Systematic underestimation of polycyclic aromatic hydrocarbon aqueous concentrations in rivers.

Polycyclic aromatic hydrocarbons (PAHs) are a widespread group of organic contaminants whose presence in water bodies is cause of severe concern. With few exceptions, the majority of PAHs is hydrophobic, presents a high adsorption affinity, and is thus primarily transported within river systems during high-flow events together with suspended particulate matter (SPM). Evidence exists of analytical challenges related to the incomplete extraction of PAHs adsorbed to solids and thus to a potential negative bias in the chemical analysis of PAHs in bulk water samples with high SPM content. Despite this, partly due to the elevated efforts required to collect representative samples containing sufficient SPM for the separate PAH analysis in this matrix, several investigations rely on the analysis of aqueous samples. This study tests the hypothesis that surveys based exclusively on bulk water may lead to a systematic underestimation of the real contamination level and transport of PAHs in rivers. Six high-turbidity events were examined in three Austrian rivers applying time-integrated sampling and simultaneously analyzing PAHs in total bulk water, filtered water, SPM, and supernatant. Despite an unavoidable degree of uncertainty in such challenging sampling scheme, the results indicate that measurements performed with best available standard methods in bulk water samples determined in average only about 40% of the theoretically expected total PAHs concentrations derived from the analyses in SPM. Such deviation has important implications for the reliable assessment of the compliance with environmental quality standards as well as for surveys aimed to estimate riverine loads, validate emission models, and understand the transport dynamics of PAHs in rivers. Whereas the first objective, e.g., in European countries, is alternatively achieved via monitoring in biota, the latter ones require efforts directed to complement monitoring campaigns with separate sampling of SPM, with monitoring of suspended solids transport to appropriately select and interpret the results of water samples and to improve the chemical analysis of PAHs in bulk water samples with high solids content.

Systematic data-driven exploration of Austrian wastewater and sludge treatment - implications for phosphorus governance, costs and environment.

Within the new policy framework shaped by the EU Green Deal and the Circular Economy Action Plans, the field of wastewater and sludge treatment in Europe is subject to high expectations and new challenges related to mitigation of greenhouse gas emissions, micropollutant removal and resource recovery. With respect to phosphorus recovery, several technologies and processes have been thoroughly investigated. Nevertheless, a systemic and detailed understanding of the existing infrastructure and of the related environmental and economic implications is missing. Such basis is essential to avoid unwanted consequences in designing new strategies, given the long lifespan of any infrastructural change. This study couples a newly collected and highly detailed database for all wastewater treatment plants in Austria bigger than 2000 population equivalent with a combination of analyses, namely Substance Flow Analysis with focus on nutrient and metal distribution in different environmental and anthropogenic compartments, Energy Flow Analysis, Life Cycle Assessment and cost estimation. The case study of Austria is of special interest, given its highly autonomous administration in federal states and its contrasting traits, ranging from flat metropolitan areas like Vienna to low-populated alpine areas. The significant impact of electricity demand of wastewater treatment on the overall Cumulative Energy Demand (CED) shows the importance of optimization measures. Further, the current system of wastewater and sludge disposal have a low efficiency in recovering nutrients and in directing pollutants as heavy metals into final sinks. Sludge composting with subsequent use in landscaping does not only show an unfavorable environmental balance, but it is the only relevant route leading to additional CED and Global Warming Potential emissions and to the highest transport volume. Altogether, the outcomes of this study provide a sound basis to further develop national strategies for resource recovery aimed to optimize trade-offs between different economic and environmental objectives.

Thiol-functionalized copolymeric polyesters by lipase-catalyzed esterification and transesterification of 1,12-dodecanedioic acid and its diethyl ester, respectively, with 1-thioglycerol.

Copolymeric polyoxoesters containing branched-chain methylenethiol functions, i.e., poly(1,12-dodecanedioic acid-co-1-thioglycerol) and poly(diethyl 1,12-dodecanedioate-co-1-thioglycerol), were formed by lipase-catalyzed polyesterification and polytransesterification of 1,12-dodecanedioic acid and diethyl 1,12-dodecanedioate, respectively, with 1-thioglycerol (3-mercaptopropane-1,2-diol) using immobilized lipase B from Candida antarctica (Novozym 435) in vacuo without drying agent in the reaction mixture. After 360-480 h, both polyoxoesters were purified by extraction from the reaction mixtures followed by solvent fractionation. The precipitate of poly(1,12-dodecanedioic acid-co-1-thioglycerol) demonstrated a M(W) of ~170,000 Da, whereas a M(W) of ~7,100 Da only was found for poly(diethyl 1,12-dodecanedioate-co-1-thioglycerol). Both polycondensates were analyzed by GPC/SEC, alkali-catalyzed transmethylation, NMR- and FTIR-spectrometry.

Highly efficient preparation of lipophilic hydroxycinnamates by solvent-free lipase-catalyzed transesterification.

Various medium- or long-chain alkyl cinnamates and hydroxycinnamates, including oleyl p-coumarate as well as palmityl and oleyl ferulates, were prepared in high yield by lipase-catalyzed transesterification of an equimolar mixture of a short-chain alkyl cinnamate and a fatty alcohol such as lauryl, palmityl, and oleyl alcohol under partial vacuum at moderate temperature in the absence of solvents and drying agents in direct contact with the reaction mixture. Immobilized lipase B from Candida antarctica was the most effective biocatalyst for the various transesterification reactions. Transesterification activity of this enzyme was up to 56-fold higher than esterification activity for the preparation of medium- and long-chain alkyl ferulates. The relative transesterification activities found for C. antarctica lipase were of the following order: hydrocinnamate > cinnamate > 4-hydroxyhydrocinnamate > 3-methoxycinnamate > 2-methoxycinnamate approximately 4-methoxycinnamate approximately 3-hydroxycinnamate > hydrocaffeate approximately 4-hydroxycinnamate > ferulate > 2-hydroxycinnamate > caffeate approximately sinapate. With respect to the position of the hydroxy substituents at the phenyl moiety, the transesterification activity of C. antarctica lipase B increased in the order meta > para > ortho. The immobilized lipases from Rhizomucor miehei and Thermomyces lanuginosus demonstrated moderate and low transesterification activity, respectively. Compounds with inverse chemical structure, that is, 3-phenylpropyl alkanoates such as 3-(4-hydroxyphenyl)propyl oleate and 3-(3,4-dimethoxyphenyl)propyl oleate, were obtained by C. antarctica lipase-catalyzed transesterification of fatty acid methyl esters with the corresponding 3-phenylpropan-1-ols in high yield, as well.

Dialkyl 3,3'-thiodipropionate and dialkyl 2,2'-thiodiacetate antioxidants by lipase-catalyzed esterification and transesterification.

Medium- and long-chain dialkyl 3,3'-thiodipropionate antioxidants such as dioctyl 3,3'-thiodipropionate, didodecyl 3,3'-thiodipropionate, dihexadecyl 3,3'-thiodipropionate, and di-(cis-9-octadecenyl) 3,3'-thiodipropionate were prepared in high yield by lipase-catalyzed esterification and transesterification of 3,3'-thiodipropionic acid and its dimethyl ester, respectively, with the corresponding medium- or long-chain 1-alkanols, i.e., 1-octanol, 1-dodecanol, 1-hexadecanol, and cis-9-octadecen-1-ol, in vacuo (80 kPa) at moderate temperatures (60-80 degrees C) without solvents. Immobilized lipase B from Candida antarctica (Novozym 435) was the most active biocatalyst for the preparation of medium- and long-chain dialkyl 3,3'-thiodipropionates showing enzyme activities up to 1489 units/g, whereas the immobilized lipases from Rhizomucor miehei (Lipozyme RM IM) and Thermomyces lanuginosus (Lipozyme TL IM) were by far less active ( approximately 10 enzyme units/g). Maximum conversions to dialkyl 3,3'-thiodipropionates were as high as 92-98% after 4 h of reaction time. Similarly, dihexadecyl 2,2'-thiodiacetate was prepared in high yield using 2,2'-thiodiacetic acid or diethyl 2,2'-thiodiacetate and 1-hexadecanol as the starting materials and Novozym 435 as the biocatalyst.

Solvent-free lipase-catalyzed preparation of long-chain alkyl phenylpropanoates and phenylpropyl alkanoates.

An enzymatic method was developed for the preparation of medium- or long-chain alkyl 3-phenylpropenoates (alkyl cinnamates), particularly alkyl hydroxy- and methoxy-substituted cinnamates such as oleyl p-coumarate and oleyl ferulate. The various alkyl cinnamates were formed in high to moderate yield by lipase-catalyzed esterification of cinnamic acid and its analogues with fatty alcohols in vacuo at moderate temperatures in the absence of drying agents and solvents. Immobilized Candida antarctica lipase B was the most effective biocatalyst for the various esterification reactions. The relative esterification activities were of the following order: dihydrocinnamic > cinnamic > 3-methoxycinnamic > dihydrocaffeic approximately 3-hydroxycinnamic > 4-methoxycinnamic > 2-methoxycinnamic > 4-hydroxycinnamic > ferulic approximately 3,4-dimethoxycinnamic > 2-hydroxycinnamic acid. With respect to the position of the substituents at the phenyl moiety, the esterification activity increased in the order meta > para > ortho. Rhizomucor miehei lipase demonstrated moderate esterification activity. Compounds with inverse chemical structure, that is, 3-phenylpropyl alkanoates such as 3-(4-hydroxyphenyl)propyl oleate, were also obtained in high yield by esterification of fatty acids with the corresponding 3-phenylpropan-1-ols.

Effects of Video-Based Visual Training on Decision-Making and Reactive Agility in Adolescent Football Players.

This study investigated the trainability of decision-making and reactive agility via video-based visual training in young athletes. Thirty-four members of a national football academy (age: 14.4 ± 0.1 years) were randomly assigned to a training (VIS; n = 18) or a control group (CON; n = 16). In addition to the football training, the VIS completed a video-based visual training twice a week over a period of six weeks during the competition phase. Using the temporal occlusion technique, the players were instructed to react on one-on-one situations shown in 40 videos. The number of successful decisions and the response time were measured with a video-based test. In addition, the reactive-agility sprint test was used. VIS significantly improved the number of successful decisions (22.2 ± 3.6 s vs. 29.8 ± 4.5 s; p < 0.001), response time (0.41 ± 0.10 s vs. 0.31 ± 0.10 s; p = 0.006) and reactive agility (2.22 ± 0.33 s vs. 1.94 ± 0.11 s; p = 0.001) pre- vs. post-training. No significant differences were found for CON. The results have shown that video-based visual training improves the time to make decisions as well as reactive agility sprint-time, accompanied by an increase in successful decisions. It remains to be shown whether or not such training can improve simulated or actual game performance.

Solvent-free lipase-catalyzed preparation of diacylglycerols.

Various methods have been applied for the enzymatic preparation of diacylglycerols that are used as dietary oils for weight reduction in obesity and related disorders. Interesterification of rapeseed oil triacylglycerols with commercial preparations of monoacylglycerols, such as Monomuls 90-O18, Mulgaprime 90, and Nutrisoft 55, catalyzed by immobilized lipase from Rhizomucor miehei (Lipozyme RM IM) in vacuo at 60 degrees C led to extensive (from 60 to 75%) formation of diacylglycerols. Esterification of rapeseed oil fatty acids with Nutrisoft, catalyzed by Lipozyme RM in vacuo at 60 degrees C, also led to extensive (from 60 to 70%) formation of diacylglycerols. Esterification of rapeseed oil fatty acids with glycerol in vacuo at 60 degrees C, catalyzed by Lipozyme RM and lipases from Thermomyces lanuginosus (Lipozyme TL IM) and Candida antarctica (lipase B, Novozym 435), also provided diacylglycerols, however, to a lower extent (40-45%). Glycerolysis of rapeseed oil triacylglycerols with glycerol in vacuo at 60 degrees C, catalyzed by Lipozyme TL and Novozym 435, led to diacylglycerols to the extent of

Lipophilic (hydroxy)phenylacetates by solvent-free lipase-catalyzed esterification and transesterification in vacuo.

Various long-chain alkyl (hydroxy)phenylacetates were prepared in high yield by lipase-catalyzed transesterification of the corresponding short-chain alkyl hydroxyphenylacetates and fatty alcohols in equimolar ratios. The reactions were performed in vacuo at moderate temperatures in the absence of solvents and drying agents in direct contact with the reaction mixture. Immobilized lipase B from Candida antarctica (Novozym 435) was the most effective biocatalyst for the various transesterification reactions. Generally, Novozym 435-catalyzed transesterifications of short-chain alkyl (hydroxy)phenylacetates with long-chain alcohols led to higher conversions and enzyme activities than the corresponding esterifications. For example, the transesterification activity was up to 4-fold higher than the esterification activity for the formation of oleyl 4-hydroxy-3-methoxyphenylacetate using Novozym 435 as a biocatalyst. The relative transesterification activities were as follows: phenylacetate > 3-methoxyphenylacetate approximately 4-methoxyphenylacetate > 4-hydroxy-3-methoxyphenylacetate > 3-hydroxyphenylacetate approximately 4-hydroxyphenylacetate >> 2-methoxyphenylacetate >> 3,4-dihydroxyphenylacetate. With respect to the position of methoxy and hydroxy substituents, the transesterification activity of Novozym 435 decreased in the order meta approximately para >> ortho. Compounds with inverse chemical structures, for example, tyrosyl oleate, were obtained by Novozym 435-catalyzed esterification and transesterification of fatty acids and their methyl esters, respectively, with 2-phenylethan-1-ols. In contrast to the transesterifications of short-chain alkyl (hydroxy)phenylacetates with fatty alcohols, higher conversions and enzyme activities were observed for the Novozym 435-catalyzed esterifications of (hydroxy)phenylethanols with long-chain fatty acids than the corresponding transesterifications with fatty acid methyl esters.

Thio wax ester biosynthesis utilizing the unspecific bifunctional wax ester synthase/acyl coenzyme A:diacylglycerol acyltransferase of Acinetobacter sp. strain ADP1.

The bifunctional wax ester synthase/acyl coenzyme A (acyl-CoA):diacylglycerol acyltransferase (WS/DGAT) from Acinetobacter sp. strain ADP1 (formerly Acinetobacter calcoaceticus ADP1) mediating the biosyntheses of wax esters and triacylglycerols was used for the in vivo and in vitro biosynthesis of thio wax esters and dithio wax esters. For in vitro biosynthesis, 5'His(6)WS/DGAT comprising an N-terminal His(6) tag was purified from the soluble protein fraction of Escherichia coli Rosetta(DE3)pLysS (pET23a::5'His(6)atf). By employing SP-Sepharose high-pressure and Ni-nitrilotriacetic acid fast-protein liquid chromatographies, a 19-fold enrichment with a final specific activity of 165.2 nmol mg of protein(-1) min(-1) was achieved by using 1-hexadecanol and palmitoyl-CoA as substrates. Incubation of purified 5'His(6)WS/DGAT with 1-hexadecanethiol and palmitoyl-CoA as substrates resulted in the formation of palmitic acid hexadecyl thio ester (10.4% relative specific activity of a 1-hexadecanol control). Utilization of 1,8-octanedithiol and palmitoyl-CoA as substrates led to the formation of 1-S-monopalmitoyloctanedithiol and minor amounts of 1,8-S-dipalmitoyloctanedithiol (59.3% relative specific activity of a 1-hexadecanol control). The latter dithio wax ester was efficiently produced when 1-S-monopalmitoyloctanedithiol and palmitoyl-CoA were used as substrates (13.4% specific activity relative to that of a 1-hexadecanol control). For the in vivo biosynthesis of thio wax esters, the knockout mutant Acinetobacter sp. strain ADP1acr1OmegaKm, which is unable to produce fatty alcohols, was used. Cultivation of Acinetobacter sp. strain ADP1acr1OmegaKm in the presence of gluconate, 1-hexadecanethiol, and oleic acid in nitrogen-limited mineral salts medium resulted in the accumulation of unusual thio wax esters that accounted for around 1.19% (wt/wt) of the cellular dry weight and consisted mainly of oleic acid hexadecyl thioester as revealed by gas chromatography-mass spectrometry.

Stereospecific incorporation of palmitoyl, oleoyl and linoleoyl moieties into adipose tissue triacylglycerols of rats results in constant sn-1:sn-2:sn-3 in rats fed rapeseed, olive, conventional or high oleic sunflower oils, but not in those fed coriander oil.

We report the stereospecific (sn-1, sn-2, sn-3) distribution of fatty acids in subcutaneous adipose tissue triacylglycerols of male weaned Wistar rats fed either a standard diet or diets containing, in addition to 20 g corn oil/kg feed, 120 g/kg feed, each, of canola-type rapeseed oil, olive oil, conventional or high oleic sunflower oil or high petroselinic coriander oil for 10 wk. The regiospecific distribution of the major acyl moieties in the sn-1 (3) vs. sn-2 positions of the adipose tissue triacylglycerols broadly reflected that of the dietary oils. The saturated palmitoyl and stearoyl moieties were more abundant in the sn-1 and sn-3 positions compared with the sn-2 position of the adipose tissue triacylglycerols, and both occurred at a higher proportion in the sn-1 than in the sn-3 position. Oleoyl moieties were abundant in all the three positions of the adipose tissue triacylglycerols, whereas petroselinoyl moieties were more abundant in the sn-1 and sn-3 positions compared with the sn-2 position. Linoleoyl moieties occurred predominantly in the sn-2 position compared with the sn-1 and sn-3 positions of the adipose tissue triacylglycerols; however, they were more abundant in the sn-3 than in the sn-1 position. Despite widely varying proportions of the palmitoyl, oleoyl and linoleoyl moieties at the three positions of the dietary triacylglycerols, the ratios of each of these acyl moieties at the sn-1, sn-2, and sn-3 positions in adipose tissue triacylglycerols were essentially constant for all groups, with the exception of the group fed coriander oil, indicating a rigid stereospecific incorporation.

The composition of the major molecular species of adipose tissue triacylglycerols of rats reflects those of dietary rapeseed, olive and sunflower oils.

We report the composition of constituent fatty acids and molecular species of adipose tissue triacylglycerols of male weaned Wistar rats fed diets containing, in addition to 20 g corn oil/kg feed, 120 g per kg feed canola-type rapeseed oil, olive oil or conventional sunflower oil for 10 wk. The composition of fatty acids and molecular species of the triacylglycerols of subcutaneous, epididymal and perirenal adipose tissues did not differ among groups (P > 0.01), broadly reflecting the corresponding compositions of the dietary oils. The major molecular species of dietary triacylglycerols, especially trioleoylglycerol (OOO) and linoleoyl-dioleoylglycerols (LOO) in the rapeseed oil and olive oil diets, dioleoyl-palmitoylglycerols (OOP) in the olive oil diet, dilinoleoyl-oleoylglycerols (LLO) in the rapeseed oil and sunflower oil diets, and dilinoleoyl-palmitoylglycerols (LLP), linoleoyl-oleoyl-palmitoylglycerols (LOP) as well as trilinoleoylglycerol (LLL) in the sunflower oil diet were also prominent constituents of the corresponding adipose tissue triacylglycerols. On the other hand, predominant molecular species containing alpha-linolenoyl (Ln) moieties, e.g., alpha-linolenoyl-linoleoyl-oleoylglycerols (LnLO) and alpha -linolenoyl-dioleoylglycerols (LnOO) from the rapeseed oil diet were not prominent constituents of rat adipose tissue triacylglycerols, whereas LOP from rapeseed oil and olive oil diets and OOP from rapeseed oil and sunflower oil diets were distinctly enriched in the corresponding adipose tissues. Most of the minor molecular species of the dietary triacylglycerols from all the three diets were distinctly present in the corresponding adipose tissues. Thus, despite numerous biochemical processes involved in the metabolism of dietary triacylglycerols, a substantial proportion of the molecular species of adipose tissue triacylglycerols containing linoleoyl (L), oleoyl (O) and palmitoyl (P) moieties resemble those of dietary triacylglycerols.