Biological monitoring of polyfluoroalkyl substances: A review

Polyfluoroalkyl substances (PFSs) are used in industrial and commercial products and can degrade to persistent perfluorocarboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs). Temporal trend studies using human, fish, bird, and marine mammal samples indicate that exposure to PFSs has increased significantly over the past 15-25 years. This review summarizes the biological monitoring of PFCAs, PFSAs, and related PFSs in wildlife and humans, compares concentrations and contamination profiles among species and locations, evaluatesthe bioaccumulation/biomagnification in the environment, discusses possible sources, and identifies knowledge gaps. PFSs can reach elevated concentrations in humans and wildlife inhabiting industrialized areas of North America, Europe, and Asia (2-30,000 ng/ mL or ng/g of wet weight (ww)). PFSs have also been detected in organisms from the Arctic and mid-ocean islands (< or = 3000 ng/g ww). In humans, PFSAs and PFCAs have been shown to vary among ethnic groups and PFCA/PFSA profiles differ from those in wildlife with high proportions of perfluorooctanoic acid and perfluorooctane sulfonate. The pattern of contamination in wildlife varied among species and locations suggesting multiple emission sources. Food web analyses have shown that PFCAs and PFSAs can bioaccumulate and biomagnify in marine and freshwater ecosystems. Knowledge gaps with respect to the transport, accumulation, biodegradation, temporal/spatial trends and PFS precursors have been identified. Continuous monitoring with key sentinel species and standardization of analytical methods are recommended.     

Biology-based modeling to analyze uranium toxicity data on Daphnia magna in a multigeneration study

Recent studies have investigated chronic toxicity of waterborne depleted uranium on the life cycle and physiology of Daphnia magna. In particular, a reduction in food assimilation was observed. Our aims here were to examine whether this reduction could fully account for observed effects on both growth and reproduction, for three successive generations, and to investigate through microscope analyses whether this reduction resulted from direct damage to the intestinal epithelium. We analyzed data obtained by exposing Daphnia magna to uranium over three successive generations. We used energy-based models, which are both able to fit simultaneously growth and reproduction and are biologically relevant. Two possible modes of action were compared - decrease in food assimilation rate and increase in maintenance costs. In our models, effects were related either to internal concentration or to exposure concentration. The model that fitted the data best represented a decrease in food assimilation related to exposure concentration. Furthermore, observations of consequent histological damage to the intestinal epithelium, together with uranium precipitates in the epithelial cells, supported the assumption that uranium has direct effects on the digestive tract. We were able to model the data in all generations and showed that sensitivity increased from one generation to the next, in particular through a significant increase of the intensity of effect, once the threshold for appearance of effects was exceeded.     

Heartwood dry extract: a key fraction for the quality and the diversity of rums and spirits

Oak heartwood provides easily soluble dry extract. The fraction is rich in various polymers including polysaccharides, polyphenols and lignin. During cask ageing, spirit composition improves by the addition of oak dry extract. New spirits, such as white rums, develop colour and character such as softness and sweetness. Mouthfeel and presentation of the final product are completely changed. The content of alcohol and dry extract influence the thickness and taste of the spirit. Microviscosity was measured in a commercial rums and other spirits, highlighting a direct correlation between dry extract and microviscosity. Two indices are proposed for the evaluation of ageing in oak casks: the ratio of Total Polyphenols Index (TPI)/dry extract and the Global Tastefully Index integrating microviscosity and TPI. The proposed indices allowed the differentiation between (i) long aged products, (ii) short ageing and (iii) white spirits with short ageing and artificial treatments mimicking cask ageing. © 2020 The Institute of Brewing & Distilling     

Characterization and determination of brewer's solid wastes composition

Agro‐industrial wastes are produced in large quantities around the world from the processing and manufacturing of food and beverages. The disposal of these wastes into the environment leads to damage to ecosystems owing to their composition rich in organic matter. In this context it may be noted that the brewing industry, whose production process includes processing steps and fermentation of vegetable raw materials such as barley and/or other grains used as adjuncts and hops, generates various byproducts. The worldwide consumption of these beverages and the current model of breweries, which includes production on a large scale, lead to the generation of large amounts of brewery waste, namely spent grain, hot trub and residual yeast. Owing to its composition, these residues exhibit significant potential for application in bioprocess technologies. In this study the three residues mentioned had their composition determined as a function of moisture, ash, total organic carbon (TOC), total and soluble nitrogen, reducing sugar and soluble free amino nitrogen. Moreover, the residues were characterized for total acidity, pH and chemical oxygen demand (COD) of total and soluble fractions. The three residues evaluated had high moisture content (>80%) and high organic matter content (TOC and COD, ~50% and >1000 mg/g, respectively), which can highlights the significant protein fraction (almost 50% for hot trub and residual yeast), suggesting the possibility of using these wastes for recovery. Copyright © 2015 The Institute of Brewing & Distilling     

Study of Ozonated Sunflower Oil Using 1H NMR and Microbiological Analysis

Prior studies have proven that ozonated vegetable oils present a high germicidal power. Ozonation of sunflower oil at different applied ozone dosage was carried out and peroxide and aldehydes indices along with antimicrobial activity were determined. The reaction products were identified using Proton Nuclear Magnetic Resonance Spectroscopy (¹H NMR). The principal signals intensity values were used for following the reaction course between ozone and sunflower oil. The reaction was following up to peroxide index values of 1202 mmol-equi/kg. The intensities of olefinic proton signals decreased with the gradual increase in ozone concentration but without disappearing completely. The Criegee ozonides obtained at 107.1 mg/g of ozone doses were approximately 3.9-fold higher than that at beginning of the reaction. The aldehyde protons were observed as a weak intensity signal in all the spectra. The signals belonging to olefinic protons from hydroperoxides appeared weak and increased with the increase in ozone doses. Signals from other oxygenated groups were assigned. The highest action spectrum of antimicrobial activity was obtained with the higher peroxide index. It was concluded that at higher applied ozone doses, the higher the antimicrobial activity potential of ozonized sunflower oil     

Driving an electric vehicle. A sociological analysis on pioneer users

In most of the western countries, car is the prevalent means of transport for local mobility. At the same time, sensitivity to environmental issues is increasing, correlated to the consciousness that carbon dioxide emissions have to be reduced. In regard to these two trends (individual mobility and public opinions favourable to a reduction of carbon emissions), energy-efficient vehicles will probably develop in the future—car manufacturers actually prepare new offers for the mass market. Comparable cases have occurred during the last decades—probably more modest but full of learning: some local authorities have promoted innovations based on electric vehicles in the 1990s, and some people have chosen this kind of cars for their daily travels. This article deals with these pioneers (This article comes from a communication at the ECEEE Summer Study, June 2009, Panel 6: Energy efficiency in transport and mobility.). Reporting studies carried out in 2006 and 2008, we intend to identify the reasons of this innovative modal choice, to show the difficulties that electric vehicle drivers then encountered and to analyse the patterns of use that governed their mobility and their use of electric vehicles.     

Distance field computation for geological slab surface data sets

The three-dimensional shapes of tectonic plates that sink into the Earth’s mantle (slabs) are the starting point for a range of geoscience studies, from determining the forces driving the motion of tectonic plates, to potential seismic and tsunami hazards, to the sources of magmas beneath active volcanos. For many of these applications finite element methods are used to model the deformation or fluid flow, and therefore the input model parameters, such as feature geometries, temperature or viscosity, must be defined with respect to a smooth, continuous distance field around the slab. In this paper we present a framework for processing sparse and noisy seismic data (earthquake locations), defining the shape of the slab and computing a continuous distance function on a mesh with variable node spacing. Due to the inhomogeneous volumetric distribution of earthquakes within the slab and significant inaccuracies in the locations of earthquakes occurring hundreds of kilometers below the Earth’s surface, the seismicity data set is extremely noisy and incomplete. Therefore, the preprocessing is the major part of the framework consisting of several steps including a point based smoothing procedure, a powerful method to use other observational constraints on slab location (e.g., seismic tomography or geologic history) to extend of the slab shape beyond earthquake data set and continuous resampling using moving least squares method. For the preprocessed point data we introduce approaches for finding the three-dimensional boundary of the slab and a subdivision of the slab into quadric implicit polynomials. The resulting distance field is then compiled from distances to the piecewise continuous approximation of the slab and distances to slab boundary.     

A New SiF–Dipropargyl Glycerol Scaffold as a Versatile Prosthetic Group to Design Dimeric Radioligands: Synthesis of the [18F]BMPPSiF Tracer to Image Serotonin Receptors

A novel SiX–dipropargyl glycerol scaffold (X: H, F, or ¹⁸F) was developed as a versatile prosthetic group that provides technical advantages for the preparation of dimeric radioligands based on silicon fluoride acceptor pre‐ or post‐labeling with fluorine‐18. Rapid conjugation with the prosthetic group takes place in microwave‐assisted click conjugation under mild conditions. Thus, a bivalent homodimeric SiX–dipropargyl glycerol derivatized radioligand, [¹⁸F]BMPPSiF, with enhanced affinity was developed by using click conjugation. High uptake of the radioligand was demonstrated in 5‐HT_1A receptor‐rich regions in the brain with positron emission tomography. Molecular docking studies (rigid protein–flexible ligand) of BMPPSiF and known antagonists (WAY‐100635, MPPF, and MefWAY) with monomeric, dimeric, and multimeric 5‐HT_1A receptor models were performed, with the highest G score obtained for docked BMPPSiF: ?6.766 as compared with all three antagonists on the monomeric model. Multimeric induced‐fit docking was also performed to visualize the comparable mode of binding under in vivo conditions, and a notably improved G score of ?8.455 was observed for BMPPSiF. These data directly correlate the high binding potential of BMPPSiF with the bivalent binding mode obtained in the biological studies. The present study warrants wide application of the SiX–dipropargyl glycerol prosthetic group in the development of ligands for imaging with enhanced affinity markers for specific targeting based on peptides, nucleosides, and lipids.     

Contaminant blubber burdens in Atlantic bottlenose dolphins (Tursiops truncatus) from two southeastern US estuarine areas: Concentrations and patterns of PCBs, pesticides, PBDEs, PFCs, and PAHs

Polychlorinated biphenyls (PCBs), chlorinated pesticides (i.e., dichlorodiphenyltrichloroethane (DDT) and its metabolites, chlordanes (CHLs), dieldrin, hexachlorobenzene (HCB), and mirex), polybrominated diphenyl ethers (PBDEs), perfluorinated chemicals (PFCs), and polyaromatic hydrocarbons (PAHs) were measured in blubber biopsy samples collected from 139 wild bottlenose dolphins (Tursiops truncatus) during 2003-2005 in Charleston (CHS), SC and the Indian River Lagoon (IRL), FL. Dolphins accumulated a similar suite of contaminants with ∑ PCB dominating (CHS 64%, IRL 72%), followed by ∑ DDT (CHS 20%, IRL 17%), ∑ CHLs (CHS 7%; IRL 7%), ∑ PBDE (CHS 4%, IRL 2%), PAH at 2%, and dieldrin, PFCs and mirex each 1% or less. Together ∑ PCB and ∑ DDT concentrations contributed ∼ 87% of the total POCs measured in blubber of adult males. ∑ PCBs in adult male dolphins exceed the established PCB threshold of 17 mg/kg by a 5-fold order of magnitude with a 15-fold increase for many animals; 88% of the dolphins exceed this threshold. For male dolphins, CHS (93,980 ng/g lipid) had a higher ∑ PCBs geomean compared to the IRL (79,752 ng/g lipid) although not statistically different. In adult males, the PBDE geometric mean concentration was significantly higher in CHS (5920 ng/g lipid) than the IRL (1487 ng/g). Blubber ∑ PFCs concentrations were significantly higher in CHS dolphins. In addition to differences in concentration of PCB congeners, ∑ PBDE, TEQ, ∑ CHLs, mirex, dieldrin, and the ratios ∑ DDE/∑DDT and trans-nonachlor/cis-nonachlor were the most informative for discriminating contaminant loads in these two dolphin populations. Collectively, the current ∑ PCB, ∑ DDT, and ∑ PBDEs blubber concentrations found in CHS dolphins are among the highest reported values in marine mammals. Both dolphin populations, particularly those in CHS, carry a suite of organic chemicals at or above the level where adverse effects have been reported in wildlife, humans, and laboratory animals warranting further examination of the potential adverse effects of these exposures.