New organic contaminants in the Norwegian environment
The survey was done on behalf of the Norwegian State Pollution Control Authority (SFT) by the Norwegian Institute for Air Research (NILU), the Norwegian Institute for Water Research (NIVA) and the Norwegian Centre for Soil and Environmental Research (Jordforsk).
The survey had two main objectives. The first objective was to follow up the work of the first screening survey of a selection of novel environmental contaminants in Norway (Schlabach et al., 2002). As in the first survey, the study was on the environmental presence of brominated flame retardants together with chlorinated paraffins, and in addition, include analyses of bisphenol A and triclosan. The focus was on the concentrations of these substances in soil and sediment samples from landfills and industrial sites; in marine and freshwater sediments; and in freshwater fish, cod liver and blue mussels.
The second objective focused on the pollution of PBDEs in Lake Mjøsa, where unusually high concentrations have been found in fish (Fjeld et al., 2001, NIVA/NILU 2003). The objective of this part of the survey was to make a broader documentation of the PBDE levels in sediments and fish, and to localize areas with point sources of PBDEs.
Also reported are levels of polychlorinated dibenzodioxins and furans (PCDDs/PCDFs) and polychlorinated biphenyls (PCBs) in a minor selection of the fish samples. These analyses were done on behalf of the National Food Safety Authority (Mattilsynet).
Material and methods
Most of the fieldwork was done during 2003, and the sampling took place at following localities or sampling sites:
Landfills or industrially contaminated sites
Samples of leachate water, process water, ground water and surface water were collected from ten sites in southern Norway, whereas sediment samples from leachate ponds, soil samples or pond/riverbed sediments were collected from eight of these sites.
The lake is situated in Southeast Norway and is the country’s largest lake (365 km2, average depth: 153 m, max depth: 449 m). Surface sediment samples (0–2 cm) were collected from 14 stations. One sediment sample was also collected from the main inlet river at Lake Losna, 25 km north of lake Mjøsa. Fish were collected from the inlet river at Lake Losna, from Lake Mjøsa, from the outlet river Vorma, and from Lake Øyeren further down the watercourse.
Fish samples were homogenates of whole body or muscle fillets (pooled samples, typically 7–20 individuals per sample). The indicator species were brown trout (Salmo trutta), perch (Perca fluviatilis), pike (Esox lucius), burbot (Lota lota), vendace (Coregonus albula) and smelt (Osmerus eperlanus). Archived samples of vendace fished during 1993–2002 were also included. Passive samplers (SMPDs, semipermeable membrane devices) for lipophilic contaminants were deployed at four different stations in Lake Mjøsa (one in 2002, three in 2003).
Drammens River and the Drammensfjord
The Drammens River and the Drammensfjord are located in an industrialized area in Southeast Norway. The average discharge of the river is about 300 m3/s. Sediment samples were taken from 7 stations in the river, from the outlet of Lake Tyrifjorden to the outlet at Drammensfjorden. Four sediment samples (0–2 cm) were taken in the Drammensfjord, one in the main basin and three close to industrial sites. Homogenated fish samples (tissue from 5–20 individuals per pooled sample; muscle fillets;) were prepared from fish caught in the Drammensfjord. The species were anadromous brown trout, perch, orfe (Leuciscus idus), cod (Gadus morhua), flounder (Platichthys flesus) and eel (Anguilla anguilla).
Coastal marine environment
The marine samples were taken along the Norwegian coast from near the Russian border to the outer Oslofjord. Sediment samples were taken at six different stations. Two of the stations were located to harbors, one in a fjord with industrial contamination, and three in open coastal waters. Blue mussels (Mytilus edulis) were collected from five presumptive unpolluted stations; 1–2 pooled samples of soft tissue were prepared from each station (50 ind. per sample). Cod were sampled from five other presumably unpolluted areas. Three pooled liver samples were prepared for each site (7 ind. per sample).
The following chemical substances were analyzed: Polybrominated diphenyl ethers, (PBDEs, IUPAC numbers: BDE-28, -47, -49, -71, -77, -100, -119, -138, -153, -154, -183, and -209); hexabromocyclododecane (HBCD, a-, b- and g-isomers); tetrabromobisphenol A (TBBPA); bisphenol A; triclosan; short and medium chained chlorinated paraffins (SCCP and MCCP).
Polybrominated diphenyl ethers, PBDEs
The concentrations of PBDEs in leachate sediments or soils from landfills or industrial sites varied between 0.5–181 ng/g dry weight (d.w.), whereas the concentrations of PBDEs in different water samples (leachate water, process water, ground and surface water) from landfills and industrial sites were in the range of 1–15 ng/L. BDE-209 dominated strongly among the different PBDE congeners.
The concentrations of PBDEs in sediments from Lake Mjøsa were in the range 0.6–27 ng/g d.w. The levels were highest in the northern part (the inlet basin, close the town of Lillehammer) and lowest close to the outlet in the south. Based on the content of organic carbon (TOC), the concentrations outside Lillehammer were 600–740 ng/g TOC, whereas the concentrations elsewhere varied between 50–350 ng/g TOC. Tri- to hexa-BDEs (BDE-47, -99, -100, -153 and -154) constituted 60–70 % of the sum PBDEs in sediments from the northern part. Elsewhere, BDE-209 was the dominating congener with 50–90 / %. The concentration in sediments from Lake Losna (the lake in the inlet river) was 21 ng/g TOC, with a BDE-209 percentage close to 67 %. We conclude that the high concentrations of PBDEs in sediments close to Lillehammer, together with the high percentage of tri- to hexa-BDEs, strongly indicate that the technical product “pentaBDE” has been discharged to the lake here.
Passive sampling devices (SPMDs) did not accumulate any PBDE from Lake Losna (in the main inlet river). In Lake Mjøsa, the accumulation rate was approximatly 3–6 times higher in the central part of the lake (outside the town of Gjøvik) compared to the stations in the Furnesfjorden basin and outside the town of Hamar.
The concentrations of sum PBDEs in pooled fish samples from Lake Mjøsa were in the range 50–90 ng/g wet-weight (w.w.) or 1 200–22 000 ng/g lipid. The lowest levels were in vendace and smelt (zooplankton-feeding species), whereas the highest levels were in perch, pike, trout and burbot (fish-eating species). Average concentration of 10 individual trout samples (mean weight: 3.5 kg) was 5 450 ng/g lipid, with individual concentrations in the range of 3 300–17 500 ng/g lipid. These are the highest concentrations in free-living salmonids reported internationally. Average concentration of 10 individual burbot samples from Lillehammer (mean weight: 1.5 kg) was 22 000 ng/g lipid, with individual concentrations in the range of 7 100–45 000 ng/g lipid. This is close to the highest concentration ever reported internationally in fish (47 000 ng/g lipid). The concentration of sum PBDE in burbot from Lake Losna (in the inlet river) was 49 ng/g lipid, whereas the concentrations in two trout samples from the outlet river Vorma was 5 750 and 7 900 ng/g lipid. BDE-99 was the dominating congener (21–45%), with BDE-47 as number two (24–35%) and BDE-100 as number three (8–15%).
The concentrations of PBDEs in sediments from the Drammens River were in the range 4–80 ng/g d.w. Adjusted for the organic carbon content, the concentrations were in the range of 86–6 900 ng/g TOC. The highest concentration was found at the station highest up in the river at the outlet of lake Tyrifjorden, in a presumptive rather unpolluted area. We would like to see this station be resampled to confirm this level. In the Drammensfjord the concentrations were 7–25 ng/g d.w. or 160–1950 ng/g TOC. The highest level was found outside a quay for shipping of materials (shredding) from recycled automobiles. BDE-209 dominated the concentrations in both river and marine sediments (80–99%). The concentrations of PBDEs in muscle tissue of fish (eel, trout, orfe, perch) from the Drammensfjord varied between 1–2 ng/g w.w. or 10–170 ng/ lipid, lowest for eel and trout, highest for perch and orfe. The concentrations in liver of cod and flounder were 41 and 172 ng/g lipid, respectively. BDE-47 was dominating among the congeners in the fish samples with 41–72%, with BDE-100 as second (9–22%). The percentage of BDE-99 was low in orfe, cod, flounder and eel (0.3–5%), but relatively high in trout and perch (14 and 31%).
BDE-209 was the dominating congener among the PBDEs in marine sediments from the Norwegian coast, with concentrations in the range 0.4–12 ng/g d.w. BDE-47 and -99 were also detected, usually in far lower concentrations (0.1–0.18 ng/g d.w.). In blue mussels, only BDE-47 and -99 were found in detectable concentrations. The concentrations (sum of BDE-47 and -99 ) were 1.5–19 ng/g lipid, except for one exceptionally high measurement of 93 ng/g lipid at Lista, South Norway. The concentrations of PBDEs in cod liver were in the range 15–52 ng/g lipid. The dominating congeners were BDE-47 (50–73%), BDE-100 (6–16%), sum of BDE-49 and BDE-71 (2-17%). BDE-99 had a rather low representation in cod liver (1-4%), especially when compared to the results from the freshwater species.
Detectable concentrations of HBCD were only found in two of the eight samples soil and sediment samples from landfills and industrial sites (2.5 and 7.7 ng/g d.w.)
Of the sediment samples from Lake Mjøsa and Lake Losna, the only detectable level was found outside the town of Lillehammer in the northern part of Lake Mjøsa. Only b-HBCD was found here, with a concentration of 7.9 ng/g d.w. Detectable concentrations of a-HBCD (0.9–1.5 ng/g d.w.) and g-HBCD (0.3–3.1 ng/g d.w.) were found in the Drammens River. In the Drammensfjord, detectable concentrations of all three isomers were found at one station close to an industrial area (concentration of a-, b-, and g-HBCD were 10.2, 0.7 and 3.3 ng/g, respectively).
HBCD was found in fish from Lake Mjøsa and further down the watercourse in the river Vorma and Lake Øyeren. The levels were in the range of 90–880 ng/g lipid. The a-isomer dominated the concentrations. The highest level was found in a pike sample from Lake Mjøsa. In fish from the Drammensfjord there were in general low concentrations of a-HBCD (5–23 ng/g lipid). Liver of cod from the Norwegian coast had low concentrations of a-HBCD (2–9 ng/g lipid).
Tetrabromobisphenol A (TBBPA) and bisphenol A
TBBPA was found in all soil and sediment samples from landfills and industrial sites (0.06–6.2 ng/g d.w.) Bisphenol A was found in significantly higher concentrations (7–370 ng/g d.w.).
In sediments from Lake Mjøsa and Lake Losna, low concentrations of TBBPA were found (0.04–0.13 ng/g d.w.). Bisphenol A was found in significantly higher concentrations (11–48 ng/g d.w.).
Sediments from the Drammens River had concentrations of TBBPA in the range of 0.2–10 ng/g d.w., with the highest concentration close to an industrial area. The concentrations of bisphenol A were 6–280 ng/g d.w., with increasing levels downstream. Sediments from the Drammensfjord had concentrations of TBBPA in the range of 0.3–39 ng/g d.w., with the highest level close to an industrial area. The concentrations of bisphenol A in the Drammensfjord sediments were 120–620 ng/g d.w., with the highest close to the aforementioned industrial area.
The other marine sediments had concentrations of TBBPA in the range of 0.01–2.4 ng/g d.w., whereas the concentrations of bisphenol A were 1– 22 400 ng/g. The highest levels were found in harbors.
Tricosan was found in all soil and sediment samples from landfills and industrial sites, with concentrations in the range of 0,9–105 ng/g d.w.
Sediments from Lake Mjøsa and Lake Losna had triclosan concentrations between 0.3–2.8 ng/g d.w.. The lowest level was found in Lake Losna, the highest in Lake Mjøsa, close to the town of Lillehammer.
Concentrations of triclosan in sediments from the Drammens River varied between 0.02–11 ng/g d.w., with increasing levels downstream. Sediments from the Drammensfjord had levels between 10–30 ng/g d.w., with the highest concentration at the station in the main basin.
Concentrations of triclosan in other marine sediments were 0.4-14 ng/g d.w., with the highest level in the harbor of Trondheim city.
Fish from Lake Mjøsa and further down the watercourse (Vorma River, Lake Øyeren) had triclosan levels in the range of 0.9–13 ng/g lipid. The lowest concentration was found in a trout sample from the Vorma River, the highest in a pike sample from Lake Mjøsa.
Chlorinated paraffins were found in all soil and sediment samples from landfills and industrial sites, and in all sediment samples from both freshwater and marine environment. In general, the concentrations of medium chained chlorinated paraffins (MCCP) exceeded those of short chained paraffins (SCCP).
The concentrations of SCCP in soil and sediment samples from landfills and industrial sites were 11– 16 500 ng/g d.w., whereas the concentrations of MCCP were 10– 47 000 ng/g d.w.
Sediments from Lake Mjøsa and Lake Losna had concentrations of SCCP+MCCP in the range of 30–770 ng/g d.w. The lowest concentration was found in Lake Losna, and the highest in Lake Mjøsa.
In the Drammens River, the concentrations of SCCP+MCCP varied between 10–7 400 ng/g d.w., with increasing concentrations downstream. In the Drammensfjord were the concentrations in the range of 750–7 750 ng/g d.w., with the highest concentrations close to a floating dock.
In the fish samples, the concentrations of SCCP were clearly larger then the concentrations of MCCP. Fish from Lake Mjøsa and further down the watercourse (the Vorma River and Lake Øyeren) had concentrations of SCCP+MCCP in the range of 28–4 375 ng/g lipid. The concentrations were lowest for zooplankton-feeding vendace and smelt from Lake Mjøsa, and highest in a trout sample from the Vorma River.
Fish from the Drammensfjord had concentrations of SCCP+MCCP between 46–495 ng/g lipid. The lowest concentration was found in an eel sample, the highest in a sample of flounder liver. In the cod liver samples from the Norwegian coast, the concentrations varied between 70–290 ng/g lipid.