the west coast is problematic and should

be considered when comparing actual concentrations. The Baltic clam is under favourable conditions a

deposit feeder living in sediment and could in theory be more exposed to PAHs than Blue mussels

sampled at the same site. However, since there is no sampling site in this study where both species

have been sampled, such comparison is impossible to make. As the Swedish coastline has a strongly

increasing salinity gradient from the Bothnian Bay to Skagerrak on the west coast, the low salinity

inhibits the presence of the Blue mussel in the Bothnian Bay. In contrast to the Blue mussel, the Baltic

clam is present along the entire coast and could therefore serve as an additional monitoring species in

the Swedish National Monitoring Programme for Contaminants to cover the entire coastline by the

same mussel species within the ongoing monitoring of PAHs. Additionally, this species could also

serve as a baseline organism for other monitoring species sampled in the same area to allow for more

accurate trophic position estimates in line with the recommendations within the Water Framework

Directive (WFD).

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6 References

1. Aarnio, K.; Bonsdorff, E. Passing the gut of juvenile flounder, Platichthys flesus: differential

survival of zoobenthic prey species. Marine Biology 1997, 129 (1), 11-14.

2. Björlenius, B.; Ripszám, M.; Haglund, P.; Lindberg, R. H.; Tysklind, M.; Fick, J.

Pharmaceutical residues are widespread in Baltic Sea coastal and offshore waters–Screening

for pharmaceuticals and modelling of environmental concentrations of carbamazepine.

Science of the Total Environment 2018, 633, 1496-1509.

3. Burgess, R. M.; Ahrens, M. J.; Hickey, C. W.; den Besten, P. J.; ten Hulscher, D.; van Hattum,

B.; Meador, J. P.; Douben, P. E. T. PAHs: An ecotoxicological perspective. 2003

4. ECHA 2019 European Chemicals Agency https://echa.europa.eu/-/chemicals-in-our-life-

why-are-chemicals-important

5. FASS 2019 www.fass.se

6. Fick, J.; Lindberg, R. H.; Tysklind, M.; Larsson, D. J. Predicted critical environmental

concentrations for 500 pharmaceuticals. Regulatory Toxicology and Pharmacology 2010, 58

(3), 516-523.

7. Grabic, R.; Fick, J.; Lindberg, R. H.; Fedorova, G.; Tysklind, M. Multi-residue method for

trace level determination of pharmaceuticals in environmental samples using liquid

chromatography coupled to triple quadrupole mass spectrometry. Talanta 2012, 100, 183-

195.

8. Gunnarsson, L.; Jauhiainen, A.; Kristiansson, E.; Nerman, O.; Larsson, D. J. Evolutionary

conservation of human drug targets in organisms used for environmental risk assessments.

Environmental science & technology 2008, 42 (15), 5807-5813.

9. Liang, D.-W.; Zhang, T.; Fang, H. H.; He, J. Phthalates biodegradation in the environment.

Applied microbiology and Biotechnology 2008, 80 (2), 183.

10. Lindberg, R. H.; Östman, M.; Olofsson, U.; Grabic, R.; Fick, J. Occurrence and behaviour of

105 active pharmaceutical ingredients in sewage waters of a municipal sewer collection

system. Water research 2014, 58, 221-229.

11. McCallum, E. S.; Krutzelmann, E.; Brodin, T.; Fick, J.; Sundelin, A.; Balshine, S. Exposure to

wastewater effluent affects fish behaviour and tissue-specific uptake of pharmaceuticals.

Science of the Total Environment 2017, 605, 578-588.

12. Norling, P.; Kautsky, N. Structural and functional effects of Mytilus edulis on diversity of

associated species and ecosystem functioning. Marine Ecology Progress Series 2007, 351,

163-175.

13. Olafsson, E. Density dependence in suspension-feeding and deposit-feeding populations of the

bivalve Macoma balthica: a field experiment. The Journal of Animal Ecology 1986, 517-526.

14. Roos, A.; Loso, K.; Fång, J. Mätningar av läkemedelsrester i blod och urin från utter. Report

No. 7:2017 The Swedish Museum of Natural History, Stockholm, Sweden, (2017).

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Appendix

Table 1: Overview of the quantified pharmaceuticals, phthalates and PAHs in bivalves; additional information is given on the sampling sites, species, sampling year and the limit of

quantification (LOQ); coordinates are given in the SWEREF99 coordinate system; asterisks indicate that the sample’s concentrations was below the LOQ.

Site

Norrbyn-Örefjärden

Gaviks-fjärden

Långvinds-Skärsåfjärden

Kas-Ängsfjärden

Simpnäs-klubb

Dragviks-fjärden

Östergarns-holm Högby fyr Utlängan Abbekås Landskrona Kullen Glommen

Species Baltic clam Baltic clam Baltic clam Baltic clam Blue mussel Blue mussel Blue mussel Blue mussel Blue mussel Blue mussel Blue mussel Blue mussel Blue mussel

NKOO 7049104 6973343 6808382 6684201 6645727 6514342 6374743 6335962 6200690 6139573 6188334 6240499 6313315

EKOO 739058 664149 614307 703167 727755 637498 740809 623642 548773 412057 364247 343179 339195

Year 2017 2017 2017 2017 2015 2015 2016 2015 2015 2015 2015 2015 2015

Pharmaceuticals LOQ (ng/g)

Alfuzosin 0.1 * * * * 0.20 * * * * * * * *

Alprazolam 10 * * * * * * * * * * * * *

Amiodarone 50 * * * * * * * * * * * * *

Amytriptyline 5 * * * * * * * * * * * * *

Atenolol 5 * * * * * * * * * * * * *

Atorvastatin 10 * * * * * * * * * * * * *

Atracurium 0.5 * * * * * * * * * * * * *

Azelastine 5 * * * * * * * * * * * * *

Azithromycine 5 * * * * * * * * * * * * *

Biperiden 0.1 * 1.1 * * * * * * * * * * 2.0

Bisoprolol 0.1 * * * 0.11 * * * * * * * * *

Bromocriptine 5 * * * * * * * * * 6.4 * * *

Budesonide 10 * * * * * * * * * * * * *

Buprenorphine 10 * * * * * * * * * * * * *

Bupropion 0.1 * * * * * * * * * * * * *

Carbamazepin 1 * * * * * * * * * * * * *

Chlorpromazine 5 * * * * * * * * * * * * *

Chlorprothixene 10 * * * * * * * * * * * * *

Cilazapril 1 * * * * * * * * * * * * *

Ciprofloxacin 10 * * * * * * * * * * * * *

Citalopram 5 * * * * * * * * * * * * *

Clarithromycine 1 * * * * * * * * * * * * *

Clemastine 0.5 * * * * * * * * * * * * *

Clindamycine 1 * * * * * * * * * * * * *

Clomipramine 0.5 0.75 * * 0.50 * * * * * * * * *

Clonazepam 5 * * * * * * * * * * * * *

Clotrimazol 1 * * * * * * * * * * * * *

Codeine 0.5 * * * * * * * * * * * * *

Cyproheptadine 5 * * * * * * * * * * * * *

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Desloratidin 0.5 * * * * * * * * * * * * *

Diclofenac 10 * * * * * * * * * * * * *

Dicycloverine 5 * * * * * * * * * * * * *

Dihydroergotamine 15 * * * * * * * * * * * * *

Diltiazem 0.5 * * * * * * * * * * * * *

Diphenhydramine 0.05 * * * * * * * 0.078 * 0.10 * 0.053 *

Dipyridamol 1 * * * * * * * * * * * * *

Donepezil 0.5 * * * * * * * * * * * * *

Duloxetine 1 * * * * * * * * * * * * *

Eprosartan 5 * * * * * * * * * * * * *

Erythromycine 20 * * * * * * * * * * * * *

Ezetimibe 50 * * * * * * * * * * * * *

Felodipine 10 * * * * * * * * * * * * *

Fenofibrate 10 * * * * * * * * * * * * *

Fentanyl 0.5 * * * * * * * * * * * * *

Fexofenadine 5 * * * * * * * * * * * * *

Finasteride 10 * * * * * * * * * * * * *

Flecainide 0.1 * * 0.11 * 0.32 * * * 0.13 * 0.10 * *

Fluconazole 0.5 * 0.63 * * * * * * * * * * *

Flunitrazepam 10 * * * * * * * * * * * * *

Fluoxetine 5 * * * * * * * * * * * * *

Flupentixol 5 * * * * * * * * * * * * *

Fluphenazine 10 * * * * * * * * * * * * *

Flutamide 5 * * * * * * * * * * * * *

Glibenclamide 10 * * * * * * * * * * * * *

Glimepiride 10 * * * * * * * * * * * * *

Haloperidol 0.1 * 0.23 * * * * * 0.28 0.35 * * * 0.35

Hydroxyzine 0.5 * * * 1.2 * * * * * * * 2.6 1.3

Irbesartan 0.5 * * * * * * * * * * * * *

Ketoconazole 10 * * * * * * * * * * * * *

Levomepromazine 50 * * * * * * * * * * * * *

Loperamide 0.5 * * * * * * * * * * * * *

Maprotiline 5 * * * * * * * * * * * * *

Meclozine 5 * * * * * * * * * * * * *

Memantine 0.5 * * * * * * * * * * * * *

Metformin 50 * * * * * * * * * * * * *

Metoprolol 5 * * * * * * * * * * * * *

Mianserin 1 * * * * * * * * * * * * *

Miconazole 5 * * * * * * * * * * * * *

Mirtazapine 10 * * * * * * * * * * * * *

Naloxone 1 * * * * * * * * * * * * *

Nefazodone 0.5 * * * * * * * * * * * * *

Norfloxacin 10 * * * * * * * * * * * * *

Ofloxacin 10 * * * * * * * * * * * * *

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Orphenadrine 0.1 * * 0.12 * * * 0.14 0.12 * 0.18 0.13 * *

Oxazepam 5 * * * * * * * * * * * * *

Oxytetracycline 10 * * * * * * * * * * * * *

Paracetamol 10 * * * * * * * * * * * * *

Paroxetine 10 * * * * * * * * * * * * *

Perphenazine 10 * * * * * * * * * * * * *

Pizotifen 0.5 0.65 * 0.85 * * * * * 0.62 1.0 * * *

Promethazine 10 * * * * * * * * * * * * *

Propranolol 50 * * * * * * * * * * * * *

Ranitadine 5 * * * * * * * * * * * * *

Repaglinide 0.5 * * * * * * * * * * * * *

Risperidone 0.1 * * * 0.12 0.88 0.42 0.40 0.75 0.58 1.2 0.71 0.48 0.58

Rosuvastatin 10 * * * * * * * * * * * * *

Roxithromycine 15 * * * * * * * * * * * * *

Sertraline 10 * * * * * * * * * * * * *

Sotalol 0.5 * * * * * * * * * * * * *

Sulfamethoxazol 5 * * * * * * * * * * * * *

Tamoxifen 5 * * * * * * * * * * * * *

Telmisartan 1 * * 1.1 * * * * * * * * * *

Terbutaline 0.5 * * * * * * * * * * * * *

Tetracycline 50 * * * * * * * * * * * * *

Tramadol 5 * * * * * * * * * * * * *

Trihexyphenidyl 0.1 * * * * * * * * * 0.17 * * *

Trimethoprim 0.1 * * * * * * * * * * * 0.42 0.55

Venlafaxine 0.5 * * * 5.8 * * 2.5 * * * * * *

Verapamil 10 * * * * * * * * * * * * *

Zolpidem 0.5 * * * * * * * * * * * * *

Phthalates LOQ

(mg/g)

Dimethyl phthalate 0.05 * * * * * * * * * * * * *

Di-ethyl phthalate 0.05 * * * * * * * * * * * * *

Di-n-propylphthalate 0.050 * * * * * * * * * * * * *

Di-n-butylphthalate (DBP) 0.050 * * * * * * * * * * * * *

Di-iso-butyl phthalate 0.050 * * * * * * * * * * * * *

Di-pentyl phthalate 0.050 * * * * * * * * * * * * *

Di-n-octyl phthalate (DNOP) 0.050 * * * * * * * * * * * * *

Di-(2-ethylhexyl) phthalate (DEHP) 0.050 * * 0.074 0.14 * * * * * * * * 0.067

Butyl benzyl phthalate (BBP) 0.050 * * * * * * * * * * * * *

Dicyclohexyl phthalate 0.050 * * * * * * * * * * * * *

Diisodecyl phthalate 2.5 * * * * * * * * * * * * *

Di-iso-nonyl Phthalate (DINP) 2.6 * * * * * * * * * * * * *

Di-n-hexyl phthalate (DNHP) 0.050 * * * * * * * * * * * * *

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PAHs LOQ (ng/g)

Naphtalene 5 <5.0 * * * * * * * * * * * *

Acenaphthylene 1 <1.0 * * * * * * * * * * * *

Acenaphtene 1 <1.0 * * * * * * * * * * * *

Flourene 1 <1.0 * * * * * * * * * * * *

Phenanthrene 1 <1.0 * 1.8 1.7 * * * 1.6 * * 2.5 * 1.4

Anthracene 1 <1.0 * * * * * * * * * * * *

Flouranthene 1 5.2 4.6 3 3.5 * * * 1.6 * * 3.2 * 1.6

Pyrene 1 3.3 2.3 1.9 2.3 * * * * * * 1.8 * 1.2

Benz(a)anthracene 1 1.8 * 1.1 1.2 * * * * * * * * *

Chrysene 1 2 * * 1 * * * * * * 1.2 * *

Benzo(b)flouranthene 1 1.2 * 1.5 * * * * * * * * * *

Benzo(k)flouranthene 1 <1.0 * * * * * * * * * * * *

Benzo(a)pyrene 0.15-0.16 0.6 0.26 0.66 0.49 * * 0.21 0.35 0.17 0.28 0.49 0.17 0.24

Dibenzo(a,h)anthracene 1 <1.0 * * * * * * * * * * * *

Benzo(g,h,i)perylene 1 <1.0 * 1.3 * * * * * * * * * *

Ideno(1,2,3-c,d)pyrene 1 <1.0 * 1.4 * * * * * * * * * *

sumPAHs (16 US EPA PAHs) 14.1 7.2 12.7 10.2 ---------- ---------- 0.21 3.6 0.17 0.28 9.2 0.17 4.4


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