Polyfluorinated chemicals in a spatially and temporally integrated food web in the Western Arctic

This study reports on an investigation of the presence of polyfluorinated chemicals in a spatially and temporally integrated set of biological samples representing an Arctic food web. Zooplankton, Arctic cod, and seal tissues from the western Canadian Arctic were analyzed for perfluoroalkyl sulfonates [PFAS], perfluorocarboxylates [PFCAs], and other polyfluorinated acids. Perfluorooctane sulfonate [PFOS] was found in all samples [0.20-34 ng/g] and in the highest concentrations. PFCAs from nine to 12 carbons were quantified in most of the samples [0.28-6.9 ng/g]. PFCAs with carbon chain lengths of eight or less were not detected. Likewise, 8-2 fluorotelomer acid [8-2 FTA] and 8-2 fluorotelomer unsaturated acid [8-2 FTUA], products of fluorotelomer environmental transformation, were not detected. 2H,2H,3H,3H, heptadecafluoro decanoic acid [7-3 Acid], an additional metabolite from fluorotelomer biological transformation, was detected only in seal liver tissue [0.5-2.5 ng/g]. The ratios of branched to linear PFOS isomers in fish and seal tissue were not similar and did not match that of technical PFOS as manufactured. No branched PFCA isomers were detected in any samples. It is concluded that differing pharmacokinetics complicate the use of branched to linear ratios of PFCAs in attributing their presence to a specific manufacturing process. A statistical analysis of the data revealed significant correlations between PFOS and the PFCAs detected as well as among the PFCAs themselves. The 7-3 Acid was not correlated with either PFCAs or PFAS, which suggests that it may have a different exposure pathway.     

Synthesis and characterization of antibacterial bio-nano films for food packaging

This study prepared antibacterial nanocomposite films for food packaging from Montmorillonite, which was modified by quaternary ammonium salts such as cetyltrimethylammonium bromide (CT), hexadecyl-tributyl phosphonium bromide (HD) and corn starch (CS). After this, it determined the antimicrobial activity of CS nanofilms against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) bacteria. Dispersion of silicate layers and starch nanocomposite films was analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM), and the results indicated that presence of quaternary ammonium salts enhanced clay dispersion, and the starch films incorporated with quaternary ammonium salts would provide potential use in food packaging as nanostructural materials. The nanofilms that were obtained based on the results of the antibacterial analysis were confirmed to have much stronger antibacterial properties than those in similar studies in the literature.     

Micellar-enhanced ultrafiltration (MEUF) with mixed surfactants for removing Cu(II) ions

A nonionic surfactant, polyoxyethylene Octyl phenyl ether (Triton-X), is added to a micellar-enhanced ultrafiltration process to lower the critical micellar concentration (CMC) of an anionic surfactant, sodium dodecyl sulfate (SDS). The effects of adding Triton-X on the copper removal efficiency, the permeate SDS concentration, the copper binding capacity of SDS micelles, and membrane fouling are investigated. Our results show that the addition of Triton-X at concentrations greater than its CMC can reduce the SDS dosage required for effective Cu removal, and at the same time, minimize the permeate SDS concentration. Although, no adverse effect on the copper binding capacity of SDS micelle is observed by the addition of Triton-X, the membrane fouling is worsen. Cleaning the membrane with DI water allowed restoring the membrane flux, indicating that the fouling caused by Triton-X was reversible.     

Determination of dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) in paper pulp mill defoamer additives and in paper pulp samples

An analytical procedure has been developed for quantitatively measuring dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) present at part-per-billion levels in paper mill defoamers and paper pulp using gas chromatography coupled with either low resolution mass spectrometry (GC-LRMS) or high resolution mass spectrometry (GC-HRMS).     

Perfluorinated surfactants (PFSs) in size-fractionated street dust in Tokyo

We investigated perfluorinated surfactants (PFSs) in size-fractionated street dust to identify their occurrence, contributions from traffic, and potential routes of entry into waters. Street dust was collected from residential areas and heavily trafficked areas in Tokyo and sorted into fine (<63 microm) and coarse fractions (63-2000 microm). Five PFS species were analyzed by liquid chromatography-tandem mass spectrometry: perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), and perfluoroundecanoate (PFUA). In fine fractions, PFS contents were significantly higher in heavily trafficked street dust than in residential street dust, but in coarse fractions, no significant differences were observed. Additionally, in heavily trafficked areas, PFS contents were significantly higher in fine fractions than in coarse fractions, but in residential areas, no significant differences were observed. PFS compositions differed between size fractions, not locations, indicating differences in sources between size fractions. Fine particles from traffic contributed to PFSs in street dust. Street dust possibly acts as the origin of PFSs in street runoff and eventually enters waters. This is the first report of PFSs in street dust.     

Extraction procedure optimization for perfluorooctane sulfonate and perfluorooctanoic acid in food packaging determination by LC-MS/MS

This research aimed to optimize the extraction method parameters for sample pretreatment and determine the levels of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) contamination in food packaging made of paper. Techniques used were pressurized liquid extraction (PLE) followed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Influence parameters of PLE were carefully evaluated for extracted concentration of samples in low level (ng g^?1). The study found that the optimal conditions for PLE were 30 min static extraction time with a flush volume of 100% cell volume and one extraction cycle at 80°C and 1,000 psi. The extraction technique validated the absolute recovery from PFOS and PFOA fortified control samples at three different levels (5, 50, and 200 ng g^?1), with seven repeats at each fortification level. The average recoveries were 79% or higher, with relative standard deviation (RSD) less than 11%. Optimization of the PLE method was established based on recovery data, accuracy, precision, and repeatability of the method. Using optimal PLE technique, PFOS and PFOA were extracted from 34 food-packaging samples collected in Thailand. PFOS and PFOA were detected in all kinds of collected samples, with average concentrations of 4.89 and 2.87 ng g^?1, respectively. The concentrations of PFOS and PFOA were highest in fast-food container samples: 36.99 and 9.99 ng g^?1, respectively.     

Use of ozone and/or UV in the treatment of effluents from board paper industry

The aim of this work has been to study the viability of ozone and/or UV in the treatment of cardboard industry effluents. Several model compounds have been chosen for the experiments: guaicol, eugenol, glucose, acetate and butyrate. Significant differences in the ozonisation rates are observed between phenolic products coming from lignin (eugenol and guaiacol) and aliphatic compounds. Reactions fit in all cases a pseudo-first order kinetics and are influenced by the pH of the solution. Real effluents have also been tested, and the COD decrease has been found to depend on the fatty acids/phenols ratio. Finally, respirometric studies have shown an increase in the BODst in effluents subjected to a mild oxidation, while under stronger conditions a BODst decrease is observed.     

The environmental fate of the primary degradation products of alkylphenol ethoxylate surfactants in recycled paper sludge.

Alkylphenol ethoxylates (APEOs) are a group of non-ionic surfactants that are degraded microbially into more lipophilic degradation products with estrogenic potential, including nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO), octylphenol (4-tOP) and nonylphenol (4-NP). Nonylphenol ethoxylates are used in paper recycling plants for de-inking paper and have the potential to be released into the environment through spreading of wastewater treatment sludge for soil amendment. Three samples of recycled paper sludge were collected from farmers' fields and analyzed for concentrations of NP1EO, NP2EO, 4-NP and 4-tOP. Each sample differed in the amount of time elapsed since the sludge was placed on farmers' fields. Primary degradation products of APEOs were present at low micrograms/g concentrations in the sludge samples. Differences in the concentrations of these analytes in sludge samples indicated that APEO concentrations declined by 84% over a period of 14 weeks on farmers' fields. Changes in the chromatographic patterns of acetylated 4-NP indicated that there is a group of recalcitrant nonylphenol isomers that degrades more slowly than other isomers. These data indicate that microbial degradation may reduce the risk of environmental contamination by these compounds, but more work is required to assess the toxic potential of APEOs in sludges used for soil amendment.     

Effect of surfactants on persistence of azadirachtin-A (neem based pesticide)

Photostability of azadirachtin-A, a neem based pesticide, was studied in the presence of non-ionic surfactants. Surfactants such as Span-80, Atlox 3400B, Tween-80, Agrimul 52B, and Agrimul N4S enhanced the rate of photodegradation of azadirachtin-A, whereas surfactants such as Triton-X, Emulsol CFA, Tween-20, Emulsol MAS, and Emulsol-N-33 decreased the rate of degradation. Emulsol-N-33 was found to be the most effective surfactant, as half life of azadirachin-A in the presence of Emulsol-N-33 was found to be 94.93 min in comparison to 48 min for azadirachtin-A alone under UV light.     

Polyfluorinated compounds in ambient air from ship- and land-based measurements in northern Germany

Neutral volatile and semi-volatile polyfluorinated organic compounds (PFC) and ionic perfluorinated compounds were determined in air samples collected at two sites in the vicinity of Hamburg, Germany, and onboard the German research vessel Atair during a cruise in the German Bight, North Sea, in early November 2007. PUF/XAD-2/PUF cartridges and glass fiber filters as sampling media were applied to collect several fluorotelomer alcohols (FTOH), fluorotelomer acrylates (FTA), perfluoroalkyl sulfonamides (FASA), and perfluoroalkyl sulfonamido ethanols (FASE) in the gas- and particle-phase as well as a set of perfluorinated carboxylates (PFCA) and sulfonates (PFSA) in the particle-phase. This study presents the distribution of PFC in ambient air of the German North Sea and in the vicinity of Hamburg for the first time. Average total PFC concentrations in and around Hamburg (180 pg m^?3) were higher than those observed in the German Bight (80 pg m^?3). In the German Bight, minimum–maximum gas-phase concentrations of 17–82 pg m^?3 for ΣFTOH, 2.6–10 pg m^?3 for ΣFTA, 10–15 pg m^?3 for ΣFASA, and 2–4.4 pg m^?3 for ΣFASE were determined. In the vicinity of Hamburg, minimum–maximum gas-phase concentrations of 32–204 pg m^?3 for ΣFTOH, 3–26 pg m^?3 for ΣFTA, 3–18 pg m^?3 for ΣFASA, and 2–15 pg m^?3 for ΣFASE were detected. Concentrations of perfluorinated acids were in the range of 1–11 pg m^?3. FTOH clearly dominated the substance spectrum; 8:2 FTOH occurred in maximum proportions. Air mass back trajectories, cluster, and correlation analyses revealed that the air mass origin and thus medium to long range atmospheric transport was the governing parameter for the amount of PFC in ambient air. Southwesterly located source regions seemed to be responsible for elevated PFC concentrations, local sources appeared to be of minor importance.     

Perfluoroalkyl substances (PFASs) in food and water from Faroe Islands

Diet and drinking water are suggested to be major exposure pathways for perfluoroalkyl substances (PFASs). In this study, food items and water from Faroe Islands sampled in 2011/2012 were analyzed for 11 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkane sulfonic acids (PFSAs). The food samples included milk, yoghurt, crème fraiche, potatoes, fish, and fish feed, and the water samples included surface water and purified drinking water. In total, nine PFCAs and four PFSAs were detected. Generally, the levels of PFAS were in the lower picogram per gram range. Perfluorobutanoic acid was a major contributor to the total PFASs concentration in water samples and had a mean concentration of 750 pg/L. Perfluoroundecanoic acid (PFUnDA) was predominating in milk and wild fish with mean concentrations of 170 pg/g. Perfluorooctane sulfonic acid (PFOS) was most frequently detected in food items followed by PFUnDA, perfluorononanoic acid, and perfluorooctanoic acid (PFOA). Levels of PFUnDA and PFOA exceeded those of PFOS in milk and fish samples. Prevalence of long-chain PFCAs in Faroese food items and water is confirming earlier observations of their increase in Arctic biota. Predominance of short-chain and long-chain homologues indicates exposure from PFOS and PFOA replacement compounds.     

Non-steady state partitioning of dry cleaning surfactants between tetrachloroethylene (PCE) and water in porous media

Trapped organic solvents, in both the vadose zone and below the water table, are frequent sources of environmental contamination. A common source of organic solvent contamination is spills, leaks, and improper solvent disposal associated with dry cleaning processes. Dry cleaning solvents, such as tetrachloroethylene (PCE), are typically enhanced with the addition of surfactants to improve cleaning performance. The objective of this work was to examine the partitioning behavior of surfactants from PCE in contact with water. The relative rates of surfactants partitioning and PCE dissolution are important for modeling the behavior of waste PCE in the subsurface, in that they influence the interfacial tension of the PCE, and how (or if) interfacial tension changes over time in the subsurface. The work described here uses a flow-through system to examine simultaneous partitioning and PCE dissolution in a porous medium. Results indicate that both nonylphenol ethoxylate nonionic surfactants and a sulfosuccinate anionic surfactant partition out of residual PCE much more rapidly than the PCE dissolves, suggesting that in many cases interfacial tension changes caused by partitioning may influence infiltration and distribution of PCE in the subsurface. Non-steady-state partitioning is found to be well-described by a linear driving force model incorporating measured surfactant partition coefficients.     

Flame retardants, surfactants and organotins in sediment and mysid shrimp of the Scheldt estuary (The Netherlands)

Sediment and mysids from the Scheldt estuary, one of the largest and most polluted estuaries in Western Europe, were analyzed for a number of contaminants that have been shown to possess endocrine-disrupting activity, i.e. organotins, polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA), nonylphenol ethoxylates (NPE) and transformation products, nonylphenol (NP) and nonylphenol ether carboxylates (NPEC). In addition, in vitro estrogenic and androgenic potencies of water and sediment extracts were determined. Total organotin concentrations ranged from 84 to 348 ng/g dw in sediment and 1110 to 1370 ng/g dw in mysid. Total PBDE (excluding BDE-209) concentrations ranged from 14 to 22 ng/g dw in sediment and from 1765 to 2962 ng/g lipid in mysid. High concentrations of BDE-209 (240-1650 ng/g dw) were detected in sediment and mysid (269-600 ng/g lipid). Total HBCD concentrations in sediment and mysid were 14-71 ng/g dw and 562-727 ng/g lipid, respectively. Total NPE concentrations in sediment were 1422 ng/g dw, 1222 ng/g dw for NP and 80 ng/g dw for NPEC and ranged from 430 to 1119 ng/g dw for total NPE and from 206 to 435 ng/g dw for NP in mysid. Significant estrogenic potency, as analyzed using the yeast estrogen assay, was detected in sediment and water samples from the Scheldt estuary, but no androgenic activity was found. This study is the first to report high levels of endocrine disruptors in estuarine mysids.     

Disposition of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in two Norwegian epibenthic marine food webs

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are a group of halogenated hydrocarbons, comprising 210 different, theoretically possible congeners. They are relatively hydrophobic and persistent to biodegradation, thereby rendering them subject to bioaccumulation. This study was conducted in Frierfjord and Eidangerfjord in the Grenland fjord system, Norway, heavily polluted by PCDD/PCDF discharges from the magnesium production at Herøya from 1951 to 2001. Pooled samples of surface-sediments and the following organisms were collected for the Frierfjord and Eidangerfjord study areas: common shrimp (Crangon crangon), polychaetes (mainly Nereis diversicolor), shore crab (Carcinus maenas), cod (Gadus morhua), flounder (Platichthys flesus), trout (Salmo trutta), herring (Clupea harengus), benthic amphipods and zooplankton. Concentrations of 2,3,7,8-PCDD/Fs were quantified in pooled samples for all species. The relative abundances of stable isotopes of nitrogen (δ¹⁵N) were evaluated in the organisms as a measure of chemically-derived trophic level. Contrary to earlier studies on other persistent organochlorines, it was found that the concentrations of PCDD/Fs declined with increasing trophic level. Principal Component Analysis (PCA) also showed differences between species in the pattern of PCDD/Fs. Higher chlorinated congeners constituted lower percentages of the PCDD/F-concentrations higher in the food chain as compared to lower trophic levels. In general, congener patterns did not differ between fjords. Infauna (polychaetes) and zooplankton had congener patterns most similar to the pollution source. The results indicate lower accumulation of higher chlorinated congeners in species at higher trophic levels (fish), presumably due to low membrane permeability (high molecular size) and possibly slow transport through intestinal aqueous phases because of low aqueous solubility.     

Bioaccumulation and depuration of anthracene in Penaeus monodon (Fibricius) through food ingestion

Understanding on the bioaccumulation and depuration of PAHs (polycyclic aromatic hydrocarbons) in Penaeus monodon is important in seafood safety because it is one of the most popular seafood consumed worldwide. In this study, we used anthracene as the precursor compound for PAHs accumulation and depuration in the shrimp. Commercial feed pellets spiked with anthracene were fed to P. monodon. At 20 mg kg⁻¹ anthracene, P. monodon accumulated 0.1% of the anthracene from the feed. P. monodon deputed the PAH two times faster than its accumulation. The shrimp reduced its feed consumption when anthracene content in the feed exceeded 20 mg kg⁻¹. At 100 mg kg⁻¹ anthracene, P. monodon started to have necrosis tissues on the posterior end of their thorax. The bioaccumulation factor (BAF), uptake rate constant (k₁) and depuration rate constant (k₂) of anthracene in P. monodon were 1.15 × 10⁻³, 6.80 × 10⁻⁴ d⁻¹ and 6.28 × 10⁻¹ d⁻¹, respectively. The depuration rate constant is about thousand times higher than the uptake rate constant and this indicated that this crustacean is efficient in depurating hydrocarbons from their tissue.     

PCDDs, PCDFs and dioxin-like PCBs in food of animal origin (Slovakia)

The levels of 17 toxic polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and 12 non-ortho and mono-ortho polychlorinated biphenyls (PCBs) in 73 foodstuff samples of animal origin collected from shops and small farms in selected districts of Slovak Republic are presented in this paper. The concentrations expressed as WHO-TEQ in analysed samples ranged for PCDDs/PCDFs from 0.25 pg/g fat in pork to 75 pg/g fat in cod liver. The TEQ concentrations of non-ortho PCBs were between 0.007 and 181 pg/g fat and mono-ortho PCBs between 0.0083 and 66.5 pg/g fat. The mean concentrations in freshwater fish and imported species of marine fish were 0.089 pg TEQ/g fresh weight for PCDDs/PCDFs, 0.17 pg TEQ/g fresh weight for non-ortho PCBs and 0.034 pg TEQ/g fresh weight for mono-ortho PCBs. The mean total concentration of PCDDs/PCDFs and dioxin-like PCBs in samples of infant milk formula imported from EU countries was 0.98 pg TEQ/g fat.     

Consequences of elevated carbon dioxide and ozone for foliar chemical composition and dynamics in trembling aspen (Populus tremuloides) and paper birch (Betula papyrifera).

Atmospheric chemical composition affects foliar chemical composition, which in turn influences the dynamics of both herbivory and decomposition in ecosystems. We assessed the independent and interactive effects of CO2 and O3 fumigation on foliar chemistry of quaking aspen (Populus tremuloides) and paper birch (Betula papyrifera) at a Free-Air CO2 Enrichment (FACE) facility in northern Wisconsin. Leaf samples were collected at five time periods during a single growing season, and analyzed for nitrogen. starch and condensed tannin concentrations, nitrogen resorption efficiencies (NREs), and C:N ratios. Enriched CO2 reduced foliar nitrogen concentrations in aspen and birch; O3 only marginally reduced nitrogen concentrations. NREs were unaffected by pollution treatment in aspen, declined with 03 exposure in birch, and this decline was ameliorated by enriched CO2. C:N ratios of abscised leaves increased in response to enriched CO2 in both tree species. O3 did not significantly alter C:N ratios in aspen, although values tended to be higher in + CO2 + O3 leaves. For birch, O3 decreased C:N ratios under ambient CO2 and increased C:N ratios under elevated CO2. Thus, under the combined pollutants, the C:N ratios of both aspen and birch leaves were elevated above the averaged responses to the individual and independent trace gas treatments. Starch concentrations were largely unresponsive to CO2 and O3 treatments in aspen. but increased in response to elevated CO2 in birch. Levels of condensed tannins were negligibly affected by CO2 and O3 treatments in aspen, but increased in response to enriched CO2 in birch. Results from this work suggest that changes in foliar chemical composition elicited by enriched CO2 are likely to impact herbivory and decomposition, whereas the effects of O3 are likely to be minor, except in cases where they influence plant response to CO2.     

Assessing contamination of smoked sprats (Sprattus sprattus) with polycyclic aromatic hydrocarbons (PAHs) and changes in its level during storage in various types of packaging

The analysis of material used in this study demonstrated that the amount of polycyclic aromatic hydrocarbons (PAHs) in smoked sprats varies from the level below the lowest detection limit in muscles up to 9.99 µg kg^?1 of benzo[a]pyrene (BaP) in fish skin. Such a high level of PAHs in skin was reported only in one of six batches of sprats, while mean BaP level was at 1.69 µg kg^?1. Regardless such a high BaP level in skin, its concentration in muscles did not exceed the maximum acceptable level. The study objective was to assess to what extent packaging materials adsorb PAH compounds from food. Changes in the PAH levels were monitored in fish during their storage in packages made of various materials. The storage time was from 0 to 168 hours. The obtained results varied considerably, therefore their scatter did not allow to confirm unequivocally the preliminary hypothesis about the reduction of PAHs due to their migration to packaging material. However, analysis of the packaging used in this study demonstrated a significant increase in the level of total 16 PAHs. When high-density polyethylene (HDPE) packaging was analysed, a six-fold increase in the total 16 PAHs was observed comparing to the blank sample.     

Analysis of polychlorodibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs) in baked-salt food additives in Korea

Thirty-one samples of baked-salt products used in commercial food additives were analyzed for the presence of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Dioxins were highly detected in 12 samples of baked salts. The amount of dioxins found in the samples ranged from 12.47 pg/g to 406.56 pg/g (0.71 pg TEQ/g to 23.51 pg TEQ/g, respectively). The most abundant congeners, as TEQ values, were 2,3,4,7,8-PeCDF; 1,2,3,7,8-PeCDF; and 1,2,3,4,7,8-HxCDF in PCDF congeners and 1,2,3,7,8-PeCDD; 1,2,3,6,7,8-HxCDD; and 1,2,3,7,8,9-HxCDD in PCDD congeners. Meanwhile, PCDDs/PCDFs were analyzed in high-temperature-treated samples of natural sea salt alone and natural sea salt to which di-(2-ethylhexyl)phthalate (DEHP) had been added. In the former case, PCDD/PCDF formation was most evident at temperatures near 450 degrees C, the total amount of dioxins was 90.07 pg/g (6.07 pg TEQ/g), and PCDD congeners comprised less than 50% of the total PCDDs/PCDFs. However, when the latter samples were heated, the total PCDD/PCDF concentration was 512.30 pg/g (21.53 pg TEQ/g), with PCDD congeners comprising over 87% of the total PCDDs/PCDFs.