PFAS Degradation in Ultrapure and Groundwater Using Non-Thermal Plasma.

Perfluoroalkyl substances (PFAS) represent one of the most recalcitrant class of compounds of emerging concern and their removal from water is a challenging goal. In this study, we investigated the removal efficiency of three selected PFAS from water, namely, perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and pefluorooctanesulfonic acid (PFOS) using a custom-built non-thermal plasma generator. A modified full factorial design (with 2 levels, 3 variables and the central point in which both quadratic terms and interactions between couple of variables were considered) was used to investigate the effect of plasma discharge frequency, distance between the electrodes and water conductivity on treatment efficiency. Then, the plasma treatment running on optimized conditions was used to degrade PFAS at ppb level both individually and in mixture, in ultrapure and groundwater matrices. PFOS 1 ppb exhibited the best degradation reaching complete removal after 30 min of treatment in both water matrices (first order rate constant 0.107 min-1 in ultrapure water and 0.0633 min-1 in groundwater), while the degradation rate of PFOA and PFHxA was slower of around 65% and 83%, respectively. During plasma treatment, the production of reactive species in the liquid phase (hydroxyl radical, hydrogen peroxide) and in the gas phase (ozone, NOx) was investigated. Particular attention was dedicated to the nitrogen balance in solution where, following to NOx hydrolysis, total nitrogen (TN) was accumulated at the rate of up to 40 mgN L-1 h-1.

The characteristic smell emitted from two scale insects, Ceroplastes japonicus and Ceroplastes rubens.

The volatile components emitted from two scale insects, Ceroplastes japonicus and Ceroplastes rubens, were identified using GC-MS analysis. The major volatile components of the solvent extract from C. japonicus were α-humulene (35.8%) and δ-cadinene (17.0%), while those of C. rubens were ß-selinene (10.3%) and ß-elemene (5.1%). In GC/olfactometry, linalool, butyric acid, 3-methylbutyric acid, 2-methylbutyric acid, and vanillin were identified as the odor-active components of the extract from C. japonicus, in addition to trace amounts of trans-4,5-epoxy-(2E)-decenal, 4-methyl-(3E)-hexenoic acid, and phenylacetic acid. With regard to C. rubens, trans-4,5-epoxy-(2E)-decenal, 3-methylbutyric acid, and phenylacetic acid were identified as the odor-active components. Besides, decan-1,4-olide (γ-decalactone) with milky cherry-like note and 3-hydroxy-4,5-dimethylfuran-2(5H)-one (sotolone) with brown sugar-like note were also detected as the characteristic cherry-like sweet-and-sour note of these two scale insects. ABBREVIATIONS: GC: Gas chromatography; GC/O: gas chromatography/olfactometry.

Evaluation of BP-M-CPF4 polyhydroxyalkanoate (PHA) synthase on the production of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) from plant oil using Cupriavidus necator transformants.

Among the various types of polyhydroxyalkanoate (PHA), poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate] [P(3HB-co-3HHx)] has a high potential to serve as commercial bioplastic due to its striking resemblance to petroleum-based plastics. In this study, five different genotypes of Cupriavidusnecator transformants harbouring the phaCBP-M-CPF4 gene (including PHB¯4/pBBR1-CBP-M-CPF4) were developed to evaluate the efficiency of 3HHx monomer incorporation. The fraction of 3-hydroxyhexanoate (3HHx) monomer that was incorporated into the PHA synthesized by these C. necator transformants using palm oil as the sole carbon source, was examined. Overall, co-expression of enoyl-CoA hydratase gene (phaJ1) from Pseudomonas aeruginosa, along with PHA synthase (PhaC), increased the 3HHx composition in the PHA copolymer. The differences in the enzyme activities of ß-ketothiolase (PhaACn) and NADPH-dependent acetoacetyl-CoA reductase (PhaBCn) of the C. necator mutant hosts used in this study, were observed to alter the 3HHx composition and molecular weight of the PHA copolymer produced. The 3HHx fractions in the P(3HB-co-3HHx) produced by these C. necator transformants ranged between 1 and 18 mol%, while the weight-average molecular weight ranged from 0.7 × 106 to 1.8 × 106 Da. PhaCBP-M-CPF4 displayed a typical initial lag-phase and a relatively low synthase activity in the in vitro enzyme assay, which is thought to be the reason for the higher molecular weights of PHA obtained in this study.

Selective Separation of Acetic and Hexanoic Acids across Polymer Inclusion Membrane with Ionic Liquids as Carrier.

This paper first reports on the selective separation of volatile fatty acids (VFAs) (acetic and hexanoic acids) using polymer inclusion membranes (PIMs) containing quaternary ammonium and phosphonium ionic liquids (ILs) as the carrier. The affecting parameters such as IL content, VFA concentration, and the initial pH of the feed solution as well as the type and concentration of the stripping solution were investigated. PIMs performed a much higher selective separation performance toward hexanoic acid. The optimal PIM composed of 60 wt% quaternary ammonium IL with the permeability coefficients for acetic and hexanoic acid of 0.72 and 4.38 µm s-1, respectively, was determined. The purity of hexanoic acid obtained in the stripping solution increased with an increase in the VFA concentration of the feed solution and decreasing HCl concentration of the stripping solution. The use of Na2CO3 as the stripping solution and the involvement of the electrodialysis process could dramatically enhance the transport efficiency of both VFAs, but the separation efficiency decreased sharply. Furthermore, a coordinating mechanism containing hydrogen bonding and ion exchange for VFA transport was demonstrated. The highest purity of hexanoic acid (89.3%) in the stripping solution demonstrated that this PIM technology has good prospects for the separation and recovery of VFAs from aqueous solutions.

Improvement of n-caproic acid production with Ruminococcaceae bacterium CPB6: selection of electron acceptors and carbon sources and optimization of the culture medium.

BACKGROUND: Global energy and resource shortages make it necessary to quest for renewable resources. n-Caproic acid (CA) production based on carboxylate platform by anaerobic fermentation is booming. Recently, a novel Ruminococcaceae bacterium CPB6 is shown to be a potential biotransformation factory for CA production from lactate-containing wastewater. However, little is known about the effects of different electron acceptors (EAs) on the fermentative products of strain CPB6, as well as the optimum medium for CA production. RESULTS: In this study, batch experiments were performed to investigate the fermentative products of strain CPB6 in a lactate medium supplemented with different EAs and sugars. Supplementation of acetate, butyrate and sucrose dramatically increased cell growth and CA production. The addition of propionate or pentanoate resulted in the production of C5 or C7 carboxylic acid, respectively. Further, a Box-Behnken experiment was conducted to optimize the culture medium for CA production. The result indicated that a medium containing 13.30 g/L sucrose, 22.35 g/L lactate and 16.48 g/L butyrate supported high-titer CA production (16.73 g/L) with a maximum productivity of 6.50 g/L/day. CONCLUSIONS: This study demonstrated that strain CPB6 could produce C6-C7 carboxylic acids from lactate (as electron donor) with C2-C5 short-chain carboxylic acids (as EAs), but CA (C6 carboxylic acid) was the most major and potential product. Butyrate and sucrose were the most significant EA and carbon source respectively for CA production from lactate by strain CPB6. High titer of CA can be produced from a synthetic substrate containing sucrose, lactate and butyrate. The work provided significant implications for improving CA production in industry-scale.

High metabolic versatility of different toxigenic and non-toxigenic Clostridioides difficile isolates.

Clostridioides difficile (formerly Clostridium difficile) is a major nosocomial pathogen with an increasing number of community-acquired infections causing symptoms from mild diarrhea to life-threatening colitis. The pathogenicity of C. difficile is considered to be mainly associated with the production of genome-encoded toxins A and B. In addition, some strains also encode and express the binary toxin CDT. However; a large number of non-toxigenic C. difficile strains have been isolated from the human gut and the environment. In this study, we characterized the growth behavior, motility and fermentation product formation of 17 different C. difficile isolates comprising five different major genomic clades and five different toxin inventories in relation to the C. difficile model strains 630Δerm and R20291. Within 33 determined fermentation products, we identified two yet undescribed products (5-methylhexanoate and 4-(methylthio)-butanoate) of C. difficile. Our data revealed major differences in the fermentation products obtained after growth in a medium containing casamino acids and glucose as carbon and energy source. While the metabolism of branched chain amino acids remained comparable in all isolates, the aromatic amino acid uptake and metabolism and the central carbon metabolism-associated fermentation pathways varied strongly between the isolates. The patterns obtained followed neither the classification of the clades nor the ribotyping patterns nor the toxin distribution. As the toxin formation is strongly connected to the metabolism, our data allow an improved differentiation of C. difficile strains. The observed metabolic flexibility provides the optimal basis for the adaption in the course of infection and to changing conditions in different environments including the human gut.

Discovery, Synthesis, and Functional Characterization of a Novel Neuroprotective Natural Product from the Fruit of Alpinia oxyphylla for use in Parkinson's Disease Through LC/MS-Based Multivariate Data Analysis-Guided Fractionation.

Herein we report the discovery of a novel lead compound, oxyphylla A [(R)-4-(2-hydroxy-5-methylphenyl)-5-methylhexanoic acid] (from the fruit of Alpinia oxyphylla), which functions as a neuroprotective agent against Parkinson's disease. To identify a shortlist of candidates from the extract of A. oxyphylla, we employed an integrated strategy combining liquid chromatography/mass spectrometry, bioactivity-guided fractionation, and chemometric analysis. The neuroprotective effects of the shortlisted candidates were validated prior to scaling up the finalized list of potential neuroprotective constituents for more detailed chemical and biological characterization. Oxyphylla A has promising neuroprotective effects: (i) it ameliorates in vitro chemical-induced primary neuronal cell damage and (ii) alleviates chemical-induced dopaminergic neuron loss and behavioral impairment in both zebrafish and mice in vivo. Quantitative proteomics analyses of oxyphylla A-treated primary cerebellar granule neurons that had been intoxicated with 1-methyl-4-phenylpyridinium revealed that oxyphylla A activates nuclear factor-erythroid 2-related factor 2 (NRF2)-a master redox switch-and triggers a cascade of antioxidative responses. These observations were verified independently through western blot analyses. Our integrated metabolomics, chemometrics, and pharmacological strategy led to the efficient discovery of novel bioactive ingredients from A. oxyphylla while avoiding the nontargeting, labor-intensive steps usually required for identification of bioactive compounds. Our successful development of a synthetic route toward oxyphylla A should lead to its availability on a large scale for further functional development and pathological studies.

Reversible and irreversible sorption of perfluorinated compounds (PFCs) by sediments of an urban reservoir.

Uncertainty about the extent to which contaminant sorption by suspended solids and bed sediments is irreversible is a major impediment for modeling and managing the water quality of surface water resources. This study examined reversible and irreversible sorption of several perfluorinated compounds (PFCs) to bed sediments from an urban reservoir. PFCs investigated include C4, C6, C8, C9 and C10 perfluoroalkanoate homologues (PFBA, PFHxA, PFOA, PFNA and PFDA, respectively) and perfluorooctane and hexane sulfonate (PFOS and PFHxS, respectively). Although sorption branches of the PFOS, PFNA and PFDA isotherms were nearly linear (implying a partitioning-like process), desorption experiments indicated that a fraction of the sorbed PFCs were entrapped and resistant to desorption. The hysteretic desorption branches were approximately linear. Irreversibility increased with chain length and was nearly complete for PFDA (thermodynamic irreversibility index (TII) 0.98). For the weakly sorbing PFOA and PFHxS, sorption was largely reversible. Data suggest that (1) for the strongly sorbing PFCs, e.g. PFNA, PFDA and PFOS, bed sediments acted predominantly as irreversible sinks, (2) aqueous concentrations of the moderately sorbing PFCs (PFOA and PFHxS) are buffered by reversibly sorbing suspended solids, and (3) the short-chain PFCs (PFBA and PFHxA) are not significantly sorbed and therefore not expected to be significantly influenced by sediment transport. Situations in which highly contaminated particles entering relatively clean water bodies, equilibrium is approached from the reverse (desorption) direction. For irreversibly sorbed contaminants field-based K(D) values will be higher than the K(D) values derived from laboratory sorption data obtained from forward sorption experiments.

Determination of perfluoroalkylated substances (PFASs) in drinking water from the Netherlands and Greece.

In the present study 11 perfluoroalkylated substances (PFASs) were analysed in drinking tap water samples from the Netherlands (n = 37) and from Greece (n = 43) by applying LC-MS/MS and isotope dilution. PFASs concentrations above the limit of quantification, LOQ (0.6 ng/l) were detected in 20.9% of the samples from Greece. Total PFAS concentrations ranged between 8) were only rarely detected. In the drinking water samples from the eastern part of the Netherlands, where drinking water is sourced from groundwater reservoirs, no PFASs were detected. This demonstrates that exposure to PFASs through drinking water in the Netherlands is dependent on the source. Additionally, five samples of bottled water from each country were analysed in the current study, with all of them originating from ground wells. In these samples, all PFASs were below the LOQ.

In-line and selective phase separation of medium-chain carboxylic acids using membrane electrolysis.

We had extracted n-caproate from bioreactor broth. Here, we introduced in-line membrane electrolysis that utilized a pH gradient between two chambers to transfer the product into undissociated n-caproic acid without chemical addition. Due to the low maximum solubility of this acid, selective phase separation occurred, allowing simple product separation into an oily liquid containing ∼90% n-caproic and n-caprylic acid.

Comparison of the sorption behaviors and mechanisms of perfluorosulfonates and perfluorocarboxylic acids on three kinds of clay minerals.

The sorption of four perfluoroalkyl acids (PFAAs) [perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA)] on three typical minerals [montmorillonite (MM), kaolinite (KL) and hematite (HM)] was studied. The sorption of PFOS and PFHxS was much stronger than PFOA and PFHxA. The sorption of each PFAA on the minerals followed an order of HM>KL>MM, even though MM was positively while KL and HM were negatively charged, implying that the sorption is driven by some other interactions besides electrostatic attraction. The sorption decreased with an increase in pH and a decrease in ionic strength of the solution, and their impacts on PFOS were much stronger than other three PFAAs. Surface complexing and hydrogen-bonding could make great contributions to the sorption of PFOS on the minerals. The results are important for understanding the transport and fate of PFAAs in sediment and ground water.

Influence of the type of fiber coating and extraction time on foal dry-cured loin volatile compounds extracted by solid-phase microextraction (SPME).

Extraction of dry-cured loin volatile compounds by solid-phase microextraction (SPME) was optimized. Two different fiber coatings: carboxen/polydimethylsiloxane (CAR/PDMS) and divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS), and three extraction times (15, 30 and 45 min) were assayed. Between the fibers tested, CAR/PDMS coated fibers extracted between two and three times more total amount of volatile compounds than the DVD/CAR/PDMS coating (1314×10(6) vs. 526×10(6) area units). Fifty five compounds were extracted by the CAR/PDMS fiber, while only 48 of these were found with the DVB/CAR/PDMS fiber. On the other hand, 6 additional volatile compounds were extracted by the CAR/PDMS coating, all of them being of low molecular weight. Three of the major compounds extracted, hexanoic acid, methyl ester; butanoic acid, 3-methyl-, methyl ester and hexanal, were found in high proportion in both fiber coatings. The effect of exposure time was more marked for the DVD/CAR/PDMS fiber than for the CAR/PDMS coating. Fifteen minutes of extraction provided a volatile compounds profile with lower area counts for most compounds and significantly different to that obtained with 30 and 45 min of extraction. The extraction yields of dry-cured loin volatile compounds varied according to the fiber coating used and the time of exposure. Therefore, extraction conditions should be selected depending on the objective of the study. Finally, it can be concluded that both porous fibers tested, CAR/PDMS and DVB/CAR/PDMS, provide a similar volatile compounds profile for dry-cured foal loin.

Antidyslipidemic and antioxidant activity of an unusual amino acid (2-amino-5-hydroxyhexanoic acid) isolated from the seeds of Crotalaria juncea.

In continuation of our drug discovery programme on Indian medicinal plants, we isolated an unusual amino acid, i.e. 2-amino-5-hydroxyhexanoic acid (1) from the seeds of Crotalaria juncea. The 2-amino-5-hydroxyhexanoic acid (1) showed dose dependent lipid lowering activity in the in vivo experiments and also showed good in vitro antioxidant activity. The cyclized compound, 3-amino-6-methyltetrahydro-2H-pyran-2-one (2) showed better lipid lowering and antioxidant profile than the parent compound 1.

In situ extractive fermentation for the production of hexanoic acid from galactitol by Clostridium sp. BS-1.

Clostridium sp. BS-1 produces hexanoic acid as a metabolite using galactitol and enhanced hexanoic acid production was obtained by in situ extractive fermentation with Clostridium sp. BS-1 under an optimized medium composition. For medium optimization, five ingredients were selected as variables, and among them yeast extract, tryptone, and sodium butyrate were selected as significant variables according to a fractional factorial experimental design, a steepest ascent experimental design, and a Box-Behnken experimental design. The optimized medium had the following compositions in modified Clostridium acetobutyricum (mCAB) medium: 15.5gL(-1) of yeast extract, 10.13gL(-1) of tryptone, 0.04gL(-1) of FeSO4·7H2O, 0.85gL(-1) of sodium acetate, and 6.47gL(-1) of sodium butyrate. The predicted concentration of hexanoic acid with the optimized medium was 6.98gL(-1), and this was validated experimentally by producing 6.96gL(-1) of hexanoic acid with Clostridium sp. BS-1 under the optimized conditions. In situ extractive fermentation for hexanoic acid removal was then applied in a batch culture system with the optimized medium and 10% (v/v) alamine 336 in oleyl alcohol as an extractive solvent. The pH of the culture in the extractive fermentation was maintained at 5.4-5.6 by an acid balance between production and retrieval by extraction. During a 16 day culture, the hexanoic acid concentration in the solvent increased to 32gL(-1) while it was maintained in a range of 1-2gL(-1) in the medium. The maximum rate of hexanoic acid production was 0.34gL(-1)h(-1) in in situ extractive fermentation.

In situ biphasic extractive fermentation for hexanoic acid production from sucrose by Megasphaera elsdenii NCIMB 702410.

Hexanoic acid production by a bacterium using sucrose as an economic carbon source was studied under conditions in which hexanoic acid was continuously extracted by liquid-liquid extraction. Megasphaera elsdenii NCIMB 702410, selected from five M. elsdenii strains, produced 4.69 g l⁻¹ hexanoic acid in a basal medium containing sucrose. Production increased to 8.19 g l⁻¹ when the medium was supplemented by 5 g l⁻¹ sodium butyrate. A biphasic liquid-liquid extraction system with 10 % (v/v) alamine 336 in oleyl alcohol as a solvent was evaluated in a continuous stirred-tank reactor held at pH 6. Over 90 % (w/w) of the hexanoic acid in a 0.5 M aqueous solution was transferred to the extraction solvent within 10 h. Cell growth was not significantly inhibited by direct contact of the fermentation broth with the extraction solvent. The system produced 28.42 g l⁻¹ of hexanoic acid from 54.85 g l⁻¹ of sucrose during 144 h of culture, and 26.52 and 1.90 g l⁻¹ of hexanoic acid was accumulated in the extraction solvent and the aqueous fermentation broth, respectively. The productivity and yield of hexanoic acid were 0.20 g l⁻¹ h⁻¹ and 0.50 g g⁻¹ sucrose, respectively.

JBIR-107, a new metabolite from the marine-sponge-derived actinomycete, Streptomyces tateyamensis NBRC 105047.

As part of our chemical screening program for new microbial secondary metabolites, we discovered a new compound, JBIR-107 (1), from the culture of Streptomyces tateyamensis NBRC 105047 isolated from a marine sponge sample. Extensive NMR and MS spectroscopic data enabled the structure of 1 to be determined as 5-acetamido-6-(4-(methyl(2-oxo-3-phenylpropyl)amino)phenyl)-4-oxohexanoic acid.

[Chemical constituents from the fruits of Kadsura marmorata].

OBJECTIVE: To study the chemical constituents from the fruits of Kadsura marmorata. METHODS: The chemical constituents were isolated and purified by chromatography on silica gel, Sephadex LH-20 column and HPLC. RESULTS: 9 compounds were isolated and identified as 4,5-dihydroxy-3-methoxybiphenyl (I), eriobofuran (II), 3beta, 16beta-dihydroxy urs-2-ene (III), 2alpha, 3beta, 6beta, 23-tetrahydroxy urs-12,18-dien-28-oic acid (IV), 2alpha,3beta,23-trihydroxy urs-12-en-28-oic acid (V), rutin (VI), 2-ethylhexanoic acid (VII), 2-monolaurin (VIII), glyceryl monoricinoleate (IX) on the basis of NMR and EI-MS spectroscopic analysis. CONCLUSION: All these compounds are isolated from this genus for the first time.

Enhanced recovery and purification of P(3HB-co-3HHx) from recombinant Cupriavidus necator using alkaline digestion method.

A simple, efficient and economical method for the recovery of P(3HB-co-3HHx) was developed using various chemicals and parameters. The initial content of P(3HB-co-3HHx) in bacterial cells was 50-60 wt%, whereas the monomer composition of 3HHx used in this experiments was 3-5 mol%. It was found that sodium hydroxide (NaOH) was the most effective chemical for the recovery of biodegradable polymer. High polyhydroxyalkanoate purity and recovery yield both in the range of 80-90 wt% were obtained when 10-30 mg/ml of cells were incubated in NaOH at the concentration of 0.1 M for 60-180 min at 30 °C and polished using 20 % (v/v) of ethanol.

[Inhibitory activity of hydrosols prepared from 18 Japanese herbs of weak aromatic flavor against filamentous formation and growth of Candida albicans].

Leaf hydrosols prepared from 18 weakly aromatic Japanese herbs used traditionally were tested on the filamentation-inhibitory activity of Candida albicans. These hydrosols were divided into two classes, A and B. The inhibitory activity of 13 hydrosols belonging to class A was markedly altered depending on the drying process of the parent herbs. On the other hand, the remaining 5 hydrosols belonging to class B showed no significant change on the composition and inhibitory activity upon drying. The change of the bioactivity was correlated with the change and concentration of the respective major constituents. Especially strong bioactivity shown by hydrosols of dried Houttuynia cordata and fresh Prunus pendula was ascribed to n-capric acid and cyanide, respectively. Eight hydrosols exhibited weak or moderate activity against the growth of C. albicans.

The N-terminal amino acid of apolipoprotein D is putatively covalently bound to 3-hydroxy-3-methyl hexanoic acid, a key odour compound in axillary sweat.

Axillary sweat is odourless when freshly collected at the surface of human skin, but it contains non-odoriferous precursors, which can be transformed into odorous substances by bacteria. E-3-methyl-2-hexanoic acid (3M2H) is one of the key odorous substances, but there are two contradictory reports about its precursor form. One report states that 3M2H linked non-covalently to apolipoprotein D (apoD) is the precursor, while a second report states that 3M2H-Gln identified in human axillary sweat is the precursor. Recently, 3-hydroxy-3-methyl hexanoic acid (HMHA) and 3-methyl-3-sulfanylhexane-1-ol (3M3T) have also been identified and reported as characteristic components found in apocrine sweat. To better understand the formation of axillary odours and the structural relationships between these compounds and apoD, we characterized the linkage between odorous substances and apoD in human axillary secretions. ApoD was purified from human axillary secretions collected from 50 healthy female volunteers and was then digested by trypsin and analysed by MALDI-TOF mass spectrometry. A Mascot search showed that 8 peaks identified in the trypsin-digested samples correspond to the masses calculated for theoretically digested apoD sequences and the purified protein was assigned as a precursor of apoD [Homo sapiens]. One spectrum corresponded to the theoretical peak of HMHA linked covalently to the N-terminal fragment of apoD. In contrast, no spectrum corresponded to the theoretical peak of a 3M2H adduct or to an unmodified N-terminal fragment of apoD. These results indicate a possibility that HMHA binds covalently to the N-terminal amino acid of apoD in human axillary secretions.