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Distribution and conversions of metal- and POP concentrations among various tissues in herring Sara Danielsson, Jonathan Benskin, Anders Bignert, Ekhine Bizkarguenaga, Cynthia de Wit, Anna-Lena Egebäck, Ulla Eriksson, Suzanne Faxneld, Pär Hjelmquist, Ann-Marie Johansson, Douglas Jones, Martin Kruså, Eva Kylberg, Jan Mechedal, Elisabeth Nyberg, Marcus Sundbom ___________________________________________ Swedish Museum of Natural History Department of Environmental Research and Monitoring P.O. Box 50 007 SE - 104 05 Stockholm Sweden Report nr 2:2018 Överenskommelse: 2213-16-012

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Page 1: Distribution and conversions of metal- and POP ...nrm.diva-portal.org/smash/get/diva2:1273434/FULLTEXT01.pdfChemists: Hg; Ann-Marie Johansson, metals; Pär Hjelmquist, Jan Mechedal

Distribution and conversions of metal- and POP

concentrations among various tissues in herring

Sara Danielsson, Jonathan Benskin, Anders Bignert, Ekhine Bizkarguenaga, Cynthia de

Wit, Anna-Lena Egebäck, Ulla Eriksson, Suzanne Faxneld, Pär Hjelmquist, Ann-Marie

Johansson, Douglas Jones, Martin Kruså, Eva Kylberg, Jan Mechedal, Elisabeth

Nyberg, Marcus Sundbom

___________________________________________

Swedish Museum of Natural History

Department of Environmental Research and Monitoring P.O. Box 50 007 SE - 104 05 Stockholm Sweden

Report nr 2:2018

Överenskommelse: 2213-16-012

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Distribution and conversions of metal- and POP concentrations

among various tissues in herring

Project leader and data analyses:

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

Sara Danielsson, Anders Bignert, Suzanne Faxneld, Elisabeth Nyberg

Sample collection and preparation:

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

Mikael Andersson, Douglas Jones, Eva Kylberg, Jenny Strömquist

Analysis of trace metals:

Department of Environmental Science and Analytical Chemistry, Stockholm University.

Chemists: Hg; Ann-Marie Johansson, metals; Pär Hjelmquist, Jan Mechedal. QC by Marcus Sundbom

Analysis of per- and polyfluoroalkyl substances:

Department of Environmental Science and Analytical Chemistry, Stockholm University

Extraction, analysis and data processing by E. Bizkarguenaga. QC by Jonathan Benskin.

Analysis of organochlorines and brominated flame retardants:

Department of Environmental Science and Analytical Chemistry, Stockholm University

Chemists: Cynthia de Wit, Anna-Lena Egebäck, Ulla Eriksson, Martin Kruså

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Contents Introduction ............................................................................................................................................. 4

Methods ................................................................................................................................................... 5

Fish sampling ...................................................................................................................................... 5

Sample preparation .............................................................................................................................. 5

Part I: Contaminants in individuals; muscle, liver, stomach / intestine and carcass ....................... 6

Part II: Contaminants in various organs, pooled samples ............................................................... 7

Analytical method ............................................................................................................................... 9

Organochlorines and brominated flame retardants .......................................................................... 9

Metals .............................................................................................................................................. 9

Per- and polyfluoroalkyl substances .............................................................................................. 10

Data treatment ................................................................................................................................... 11

Calculation of whole fish concentrations ...................................................................................... 11

Data analysis.................................................................................................................................. 11

Results and discussion ........................................................................................................................... 13

Metals ................................................................................................................................................ 13

Mercury (Hg) ................................................................................................................................. 13

Cadmium (Cd) ............................................................................................................................... 15

Lead (Pb) ....................................................................................................................................... 18

Per- and polyfluoralkyl substances (PFASs) ..................................................................................... 20

PFOS ............................................................................................................................................. 20

Perfluorinated sulphonates, their precursors and carboxylic acids ................................................ 23

Organo brominated and chlorinated compounds ............................................................................... 25

Conclusion ............................................................................................................................................. 28

References ............................................................................................................................................. 29

Appendix ............................................................................................................................................... 31

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Introduction

The Swedish national program for contaminant monitoring in biota has a long history with

time series starting in the 1970s, mainly designed to follow temporal and geographical trends

of contaminants in the environment. Within the contaminant monitoring program, chemical

analyses are normally carried out in well-defined tissues, e.g. liver and muscle. This is done in

order to reduce the variation between the samples but also to get as high concentration as

possible during the chemical analyses, e.g. heavy metals have been found in much higher

concentrations in liver compared to muscle tissue (Faxneld et al. 2015).

New requirements for the national contaminant monitoring have emerged over time and

compliance with international threshold values has become an important part of international

evaluations of the environment. Within the EU, there are currently eleven chemicals or

chemical groups for which threshold values in biota have been derived, called Environmental

Quality Standards EQS (2013/39/EU). These EQS values are derived to protect the marine

and freshwater ecosystems from adverse effects of chemicals. Other threshold values that are

used in national data evaluation of contaminants are Environmental Assessment Criteria EAC,

derived within OSPAR (OSPAR Commission 2014) or national threshold values or food

legislation values (OJEC No. L364 20.12.2006 2006). These different threshold values are in

some cases derived for matrices other than those regularly monitored in the national program.

For example, the EQS for perfluorooctane sulfonate (PFOS) is set for human consumption of

fish (as humans in this case are considered to be the most vulnerable group), thus the

threshold value is relevant to muscle tissue but the regular monitoring is performed on liver

tissue. In addition, there is also another threshold value, a Qality Standard (QS) value, for

PFOS based on secondary poisoning (i.e. whole-body). Within the process of deriving EQS

values, QS values are derived for different compartments of the aquatic environment e.g.

protection of top predators from secondary poisoning. The QS that is considered the most

protective value is then chosen as EQS value. PFOS has been found in relatively low

concentrations in muscle compared to liver (Faxneld et al. 2014), which could result in higher

concentrations based on whole-body compared to concentrations in muscle, the difference

might even be so big that the threshold value (the QS value to protect from secondary

poisoning) is exceeded in whole-body even though the EQS in muscle tissue is not. Other

chemicals, like hexabromocyclododecane (HBCDD) and mercury have an EQS set for top

predator prey fish (where top predators are considered the most sensitive group) which then

refers to whole fish, but both these substances are measured in muscle tissue. In addition,

cadmium and lead are measured in liver tissue but the threshold values are based on content in

muscle tissue for food regulation and in whole fish for EU Quality Standards (QS).

Thus, to ensure continuity in the spatial and temporal trend monitoring but still use the

information from these studies in compliance monitoring there is a need for conversion

factors between contaminant concentrations in different fish tissues. Earlier studies have

examined metals in liver, muscle and whole-body in limnic perch and herring and perch from

the Baltic Sea (Faxneld et al. 2015, Boalt et al. 2014). Unfortunately, the concentrations in

muscle were generally below quantification limits. Another study compared PFOS liver and

muscle concentrations in herring and limnic and marine perch but no whole-body

concentrations were measured (Faxneld et al. 2014).

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In an EU guidance document on how to assess chemical status (EU 2014) it is stated that fat-

soluble substances are considered to be evenly distributed in the fat regardless of tissue. In

order to examine if this assumption is correct, there is a need for analyses on individual fish

organs.

The overall aim of this study was to look at possible correlations between distributions of

contaminants in different parts of fish, in order to compare between tissues, and suggest

relevant conversion factors for specific contaminants.

Herring, which is the most common species in the Swedish national monitoring program, was

used. The main focus was on the EQS values where the specified matrix differs from the

matrix monitored in the regular program; PFOS, HBCDD and mercury and to some extent

also polybrominated diphenyl ethers (PBDEs) and hexachlorobenzene (HCB). The purpose

was to: 1) explore the distribution of chemicals in different tissues, 2) examine if there were

any correlations between the concentrations in different tissues, 3) calculate conversion

factors/equations between the different tissues, 4) calculate relevant corresponding threshold

values for these contaminants in the monitored tissue and finally to 5) examine the

assumption that lipid soluble contaminants are evenly distributed in the lipids of the fish in

various organs.

Methods

Fish sampling

Baltic herring (Clupea harengus) were collected in August 2016, from Lilla Värtan,

Stockholm archipelago (N59.20 E 18 10.15; WGS84) using gillnets (Lundgrens, 34 mm mesh

size, 2.5 m deep, 30 m long). Elevated concentrations compared to the national reference

stations were earlier found here (Danielsson et al. 2014) and in order to avoid levels below

quantification limits this site was considered appropriate. After retrieval from the gillnets, fish

were stunned by a blow to the head, packaged individually in plastic bags (low density

polyethylene, LDPE) and frozen using dry ice. Fish were transported frozen to the Swedish

Museum of Natural History (SMNH), Stockholm, and stored in a freezer at -25 °C.

Sample preparation

Prior to sampling, fish were aged, sexed, measured (standard length and total length) and

weighed. Fish were aged by reading scales picked from behind the gill area. Scales (6 per

fish) were cleaned in tap water, and mounted on glass microscope slides. After mounting, the

scales were placed under a light microscope (Leica MZ16) and winter annuli were counted.

Sex was determined by opening the fish and inspecting the gonads. Reproduction phase was

determined for each individual fish according to gonad ripeness and size (Bignert et al. 2017).

All incisions and handling of fish were carried out using ceramic (Zirconium dioxide) blades

and forceps. Pyrex jars used for homogenizing tissue were washed in a 4 stage process (Nitric

acid 15%, rinsed in distilled water twice, and spectrographic ethanol and acetone 1:1) and

burned at 400 °C prior to sampling. Samples for analysis of chlorinated and brominated

compounds were stored in glass jars rinsed in spectrographic ethanol and burned at 400 °C.

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Samples for metal analysis were stored in acid-washed plastic jars and samples for analysis of

per- and polyfluoralkyl substances (PFAS) in sterile plastic tubes (13 mm, Sarstedt).

Homogenization of tissue and individuals were carried out using a mixer (IKA Ultraturrax T

25) and a stainless steel shaft dispersion tool, except for tissue for heavy metal analysis which

was homogenized using a plastic dispersion tool.

Part I: Contaminants in individuals; muscle, liver, stomach / intestine and carcass

12 fish were sampled for chlorinated pesticides and PCBs (Polychlorinated biphenyls) (ClCs)

and polybrominated diphenyl ethers and HBCDD (BFRs) in muscle tissue and carcass. Skin

and subcutaneous fat was scraped from the left (sinistral) side of a frozen fish and placed into

a pyrex jar. Muscle tissue (~10 g) was removed and placed in a glass jar, and stored in a

freezer for analysis. The rest of the body was placed in the pyrex jar with the skin and

subcutaneous fat and homogenized. Part of this homogenate (~10 g) was placed in a glass jar

and frozen for analysis.

24 separate individuals were sampled for PFAS (n = 12) and metals (n = 12) in muscle tissue,

liver tissue, stomach/intestines and carcass. Skin and subcutaneous fat was removed, as

described above. Muscle tissue for PFAS (~2 g) and metal (~1.5 g) analysis were sampled and

frozen for analysis. After removal of the muscle sample, fish were opened by making

incisions along the lateral line and behind the gill. Whole liver was removed, weighed and

frozen for analysis. The whole stomach and intestines were also removed, weighed and frozen

for analysis. The rest of the fish was placed in the pyrex jar with skin and subcutaneous fat

and homogenized. The homogenate was sampled (~2 g and ~1.5 g respectively for PFAS and

heavy metals) and frozen for analysis. A summary of the sampling regime can be seen in

Table 1 and the biological variables for the analysed individuals in Table 2.

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Table 1. Summary of the sampling regime carried out in Part I, with the weight of samples sent for analysis (g).

Note that extracts for analysis of chlorinated pesticides, PCBs, PBDEs and HBCDD are taken from the same

tissue sample. The whole liver and stomach/intestines were sent for analysis, hence the range in sample amounts.

Organ n

Sample weight (g)

PFASs Metals ClCs BFRs

Liver 12 ~0.4 ~0.8 ~0.5 ~0.8

Muscle 12 ~2.0 ~1.5 ~10.0

Carcass 12 ~2.0 ~1.5 ~10.0

Stomach /

Intestine 12 ~1.5 ~2.3 ~1.6 ~2.5

Table 2. Summary of the biological variables for the individuals analysed for respective contaminant group,

mean values and ranges in parenthesis, m=male, f=female.

Substance n

sex

(n) age weight (g)

total length

(cm)

body length

(cm)

liver weight

(g)

Metals 12

m:6

f:6 4.8 (3-6)

35.7

(29.7-41.4)

17.2

(16.3-17.9)

14.3

(13.3-14.9)

0.62

(0.45-0.80)

PFAS 12

m:7

f:5 5.3 (3-7)

36.2

(29.4-42.4)

17.1

(14.6-18.0)

14.4

(13.6-15.0)

0.59

(0.41-0.81)

ClC &

BFR 12

m:9

f:3 4.8 (4-6)

36.2

(30.6-40.39

17.0

(16.3-18.1)

14.2

(13.5-15.3)

Part II: Contaminants in various organs, pooled samples

Two pools (n = 25 females, n = 25 males) of individuals were sampled for contaminant

analysis in selected organs (Table 3 and 4). Fish were dissected individually and organs

placed in separate pyrex jars. The weight of the organs was recorded and after all fish had

been dissected the samples were homogenized. Dissection of fish occurred as follows. An

individual was removed from the freezer and pectoral, pelvic, anal, dorsal and caudal fins

were removed and placed in a pyrex jar (carcass or rest). The eyes were removed from the eye

sockets whilst still frozen. The skin and subcutaneous fat were removed from the left side of

the fish. A sample of muscle tissue (~2 g) was removed for analysis; the remaining muscle

tissue on the distral side was removed from the fish and weighed. The liver, stomach,

intestines and gonads were removed and separated for analysis. The swim bladder and gall

bladder were removed and placed in the carcass jar. The kidney was scraped away from the

spine. The hemal spine (without ribs) and hypural were dissected from the fish and muscle

tissue was scraped from the bone using a scalpel. The muscle tissue scraped from the spine

was placed in the carcass jar. The spine and hypural were then cleaned using a soft brush and

warm distilled water so that all visible soft tissue was removed. The fish was turned over and

a sample (~2 g) of muscle with skin and subcutaneous fat was taken. The remaining muscle,

skin and subcutaneous fat tissue was removed and weighed together. The brain was removed

from the cranium by making a horizontal incision above the eye sockets and lifting out the

brain tissue. Finally, the gills (arch and filaments) were detached from the head. The

remaining tissue was placed in the carcass jar. After dissection of all individuals for 1 pool the

organs were homogenized and disseminated into jars / tubes for contaminant analysis (see

Table 3)

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Table 3. Summary of the sampling regime carried out in Part II with the weights of samples sent for analysis (g).

Note that extracts for analysis of chlorinated pesticides, PCBs, PBDEs and HBCDD are taken from the same

tissue sample. The amount of available tissue limited sample sizes for the brain and kidney.

Sample weight (g)

Organ No. of

pools

n per

pool

PFASs

Metals

Chlorinated

pesticides +

PCBs

PBDEs+

HBCDD

Eyes 2 25 ~2.0 ~4.0 ~10.0

Skin and sub. fat 2 25 ~2.0 ~4.0 ~10.0

Muscle 2 25 ~2.0 ~4.0 ~10.0

Skin, sub. fat and

muscle

2 25 ~2.0 ~4.0 ~10.0

Liver 2 25 ~2.0 ~4.0 ~6.0

Gonads 2 25 ~2.0 ~4.0 ~10.0

Stomach and

intestines

2 25 ~2.0 ~4.0 ~10.0

Kidney 2 25 ~1.0 ~2.5 ~2.0

Brain 2 25 ~0.5 ~1.0 ~1.5

Gills 2 25 ~2.0 ~4.0 ~10.0

Bone (spine) 2 25 ~3.5 ~5.0

Rest (carcass) 2 25 ~2.0 ~4.0 ~10.0

Table 4. Summary of the organ weights and fish length for the fish included in the two pooled samples, mean

values and range in parenthesis.

Organ Female sample Male sample

n 25 25

Muscle with skin (g) 13 (12-16) 12 (11-14)

Muscle (g) 11 (9.4-12) 10 (8.5-12)

Skin (g) 1.2 (0.94-1.6) 1.3 (1.1-1.7)

Intestines (g) 2.5 (1.9-3.7) 2.0 (1.3-3.0)

Gills (g) 1.3 (1.1-1.8) 1.2 (0.89-1.5)

Gonads (g) 0.89 (0.29-1.8) 2.1 (0.67-3.8)

Eyes (g) 0.86 (0.59-1.1) 0.88 (0.65-1.2)

Skeleton (cleaned) (g) 0.14 (0.0.10-0.18) 0.20 (0.12-0.30)

Liver (g) 0.72 (0.47-0.86) 0.55 (0.41-0.74)

Kidney (g) 0.28 (0.15-0.36) 0.27 (0.16-0.34)

Brain (g) 0.18 (0.13-0.21) 0.17 (0.13-0.22)

Rest (g) 5.5 (4.2-6.5) 5.3 (4.4-6.6)

Body weight (g) 40 (36-45) 38 (35-44)

Calculated body weight (g) 38 (35-42) 37 (34-42)

Calc b.w./b.w. 0.95 (0.92-0.99) 0.97 (0.94-1.0)

Body length (cm) 15 (14-16) 15 (14-16)

Total length (cm) 18 (17-19) 18 (17-19)

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Analytical method

Organochlorines and brominated flame retardants

The extraction method originates from the method described by Jensen et al. (1983) where

wet tissues are extracted with a mixture of polar and non-polar solvents. Samples were

homogenized and extracted with a mixture of acetone, n-hexane and diethyl ether. The

organic phase was liquid/liquid partitioned with a solution of sodium chloride/phosphoric

acid. The aqueous phase was re-extracted with n-hexane and the combined organic phases

were evaporated to dryness in beakers. The lipid content was determined gravimetrically. The

lipids were dissolved in isooctane, containing CB-53 as internal standard for chlorinated

substances and dechlorane for brominated substances. The dissolved lipids were treated with

concentrated sulfuric acid (Jensen et al., 1983). The organic phase was removed and analyzed

directly for chlorinated substances whereas 500 µL were blown down to 100 µL and analyzed

for brominated substances.

Chlorinated substances, i.e. PCBs (CB-28-CB-180), HCB, DDTpp ((1,1,1-trichloro-2,2-bis(4-

chlorophenyl)ethane)and its breakdown products DDEpp ((1,1'-(2,2-Dichloro-1,1-

ethenediyl)bis(4-chlorobenzene)) and DDDpp ((1,1'-(2,2-Dichloro-1,1-ethanediyl)bis(4-

chlorobenzene)) as well as the insecticide γ-HCH (hexachlorocyclohexane, Lindane) and it´s

α- and β-isomers were analyzed on a gas chromatograph equipped with two EC-detectors.

Two fused capillary columns were used in parallel: 60 m x 0.25 mm, film thickness 0.25 µm

TG5MS respectively DB1701. Helium was used as carrier gas and Argon/Methane as make-

up gas (Eriksson et al. 1997). The laboratory is accredited by SWEDAC for determination of above

listed substances and lipid content.

The brominated substances, BDE-47, -99,-100, -153, -154 and HBCDD, were analyzed on a

GC using a 30 m x 0.25 mm, I.D 0.25 µm TG5SilMS column connected to a mass

spectrometer operating in electron capture negative ionization mode (NICI). Ammonia was

used as the reaction gas and the mass fragments monitored were m/z 79 and 81 (Sellström et

al., 1998).

The laboratory participates in the QUASIMEME intercalibration rounds for both the

chlorinated and brominated substances.

Metals

Fish tissue samples were freeze-dried and homogenized before digestion and metal analysis.

For trace metal analysis about 100 mg dry sample was digested with nitric acid and hydrogen

peroxide using a microwave (CEM MARS5) according to the Swedish standards SS-EN

13805:2009 (Foodstuffs – Determination of trace elements – Pressure digestion). Metal

concentrations were determined using ICP-MS (Thermo Scientific XSeries II) according to

the SS-EN ISO 17294-2:2005 (Water quality – Application of inductively coupled plasma

mass spectrometry (ICP-MS) – Part 2: Determination of 62 elements). Mercury in muscle is

determined without sample digestion according to the US EPA Method 7473 (mercury in

solids and solutions by thermal decomposition, amalgamation and atomic absorption

spectrophotometry). The laboratory is accredited by SWEDAC for determination of dry

matter (by freeze drying), Ag, Al, As, Cd, Cr, Cu, Ni, Pb, Zn and Hg in biota, and participates

in the periodic QUASIMEME intercalibration rounds.

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Certified Reference Material (CRMs) used for mercury are:

DORM-2 and DORM-3 (dogfish muscle)

For all other metals, CRMs used are:

DORM-2 (Dogfish muscle)

DOLT-3 (Dogfish liver)

TORT-2 (lobster hepatopancreas)

NIST 1566 (oyster tissue).

Per- and polyfluoroalkyl substances

Results for the standard suite of PFCAs (perfluoroalkyl carboxylic acids), PFSAs

(perfluoroalkylsulfonic acids), and FOSA (perfluorooctane sulfonamide) were quantified with

authentic standards and (in most cases) exactly-matched isotopically labeled internal

standards. Results for PFPeDA (perfluoropentadecanoate) should be considered semi-

quantitative as a standard does not exist for this substance so its concentration was estimated

using the calibration curve for PFTeDA (perfluorotetradecanoate).

Standards and reagents

All native and isotope-labeled standard compounds were purchased from Wellington

Laboratories (Guelph, ON, Canada) in 2 μg/mL solution mixtures (MPFAC-MXA, PFAC-

MXB) or as single compounds at 50 µg/mL. The Internal standard mixture (ISTD) used was

prepared in-house at a concentration of 20 pg/µL. A recovery standard (RTSD) was also

prepared in-house at a concentration of 20 pg/µL. The following reagents and solvents were

used: glacial acetic acid (Sigma-Aldrich), ammonium acetate (Merck, Darmstadt, Germany),

MeOH LiChrosolv grade (Merck), acetonitrile (CHROMASOLV™, for HPLC, gradient

grade, ≥99.9%, Honeywell Riedel-de Haën™), Supelclean ENVI-Carb 120/400 (Supelco

57210-U) and Milli-Q water (produced in-house). All reagents and solvents were purchased

with the highest purity available and used as received.

Method

Tissue samples (0.4 - 2.3g) were weighed into a 13 mL polypropylene tube and spiked with

50 μL of a 20 pg/µL ISTD. 5 mL of acetonitrile along with 7 beads (4.8 mm diameter,

stainless steel) were added and the samples were homogenized using a bead blender (SPEX

SamplePrep 1600 MiniG ®) for 4 minutes at 1500 rpm. After centrifuging (2000 rpm, 5 min)

the organic phase was transferred to a new 13 mL polypropylene tube and the extraction was

repeated (total of 2 extractions). The combined extracts were concentrated to ~1 mL under a

stream of nitrogen. The extract was then transferred to an eppendorf tube containing 25 mg

ENVI-Carb and 50 µL glacial acetic acid and vortex-mixed thoroughly. The extracts were

centrifuged (10000 rpm, 10 min) and 500 µL of extract was transferred to a new eppendorf

tube. 50 µL RSTD solution (20 pg/µL) and 450 µL 4mM NH4OAc in water was added. Final

extracts were frozen prior to analysis. On the day of analysis, extracts were warmed to room

temperature, vortex mixed and centrifuged (10000 rpm, 10 min) before transferred to auto

sampler vial for UPLC-MS/MS analysis.

Quality Control

Samples were processed along with 1 blank and 1 quality control sample per batch. Method

detection limits (MDLs) and method quantification limits (MQLs) were determined based on

the concentrations producing a signal-to-noise ratio of 3 or 10 respectively. MDLs and MQLs

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varied slightly depending on the quantity of tissue extracted. Br-PFOS and L-PFOS were

quantified using both 499-80 and 499-99 transitions and the concentrations were averaged. A

comparison of in-house control fish muscle analysed in this batch to previously analysed

control fish revealed reasonable reproducibility for high concentration targets. PFPeDA,

PFHxDA (Perfluorohexadecanoate) and PFODA (Perfluorooctadecanoate) were the only

substances (with the exception of branched isomers) for which an authentic standard was not

available for quantification. Consequently, the calibration curve for PFTeDA was used for

estimating the concentrations of PFPeDA, PFHxDA and PFODA. These data should be

considered semi-quantitative.

Data treatment

Calculation of whole fish concentrations

Whole fish concentrations for the individual samples (part I) were calculated according to the

formula below (W= weight and C=concentration on wet weight basis):

Cwhole fish= (Ccarcass x Wcarcass) + (Cmuscle x Wmuscle sample) + (Cliver x Wliver sample) + (Cstomach xWstomach sample)

Wwhole fish

Where Wcarcass = Wwhole fish-Wmuscle sample -Wliver sample –Wstomach sample

Whole fish concentrations for the pooled samples (part II) were calculated according to:

Ctissue 1 x W tissue 1 + Ctissue 2 x W tissue 2 + …. C tissue 12 x W tissue 12

W whole fish (Σ Wtissue 1-12)

(See Table 3 for tissue 1-12).

Values below the limit of quantification (LOQ) or limit of detection (LOD) were replaced by

the reported LOQ or LOD divided by the square root of 2, prior to calculation of the whole

fish concentration. For part I, individual whole fish calculations were carried out, while for

part II, mean values of organ weights from the 25 fish in each pooled sample were used for

the whole fish concentration calculations.

Data analysis

Evaluation of contaminant concentrations between different tissues for individual samples

(part I) were carried out according to a procedure modified from Bevelhimer et al. (1997)

(Figure 1). The procedure involves a paired t-test, regression analysis and a check to decide if

the slope differs from one, i.e. if the 95% confidence interval of the slope overlap one. In the

case of suspected outliers, a non-parametric regression was performed as a complement to the

regular regression analysis.

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12

Figure 1. Data analysis procedure to examine contaminant concentrations between different tissues. Modified

figure from Bevelhimer et al. (1997).

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13

Results and discussion

Metals

Mercury (Hg)

The Hg concentration in different tissues (Figure 2, appendix Table 1, 2) from the pooled

samples (part II) showed that the highest concentrations were found in muscle (140 - 200 ng/g

wet weight (ww)) with similar concentrations in liver (110 - 160 ng/g ww), followed by

kidney (70-90 ng/g ww) and stomach/intestines (~ 60 ng/g ww). Since a great part of the fish

consists of muscle tissue, the whole fish concentration was also relatively high (~130 ng/g

ww). The lowest concentration was found in the eyes (10-20 ng/g ww). The results from the

individual samples (part I) were consistent with results from part II, with the highest

geometric mean concentrations in muscle (130 ng/g ww) and liver (120 ng/g ww) compared

to stomach/intestines (Figure 3, appendix Table 3).

Hg in various tissue

Mean Min-Max

mu

scle

, skin

, su

b fa

t

Mu

scle

Skin

, su

b. fa

t

Sto

ma

ch

Go

na

d

Gill

s

Eye

s

Liv

er

Kid

ne

y

Bra

in

Ske

leto

n

Re

sid

ue

wh

ole

bo

dy

0

20

40

60

80

100

120

140

160

180

200

220

ng

/g w

w

Figure 2. Concentrations of Hg (ng/g ww) in different tissue of herring. The boxes show the range of two pooled

samples of 25 fish each (1 male pool and 1 female pool) together with their mean value.

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14

Hg concentrations

Median 25%-75% Non-Outlier Range Outliers

liver muscle stomach carcass whole fish

tissue

20

40

60

80

100

120

140

160

180

200

220

240

260

280

300

ng

/g w

w

Figure 3. Concentrations of Hg (ng/g ww) in liver, muscle, stomach/intestines (stomach in the figure), and

whole body (calculated) in herring.

Significant correlations were found between all four tissue types (Figure 4); muscle, liver,

stomach/intestines and whole fish. Strongest correlations were found between whole fish vs.

muscle with an r2-value of 0.99, but there were also strong correlations between whole fish vs.

liver and muscle vs. liver. Correlation with stomach/intestines and other tissues were weaker

with r2-values ranging from 0.42 – 0.50. A paired t-test showed significant differences in

concentrations between the different tissues except for muscle vs. liver with liver and muscle

concentrations > concentration in whole body > concentrations in stomach/intestines, see

Table 12 appendix.

In the Swedish national monitoring program for contaminants, Hg is analysed annually in

muscle tissue. The EU EQS for Hg in fish (20 ng/g ww) is set for top predators and the

compliance check should thus be performed on values representative for whole body. To

translate the whole-body concentration of Hg to muscle tissue concentrations the tabulated

regression model in Table 12 appendix (Y = 11.9 + 0.733X) can be used.

The EQS, 20 ng Hg/g ww in whole fish then corresponds to a muscle value of 11.1 ng/g ww.

This value is lower than the whole fish value in contradiction to the results from the paired t-

test where the muscle concentrations are higher than the whole body concentration (appendix

Table 12). It is thus questionable if it is correct to use the regression model in this case. The

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15

regression model is generated from values in a higher concentration range (43-280 ng/g ww)

than the value for the EQS (20 ng/g ww) and it is uncertain how the relations between muscle

and whole fish are at lower concentrations. The intercept of the regression model will have a

great influence on the estimation of muscle values at lower concentrations (outside the range

of the regression that gave the function). If the ratio between muscle and whole fish

(M/WB:1.2, appendix Table 12) is used instead, the corresponding muscle value for the EQS

is 24 ng/g ww. If the regression is run by forcing the regression line through the origin then,

an EQS of 20 ng/g ww in whole fish corresponds to 25 ng/g ww in muscle if the equation is

used. In Faxneld et al. (2015) a regression model was used to calculate a muscle value from a

whole body concentration, and here they retrieved a value of 21 ng/g ww. In Boalt et al.

(2014) they found a ratio between whole fish:muscle in herring=0.86, if recalculating this to

muscle:whole fish instead the ratio = 1.2, hence the same as in this study.

Figure 4. Regression analyses of Hg concentrations in whole fish (whole in the figure), muscle, liver and

stomach/intestines (stomach in the figure).

Cadmium (Cd)

The highest concentrations of Cd (0.69 and 0.76 µg/g dry weight (dw)) were found in kidney

tissue in the two pooled herring samples (Figure 5, appendix Table 1). Liver samples had

approximately a third of the kidney concentrations (0.23 and 0.27 µg/g dw) followed by

stomach/intestines (0.13 and 0.15 µg/g dw). Concentrations in other organs were relatively

low with levels below LOQ for the muscle samples (Figure 5, appendix Table 1, 2). The

geometric mean value for the individual Cd concentrations in liver (0.52 µg/g dw) were

Page 16: Distribution and conversions of metal- and POP ...nrm.diva-portal.org/smash/get/diva2:1273434/FULLTEXT01.pdfChemists: Hg; Ann-Marie Johansson, metals; Pär Hjelmquist, Jan Mechedal

16

higher than the stomach/intestine concentration (0.34 µg/g dw) but not significantly different

(Figure 6, appendix Table 3). A paired t-test showed significantly higher concentrations in

stomach/intestines compared to whole fish (geometric mean 0.062 µg/g dw) and significantly

higher concentrations in whole fish compared to muscle tissue where all except three samples

were below LOQ.

Cd and Pb in various tissue

Cd Pbm

uscle

, skin

, su

b fa

t

Mu

scle

Skin

, su

b. fa

t

Sto

ma

ch

Go

na

d

Gill

s

Eye

s

Liv

er

Kid

ne

y

Bra

in

Ske

leto

n

Re

sid

ue

wh

ole

bo

dy

-0,1

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

ug

/g d

w

Figure 5. Concentrations of Cd and Pb (µg/g dw) in different herring tissue. The boxes show the range of two

pooled samples of 25 fish each (1 male pool and 1 female pool) together with their mean value.

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17

Cd concentrations

Median 25%-75% Non-Outlier Range Outliers Extremes

liver muscle stomach carcass whole fish

tissue

-0,2

0,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

ug

/g d

w

Figure 6. Concentrations of Cd (µg/g dw) in liver, muscle, stomach/intestines (stomach in the figure), and

whole body (calculated) in herring.

The regression analysis showed significant correlations between whole body and liver

(r2=0.62) and between whole body and stomach/intestines (r2=0.49) (Figure 7).

For Cd there is a quality standard (QS) derived within EU (0.16 µg/g ww) protecting top

predators from secondary poisoning, which means that the QS is derived for concentrations in

whole fish (EC 2005). Cd concentration is analysed annually within the Swedish contaminant

monitoring program, but in liver tissue. By using the significant regression model (Figure 7)

for Cd in whole fish vs. liver, a corresponding value can be calculated for a Cd concentration

in liver dry weight. The recommended dry weight content for fish of 26% (EC 2014) was

used to translate the QS to a dry weight value (0.62 µg/g dw). The regression model was then

used to calculate what the QS value would be expressed in liver: Y = 0.035 + 0.049X, gives a

liver value of 12 µg/g dw.

In Faxneld et al. (2015), the QS of 0.16 µg/g ww was recalculated to a liver value of 37.5

µg/g dw, hence three times as high. However, this study was instead based on perch and

species specific differences could be a possible explanation to the different results.

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18

There is also a threshold value for EC foodstuff regulation set as a maximum value of 0.05

µg/g ww muscle tissue. If the concentration ratio liver/muscle (=143) (appendix Table 12)

was used a muscle concentration of 0.19 µg/g dw (the threshold value expressed on dry

weight with an assumed dry weight of 26% according to EC 2014), would represent a liver

concentration of 27.5 µg/g dw. It should however be noted that the muscle concentration were

all below LOQ which means that the calculation was only based on estimates of the muscle

concentrations by dividing the reported LOQ values by the square root of 2.

Figure 7. Regression analyses of Cd concentrations in whole fish (whole in the figure), muscle, liver and

stomach/intestines (stomach in the figure).

Lead (Pb)

The highest Pb concentration in the pooled samples were found in the skeleton (0.398 µg/g

dw) in the female pool and in the skin with subcutaneous fat (0.466 µg/g dw) in the male pool

(Figure 5, appendix Table 1, 2). Concentrations decreased in the following order:

stomach/intestines > gills > liver > kidney (Figure 5). Levels in eyes, gonads and muscle were

very low and below LOQ in one of the muscle samples. The highest concentration in the

individual samples was found in stomach/intestines (0.256 µg/g dw), (Figure 8, appendix

Table 3) consistent with the results from the pooled samples.

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19

Pb concentrations

Median 25%-75% Non-Outlier Range Extremes

liver muscle stomach carcass whole fish

tissue

-0,1

0,0

0,1

0,2

0,3

0,4

0,5

ug

/g d

w

Figure 8. Concentrations of Pb (µg/g dw) in liver, muscle, stomach/intestines (stomach in the figure), and whole

body (calculated) in herring.

The regression analysis showed a significant correlation between whole fish vs. liver (r2 =

0.76) (Figure 9). The regression model can thus be used to calculate the corresponding

threshold value in liver compared to the QS secondary poisoning of 1000 µg/kg ww (or 1

µg/g ww) whole fish. The recommended dry weight for fish (26%) in EC 2014 was used to

express the QS in dry weight (3.8 µg/g dw). The regression model was used to translate the

whole fish value into a liver value: Y = 0.035 + 0.20X which gives a value of 19 µg/g dw in

liver. This value is almost ten times as high as what was found in Faxneld et al. (2015), 1.64

µg/g dw, where concentration in whole body was higher than in liver, opposite the results in

this study. However, in Faxneld et al. (2015) the study species was perch and species specific

differences could be a possible explanation to the different results.

There is also a threshold value for EC foodstuff regulation set as a maximum value of 0.3

µg/g ww in muscle tissue. If the concentration ratio liver/muscle (=15.2) (appendix Table 12)

was used, a muscle concentration of 1.15 µg/g dw (the threshold value expressed on dry

weight with an assumed dry weight of 26% according to EC 2014) would represent a liver

concentration of 17.5 µg/g dw. It should however be noted that the muscle concentrations

were all below LOQ, which means that the calculation were only based on estimates of the

muscle concentrations by dividing the reported LOQ values by the square root of 2.

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20

Figure 9. Regression analyses of Pb concentrations in whole fish (whole in the figure), muscle, liver and

stomach/intestines (stomach in the figure).

Per- and polyfluoralkyl substances (PFASs)

PFOS

The highest concentrations of ∑PFOS (Br-PFOS and L-PFOS) in the pooled samples (part II)

were observed in liver tissue (25 – 28 ng/g ww) and kidney tissue (22 – 23 ng/g ww) (Figure

10, appendix Table 9). Concentrations in gonad samples, stomach/intestines, and brain tissue

were approximately half of those observed in liver and kidney tissue (Figure 10, appendix

Table 9). The lowest concentrations were found in muscle tissue (1.4 – 1.6 ng/g ww) with

somewhat higher concentrations in skin and subcutaneous fat (5.3 – 6.2 ng/g ww) (Figure 10,

appendix Table 9). The results from the individual analysis (part I) showed consistency with

results presented in part II with the highest geometric mean concentration in liver (29 ng/g

ww), followed by stomach/intestines (14 ng/g ww), and the lowest concentration in muscle

(1.5 ng/g ww) (Figure 11, appendix Table 11). The mean concentration calculated for whole

fish was equal in both part I (5.9 ng/g ww) and II (5.7 ng/g ww) (appendix Table 9, 11).

Page 21: Distribution and conversions of metal- and POP ...nrm.diva-portal.org/smash/get/diva2:1273434/FULLTEXT01.pdfChemists: Hg; Ann-Marie Johansson, metals; Pär Hjelmquist, Jan Mechedal

21

PFOS in various tissue

Median

25%-75%

Non-Outlier Range

muscle

, skin

, sub f

at

Muscle

Skin

, sub.

fat

Sto

mach

Gonad

Gill

s

Eyes

Liv

er

Kid

ney

Bra

in

Skele

ton

Resid

ue

whole

fis

h

tissue

0

5

10

15

20

25

30

ng/g

ww

Figure 10. Concentrations of ∑PFOS (ng/g ww) in different herring tissue. The boxes show the range of two

pooled samples of 25 fish each (1 male pool and 1 female pool) together with their mean value.

Page 22: Distribution and conversions of metal- and POP ...nrm.diva-portal.org/smash/get/diva2:1273434/FULLTEXT01.pdfChemists: Hg; Ann-Marie Johansson, metals; Pär Hjelmquist, Jan Mechedal

22

sumPFOS concentrations

Median 25%-75% Non-Outlier Range Outliers

liver muscle stomach carcass Whole body

tissue

-10

0

10

20

30

40

50

60

70

ng

/g w

w

Figure 11. Concentrations of ∑PFOS (ng/g ww) in liver, muscle, stomach/intestines (stomach in the figure), and

whole body (calculated) in herring.

Significant correlations were found between whole fish vs. liver (r2 =0.72), liver vs.

stomach/intestines (r2 =0.46) and whole fish vs. stomach/intestines (r2 =0.65) (Figure 12). A

paired t-test showed significant differences in concentrations between all four tissues; liver,

muscle, stomach/intestines and whole fish, analysed in the individual samples (part I).

There was no significant correlation between muscle and liver concentrations for ∑PFOS

(Figure 12), however the paired t-test showed significantly higher concentrations in liver

compared to muscle with a ratio of (L/M = 21) (appendix Table 13). The EQS value of 9.1

ng/g ww in muscle tissue can then be recalculated by using the liver/muscle ratio. Thus, a

corresponding liver value of 191 ng/g ww in liver to the muscle EQS value was calculated.

This value is slightly higher compared to Faxneld et al. (2014), in which a liver concentration

of 155 ng/g ww was estimated based on an L/M ratio of 19.

Within the process of deriving EQS values, also a QS value for protection of top predators

from secondary poisoning (QSsec.pois.) was derived. This value is set to 33 ng/g ww in whole

fish tissue for PFOS. From the results in this study, a whole fish concentration of 33 ng/g ww

corresponds to a liver concentration of 208 ng/g ww when the equation for the regression of

ΣPFOS whole fish/liver (appendix Table 13) was used and a liver value of 163 ng/g ww if the

ratio liver/whole fish of 4.96 (appendix Table 13) was used instead. The two ways of

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23

calculating the liver value from the QSsec.pois. results in both a higher and a lower value

compared to the liver value of 191 ng/g ww calculated for the EQS, suggesting that both EQS

(based on protection of human health) and QSsec. pois. are at the same level of protection.

Figure 12. Regression analyses of ∑PFOS concentrations in whole fish (‘whole’), muscle, liver and

stomach/intestines (‘stomach’).

Perfluorinated sulfonates, FOSA and carboxylic acids

Concentrations of PFHpA (Perfluoroheptanoate), PFHxA (Perfluorohexanoate), PFHxDA,

PFODA and PFBS (Perfluorobutane sulfonate) were all below the LOQ in both pooled and

individual samples in all tissues. PFPeDA and PFHxS (Perfluorohexane sulfonate)

concentrations were all, with exceptions for a few values, below LOQ (appendix Table 9,

11).

For the majority of PFASs measured in the pooled samples, the highest concentrations were

found in liver and kidney tissue (Figure 13, appendix Table 9, 10). Also stomach/intestines,

gonads and gills showed in general, relatively high values, approximately half of the liver or

kidney tissue concentrations (Figure 13, appendix Table 9, 10). However, for a few of the

long chained carboxylic acids (PFTeDA, and PFPeDA1*), the highest levels were found in the

brain (Figure 13, appendix Table 9, 10). Moreover, for PFTrDA the highest concentration was

1 * Results for PFPeDA should be considered semi-quantitative as a standard does not exist for this substance so

its concentration was estimated using the calibration curve for PFTeDA.

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24

found in kidney tissue (1.2-1.4 ng/g ww) followed by the brain (0.85-0.93 ng/g ww). The

concentrations in brain tissue was also highest for the linear form of PFDS (Perfluorodecane

sulfonate) in the female pooled sample (appendix Table 9,10).

The paired t-test for the individual samples showed that all analysed PFASs, except for PFOA

(perfluorooctanoate) and PFNA (perfluorononanoate) where stomach/intestines

concentrations were higher, have higher concentrations in liver compared to

stomach/intestines, whole fish and muscle tissue (appendix Table 11). The following

distribution of concentration was seen: liver >stomach/intestines>whole fish>muscle.

Perfluorinated carboxylic acids in various tissue

ng/g ww

PFDA

PFTeDA

muscle

, skin

, sub f

at

Muscle

Skin

, sub.

fat

Sto

mach

Gonad

Gill

s

Eyes

Liv

er

Kid

ney

Bra

in

Resid

ue

whole

fis

h

tissue

-0,2

0,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

1,8

Figure 13. Concentrations of PFDA and PFTeDA (ng/g ww) in different tissue of herring. The boxes show the

range of two pooled samples of 25 fish each (1 male pool and 1 female pool) together with their mean value.

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25

Organobromine and -chlorine compounds

Individual samples for α-HCH, lindane and DDT were not considered in the evaluation since

all concentrations were below the quantification limit (LOQ). For BDE-153, four and three

individuals had concentrations below LOQ in muscle and carcass respectively. For BDE-154

two individuals had concentrations below LOQ in muscle. For β-HCH, five individuals had

concentrations below LOQ in muscle tissue (appendix Table 8).

Concentrations of organobromine and -chlorine compounds expressed on a lipid weight basis

were quite evenly distributed between different tissues in the pooled samples (Figure 14-16,

appendix Table 4, 5). The exceptions to this were concentrations in eyes and brain tissue

where concentrations were clearly lower than concentrations in the rest of the other tissues.

This pattern was repeated for all analysed compounds with lowest concentrations in brain

tissue followed by the eyes (appendix Table 4-7). The lower concentration in the brain can

possibly be explained by the blood brain barrier preventing toxic lipid-soluble compounds

from entering the brain.

DDE and CB-153 in various tissue

DDE CB-153m

uscle

, skin

, su

b fa

t

Mu

scle

Skin

, su

b. fa

t

Sto

ma

ch

Go

na

d

Gill

s

Eye

s

Liv

er

Kid

ne

y

Bra

in

Re

sid

ue

wh

ole

fis

h

0

100

200

300

400

500

600

ng

/g lw

Figure 14. Concentrations of DDE and CB-153 (ng/g lw) in herring tissue. The boxes show the range of two

pooled samples of 25 fish each (1 male pool and 1 female pool) together with their mean value.

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26

HCB in various tissue

Mean Min-Max m

uscle

, skin

, su

b fa

t

Mu

scle

Skin

, su

b. fa

t

Sto

ma

ch

Go

na

d

Gill

s

Eye

s

Liv

er

Kid

ne

y

Bra

in

Re

sid

ue

wh

ole

fis

h

2

4

6

8

10

12

14

16

ng

/g lw

Figure 15. Concentration of HCB (ng/g lw) in herring tissue. The boxes show the range of two pooled samples

of 25 fish each (1 male pool and 1 female pool) together with their mean value.

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27

BDE-47 and HBCDD in various tissue

HBCDD BDE-47

mu

scle

, skin

, su

b fa

t

Mu

scle

Skin

, su

b. fa

t

Sto

ma

ch

Gon

ad

Gill

s

Eye

s

Liv

er

Kid

ne

y

Bra

in

Re

sid

ue

wh

ole

fis

htissue

0

2

4

6

8

10

12

14

16

18

20

22

24

26

28

30

Figure 16. Concentrations of BDE-47 and HBCDD (ng/g lw) in different tissue of herring. The boxes show the

range of two pooled samples of 25 fish each (1 male pool and 1 female pool) together with their mean value.

Only muscle tissue and the carcass were analysed for organobromine and chlorine compounds

to be able to calculate a whole fish concentration (appendix Table 8). The regression analysis

showed significant correlations for all compounds, except for β-HCH, between whole fish and

muscle tissue with high r2 values ranging from 0.69 to 0.99 (appendix Table 14). However,

the regression analysis was also carried out using the non-parametric Thiel slope estimator

because of the large effect of one individual on the data set. In this situation, this latter test is

more appropriate. (One of the individuals in the study was very lean causing high

concentration on a lipid weight basis, and hence had a great influence on the slope of the

regression line).

There are EQS values derived for HBCDD based on whole fish concentrations and for sum of

PBDEs and HCB based on muscle tissue concentrations. These substances are analysed

annually in muscle tissue only within the Swedish contaminant monitoring program and thus

a corresponding EQS value for muscle tissue is needed for HBCDD.

One of the aims of this study was to evaluate the hypothesis that lipid-soluble organic

contaminants are evenly distributed in the lipids of the fish and therefore that it would be

possible to use any tissue of the fish for analysis if the lipid content was considered. The

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28

results from the pooled samples showed similar concentrations expressed on a lipid-weight

basis in all organs except for brain tissue and the eyes. The t-tests that check for systematic

differences between whole body and muscle values were not statistically significant for a

majority of the substances. These results support the assumption that the concentration of the

organobromine and -chlorine compounds in this study were relatively evenly distributed (on a

lipid weight basis) in various tissues in herring. We therefore recommend using the muscle

tissue value for the whole fish threshold value for HBCDD as long as the lipid content is

considered.

Conclusion

The highest concentrations of mercury were found in muscle and liver while the eyes had the

lowest levels. For cadmium, kidney and liver had the highest concentrations, while most other

organs, except stomach/intestines, had very low concentrations. The highest concentrations

for lead were found in the skeleton and in the skin with subcutaneous fat. Eyes, gonads and

muscle tissue had very low levels. For a majority of the perfluorinated substances, including

PFOS, the highest concentrations were found in the liver and kidney. While for a few of the

long chained carboxylic acids (PFTeDA, and PFPeDA), highest levels were found in the

brain. The lowest concentrations for PFOS were found in the muscle tissue and in the skin

with subcutaneous fat. Concentrations of organo brominated and chlorinated compounds were

quite evenly distributed between different tissues with the exception of eyes and brain where

concentrations were clearly lower.

For mercury, the EQS of 20 ng/g ww in whole fish corresponded to 24 ng/g ww in muscle

when the ratio between muscle and whole fish was used. Since the concentration interval in

the studied herring did not cover concentrations close to the target value of 20 ng/g, and the

intercept had a great influence of the calculated muscle value the regression was considered

inappropriate to use.

For cadmium the QS of 0.16 µg/g ww whole fish was re-calculated using an equation and a

corresponding value in liver was then 12 µg/g dw. In addition, the limit value for cadmium in

fish of 0.05 µg/g ww muscle tissue from the EC foodstuff regulation was recalculated to a

liver concentration of 27.5 µg/g dw.

For lead the QS secondary poisoning of 1000 µg/kg ww whole fish was recalculated using an

equation and it gave a value of 19 µg/g dw in liver. Moreover, the limit value for lead in fish

of 0.3 µg/g ww in muscle tissue from the EC foodstuff regulation was recalculated and

represented a liver concentration of 17.5 µg/g dw.

For PFOS a liver:muscle ratio was used to recalculate the EQS value of 9.1 ng/g ww in

muscle tissue. A corresponding liver value of 191 ng/g ww was derived. Furthermore, the

QSsec. pois. value for PFOS is set to 33 ng/g ww in whole fish tissue. The corresponding liver

value, calculated by the use of the equation from the regression of liver vs whole fish (208

ng/g ww) and from the ratio liver:whole fish (163 ng/g ww) were respectively higer an lower

compared to the liver value calculated from the EQS. This result suggest that both EQS

(based on protection of human health) and QSsec. pois. are at similar level of protection.

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29

For the majority of organochlorine and –bromine substances no significant differences

between whole body and muscle concentrations on a lipid-weight basis were found. This

supports the hypothesis that the concentration of the organochlorine and -bromine compounds

in this study were relatively evenly distributed in the lipids of the various tissues in the

herring. Our recommendation for HBCDD is thus to use the muscle concentration expressed

on a lipid-weight basis as a proxy for the whole fish EQS .

References

Bevelhimer M. S., Beauchamp J. J., Sample B. E., Southworth G.R. (1997). Estimation of

Whole-fish Contaminant Concentration from Fish Fillet Data. ES/ER/TM-202, Oak Ridge

Netional Laboratory, Oak Ridge, TN, USA.

Bignert A., Danielsson S., Ek C., Faxneld S., Nyberg E. (2017) Comments concerning the

National Swedish Contaminant Monitoring Programme in Marine Biota (2016 years data),

2017. Report nr 10:2017: 340 pp.

Boalt E., Miller A., Dahlgren H. (2014) Distribution of cadmium, mercury, and lead in

different body parts of Baltic herring (Clupea harengus) and perch (Perca fluviatilis):

Implications for environmental assessments. Marine Pollution Bulletin 78:130-136

Danielsson S., Faxneld S., Nyberg E., Vasileiou M., Bignert A. (2014) Contaminants in fish

from potentially polluted sites along the Swedish coast with the national monitoring

programme as reference. NRM Report nr 8:2014. 154 pp.

EC (2005). Environmental Quality Standards (EQS), Substance Data Sheet, Priority

Substance No. 6, Cadmium and its Compounds, CAS-No. 7440-43-9. Final version, Brussels,

Belgium, 31 July 2005.

EC (2014). Common Implementation Strategy for the Water Framework Directive

(2000/60/EC) - Guidance Document No. 32 on biota monitoring (the implementation of

EQSbiota) under the water framework directive. The European Commission.

Eriksson U., Häggberg L., Kärsrud A-S., Litzén K., Asplund L. (1997). Analytical method for

determination of chlorinated organic contaminants in biological matrices. Institute of

Applied Environmental Research, Stockholm University, ITM Report no.59 (1997).

The European Union 2013. Directive 2013/39/EU of the European parliament and of the

council of 12 August 2013 amending Directives 2000/60/EC and 2008/105/EC as regards

priority substances in the field of water policy.

Faxneld S., Danielsson S., Nyberg E. (2014) Distribution of PFAS in liver and muscle of

herring, perch, cod, eelpout, arctic char, and pike from limnic and marine environments in

Sweden, Report nr 9:2014. Swedish Museum of Natural History.

Page 30: Distribution and conversions of metal- and POP ...nrm.diva-portal.org/smash/get/diva2:1273434/FULLTEXT01.pdfChemists: Hg; Ann-Marie Johansson, metals; Pär Hjelmquist, Jan Mechedal

30

Faxneld S., Danielsson S., Nyberg E., Bignert A. (2015) Conversion factors for metals

between liver, muscle and wholebody in perch. Report nr 1:2015. Swedish Museum of

Natural History.

Jensen S. (1983) Analytical methods for measuring organochlorines and methyl mercury by

gas chromatography. FAO Fisheries Technical Paper No 212:21-33

OJEC No. L364 20.12.2006 (2006). Commission regulation (EC) No 1881/2006 of 19

December 2006 setting maximum levels for certain contaminants in foodstuffs, Official

Journal of the European Union.

OSPAR Commission (2014) Levels and trends in marine contaminants and their biological

effects – CEMP Assessment Report 2013.

Sellström U., Kierkegaard A. et al. (1998) Polybrominated diphenyl ethers and

hexabromocyclododecane in sediment and fish from a Swedish river. Environmental

Toxicology and Chemistry 17:1065-1072

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Appendix

Table 1. Concentrations of metals (µg/g dry weight, except Hg ng/g wet weight) in various organs of herring. One pool of female fish (F) and one

pool of male fish (M) with 25 individuals in each pool.

Tissue P

aram

ete

r

Sam

ple

Mu

scle

, ski

n, s

ub

.

fat

Mu

scle

Skin

, su

b. f

at

Sto

mac

h/i

nte

stin

es

Go

nad

Gill

s

Eye

s

Live

r

Kid

ne

y

Bra

in

Ske

leto

n

Re

sid

ue

Wh

ole

fis

h

Weight organ (g) F 13.4 10.8 1.2 2.5 0.9 1.3 0.9 0.7 0.3 0.2 0.1 5.5 37.8

Weight organ (g) M 12.2 10.1 1.3 2.0 2.1 1.2 0.9 0.6 0.3 0.2 0.2 5.3 36.1

Total weight (g) F 39.8 39.8 39.8 39.8 39.8 39.8 39.8 39.8 39.8 39.8 39.8 39.8 -

Total weight (g) M 37.9 37.9 37.9 37.9 37.9 37.9 37.9 37.9 37.9 37.9 37.9 37.9 -

Dry % F 29.6 25.7 52.5 46.5 27.0 24.0 13.4 32.9 31.2 23.3 92.9 29.9 30.0

Dry % M 30.6 26.7 60.3 44.0 27.6 26.0 14.7 34.3 32.4 25.5 67.5 37.9 32.0

Hg F 188.5 161.8 37.5 63.8 37.9 53.2 19.8 157.1 87.2 40.6 30.4 62.0 134.6

Hg M 200.8 138.7 38.2 55.1 37.9 41.5 14.5 112.5 65.9 31.6 28.3 71.4 127.5

Cd F <LOQ <LOQ 0.004 0.133 0.015 0.011 0.002 0.228 0.694 0.002 0.012 0.006 0.021

Cd M <LOQ <LOQ 0.004 0.148 0.006 0.012 0.002 0.267 0.758 0.002 0.009 0.008 0.021

Pb F 0.010 0.004 0.066 0.134 0.006 0.095 0.004 0.067 0.059 <LOQ 0.398 0.060 0.031

Pb M 0.008 <LOQ 0.466 0.149 0.004 0.088 0.006 0.076 0.056 <LOQ 0.253 0.059 0.043

Ag F <LOQ <LOQ <LOQ 0.048 0.008 0.004 0.003 0.026 0.022 0.004 <LOQ 0.002 0.005

Ag M <LOQ <LOQ <LOQ 0.047 0.002 0.004 0.003 0.028 0.023 0.007 <LOQ 0.003 0.005

Al F <LOQ <LOQ 1.5 10.5 <LOQ 5.4 <LOQ <LOQ <LOQ <LOQ <LOQ 0.9 1.3

Al M <LOQ <LOQ 1.2 9.6 <LOQ 3.3 0.4 <LOQ <LOQ <LOQ <LOQ 0.8 1.1

As F 0.424 0.234 1.413 1.350 0.371 0.568 0.254 0.340 0.602 0.195 0.491 0.624 0.491

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32

As M 0.483 0.303 1.925 1.424 0.406 0.668 0.228 0.397 0.741 0.287 0.448 0.945 0.600

Cr F <LOQ <LOQ <LOQ 0.038 <LOQ 0.022 <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ -

Cr M <LOQ <LOQ <LOQ 0.035 <LOQ 0.017 <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ -

Cu F 0.521 0.515 0.438 1.483 0.958 0.526 0.354 3.001 1.248 0.898 0.704 0.603 0.654

Cu M 0.481 0.603 0.478 1.558 0.673 0.526 0.337 2.885 1.321 1.040 0.758 0.735 0.667

Ni F 0.228 <LOQ <LOQ 0.100 <LOQ 0.018 <LOQ <LOQ 0.112 <LOQ <LOQ <LOQ 0.095

Ni M <LOQ <LOQ <LOQ 0.102 <LOQ 0.019 <LOQ <LOQ 0.094 <LOQ <LOQ <LOQ 0.018

Se F 0.119 0.133 0.201 0.670 0.738 0.382 0.323 1.252 1.116 0.341 0.290 0.185 0.231

Se M 0.121 0.121 0.183 0.734 0.339 0.368 0.403 1.303 1.162 0.352 0.167 0.236 0.228

Sn F <LOQ <LOQ <LOQ 0.021 <LOQ 0.018 0.008 0.034 0.020 0.024 <LOQ 0.018 0.014

Sn M <LOQ <LOQ <LOQ 0.026 0.033 <LOQ 0.010 0.036 0.020 0.025 <LOQ <LOQ 0.015

Zn F 25.2 4.8 113.3 17.4 35.7 17.5 155.3 21.0 18.3 10.1 70.2 32.4 25.7

Zn M 25.7 4.8 107.8 19.4 15.1 19.3 153.4 20.8 20.0 16.6 53.2 42.2 27.2

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33

Table 2. Concentrations of metals expressed as percent of maximum value for each chemical and each pool in the different organs. One pool of

female fish (F) and one pool of male fish (M) with 25 individuals in each pool.

Par

ame

ter

Sam

ple

Mu

scle

, ski

n, s

ub

. fat

Mu

scle

Skin

, su

b. f

at

Sto

mac

h/i

nte

stin

es

Go

nad

Gill

s

Eye

s

Live

r

Kid

ne

y

Bra

in

Skel

eto

n

Re

sid

ue

Wh

ole

bo

dy

Weight F 35 29 3.2 6.6 2.4 3.4 2.3 1.9 0.74 0.47 0.37 15 100

Weight M 34 28 3.7 5.5 5.7 3.2 2.4 1.5 0.7 0.5 0.6 15 100

Dry % F 32 28 56 50 29 26 14 35 34 25 100 32 32

Dry % M 45 40 89 65 41 39 22 51 48 38 100 56 47

Hg F 100 86 20 34 20 28 10 83 46 22 16 33 71

Hg M 100 69 19 27 19 21 7.2 56 33 16 14 36 64

Cd F <LOQ <LOQ 0.6 19 2.1 1.6 0.3 33 100 0.3 1.7 0.9 3.0

Cd M <LOQ <LOQ 0.5 20 0.7 1.6 0.3 35 100 0.3 1.1 1.0 2.7

Pb F 2.6 1.0 16.6 34 1.6 24 1.1 17 15 <LOQ 100 15 7.9

Pb M 1.6 <LOQ 100 32 0.9 19 1.2 16 12 <LOQ 54 13 9.3

Ag F <LOQ <LOQ <LOQ 100 16 9 5 55 46 8.3 <LOQ 5 11

Ag M <LOQ <LOQ <LOQ 100 4.2 8.4 6.0 61 49 16 <LOQ 6 10

Al F <LOQ <LOQ 15 100 <LOQ 52 <LOQ <LOQ <LOQ <LOQ <LOQ 9 13

Al M <LOQ <LOQ 13 100 <LOQ 34 4 <LOQ <LOQ <LOQ <LOQ 9 11

As F 30 17 100 96 26 40 18 24 43 14 35 44 35

As M 25 16 100 74 21 35 12 21 38 15 23 49 31

Cr F <LOQ <LOQ <LOQ 100 <LOQ 59 <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ .

Cr M <LOQ <LOQ <LOQ 100 <LOQ 48 <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ -

Cu F 17 17 15 49 32 18 12 100 42 30 23 20 22

Cu M 17 21 17 54 23 18 12 100 46 36 26 25 23

Ni F 100 <LOQ <LOQ 44 <LOQ 8 <LOQ <LOQ 49 <LOQ <LOQ <LOQ 42

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34

Ni M <LOQ <LOQ <LOQ 100 <LOQ 19 <LOQ <LOQ 91 <LOQ <LOQ <LOQ 18

Se F 10 11 16 53 59 31 26 100 89 27 23 15 18

Se M 9.3 9.3 14 56 26 28 31 100 89 27 13 18 18

Sn F <LOQ <LOQ <LOQ 62 <LOQ 52 24 100 60 70 <LOQ 53 42

Sn M <LOQ <LOQ <LOQ 72 93 <LOQ 26 100 57 71 <LOQ <LOQ 43

Zn F 16 3.1 73 11 23 11 100 14 12 6.5 45 21 17

Zn M 17 3.1 70 13 10 13 100 14 13 11 35 27 18

Table 3. Concentrations of metals (µg/g dry weight, except Hg ng/g wet weight) in liver, muscle, stomach/intestines and a calculated whole body.

Figures are geometric mean values and range in parentheses. Blank cells mean that the concentrations are below LOQ in more than 50% of the

individuals. N=12

Tissue

Liver Muscle Stomach/intestines Cal. Whole body

Dry % 34.8 (30˗43) 26 (24˗30) 38.9 (30˗48) 32.4 (30˗38)

Ag 0.0527 (0.028˗0.13) <LOQ 0.083 (0.011˗0.26) 0.011 (0.0053˗0.02)

Al <LOQ <LOQ 13.5 (0.99˗40) 2.41 (1.2˗4)

As 1.01 (0.46˗1.5) 1.07 (0.52˗1.7) 2.88 (1.6˗4.6) 1.8 (0.91˗2.7)

Cd 0.524 (0.12˗1.4) <LOQ 0.342 (0.14˗1.1) 0.0616 (0.028˗0.1)

Cr <LOQ <LOQ 0.0813 (0.03˗0.18) 0.0639 (0.038˗0.5)

Cu 8.1 (6.9˗11) 1.43 (1.1˗2) 3.5 (1.9˗7.2) 1.95 (1.5˗2.3)

Ni <LOQ <LOQ 0.179 (0.032˗0.58) 0.0541 (0.038˗0.09)

Pb 0.133 (0.038˗0.28) <LOQ 0.256 (0.089˗0.47) 0.0619 (0.042˗0.094)

Se 3.4 (2.4˗4.1) 0.472 (0.35˗0.59) 1.63 (1.2˗2.7) 0.681 (0.52˗0.82)

Sn 0.114 (0.079˗0.21) 0.0522 (0.038˗0.081) 0.068 (0.032˗0.11) 0.064 (0.04˗0.12)

Zn 57.6 (48˗70) 12.3 (8.6˗17) 40.6 (30˗71) 55.7 (30˗92)

Hg dw 350 (174˗856) 488 (196˗1130) 198 (97˗375) 325 (128˗694)

Hg ww 122 (75˗277.7) 127 (50˗277) 77.1 (41˗134) 105 (43˗213)

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35

Table 4. Concentrations of chlorinated pesticides, PCBs, PBDEs and HBCDD (ng/g lipid weight) in various herring organs. One pool of females (F)

and one pool of male fish (M) with 25 individuals in each pool.

Tissue

Par

ame

ter

Sam

ple

Mu

scle

, ski

n, s

ub

. fat

Mu

scle

Skin

, su

b. f

at

Sto

mac

h/i

nte

stin

es

Go

nad

Gill

s

Eye

s

Live

r

Kid

ne

y

Bra

in

Skel

eto

n

Re

sid

ue

Wh

ole

fis

h

Weight organ (g) F 13 11 1.2 2.5 0.89 1.3 0.86 0.72 0.28 0.18 0.14 5.5 38

Weight organ (g) M 12 10 1.3 2.0 2.05 1.2 0.88 0.55 0.27 0.17 0.20 5.3 36

Fat % F 8.8 4.8 28 30 7.88 7.9 1.2 12 12 14 - 14 10

Fat % M 9.7 5.2 43 25 8.21 8.5 1.3 13 12 13 - 16 11

BDE-47 F 14 14 16 17 14 17 7 15 14 2.7 - 17 15

BDE-47 M 12 14 16 17 13 14 7 15 16 3.4 - 15 14

BDE-99 F 3.4 3.3 3.8 4.4 3.9 4.1 1.7 3.8 3.4 0.74 - 4.3 3.8

BDE-99 M 2.7 3.4 3.6 5.0 3.9 3.8 1.7 3.7 4.1 1.2 - 4.0 3.6

BDE-100 F 2.2 2.2 2.4 2.5 2.2 3.0 1.3 2.3 2.3 0.5 - 3.0 2.4

BDE-100 M 1.7 2.1 2.3 2.8 2.2 2.4 1.2 2.2 2.5 0.7 - 2.5 2.2

BDE-153 F 0.3 0.3 0.4 0.4 0.3 0.4 <LOQ 0.4 0.3 <LOQ - 0.4 0.4

BDE-153 M 0.3 0.3 0.3 0.4 0.3 0.4 <LOQ 0.3 0.3 <LOQ - 0.4 0.3

BDE-154 F 0.4 0.4 0.4 0.4 0.3 0.6 <LOQ 0.4 0.4 <LOQ - 0.6 0.4

BDE-154 M 0.3 0.4 0.4 0.5 0.4 0.6 <LOQ 0.5 0.4 <LOQ - 0.5 0.4

HBCDD F 19 17 25 17 21 25 5 20 17 4 - 25 20

HBCDD M 20 21 27 20 22 25 8 17 23 7 - 25 22

CB-28 F 83 83 88 77 65 77 41 71 77 18 - 77 80

CB-28 M 82 83 91 77 64 75 38 74 89 24 - 73 79

CB-52 F 152 156 167 114 113 131 66 122 140 26 - 132 139

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36

CB-52 M 154 158 175 112 99 129 53 129 164 39 - 130 143

CB-101 F 322 321 344 323 288 357 203 299 339 71 - 343 326

CB-101 M 300 321 341 343 303 340 156 305 376 98 - 320 318

CB-118 F 223 220 241 233 204 270 148 219 253 49 - 270 236

CB-118 M 209 211 231 229 214 240 107 218 256 63 - 230 220

CB-138 F 340 330 353 328 267 342 187 275 313 63 - 337 332

CB-138 M 297 315 337 358 276 323 131 266 351 83 - 305 312

CB-153 F 428 426 458 438 393 540 285 410 464 98 - 511 449

CB-153 M 380 398 428 461 425 464 206 397 488 134 - 441 415

CB-180 F 123 119 129 115 98 168 76 111 123 25 - 152 127

CB-180 M 101 108 119 129 108 147 55 109 128 33 - 128 115

DDD F 287 280 316 284 256 323 140 286 299 51 - 302 290

DDD M 283 298 325 310 269 326 117 278 359 75 - 294 296

DDE F 210 214 229 221 192 253 141 206 240 43 - 251 222

DDE M 199 211 230 244 208 231 100 206 254 62 - 226 217

HCB F 11 11 12 11 13 12 8 12 12 3 - 12 12

HCB M 12 12 13 12 11 12 8 13 15 5 - 13 12

AHCH F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

AHCH M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

BHCH F 5.4 4.6 5.8 5.0 3.9 3.9 <LOQ 4.4 4.5 <LOQ - <LOQ 4.7

BHCH M 5.0 4.9 5.8 4.9 <LOQ 3.9 <LOQ 4.4 5.0 <LOQ - 4.4 4.8

Lindane F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

Lindane M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

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37

Table 5. Concentrations of chlorinated pesticides, PCBs, PBDEs and HBCDD expressed as percent of maximum value for each chemical and each

pool in the different herring organs, based on lipid weight. One pool of female fish (F) and one pool of male fish (M) with 25 individuals in each

pool.

Par

ame

ter

Sam

ple

Mu

scle

, ski

n, s

ub

. fat

Mu

scle

Skin

, su

b. f

at

Sto

mac

h

Go

nad

Gill

s

Eye

s

Live

r

Kid

ne

y

Bra

in

Skel

eto

n

Re

sid

ue

Wh

ole

fis

h

Weight F 35 29 3.2 6.6 2.4 3.4 2.3 1.9 0.74 0.47 0.37 15 100

Weight M 34 28 3.7 5.5 5.7 3.2 2.4 1.5 0.7 0.5 0.6 15 100

Fat % F 29 16 93 100 26 26 4 39 40 45 - 47 34

Fat % M 23 12 100 59 19 20 3 31 27 30 - 36 26

BDE-47 F 81 81 92 98 82 100 44 88 85 16 - 100 89

BDE-47 M 66 82 91 100 77 82 39 85 90 20 - 84 81

BDE-99 F 77 75 86 100 90 95 40 86 77 17 - 99 87

BDE-99 M 55 67 73 100 77 77 34 73 82 23 - 80 72

BDE-100 F 72 71 80 83 71 99 44 77 75 16 - 100 81

BDE-100 M 60 75 81 100 80 87 44 78 88 25 - 90 78

BDE-153 F 72 75 89 81 62 93 <LOQ 99 72 <LOQ - 100 82

BDE-153 M 61 75 76 100 64 90 <LOQ 73 76 <LOQ - 94 78

BDE-154 F 70 71 78 77 58 99 <LOQ 71 71 <LOQ - 100 78

BDE-154 M 55 73 77 95 71 100 <LOQ 84 81 <LOQ - 93 76

HBCDD F 77 70 99 69 84 100 22 79 71 16 - 100 81

HBCDD M 73 76 100 74 80 92 30 62 83 26 - 90 81

CB-28 F 94 94 100 87 74 88 46 80 88 21 - 88 91

CB-28 M 90 90 100 84 71 82 41 81 97 26 - 79 87

CB-52 F 91 94 100 69 68 79 40 74 84 16 - 79 84

CB-52 M 88 91 100 64 57 74 30 74 94 22 - 74 82

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38

CB-101 F 90 90 96 91 81 100 57 84 95 20 - 96 92

CB-101 M 80 86 91 91 81 91 42 81 100 26 - 85 85

CB-118 F 83 81 89 86 75 100 55 81 93 18 - 100 87

CB-118 M 82 82 90 90 83 94 42 85 100 24 - 90 86

CB-138 F 96 93 100 93 76 97 53 78 89 18 - 95 94

CB-138 M 83 88 94 100 77 90 37 74 98 23 - 85 87

CB-153 F 79 79 85 81 73 100 53 76 86 18 - 95 83

CB-153 M 78 82 88 94 87 95 42 81 100 28 - 90 85

CB-180 F 74 71 77 68 59 100 46 66 74 15 - 91 76

CB-180 M 69 74 81 88 74 100 37 74 87 23 - 87 78

DDD F 89 87 98 88 79 100 43 88 93 16 - 94 90

DDD M 79 83 91 86 75 91 33 78 100 21 - 82 82

DDE F 83 84 90 87 76 100 55 81 95 17 - 99 88

DDE M 78 83 90 96 82 91 39 81 100 24 - 89 85

HCB F 88 88 94 89 100 96 66 96 97 23 - 97 91

HCB M 81 80 85 82 74 84 54 91 100 32 - 85 82

AHCH F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

AHCH M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

BHCH F 94 79 100 85 67 68 <LOQ 75 77 <LOQ - <LOQ 81

BHCH M 85 84 100 85 66 <LOQ 75 86 <LOQ - 76 83

Lindane F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

Lindane M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

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39

Table 6. Concentrations of chlorinated pesticides, PCBs, PBDEs and HBCDD (ng/g wet weight) in various organs of herring. One pool of female

fish (F) and one pool of male fish (M) with 25 individuals in each pool.

Tissue

Par

ame

ter

Sam

ple

Mu

scle

, ski

n, s

ub

. fat

Mu

scle

Skin

, su

b. f

at

Sto

mac

h

Go

nad

Gill

s

Eye

s

Live

r

Kid

ne

y

Bra

in

Skel

eto

n

Re

sid

ue

Wh

ole

fis

h

Weight organ (g) F 13 11 1.2 2.5 0.89 1.3 0.86 0.72 0.28 0.18 0.14 5.5 38

Weight organ (g) M 12 10 1.3 2.0 2.05 1.2 0.88 0.55 0.27 0.17 0.20 5.3 36

Fat % F 8.8 4.8 28 30 7.88 7.9 1.2 12 12 14 - 14 10

Fat % M 9.7 5.2 43 25 8.21 8.5 1.3 13 12 13 - 16 11

BDE-47 F 1.2 0.65 4.4 5.0 1.09 1.3 0.09 1.8 1.8 0.37 - 2.4 1.6

BDE-47 M 1.1 0.74 6.8 4.4 1.10 1.2 0.09 2.0 1.8 0.43 - 2.3 1.6

BDE-99 F 0.30 0.16 1.1 1.3 0.31 0.33 0.02 0.45 0.42 0.10 - 0.62 0.39

BDE-99 M 0.27 0.17 1.5 1.3 0.32 0.33 0.02 0.48 0.47 0.15 - 0.62 0.40

BDE-100 F 0.19 0.10 0.69 0.77 0.17 0.24 0.02 0.28 0.28 0.07 - 0.43 0.25

BDE-100 M 0.16 0.11 0.96 0.70 0.18 0.21 0.02 0.29 0.28 0.09 - 0.39 0.24

BDE-153 F 0.027 0.015 0.11 0.11 0.02 0.03 <LOQ 0.05 0.04 <LOQ - 0.06 0.04

BDE-153 M 0.03 0.02 0.14 0.11 0.02 0.03 <LOQ 0.04 0.04 <LOQ - 0.06 0.04

BDE-154 F 0.03 0.02 0.12 0.13 0.03 0.04 <LOQ 0.05 0.05 <LOQ - 0.08 0.05

BDE-154 M 0.03 0.02 0.18 0.13 0.03 0.05 <LOQ 0.06 0.05 <LOQ - 0.08 0.05

HBCDD F 1.7 0.83 6.91 5.21 1.6 1.9 0.07 2.3 2.1 0.54 - 3.5 2.1

HBCDD M 1.9 1.1 12 5.1 1.8 2.2 0.11 2.2 2.6 0.89 - 3.8 2.5

CB-28 F 7.3 3.9 25 23 5.1 6.1 0.49 8.4 9.5 2.5 - 11 8

CB-28 M 7.9 4.3 39 19 5.3 6.4 0.49 9.8 10 3.0 - 11 9

CB-52 F 13 7.5 47 35 8.9 10 0.81 15 17 3.6 - 19 14

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40

CB-52 M 15 8.2 74 28 8.1 11 0.69 17 19 4.9 - 20 16

CB-101 F 28 15 97 98 23 28 2.5 36 42 9.7 - 49 34

CB-101 M 29 17 145 86 25 29 2.0 40 43 12 - 50 35

CB-118 F 20 11 68 71 16 21 1.8 26 31 6.7 - 39 24

CB-118 M 20 11 98 57 18 20 1.4 29 29 7.9 - 36 24

CB-138 F 30 16 99 100 21 27 2.3 33 38 8.6 - 48 34

CB-138 M 29 16 143 90 23 28 1.7 35 40 10 - 47 34

CB-153 F 38 20 129 133 31 42 3.5 49 57 13 - 73 47

CB-153 M 37 21 182 115 35 40 2.7 52 56 17 - 68 46

CB-180 F 11 5.7 37 35 7.8 13 0.93 13 15 3.4 - 22 13

CB-180 M 9.8 5.6 50 32 8.9 13 0.71 14 15 4.2 - 20 13

DDD F 25 13 89 86 20 25 1.7 34 37 7.0 - 43 30

DDD M 27 15 138 78 22 28 1.5 37 41 9.5 - 46 33

DDE F 18 10 65 67 15 20 1.7 25 30 5.9 - 36 23

DDE M 19 11 98 61 17 20 1.3 27 29 7.8 - 35 24

HCB F 0.98 0.54 3.4 3.5 1.0 0.97 0.10 1.5 1.5 0.40 - 1.8 1.2

HCB M 1.2 0.61 5.4 3.05 0.90 1.1 0.10 1.8 1.7 0.59 - 2.0 1.3

AHCH F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

AHCH M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

BHCH F 0.48 0.22 1.6 1.5 0.31 0.31 <LOQ 0.52 0.55 <LOQ - <LOQ 0.49

BHCH M 0.48 0.25 2.5 1.2 <LOQ 0.33 <LOQ 0.57 0.57 <LOQ - 0.68 0.53

Lindane F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

Lindane M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

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41

Table 7. Concentrations of chlorinated pesticides, PCBs, PBDEs and HBCDD expressed as percent of maximum value for each chemical and each

pool in the different organs of herring, based on wet weight. One pool of female fish (F) and one pool of male fish (M) with 25 individuals in each

pool.

Par

ame

ter

Sam

ple

Mu

scle

, ski

n, s

ub

. fat

Mu

scle

Skin

, su

b. f

at

Sto

mac

h

Go

nad

Gill

s

Eye

s

Live

r

Kid

ne

y

Bra

in

Skel

eto

n

Re

sid

ue

Wh

ole

fis

h

Weight F 35 29 3.2 6.6 2.4 3.4 2.3 1.9 0.74 0.47 0.37 15 100

Weight M 34 28 3.7 5.5 5.7 3.2 2.4 1.5 0.7 0.5 0.6 15 100

Fat % F 29 16 93 100 26 26 4 39 40 45 - 47 34

Fat % M 23 12 100 59 19 20 3 31 27 30 - 36 26

BDE-47 F 24 13 87 100 22 26 2 35 35 7 - 48 31

BDE-47 M 16 11 100 64 16 18 1 29 26 6 - 34 23

BDE-99 F 22 12 80 100 23 25 2 34 31 8 - 46 30

BDE-99 M 17 11 100 81 21 21 1 31 31 9 - 40 26

BDE-100 F 25 13 89 100 22 31 2 36 36 9 - 57 33

BDE-100 M 17 11 100 73 19 22 2 30 29 9 - 41 25

BDE-153 F 25 14 100 98 20 29 <LOQ 47 35 <LOQ - 57 34

BDE-153 M 18 12 100 77 16 24 <LOQ 30 27 <LOQ - 45 26

BDE-154 F 26 15 94 100 20 33 <LOQ 36 37 <LOQ - 61 35

BDE-154 M 16 12 100 73 18 26 <LOQ 34 29 <LOQ - 44 26

HBCDD F 24 12 100 75 24 28 1 34 31 8 - 51 30

HBCDD M 17 9 100 44 15 19 1 19 22 8 - 33 21

CB-28 F 29 16 100 94 21 24 2 34 39 10 - 45 33

CB-28 M 20 11 100 49 14 16 1 25 26 8 - 29 22

CB-52 F 28 16 100 74 19 22 2 31 37 8 - 40 31

CB-52 M 20 11 100 38 11 15 1 23 25 7 - 27 21

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42

CB-101 F 29 16 99 100 23 29 3 36 42 10 - 50 34

CB-101 M 20 11 100 59 17 20 1 28 30 8 - 34 24

CB-118 F 28 15 96 100 23 30 3 37 44 9 - 55 34

CB-118 M 21 11 100 59 18 21 1 29 30 8 - 36 25

CB-138 F 30 16 100 100 21 27 2 33 39 9 - 48 34

CB-138 M 20 11 100 62 16 19 1 24 28 7 - 33 24

CB-153 F 28 15 97 100 23 32 3 37 43 10 - 55 35

CB-153 M 20 11 100 63 19 22 1 29 31 9 - 38 25

CB-180 F 30 16 100 95 21 36 3 36 42 9 - 60 36

CB-180 M 19 11 100 64 18 25 1 29 29 8 - 39 25

DDD F 28 15 100 97 23 28 2 38 41 8 - 48 34

DDD M 20 11 100 56 16 20 1 26 30 7 - 33 24

DDE F 27 15 96 100 22 30 3 37 44 9 - 53 34

DDE M 20 11 100 62 17 20 1 28 30 8 - 36 24

HCB F 28 16 98 100 29 28 3 42 44 12 - 51 35

HCB M 22 11 100 57 17 20 2 33 32 11 - 37 25

AHCH F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

AHCH M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

BHCH F 29 13 100 92 19 19 <LOQ 32 34 <LOQ - <LOQ 30

BHCH M 19 10 100 50 <LOQ 13 <LOQ 23 23 <LOQ - 28 21

Lindane F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

Lindane M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

Page 43: Distribution and conversions of metal- and POP ...nrm.diva-portal.org/smash/get/diva2:1273434/FULLTEXT01.pdfChemists: Hg; Ann-Marie Johansson, metals; Pär Hjelmquist, Jan Mechedal

43

Table 8. Concentrations of chlorinated pesticides, PCBs, PBDEs and HBCDD in muscle and a calculated whole body. The table shows both values

expressed as ng/g wet weight (ww) and ng/g lipid weight (lw). Figures are geometric mean values and range in parentheses. Blank cells mean that

the concentrations are below LOQ in more than 50% of the individuals. N=12

Muscle( ng/g ww) Calc. whole body (ng/g ww) Muscle( ng/g lw) Calc. whole body (ng/g lw)

Fat % 6.23 (2.3˗10) 13.5 (6.7˗17) 6.23 (2.3˗9.96) 13.5 (6.7˗17)

BDE-47 0.702 (0.41˗2.1) 1.79 (0.89˗4.6) 11.3 (4.1˗92) 13.2 (5.2˗69)

BDE-99 0.183 (0.13˗0.28) 0.487 (0.26˗0.71) 2.93 (1.5˗7.9) 3.61 (1.9˗6.2)

BDE-100 0.113 (0.061˗0.42) 0.303 (0.14˗0.92) 1.81 (0.61˗18) 2.25 (0.82˗14)

BDE-153 0.0172 (0.011˗0.03) 0.0402 (0.02˗0.063) 0.276 (0.16˗0.93) 0.298 (0.15˗0.72)

BDE-154 0.0229 (0.013˗0.045) 0.0602 (0.027˗0.097) 0.368 (0.16˗1.9) 0.446 (0.16˗1.4)

HBCDD 0.952 (0.67˗2.3) 2.48 (1.6˗5.3) 15.3 (6.8˗99) 18.3 (9.1˗79)

HCB 0.765 (0.52˗0.99) 1.56 (1.1˗2) 12.3 (8.9˗29) 11.5 (9.1˗17)

AHCH <LOQ <LOQ <LOQ -

BHCH 0.237 (0.12˗0.45) 0.5 (0.17˗0.85) 3.8 (2.5˗5.3) 3.7 (2.5˗5.1)

Lindane <LOQ <LOQ <LOQ -

DDE 13.1 (7.6˗30) 29.5 (20˗62) 210 (108˗1299) 219 (119˗936)

DDD 16.5 (11˗25) 37.2 (26˗55) 264 (161˗933) 276 (176˗642)

DDT <LOQ <LOQ <LOQ -

CB-28 4.41 (3.6˗5.3) 10.6 (7.7˗16) 70.8 (45˗168) 78.2 (50˗124)

CB-52 7.05 (5.1˗9.8) 19.2 (13˗27) 113 (69˗384) 142 (83˗320)

CB-101 18.8 (12˗41) 41.8 (28˗83) 302 (154˗1757) 310 (160˗1252)

CB-118 13 (7.9˗30) 28.7 (18˗61) 208 (96˗1283) 212 (103˗911)

CB-153 25.6 (15˗67) 57.1 (34˗138) 410 (198˗2917) 423 (197˗2078)

CB-138 16.8 (10˗45) 42.9 (25˗102) 270 (122˗1965) 318 (146˗1526)

CB-180 7.24 (4.9˗21) 16.1 (9.5˗39) 116 (54˗906) 119 (55˗584)

Page 44: Distribution and conversions of metal- and POP ...nrm.diva-portal.org/smash/get/diva2:1273434/FULLTEXT01.pdfChemists: Hg; Ann-Marie Johansson, metals; Pär Hjelmquist, Jan Mechedal

44

Table 9. Concentrations of per- and polyfluoroalkyl substances (ng/g wet weight) in various organs of herring. One pool of female fish (F) and one

pool of male fish (M) with 25 individuals in each pool. Tissue

Par

ame

ter

Par

ame

ter

Sam

ple

Mu

scle

, ski

n,

sub

. fat

Mu

scle

Skin

, su

b. f

at

Sto

mac

h/

inte

stin

es

Go

nad

Gill

s

Eyes

Live

r

Kid

ne

y

Bra

in

Ske

leto

n

Re

sid

ue

Wh

ole

fis

h

Weight organ (g) F 13 11 1.2 2.5 0.9 1.3 0.86 0.72 0.28 0.18 0.14 5.5 38 Weight organ (g) M 12 10 1.3 2.0 2.1 1.2 0.88 0.55 0.27 0.17 0.20 5.3 36 Sulfonates and their precursors PFBS Perfluorobutane sulfonate F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - PFBS Perfluorobutane sulfonate M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - Br-PFHxS Branched perfluorohexane sulfonate F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - Br-PFHxS Branched perfluorohexane sulfonate M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - L-PFHxS Linear perfluorohexane sulfonate F <LOQ <LOQ <LOQ 0.13 0.15 <LOQ <LOQ 0.30 0.19 <LOQ 0.11 0.05 L-PFHxS Linear perfluorohexane sulfonate M <LOQ <LOQ <LOQ 0.12 <LOQ <LOQ <LOQ 0.24 0.22 <LOQ 0.11 0.05 Br-PFOS Branched perfluorooctane sulfonate F 0.074 0.053 0.20 0.47 0.51 0.41 0.21 0.99 0.77 0.26 0.52 0.21 Br-PFOS Branched perfluorooctane sulfonate M 0.13 0.055 0.20 0.36 0.33 0.411 0.13 0.91 0.80 0.26 0.48 0.21 L-PFOS Linear perfluorooctane sulfonate F 2.0 1.3 5.1 10 14 11.10 5.9 27 22 9.4 14 5.5 L-PFOS Linear perfluorooctane sulfonate M 2.6 1.5 6.0 8.0 11 8.8 1.4 24 22 10 13 5.4 ∑PFOS Perfluorooctane sulfonate F 2.1 1.4 5.3 10.6 14.1 11.5 6.2 28.2 22.3 9.7 14.2 5.7 ∑PFOS Perfluorooctane sulfonate M 2.8 1.6 6.2 8.3 11.3 9.2 1.6 25.2 22.7 10.3 13.5 5.6 Br-PFDS Branched perfluorodecane sulfonate F <LOQ <LOQ <LOQ 0.041 0.040 <LOQ <LOQ 0.081 0.064 <LOQ <LOQ 0.015 Br-PFDS Branched perfluorodecane sulfonate M <LOQ <LOQ <LOQ 0.054 <LOQ <LOQ <LOQ 0.089 0.076 <LOQ 0.038 0.016 L-PFDS Linear perfluorodecane sulfonate F <LOQ <LOQ 0.05 0.08 0.05 0.11 0.05 0.16 0.18 0.19 0.13 0.04 L-PFDS Linear perfluorodecane sulfonate M <LOQ <LOQ 0.07 0.07 0.09 <LOQ <LOQ 0.18 0.20 0.13 0.08 0.03

Br-FOSA Branched perfluorooctanesulfonamide F <LOQ <LOQ <LOQ 0.42 0.66 1.21 0.26 1.65 1.64 <LOQ 1.17 0.32

Br-FOSA Branched perfluorooctanesulfonamide M <LOQ <LOQ <LOQ 0.26 0.52 1.63 <LOQ 1.20 1.68 <LOQ 1.35 0.34

L-FOSA Linear perfluorooctanesulfonamide F 0.2 0.2 0.2 2.3 3.8 8.0 2.2 9.6 12.6 2.6 7.3 2.0 L-FOSA Linear perfluorooctanesulfonamide M 0.2 0.2 0.4 1.5 2.7 10.3 <LOQ 7.5 12.4 2.9 7.4 2.0 ∑FOSA perfluorooctanesulfonamide F 0.21 0.18 0.25 2.7 4.5 9.2 2.4 11 14 2.8 8.5 2.4

∑FOSA perfluorooctanesulfonamide M 0.25 0.21 0.40 1.8 3.2 12 0.044 8.7 14 3.2 8.7 2.4

Carboxylic acids PFHxA Perfluorohexanoate F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - PFHxA Perfluorohexanoate M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - PFHpA Perfluoroheptanoate F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ -

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45

PFHpA Perfluoroheptanoate M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - Br-PFOA Branched perfluoroctanoate F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - Br-PFOA Branched perfluoroctanoate M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - L-PFOA Linear perfluorooctanoate F <LOQ <LOQ 0.09 0.35 0.21 0.14 0.07 0.36 0.35 <LOQ 0.19 0.088 L-PFOA Linear perfluorooctanoate M <LOQ <LOQ 0.12 0.33 0.14 0.17 0.09 0.41 0.47 <LOQ 0.23 0.10 PFNA Perfluorononanoate F 0.076 <LOQ 0.21 0.65 0.45 0.38 0.19 0.97 0.94 <LOQ 0.52 0.22 PFNA Perfluorononanoate M 0.10 0.055 0.26 0.67 0.34 0.37 <LOQ 0.83 1.04 0.27 0.52 0.23 PFDA Perfluorodecanoate F 0.096 0.081 0.34 0.74 0.75 0.63 0.33 1.4 1.5 0.24 0.80 0.32 PFDA Perfluorodecanoate M 0.14 0.076 0.40 0.72 0.53 0.63 <LOQ 1.2 1.4 0.28 0.80 0.32 PFUnDA Perfluorundecanoate F 0.080 0.074 0.28 0.45 0.61 0.49 0.29 0.94 1.1 0.28 0.61 0.24 PFUnDA Perfluorundecanoate M 0.11 0.080 0.28 0.43 0.43 0.36 <LOQ 0.86 1.1 0.32 0.56 0.23 PFDoDA Perfluorododecanoate F 0.18 0.12 0.50 0.83 0.96 0.93 0.44 1.8 1.7 0.70 1.06 0.44 PFDoDA Perfluorododecanoate M 0.38 0.11 0.54 0.61 0.90 1.20 <LOQ 1.5 1.9 0.72 1.00 0.49 PFTrDA Perfluorotridecanoate F 0.065 0.048 0.44 0.39 0.16 0.57 0.18 0.68 1.2 0.85 0.50 0.20 PFTrDA Perfluorotridecanoate M <LOQ <LOQ 0.41 0.36 0.39 <LOQ <LOQ 0.63 1.4 0.93 0.39 0.15 PFTeDA Perfluorotetradecanoate F <LOQ <LOQ 0.50 0.26 <LOQ 0.34 0.10 0.35 1.3 1.5 0.32 0.14 PFTeDA Perfluorotetradecanoate M <LOQ <LOQ 0.41 0.28 0.10 <LOQ <LOQ 0.28 1.3 1.6 0.31 0.12 PFPeDA Perfluoropentadecanoate F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ 0.15 0.54 <LOQ - PFPeDA Perfluoropentadecanoate M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ 0.61 <LOQ - PFHxDA Perfluorohexadecanoate F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - PFHxDA Perfluorohexadecanoate M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - PFODA Perfluorooctadecanoate F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - PFODA Perfluorooctadecanoate M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ -

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46

Table 10. Concentrations of per- and polyfluoroalkyl substances expressed as percent of maximum value for each chemical and each pool in the

different organs of herring, based on wet weight. One pool of female fish (F) and one pool of male fish (M) with 25 individuals in each pool.

Par

ame

ter

Sam

ple

Mu

scle

, ski

n, s

ub

. fat

Mu

scle

Skin

, su

b. f

at

Sto

mac

h/i

nte

stin

es

Go

nad

Gill

s

Eye

s

Live

r

Kid

ne

y

Bra

in

Skel

eto

n

Re

sid

ue

Wh

ole

fis

h

Weight F 35 29 3.2 6.6 2.4 3.4 2.3 1.9 0.74 0.47 0.37 15 100

Weight M 34 28 3.7 5.5 5.7 3.2 2.4 1.5 0.7 0.5 0.6 15 100

PFBS F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

PFBS M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

Br-PFHxS F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

Br-PFHxS M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

L-PFHxS F <LOQ <LOQ <LOQ 45 50 <LOQ <LOQ 100 64 <LOQ - 37 18

L-PFHxS M <LOQ <LOQ <LOQ 52 <LOQ <LOQ <LOQ 100 92 <LOQ - 44 19

Br-PFOS F 7.5 5.3 20 48 51 42 21 100 78 26 - 52 21

Br-PFOS M 15 6.1 22 40 36 45 15 100 88 28 - 53 24

L-PFOS F 7.5 4.8 19 37 50 41 22 100 79 35 - 50 20

L-PFOS M 11 6.4 25 33 45 36 6 100 90 41 - 53 22

Br-PFDS F <LOQ <LOQ <LOQ 51 50 <LOQ <LOQ 100 79 <LOQ - <LOQ 19

Br-PFDS M <LOQ <LOQ <LOQ 60 <LOQ <LOQ 100 85 <LOQ - 42 18

L-PFDS F <LOQ <LOQ 28 44 26 60 25 85 97 100 - 69 23

L-PFDS M <LOQ <LOQ 33 33 42 <LOQ <LOQ 90 100 64 - 38 16

Br-FOSA F <LOQ <LOQ <LOQ 25 40 73 16 100 99 <LOQ - 71 19

Br-FOSA M <LOQ <LOQ <LOQ 15 31 97 <LOQ 71 100 <LOQ - 80 20

L-FOSA F 1.5 1.2 1.8 18 30 63 17 76 100 20 - 58 16

L-FOSA M 1.8 1.5 3.0 12 21 83 <LOQ 60 100 23 - 59 16

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47

PFHxA F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

PFHxA M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

PFHpA F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

PFHpA M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

Br-PFOA F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

Br-PFOA M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

L-PFOA F <LOQ <LOQ 26 98 58 39 18 100 98 <LOQ - 52 24

L-PFOA M <LOQ <LOQ 26 70 31 36 19 87 100 <LOQ - 49 21

PFNA F 7.9 <LOQ 22 67 46 39 20 100 97 <LOQ - 53 22

PFNA M 10 5.3 25 64 33 36 <LOQ 79 100 26 - 50 22

PFDA F 6.3 5.3 22 49 49 42 21 95 100 16 - 52 21

PFDA M 10 5.4 28 50 37 44 <LOQ 88 100 20 - 57 23

PFUnDA F 7.3 6.7 25 41 56 45 27 85 100 26 - 55 22

PFUnDA M 10 7.1 25 38 38 32 <LOQ 76 100 28 - 50 21

PFDoDA F 10 6.4 27 46 53 52 24 100 94 39 - 58 24

PFDoDA M 20 5.7 29 33 48 64 <LOQ 78 100 38 - 53 26

PFTrDA F 5.2 3.9 35 32 13 46 15 55 100 69 - 41 16

PFTrDA M <LOQ <LOQ 29 26 28 <LOQ <LOQ 46 100 67 - 28 11

PFTeDA F <LOQ <LOQ 32 17 <LOQ 22 6.7 23 81 100 - 21 9.1

PFTeDA M <LOQ <LOQ 25 17 6.2 <LOQ <LOQ 17 83 100 - 19 7.4

PFPeDA F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ 29 100 - <LOQ -

PFPeDA M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ 100 - <LOQ -

PFHxDA F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

PFHxDA M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

PFODA F <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

PFODA M <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ - <LOQ -

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Table 11. Concentrations of per- and polyfluoroalkyl substances (ng/g wet weight) in liver, muscle, stomach/intestines and a calculated whole body.

Figures are geometric mean values and range in parentheses. Blank cells mean that the concentrations are below LOQ in more than 50% of the

individuals. N=12

Compound Tissue

Liver Muscle Stomach/intestines Cal. whole body

PFBS Perfluorobutane sulfonate <LOQ <LOQ <LOQ -

Br-PFHxS Branched perfluorohexane sulfonate <LOQ <LOQ <LOQ -

L-PFHxS Linear perfluorohexane sulfonate <LOQ <LOQ <LOQ -

Br-PFOS Branched perfluorooctane sulfonate 1.04 (0.57˗1.7) 0.056 (0.033˗0.1) 0.588 (0.38˗1.3) 0.198 (0.11˗0.31)

L-PFOS Linear perfluorooctane sulfonate 27.7 (12˗65) 1.42 (0.83˗2.4) 13 (7.4˗24) 5.7 (2˗11)

∑PFOS Perfluorooctane sulfonate 28.8 (12˗66) 1.48 (0.88˗2.4) 13.7 (8.1˗25) 5.9 (2.2˗11)

Br-PFDS Branched perfluorodecane sulfonate <LOQ <LOQ 0.0325 (0.007˗0.084) 0.0125 (0.007˗0.024)

L-PFDS Linear perfluorodecane sulfonate 0.232 (0.15˗0.53) <LOQ 0.115 (0.05˗0.19) 0.0581 (0.024˗0.1)

∑PFDS Perfluorodecane sulfonate 0.304 (0.18˗0.76) 0.0145 (0.014˗0.02) 0.151 (0.067˗0.27) 0.0713 (0.033˗0.12)

Br-FOSA Branched perfluorooctanesulfonamide 0.946 (0.47˗2.8) <LOQ 0.253 (0.13˗0.61) 0.293 (0.13˗0.53)

L-FOSA Linear perfluorooctanesulfonamide 7.34 (3.7˗14) 0.146 (0.065˗0.24) 1.89 (1.1˗2.7) 1.93 (1.3˗3)

∑FOSA Perfluorooctanesulfonamide 8.33 (4.2˗17) 0.17(0.087˗0.26) 2.15 (1.2˗3.1) 2.25 (1.7˗3.5)

Carboxylic acids PFHxA Perfluorohexanoate <LOQ <LOQ <LOQ -

PFHpA Perfluoroheptanoate <LOQ <LOQ <LOQ -

L-PFOA Linear perfluorooctanoate 0.358 (0.11˗0.63) <LOQ 0.514 (0.15˗1.01) 0.106 (0.03˗0.18)

Br-PFOA Branched perfluoroctanoate <LOQ <LOQ <LOQ -

PFNA Perfluorononanoate 0.805 (0.28˗1.7) <LOQ 0.92 (0.28˗1.6) 0.223 (0.051˗0.38)

PFDA Perfluorodecanoate 1.29 (0.42˗3.2) 0.0667 (0.031˗0.13) 1.13 (0.34˗2.4) 0.362 (0.09˗0.69)

PFUnDA Perfluorundecanoate 1.01 (0.5˗2.3) 0.0568 (0.024˗0.13) 0.649 (0.3˗1.2) 0.269 (0.092˗0.52)

PFDoDA Perfluorododecanoate 1.75 (1˗3.6) 0.117 (0.084˗0.24) 1.07 (0.7˗1.8) 0.491 (0.23˗0.86)

PFTrDA Perfluorotridecanoate 0.898 (0.51˗1.7) <LOQ 0.548 (0.29˗0.81) 0.242 (0.15˗0.42)

PFTeDA Perfluorotetradecanoate 1.05 (0.71˗1.9) <LOQ 0.498 (0.057˗1) 0.172 (0.066˗0.35)

PFPeDA Perfluoropentadecanoate <LOQ <LOQ 0.0794 (0.021˗0.27) 0.029 (0.023˗0.041)

PFHxDA Perfluorohexadecanoate <LOQ <LOQ <LOQ -

PFODA Perfluorooctadecanoate <LOQ <LOQ <LOQ -

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Table 12. Results from regression analyses, paired t-test and ratio (ratio arranged to be >1) for metals analysed in individual samples of herring

muscle (M), liver (L), stomach/intestines (S), and whole fish (WB), based on concentrations expressed on a dry weight basis except for Hg which

was based on wet weight basis. Green colour denotes that there is a significant regression. No analysis was conducted for blank cells because of

many values below LOQ.

p(reg) r2 b () a () p(t-test) *ratio ()

Hg WB/L 0.00000 0.935 .747 (.609 ,.886) 15.6 (-3.99 ,35.2) 0.00682 L/WB 1.17 (1.04 - 1.29 )

WB/M 0.00000 0.989 .733 (.677 ,.789) 11.9 (3.57 ,20.2) 0.00028 M/WB 1.21 (1.16 - 1.25 )

M/L 0.00000 0.946 1.02 (.848 ,1.19) 5.05 (-19.2 ,29.3) 0.08468 M/L 1.05 (.965 - 1.14 )

L/S 0.02164 0.425 1.23 (.221 ,2.23) 30.0 (-57.6 ,118) 0.00267 L/S 1.63 (1.33 - 1.94 )

M/S 0.01004 0.501 1.40 (.414 ,2.38) 23.7 (-61.9 ,109) 0.00098 M/S 1.71 (1.39 - 2.02 )

WB/S 0.01182 0.485 1.01 (.278 ,1.75) 30.1 (-33.9 ,94.2) 0.00565 WB/S 1.42 (1.16 - 1.67 )

Cd WB/L 0.00238 0.620 .0490 (.0219 ,.0760) .0345 (.0150 ,.0541) 0.00015 L/WB 9.16 (6.91 - 11.4 )

WB/M 0.00000 WB/M 15.6 (10.2 - 21.1 )

M/L 0.00010 L/M 143 (76.8 - 209 )

L/S 0.59104 0.030 .258 (-.777 ,1.29) .532 (.0599 ,1.00) 0.06236 L/S 2.01 (1.10 - 2.93 )

M/S 0.00022 S/M 94.8 (51.9 - 138 )

WB/S 0.02075 0.429 .0608 (.0114 ,.110) .0417 (.0192 ,.0643) 0.00048 S/WB 6.11 (4.27 - 7.96 )

Pb WB/L 0.00020 0.764 .195 (.119 ,.272) .0346 (.0222 ,.0469) 0.00022 L/WB 2.26 (1.85 - 2.67 )

WB/M 0.00000 WB/M 6.58 (5.46 - 7.70 )

M/L 0.00002 L/M 15.2 (11.0 - 19.4 )

L/S 0.70180 0.015 .0613 (-.285 ,.408) .130 (.0196 ,.241) 0.00509 S/L 2.47 (1.40 - 3.54 )

M/S 0.00002 S/M 30.0 (21.2 - 38.9 )

WB/S 0.36919 0.081 .0316 (-.0432 ,.106) .0543 (.0304 ,.0782) 0.00009 S/WB 4.76 (3.23 - 6.29

Ag WB/L - 0.00017 L/WB 5.60 (3.63 - 7.58 )

WB/M 0.00026 WB/M 3.11 (2.29 - 3.93 )

M/L 0.00004 L/M 14.8 (9.73 - 19.9 )

L/S 0.70623 0.015 -.0454 (-.306 ,.215) .0632 (.0279 ,.0984) 0.04464 S/L 2.49 (.909 - 4.08 )

M/S 0.00045 S/M 29.5 (17.4 - 41.7 )

WB/S 0.000003 0.9 .0587 (.0449 ,.0725) .00533 (.00346 ,.00720) 0.00049 S/WB 8.43 (6.22 - 10.6 )

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p(reg) r2 b () a () p(t-test) *ratio ()

Al WB/L

WB/M

M/L

L/S 0.00063 S/L 13.9 (7.78 - 20.1 )

M/S 0.0006 S/M 19.9 (11.2 - 28.6 )

WB/S 0.00063 S/WB 7.28 (4.84 - 9.72 )

As WB/L 0.00096 0.68 1.3092 ( .677, 1.942) .485 ( -.211, 1.180) 0.00000 WB/L 1.81 (1.63 - 1.99 )

WB/M 0.00002 0.856 1.4477 ( 1.029, 1.866) .254 ( -.231, .738) 0.00000 WB/M 1.69 (1.58 - 1.80 )

M/L 0.00492 0.563 .7613 ( .289, 1.234) .311 ( -.208, .830) 0.37978 M/L 1.08 (.959 - 1.20 )

L/S 0.00143 0.655 .2691 ( .131, .407) .246 ( -.188, .679) 0.00000 S/L 2.90 (2.57 - 3.24 )

M/S 0.02790 0.398 .2128 ( .028, .397) .474 ( -.107, 1.055) 0.00000 S/M 2.77 (2.30 - 3.25 )

WB/S 0.00382 0.584 .4034 ( .163, .643) .652 ( -.104, 1.408) 0.00007 S/WB 1.63 (1.40 - 1.86 )

Cr WB/L

WB/M

M/L

L/S 0.00315 S/L 2.39 (1.58 - 3.20 )

M/S 0.3662 M/S 35.0 (-40.9 - 111 )

WB/S 0.99711 S/WB 1.74 (1.08 - 2.40 )

Cu WB/L 0.00615 0.545 .1659 ( .059, .273) .609 ( -.268, 1.487) 0.00000 L/WB 4.17 (3.95 - 4.38 )

WB/M 0.151 0.194 .3181 ( -.138, .774) 1.499 ( .822, 2.176) 0.00009 WB/M 1.39 (1.23 - 1.55 )

M/L 0.238 0.136 .1148 ( -.089, .319) .519 ( -1.157, 2.194) 0.00000 L/M 5.78 (5.09 - 6.47 )

L/S 0.832 0.005 .0445 ( -.410, .499) 7.988 ( 6.159, 9.816) 0.00000 L/S 2.47 (1.90 - 3.04 )

M/S 0.793 0.007 0.00042 S/M 2.70 (1.84 - 3.55 )

WB/S 0.0482 0.336 .0843 ( .001, .168) 1.646 ( 1.311, 1.982 0.00117 S/WB 1.89 (1.48 - 2.29 )

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p(reg) r2 b () a () p(t-test) *ratio ()

Ni WB/L

WB/M

M/L

L/S 0.00153 S/L 5.68 (3.14 - 8.21 )

M/S 0.00264 S/M 6.23 (3.38 - 9.09 )

WB/S 0.00186 S/WB 4.05 (2.57 - 5.52 )

Se WB/L 0.00744 0.528 .159 (.0531 ,.265) .143 (-.223 ,.510) 0.00000 L/WB 5.02 (4.64 - 5.40 )

WB/M 0.75583 0.01 .162 (-.965 ,1.29) .612 (.0706 ,1.15) 0.00006 WB/M 1.47 (1.27 - 1.68 )

M/L 0.93476 0.001 .00361 (-.0923 ,.100) .464 (.132 ,.795) 0.00000 L/M 7.34 (6.37 - 8.31 )

L/S 0.41973 0.066 .262 (-.432 ,.957) 2.99 (1.78 ,4.20) 0.00000 L/S 2.14 (1.82 - 2.46 )

M/S 0.39775 0.072 0.00000 S/M 3.65 (2.74 - 4.57 )

WB/S 0.16330 0.185 .0959 (-.0461 ,.238) .527 (.279 ,.775) 0.00001 S/WB 2.46 (2.09 - 2.84 )

Sn WB/L 0.659 0.02 .0848 (-.330, .500) .058 ( .005, .110) 0.00181 L/WB 1.95 (1.32 - 2.58 )

WB/M NS 0.04093 WB/M 1.27 (1.03 - 1.52 )

M/L 0.593 0.03 .0628 (-.190, .316) .046 ( .015, .078) 0.00016 L/M 2.33 (1.73 - 2.93 )

L/S NS 0.00075 L/S 1.76 (1.40 - 2.11 )

M/S NS 0.00600 S/M 1.36 (1.12 - 1.60 )

WB/S NS 0.65228 S/WB 1.14 (.883 - 1.39 )

Zn WB/L 0.00042 0.728 1.90 (1.08 ,2.73) -52.7 (-101 ,-4.75) 0.94199 L/WB 1.05 (.915 - 1.19 )

WB/M 0.14714 0.198 3.04 (-1.27 ,7.35) 19.7 (-35.1 ,74.5) 0.00000 WB/M 4.64 (4.00 - 5.28 )

M/L 0.15477 0.192 .143 (-.0640 ,.350) 4.23 (-7.86 ,16.3) 0.00000 L/M 4.73 (4.28 - 5.18 )

L/S 0.06752 0.296 .316 (-.0275 ,.660) 44.7 (29.8 ,59.7) 0.00019 L/S 1.45 (1.25 - 1.65 )

M/S 0.27068 0.12 .0657 (-.0598 ,.191) 9.77 (4.31 ,15.2) 0.00000 S/M 3.39 (2.84 - 3.95 )

WB/S 0.02114 0.427 .848 (.156 ,1.54) 22.2 (-7.84 ,52.3) 0.00079 WB/S 1.41 (1.19 - 1.64 )

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Table 13. Results from regression analyses, paired t-test and ratio (ratio arranged to be >1) for per- and polyfluoralkyl substances analysed in

individual samples of herring muscle (M), liver (L), stomach/intestines (S), and whole fish (WB), based on concentrations expressed on a wet weight

basis. Green colour denotes that there is a significant regression. No analysis was conducted for blank cells because of many values below LOQ.

p(reg) r2 b () a () p(t-test) ratio ()

PFHxA all below <LOQ

PFHpA all below <LOQ

L-PFOA WB/L 0.000023 0.846 .258 (.180 ,.335) .0144 (-.0180 ,.0468) 0.00000 L/WB 3.42 (3.05 - 3.79 )

WB/M 0.00001 WB/M 6.13 (4.48 - 7.78 )

M/L 0.00000 L/M 20.6 (15.2 - 26.0 )

L/S 0.00858 0.515 .474 (.150 ,.798) .124 (-.0722 ,.321) 0.00345 S/L 1.50 (1.22 - 1.77 )

M/S 0.00001 S/M 30.1 (21.5 - 38.8 )

WB/S 0.00244 0.618 .145 (.0648 ,.226) .0333 (-.0156 ,.0822) 0.00001 S/WB 4.97 (4.26 - 5.67 )

Br-PFOA all below <LOQ

PFNA WB/L 0.000518 0.716 .194 (.108 ,.280) .0727 (-.00940 ,.155) 0.00002 L/WB 3.72 (3.14 - 4.30 )

WB/M 0.285 0.113 1.23 (-1.20 ,3.67) .195 (.0841 ,.306) 0.00000 WB/M 7.38 (5.00 - 9.76 )

M/L 0.251 0.129 .0224 (-.0186 ,.0635) .0199 (-.0193 ,.0590) 0.00001 L/M 26.3 (18.2 - 34.4 )

L/S 0.0109 0.493 .687 (.196 ,1.18) .193 (-.332 ,.718) 0.17989 S/L 1.20 (.948 - 1.46 )

M/S 0.876 0.003 .00310 (-.0399 ,.0461) .0366 (-.00943 ,.0825) 0.00000 S/M 31.1 (21.8 - 40.5 )

WB/S 0.0124 0.481 .155 (.0416 ,.269) .0879 (-.0339 ,.210) 0.00001 S/WB 4.29 (3.55 - 5.03 )

PFDA WB/L 0.000929 0.682 .183 (.0952 ,.272) .136 (-.00220 ,.273) 0.00005 L/WB 3.65 (3.11 - 4.20 )

WB/M 0.17475 0.176 2.01 (-1.06 ,5.08) .248 (.00374 ,.492) 0.00001 WB/M 6.02 (4.18 - 7.87 )

M/L 0.09035 0.26 .0236 (-.00445 ,.0517) .0402 (-.00360 ,.0841) 0.00002 L/M 21.1 (14.5 - 27.6 )

L/S 0.00264 0.612 1.01 (.444 ,1.58) .167 (-.593 ,.926) 0.16296 L/S 1.19 (.957 - 1.41 )

M/S 0.488287 0.049 .0133 (-.0279 ,.0544) .0573 (.00228 ,.112) 0.00001 S/M 19.4 (12.5 - 26.3 )

WB/S 0.003213 0.597 .222 (.0935 ,.350) .121 (-.0509 ,.293) 0.00002 S/WB 3.22 (2.72 - 3.72 )

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p(reg) r2 b () a () p(t-test) *ratio ()

PFUnDA WB/L 0.00203 0.631 .2040 ( .094, .314) .072 ( -.058, .201) 0.00001 L/WB 3.87 (3.25 - 4.48 )

WB/M 0.0326 0.381 2.1407 ( .217, 4.064) .154 ( .013, .295) 0.00001 WB/M 5.25 (3.53 - 6.98 )

M/L 0.158 0.189 .0322 ( -.015, .079) .030 ( -.025, .086) 0.00001 L/M 19.8 (13.7 - 25.8 )

L/S 0.00272 0.610 1.6121 ( .703, 2.521) -.010 ( -.660, .640) 0.00101 L/S 1.60 (1.36 - 1.85 )

M/S 0.493719 0.048 .0335 ( -.072, .139) .043 ( -.033, .118) 0.00000 S/M 13.1 (8.39 - 17.9 )

WB/S 0.00313 0.599 .4106 ( .174, .647) .014 ( -.155, .183) 0.00000 S/WB 2.49 (2.05 - 2.93 )

PFDoDA WB/L 0.00138 0.657 .2117 ( .104, .319) .130 ( -.084, .345) 0.00001 L/WB 3.65 (3.13 - 4.16 )

WB/M 0.25517 0.127 1.4820 ( -1.254, 4.218) .343 ( -.015, .700) 0.00001 WB/M 4.55 (3.32 - 5.78 )

M/L 0.03747 0.365 .0380 ( .003, .073) .052 ( -.018, .123) 0.00000 L/M 15.6 (12.7 - 18.4 )

L/S 0.00310 0.600 1.7269 ( .733, 2.721) -.058 ( -1.207, 1.092) 0.00000 L/S 1.68 (1.42 - 1.94 )

M/S 0.0426 0.350 .0829 ( .003, .162) .031 ( -.061, .123) 0.00000 S/M 9.47 (7.85 - 11.1 )

WB/S 0.00677 0.536 .4262 ( .147, .706) .051 ( -.273, .374) 0.00000 S/WB 2.27 (1.86 - 2.68 )

PFTrDA WB/L 0.00537 0.556 .213 (.0787 ,.346) .0549 (-.0779 ,.188) 0.00000 L/WB 3.85 (3.13 - 4.56 )

WB/M 0.00000 WB/M 15.5 (6.97 - 24.0 )

M/L 0.00000 L/M 53.8 (30.2 - 77.4 )

L/S 0.0495 0.333 1.09 (.00302 ,2.17) .322 (-.324 ,.967) 0.00043 L/S 1.74 (1.32 - 2.15 )

M/S 0.00000 S/M 32.9 (19.9 - 45.8 )

WB/S 0.0221 0.422 .3489 ( .061, .636) .056 ( -.116, .227) 0.00000 S/WB 2.36 (1.92 - 2.80 )

PFTeDA WB/L 0.0576 0.315 .122 (-.00478 ,.249) .0579 (-.0927 ,.208) 0.00000 L/WB 6.87 (4.47 - 9.27 )

WB/M 0.00004 WB/M 8.18 (5.84 - 10.5 )

M/L 0.00000 L/M 48.9 (35.2 - 62.6 )

L/S 0.0702 0.291 .814 (-.0809 ,1.71) .626 (.0367 ,1.22) 0.00041 L/S 2.90 (.784 - 5.02 )

M/S 0.00002 S/M 25.9 (17.5 - 34.2 )

WB/S 0.0507 0.33 .1886 ( -.001, .378) .081 ( -.044, .205) 0.00010 S/WB 3.34 (2.09 - 4.58 )

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p(reg) r2 b () a () p(t-test) *ratio ()

PFPeDA WB/L 0.00091 L/WB 5.40 (3.77 - 7.04 )

WB/M 0.00091 WB/M 1.42 (1.21 - 1.62 )

M/L

L/S 0.08502 L/S 2.60 (1.20 - 4.00 )

M/S 0.00239 S/M 4.82 (2.67 - 6.96 )

WB/S 0.00332 S/WB 3.22 (2.08 - 4.36 )

PFHxDA all below <LOQ

PFODA all below <LOQ

L-PFBS all below <LOQ

Br-PFHxS all below <LOQ

L-PFHxS all below <LOQ

Br-PFOS WB/L 0.00228 0.623 .147 (.0662 ,.227) .0475 (-.0454 ,.140) 0.00000 L/WB 5.36 (4.70 - 6.02 )

WB/M NS 0.00000 WB/M 3.74 (2.80 - 4.68 )

M/L 0.353 0.087 .0166 (-.0214 ,.0546) .0409 (-.00300 ,.0848 ) 0.00000 L/M 20.6 (13.4 - 27.7 )

L/S 0.179 0.173 .598 (-.325 ,1.52) .726 (.107 ,1.34) 0.00068 L/S 1.86 (1.49 - 2.23 )

M/S 0.0320 0.383 .0503 (.00529 ,.0953) .0278 (-.00236 ,.0580) 0.00001 S/M 11.1 (8.72 - 13.5 )

WB/S 0.0490 0.334 .155 (.00079 ,.309) .112 (.00913 ,.215) 0.00005 S/WB 3.13 (2.45 - 3.82 )

L-PFOS WB/L 0.000436 0.726 .152 (.0860 ,.217) 1.58 (-.623 ,3.79) 0.00003 WB/L 4.95 (4.34 - 5.55 )

WB/M 0.129 0.215 2.62 (-.903 ,6.14) 2.35 (-3.09 ,7.78) 0.00003 WB/M 4.27 (3.27 - 5.27 )

M/L 0.0733 0.286 .0169 (-.00192 ,.0357) .965 (.334 ,1.60) 0.00002 L/M 20.8 (15.5 - 26.0 )

L/S 0.0123 0.481 2.04 (.549 ,3.54) 2.54 (-19 ,24.2) 0.00037 L/S 2.22 (1.81 - 2.62 )

M/S 0.216 0.149 .0358 (-.0246 ,.0963) .989 (.112 ,1.87) 0.00000 S/M 9.59 (7.74 - 11.4 )

WB/S 0.00119 0.667 .428 (.215 ,.642) .344 (-2.75 ,3.44) 0.00001 S/WB 2.37 (1.94 - 2.79 )

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p(reg) r2 b () a () p(t-test) *ratio ()

∑-PFOS WB/L 0.000481 0.72 .151 (.0848 ,.218) 1.64 (-.662 ,3.94) 0.00002 L/WB 4.96 (4.36 - 5.57 )

WB/M 0.126 0.218 2.63 (-.881 ,6.15) 2.37 (-3.26 ,8.01) 0.00002 WB/M 4.24 (3.26 - 5.22 )

M/L 0.0825 0.271 .0164 (-.00254 ,.0354) 1.02 (.361 ,1.68) 0.00002 L/M 20.7 (15.5 - 25.9 )

L/S 0.0157 0.457 1.97 (.458 ,3.48) 3.41 (-19 ,26.3) 0.00036 L/S 2.20 (1.80 - 2.60 )

M/S 0.219 0.147 .0352 (-.0246 ,.0951) 1.03 (.128 ,1.94) 0.00000 S/M 9.63 (7.80 - 11.5 )

WB/S 0.00159 0.648 .418 (.201 ,.635) .436 (-2.85 ,3.72) 0.00000 S/WB 2.39 (1.96 - 2.83 )

Br-PFDS WB/L 0.00198 L/WB 5.73 (4.01 - 7.45 )

WB/M 0.00117 WB/M 1.90 (1.45 - 2.36 )

M/L

L/S 0.02726 L/S 2.74 (1.28 - 4.21 )

M/S 0.00079 S/M 5.77 (3.48 - 8.07 )

WB/S 0.00147 S/WB 3.00 (1.92 - 4.08 )

L-PFDS WB/L 0.122 0.223 .104 (-.0331 ,.242) .0367 (.00011 ,.0732) 0.00003 L/WB 4.32 (3.07 - 5.58 )

WB/M 0.00000 WB/M 8.57 (6.36 - 10.8 )

M/L 0.00001 L/M 34.1 (24.1 - 44.2 )

L/S 0.112 0.233 1.11 (-.308 ,2.53) .110 (-.0747 ,.295) 0.00064 L/S 2.20 (1.59 - 2.81 )

M/S 0.00000 S/M 16.5 (12.9 - 20.0 )

WB/S 0.476 0.052 .116 (-.233 ,.465) .0482 (.00268 ,.0937) 0.00078 S/WB 2.22 (1.51 - 2.94 )

∑-PFDS WB/L 0.0294 0.392 .102 (.0125 ,.191) .0418 (.00918 ,.0745) 0.00009 L/WB 4.53 (3.40 - 5.66 )

WB/M 0.755 0.010 1.55 (-9.19 ,12.3) .0531 (-.104 ,.210) 0.00001 WB/M 5.24 (4.03 - 6.46 )

M/L 0.872 0.003 -.00056 (-.00804 ,.00693) .0147 (.0120 ,.0174) 0.00003 L/M 23.0 (15.5 - 30.6 )

L/S 0.0628 0.305 1.42 (-.0914 ,2.93) .0987 (-.164 ,.361) 0.00154 L/S 2.17 (1.60 - 2.73 )

M/S 0.0759 0.282 .0145 (-.00182 ,.0308) .0121 (.00929 ,.0150) 0.00000 S/M 11.2 (8.69 - 13.7 )

WB/S 0.263 0.123 .147 (-.129 ,.423) .0515 (.00349 ,.100) 0.00034 S/WB 2.36 (1.66 - 3.06 )

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p(reg) r2 b () a () p(t-test) *ratio ()

Br-FOSA WB/L 0.0182 0.443 .131 (.0273 ,.234) .177 (.0461 ,.307) 0.00073 L/WB 3.44 (2.68 - 4.21 )

WB/M 0.00001 WB/M 13.9 (10.5 - 17.4 )

M/L 0.00015 L/M 46.6 (31.9 - 61.4 )

L/S 0.00000 0.932 4.96 (4.02 ,5.90) -.268 (-.551 ,.0150) 0.00025 L/S 3.85 (3.24 - 4.47 )

M/S 0.00003 S/M 11.8 (9.08 - 14.5 )

WB/S 0.0556 0.319 .569 (-.0164 ,1.15) .163 (-.0134 ,.339) 0.22635 WB/S 1.25 (.920 - 1.59 )

L-FOSA WB/L 0.267 0.121 .0677 (-.0607 ,.196) 1.47 (.425 ,2.51) 0.00001 L/WB 4.00 (3.19 - 4.81 )

WB/M 0.732 0.012 -1.12 (-8.23 ,5.98) 2.17 (1.01 ,3.32) 0.00000 WB/M 14.4 (10.3 - 18.5 )

M/L 0.869 0.003 .00102 (-.0125 ,.0145) .147 (.0373 ,.256) 0.00000 L/M 55.9 (38.4 - 73.3 )

L/S 0.0132 0.475 3.91 (1.01 ,6.81) .134 (-5.64 ,5.91) 0.00000 L/S 4.00 (3.39 - 4.61 )

M/S 0.215 0.149 .0420 (-.0287 ,.113) .0732 (-.0676 ,.214) 0.00000 S/M 13.7 (10.2 - 17.2 )

WB/S 0.153 0.193 .484 (-.214 ,1.18) 1.05 (-.340 ,2.44) 0.74452 S/WB 1.06 (.873 - 1.25 )

∑-FOSA WB/L 0.209 0.153 .0710 (-.0469 ,.189) 1.69 (.584 ,2.79) 0.00001 L/WB 3.90 (3.12 - 4.68 )

WB/M 0.526 0.041 -2.34 (-10.3 ,5.59) 2.73 (1.27 ,4.18) 0.00000 WB/M 14.3 (10.5 - 18.1 )

M/L 0.894 0.002 .00068 (-.0105 ,.0118) .171 (.0674 ,.276) 0.00000 L/M 54.1 (38.2 - 70.0 )

L/S 0.00372 0.586 4.59 (1.87 ,7.31) -1.35 (-7.54 ,4.84) 0.00001 L/S 3.98 (3.38 - 4.58 )

M/S 0.263 0.123 .0333 (-.0292 ,.0959) .104 (-.0389 ,.246) 0.00000 S/M 13.3 (10.3 - 16.4 )

WB/S 0.204 0.156 .430 (-.276 ,1.14) 1.36 (-.247 ,2.96) 0.60799 WB/S 1.08 (.883 - 1.28 )

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Table 14. Results from regression analyses, paired t-test and ratio (ratio arranged to be >1) for PBDEs, HBCDD, chlorinated pesticides and PCBs

analysed in individual samples of herring muscle (M) and whole fish (WB), based on concentrations expressed on lipid weight basis. Green colour

denotes that there is a significant regression. No analysis was conducted for blank cells because of many values below LOQ.

p(reg) r2 b () a () p(t-test) ratio ()

BDE-47 WB/M 0.000000 0.977 .698 (.623 ,.772) 5.29 (3.19 ,7.39) 0.900 WB/M 1.20 (1.06 - 1.34 )

BDE-99 WB/M 0.000779 0.693 .689 (.366 ,1.01) 1.63 (.474 ,2.78) 0.0349 WB/M 1.25 (1.12 - 1.38 )

BDE-100 WB/M 0.000000 0.987 .706 (.650 ,.762) .928 (.619 ,1.24) 0.884 WB/M 1.26 (1.12 - 1.39 )

BDE-153 WB/M 0.000046 0.823 .722 (.486 ,.958) .105 (.0171 ,.194) 0.521 WB/M 1.11 (.957 - 1.26 )

BDE-154 WB/M 0.000001 0.920 .664 (.527 ,.802) .204 (.114 ,.293) 0.398 WB/M 1.24 (1.08 - 1.39 )

HBCDD WB/M 0.000000 0.984 .734 (.669 ,.799) 6.82 (4.77 ,8.86) 0.513 M/WB 1.21 (1.10 - 1.33 )

HCB WB/M 0.000566 0.711 .356 (.196 ,.515) 7.12 (4.91 ,9.32) 0.269 M/WB 1.08 (.939 - 1.22 )

AHCH <LOQ

BHCH WB/M 0.2101 0.152 .3240 ( -.215, .863) 2.52 ( .349, 4.68) 0.644 M/WB 1.06 (.842 - 1.29 )

LINDAN <LOQ

DDEK WB/M 0.000000 0.991 .668 ( .623, .715) 73.8 ( 54.7, 93.0) 0.579 M/WB .972 (.874 - 1.07)

DDDK WB/M 0.000001 0.921 .584 ( .463, .704) 120 (76.4, 163) 0.857 M/WB .970 ( .859 - 1.08)

DDTK <LOQ

CB-28 WB/M 0.000543 0.714 .599 (.332 ,.866) 36.0 (14.4 ,57.7) 0.264 WB/M 1.12 (1.02 - 1.22 )

CB-52 WB/M 0.000007 0.880 .710 (.525 ,.895) 62.1 (34.4 ,89.8) 0.0212 WB/M 1.27 (1.15 - 1.39 )

CB-101 WB/M 0.000000 0.984 .659 (.599 ,.718) 107 (73.1 ,141) 0.572 M/WB .985 (.884 - 1.09 )

CB-118 WB/M 0.000000 0.989 .661 (.612 ,.710) 71.1 (50.9 ,91.4) 0.506 M/WB .991 (.892 - 1.09 )

CB-153 WB/M 0.000000 0.990 .668 (.621 ,.715) 142 (99.5 ,185) 0.539 M/WB .980 (.879 - 1.08 )

CB-138 WB/M 0.000000 0.989 .723 (.670 ,.775) 117 (84.5 ,149) 0.782 WB/M 1.19 (1.08 - 1.29 )

CB-180 WB/M 0.000000 0.988 .597 (.550 ,.644) 47.7 (34.7 ,60.8) 0.496 M/WB .986 (.865 - 1.11 )