Perfluorooctanesulfonate and related fluorinated hydrocarbons in marine mammals,fishes, and birds from coasts of the Baltic and the Mediterranean Seas

Perfluorooctanesulfonate (PFOS; C8F17SO3-), perfluorooctanesulfonamide (FOSA; C8F17SO2NH2), perfluorohexanesulfonate (PFHxS; C6F13SO3-), and perfluorooctanoate (PFOA; C7F15CO2-) were detected in 175 samples of liver and blood of bluefin tuna (Thunnus thynnus), swordfish (Xiphias gladius), common cormorants (Phalacrocorax carbo), bottlenose dolphins (Tursiops truncatus), striped dolphins (Stenella coeruleoalba), common dolphins (Delphinus delphi), fin whales (Balenoptera physalus), and long-finned pilot whales (Globicephala melas) from the Italian coast of the Mediterranean Sea and in livers of ringed seals (Phoca hispida), gray seals (Halichoerus grypus), white-tailed sea eagles (Haliaeetus albicilla), and Atlantic salmon (Salmo salar) from coastal areas of the Baltic Sea. PFOS was detected in all of the wildlife species analyzed. Concentrations of PFOS in blood decreased in order of bottlenose dolphins > bluefin tuna > swordfish. Mean PFOS concentrations (61 ng/ g, wet wt) in cormorant livers collected from Sardinia Island in the Mediterranean Sea were less than the concentrations of PFOA (95 ng/g, wetwt). PFOS concentrations in cormorant livers were significantly correlated with those of PFOA. FOSA was found in 14 of 19 livers or blood samples of marine mammals from the Mediterranean Sea. The highest concentration of 878 ng FOSA/g, wet wt, was found in the liver of a common dolphin. Livers of ringed and gray seals from the Bothnian Bay in the Baltic Sea contained PFOS concentrations ranging from 130 to 1,100 ng/g, wet wt. No relationships between PFOS concentrations and ages of ringed or gray seals were observed. Concentrations of PFOS in livers of seals were 5.5-fold greater than those in corresponding blood. A significant positive correlation existed between the PFOS concentrations in liver and blood, which indicates that blood can be used for nonlethal monitoring of PFOS. Trend analysis of PFOS concentrations in livers of white-tailed sea eagles collected from eastern Germany and Poland since 1979 indicated an increase in concentrations during the 1990s. Livers of Atlantic salmons did not contain quantifiable concentrations of any of the fluorochemicals monitored. PFOS is a widespread contaminant in wildlife from the Baltic and the Mediterranean Seas, while FOSA and PFOA were detected only in certain locations indicating their sporadic spatial distribution.     

Phosphate adsorption and precipitation in calcareous soils: the role of calcium ions in solution and carbonate minerals

P-removal from soil solution is mainly due to adsorption and precipitation reactions. For calcareous soils two pathways have been proposed as being relevant: partitioning on soil surfaces and precipitation induced by Ca2+ ions in solution. To define P-speciation in soil and reduce P-immobilisation following fertilisation, the relative importance of these two reactions needs to be quantitatively established. This investigation, conducted on two calcareous soils, suggests that Ca-ion activity in the liquid phase is mainly responsible for the formation of insoluble Ca-P phases. Our study was carried out by determining: a) batch sorption isotherms at different slurry concentrations, times of contact, pH and indifferent electrolyte concentrations; b) supernatant isotherms on soil suspensions; c) insolubilisation kinetics of P added to soil columns. The shape of the sorption isotherms indicated that adsorption predominated at low concentrations (below approximately 0.5 mM); above this level precipitation became predominant. Precipitation from solution was demonstrated by adding increasing amounts of phosphate to soil suspension supernatants and precipitation levels comparable to those observed in sorption isotherms were obtained. Thus, carbonate mineral surfaces were not necessary for the induction of P precipitation. The formation of Ca-P mineral phases was increased with reaction time and was governed by the concentration of Ca-ions, pH and indifferent electrolyte concentration. P added at the top of soil columns was rapidly insolubilised: after 5 weeks the P-Olsen value was reduced to about 60% and P was not transported to the deepest layers but remained in the surface ones. These results suggest that, for soils with a high reservoir of exchangeable cations able to form insoluble P phases, precipitation is the predominant mechanism which reduces P availability for plants.     

Environmental conditions affect semolina quality in durum wheat (Triticum turgidum ssp. durum L.) cultivars with different gluten strength and gluten protein composition

BACKGROUND: Sowing time may impact semolina and pasta cooking quality by changing the environmental conditions during grain filling. The effect of an optimum and a delayed sowing time on semolina quality was studied by comparing six cultivars under irrigation, in order to isolate temperature from drought effects. RESULTS: Protein content was higher in the old cultivars and in the late sowings, according to the number of days with temperature between 30 and 40 °C during ripening. Gluten index increased as temperature rose to a threshold of about 30 °C, then decreased under higher temperatures. Mixograph parameters were less sensitive to high temperatures. Gliadin:glutenin correlated with gluten strength. Spaghetti firmness and protein content were positively correlated independently of sowing date. Cultivars Trinakria and Cappelli had the highest spaghetti firmness (900 and 828 g). CONCLUSIONS: Late sowings may represent a way of increasing pasta cooking quality whenever they place grain filling under thermal conditions able to increase protein percentage, although the accompanying decrease in yield may represent a drawback in environments prone to drought stress during ripening. The lower protein percentages of modern durum wheat cultivars under conventional sowing times results in a lower pasta cooking quality despite higher gluten strength. Published 2011 by John Wiley & Sons, Ltd.     

Perfluorooctanesulfonate and related fluorochemicals in human blood from several countries

Perfluorooctanesulfonyl fluoride based compounds have been used in a wide variety of consumer products, such as carpets, upholstery, and textiles. These compounds degrade to perfluorooctanesulfonate (PFOS), a persistent metabolite that accumulates in tissues of humans and wildlife. Previous studies have reported the occurrence of PFOS, perfluorohexanesulfonate (PFHxS), perfluorooctanoate (PFOA), and perfluorooctanesulfonamide (PFOSA) in human sera collected from the United States. In this study, concentrations of PFOS, PFHxS, PFOA, and PFOSA were measured in 473 human blood/serum/plasma samples collected from the United States, Colombia, Brazil, Belgium, Italy, Poland, India, Malaysia, and Korea. Among the four perfluorochemicals measured, PFOS was the predominant compound found in blood. Concentrations of PFOS were the highest in the samples collected from the United States and Poland (>30 ng/mL); moderate in Korea, Belgium, Malaysia, Brazil, Italy, and Colombia (3 to 29 ng/mL); and lowest in India (<3 ng/mL). PFOA was the next most abundant perfluorochemical in blood samples, although the frequency of occurrence of this compound was relatively low. No age- or gender-related differences in the concentrations of PFOS and PFOA were found in serum samples. The degree of association between the concentrations of four perfluorochemicals varied, depending on the origin of the samples. These results suggested the existence of sources with varying levels and compositions of perfluorochemicals, and differences in exposure patterns to these chemicals, in various countries. In addition to the four target fluorochemicals measured, qualitative analysis of selected blood samples showed the presence of other perfluorochemicals such as perfluorodecanesulfonate (PFDS), perfluoroheptanoic acid (PFHpA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorododecanoic acid (PFDoA), and perfluoroundecanoic acid (PFUnDA) in serum samples, at concentrations approximately 5- to 10-fold lower than the concentration of PFOS. Further studies should focus on identifying sources and pathways of human exposure to perfluorochemicals.     

Analogs of squalene and oxidosqualene inhibit oxidosqualene cyclase of <Emphasis Type="Italic">Trypanosoma cruzi</Emphasis> expressed in <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis>

Recently, a number of inhibitors of the enzyme oxidosqualene cyclase (OSC; EC 5.4.99.7), a key enzyme in sterol biosynthesis, were shown to inhibit in mammalian cells the multiplication of Trypanosoma cruzi, the parasite agent of Chagas’ disease. The gene coding for the OSC of T. cruzi has been cloned and expressed in Saccharomyces cerevisiae. The expression in yeast cells could be a safe and easy model for studying the activity and the selectivity of the potential inhibitors of T. cruzi OSC. Using a homogenate of S. cerevisiae cells expressing T. cruzi OSC, we have tested 19 inhibitors: aza, methylidene, vinyl sulfide, and conjugated vinyl sulfide derivatives of oxidosqualene and squalene, selected as representative of different classes of substrate analog inhibitors of OSC. The IC₅₀ values of inhibition (the compound concentration at which the enzyme is inhibited by 50%) are compared with the values obtained using OSC of pig liver and S. cerevisiae. Many inhibitors of pig liver and S. cerevisiae OSC show comparable IC₅₀ for T. cruzi OSC, but some phenylthiovinyl derivatives are 10–100 times more effective on the T. cruzi enzyme than on the pig or S. cerevisiae enzymes. The expression of proteins of pathogenic organisms in yeast seems very promising for preliminary screening of compounds that have potential therapeutic activity.     

Detection and quantification of lanthanide complexes in cell lysates by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Gadolinium (III) complexes are under intense scrutiny as contrast agents for magnetic resonance imaging. Although currently used mainly as extracellular agents, there is a growing interest to exploit their contrast enhancing ability in the intracellular environment. To ascertain the preservation of their chemical integrity upon the intracellular entrapment, it is necessary to have a method for their dosage in the cell lysates. Herein, a mass spectrometric method for detection and quantification of gadolinium complexes in cell lysates is reported. The detection by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) was carried out by using a non-acidic matrix (2,4,6-trihydroxyacetophenone), which does not allow any leakage of gadolinium from the complex. Quantification has been possible by using as an internal standard an ytterbium complex with the same ligand of the analyte. Ytterbium was chosen because, among the lanthanides, it is the one with the isotopic distribution pattern the most similar to that of gadolinium. Sensitivity was enough to detect low micromolar quantities of a cationic complex and high micromolar quantities of a neutral complex in cell lysates of rat hepatoma cells. In the case of anionic complexes, sensitivity was too low for quantitative analysis. To the best of our knowledge, this is the first report concerning the quantification of metal complexes by MALDI-TOF-MS.     

Fetal growth restriction: adaptations and consequences

A range of pathophysiological factors can result in a perturbation or restriction of fetal growth, and the cardiovascular, neuroendocrine and metabolic adaptations of the fetus to these stimuli will depend on their nature, timing and intensity. The critical importance of these physiological adaptations for both immediate survival and long-term health outcomes has provided an impetus for experimental studies of the nature and consequences of specific fetal adaptations to a poor intrauterine environment. This review summarizes data from recent studies that have focused on the responses of the fetal cardiovascular, sympathoadrenal, hypothalamo-pituitary-adrenal and renin-angiotensin systems to experimental restriction of placental function in the sheep and discusses the consequences of these adaptations for fetal, neonatal and adult health.     

Acetylcholinesterase‐inhibitor hydrolysates obtained from ‘in vitro’ enzymatic hydrolysis of mannoproteins extracted from different strains of yeasts

In vitro inhibitory activity against acetylcholinesterase (AChE) of peptides obtained by enzymatic hydrolysis of mannoproteins extracted from strains of yeasts was investigated. Yeast mannoproteins were extracted from strains belonging to the genera Brettanomyces, Candida, Pichia and Saccharomyces isolated from dairy products. They were obtained by heat treatment in citrate buffer and purified by affinity chromatography with concanavalin A. Each purified extract was subsequently hydrolysed with proteolytic enzymes (trypsin, pepsin, chymotrypsin and proteinase K) applied individually or in combination, thus generating smaller peptides. Inhibitory activity of the latter against AChE was determined. The molecular weight of mannoproteins, determined by SDS‐PAGE, was between 6.5 and 30 kDa. As regards AChE inhibition, a preliminary screening of all hydrolysed extracts was performed, yielding variable results with 59% maximum inhibition. Subsequently, when inhibitory concentration 50 (IC50) was determined, the extracts showed higher inhibitory activity (between 6.75 and 12.3 mg mL^?1). Results showed that the mannoproteins separated from yeast strains of food origin generated bioactive peptides by enzymatic hydrolysis, which can be of interest to the manufacturing of food with potential functional properties.     

Electrochemical treatment of simulated ground water containing MTBE and BTEX with BDD anodes

BACKGROUND: Benzene, toluene, ethylbenzene, xylene (BTEX) and oxy‐fuels such as methyl tert‐butyl ether (MTBE) are typical contaminants of ground waters. Biological and physical techniques are often ineffective in removing these compounds, while promising results were obtained with advanced oxidation processes (AOPs), which are based on oxidation by hydroxyl radicals. Electrochemical oxidation with boron doped diamond (BDD) anodes occurs by OH radicals generated from water oxidation, so that it may be considered as an alternative to other AOPs. RESULTS: An experimental study on the electrochemical removal of MTBE and BTEX with BDD anodes from water with low organic concentrations and low conductivity is presented. The kinetics of the process was investigated by batch electrolyses: the removal of MTBE and benzene was controlled by the mass transfer towards the anode, while a further reaction bulk contribution was found for alkylbenzenes. The process was tested in continuous mode and the energy consumption was evaluated and compared with other AOPs. CONCLUSIONS: Removal of the pollutants higher than 95% was achieved under all the examined conditions, confirming the effectiveness of the process. The proposed electrochemical treatment was comparable with other AOPs in terms of energy consumption, and it can be considered as an alternative to other processes for ground water treatment. Copyright © 2010 Society of Chemical Industry