The environmental behavior of perfluorinated alkyl acids (PFAA)
and their precursors was investigated in lake Tyrifjorden, downstream
a factory producing paper products coated with per- and polyfluorinated
alkyl substances (PFAS). Low water concentrations (max 0.18 ng L–1 linear perfluorooctanesulfonic acid, L-PFOS) compared
to biota (mean 149 μg kg–1 L-PFOS in perch
livers) resulted in high bioaccumulation factors (L-PFOS BAFPerch liver: 8.05 × 105–5.14 × 106).
Sediment concentrations were high, particularly for the PFOS precursor
SAmPAP diester (max 1 872 μg kg–1). Biota-sediment
accumulation factors (L-PFOS BSAFPerch liver: 22–559)
were comparable to elsewhere, and concentrations of PFAA precursors
and long chained PFAA in biota were positively correlated to the ratio
of carbon isotopes (13C/12C), indicating positive
correlations to dietary intake of benthic organisms. The sum fluorine
from targeted analyses accounted for 54% of the extractable organic
fluorine in sediment, and 9–108% in biota. This, and high trophic
magnification factors (TMF, 3.7–9.3 for L-PFOS), suggests that
hydrophobic precursors in sediments undergo transformation and are
a main source of PFAA accumulation in top predator fish. Due to the
combination of water exchange and dilution, transformation of larger
hydrophobic precursors in sediments can be a source to PFAA, some
of which are normally associated with uptake from water.
The
use of aqueous film-forming foams (AFFFs) has resulted in hot
spots polluted with poly- and perfluorinated alkyl substances (PFASs).
The phase out of long-chained perfluoroalkyl acids (PFAAs) from AFFFs
resulted in the necessity for alternatives, and short-chained PFAAs
and fluorotelomer-based surfactants have been used. Here, the distribution
of PFAS contamination in the marine environment surrounding a military
site in Norway was investigated. Up to 30 PFASs were analyzed in storm,
leachate, and fjord water; marine sediments; marine invertebrates
(snails, green shore crab, great spider crab, and edible crab); and
teleost fish (Atlantic cod, European place, and Lemon sole). Perfluorooctanesulfonic
acid (PFOS) was the most abundantly detected PFAS. Differences in
PFAS accumulation levels were observed among species, likely reflecting
different exposure routes among trophic levels and different capabilities
for depuration and/or enzymatic degradation. In agreement with previous
literature, almost no 6:2 fluorotelomer sulfonate (6:2 FTS) was detected
in teleost fish. However, this study is one of the first to report
considerable concentrations of 6:2 FTS in marine invertebrates, suggesting
bioaccumulation. Biota monitoring and risk assessments of sites contaminated
with fluorotelomer sulfonates (FTSs) and related compounds should
not be limited to fish, but should also include invertebrates.
Fingerprints associated with long-range atmospheric transport, production of paper products, and use of aqueous film forming foams (AFFF) were identified.
Local point sources (mainly firefighting stations) and diffuse sources contributed to the exposure of PFAS to the marine food web near Longyearbyen on Svalbard. Certain PFOS substitutes showed a bioaccumulation potential in marine invertebrates.
Per and polyfluoroalkyl substances (PFAS) are becoming more stringently regulated and as such, a more diverse suite of environmental monitoring methods is needed. In this work a polar organic chemical integrative sampler (POCIS) with a nylon membrane and a combination of Oasis WAX and Fluoroflash® sorbents was calibrated in the laboratory and deployed in the field. A static renewal system was used to determine sampling rates for 12 PFAS which ranged between 0.69 ± 0.27 to 5.68 ± 1.80 L/day. POCIS devices were deployed for 10 days in lake Tyrifjorden, Norway which is known to be contaminated by a closed down factory producing paper products, in order to track the evolution of the PFAS contamination in a river system draining into the lake. Th sampling campaign enabled the stretch of the river which was responsible for the emissions of PFAS to lake Tyrifjorden to be identified. Freely dissolved concentrations determined with the POCIS were lowest at the site considered to reflect a diffuse PFAS contamination and highest at the site located downstream the factory. Perfluorooctanesulfonic acid (PFOS), perfluorohexanoic acid (PFHxA) and perfluorooctane sulfonamidoacetic acid (EtFOSAA) dominated the concentration profile at this site. Emissions of PFAS to lake Tyrifjorden were estimated to be 3.96 g/day for the sum of the 12 investigated PFAS.
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