Alcohol acyl transferase genes at a high-flavor intensity locus contribute to ester biosynthesis in kiwifruit.

Volatile esters are key compounds contributing to flavor intensity in commonly consumed fruits including apple (Malus domestica), strawberry (Fragaria spp.), and banana (Musa sapientum). In kiwifruit (Actinidia spp.), ethyl butanoate and other esters have been proposed to contribute fruity, sweet notes to commercial cultivars. Here, we investigated the genetic basis for ester production in Actinidia in an A. chinensis mapping population (AcMPO). A major quantitative trait loci for the production of multiple esters was identified at the high-flavor intensity (HiFI) locus on chromosome 20. This locus co-located with eight tandemly arrayed alcohol acyl transferase genes in the Red5 genome that were expressed in a ripening-specific fashion that corresponded with ester production. Biochemical characterization suggested two genes at the HiFI locus, alcohol acyl transferase 16-b/c (AT16-MPb/c), probably contributed most to the production of ethyl butanoate. A third gene, AT16-MPa, probably contributed more to hexyl butanoate and butyl hexanoate production, two esters that segregated in AcMPO. Sensory analysis of AcMPO indicated that fruit from segregating lines with high ester concentrations were more commonly described as being "fruity" as opposed to "beany". The downregulation of AT16-MPa-c by RNAi reduced ester production in ripe "Hort16A" fruit by >90%. Gas chromatography-olfactometry indicated the loss of the major "fruity" notes contributed by ethyl butanoate. A comparison of unimproved Actinidia germplasm with those of commercial cultivars indicated that the selection of fruit with high concentrations of alkyl esters (but not green note aldehydes) was probably an important selection trait in kiwifruit cultivation. Understanding ester production at the HiFI locus is a critical step toward maintaining and improving flavor intensity in kiwifruit.

Hero Turned Villain: Identification of Components of the Sex Pheromone of the Tomato Bug, Nesidiocoris tenuis.

Nesidiocoris tenuis (Reuter) (Heteroptera: Miridae) is a tropical mirid bug used as a biocontrol agent in protected crops, including tomatoes. Although N. tenuis predates important insect pests, especially whitefly, it also causes damage by feeding on tomato plants when prey populations decline, resulting in significant economic losses for growers. The pest is now established in some all-year-round tomato crops in Europe and control measures involve the application of pesticides which are incompatible with current IPM programs. As part of future IPM strategies, the pheromone of N. tenuis was investigated. Volatile collections were made from groups and individuals of mated and unmated, females and males. In analyses of these collections by gas chromatography coupled with electroantennographic (EAG) recording from antennae of male bugs, two EAG-active components were detected and identified as 1-octanol and octyl hexanoate. Unlike other mirids, both male and female N. tenuis produced the two compounds, before and after mating, and both sexes gave EAG responses to both compounds. Furthermore, only octyl hexanoate was detected in whole body solvent washes from both sexes. These compounds are not related to the derivatives of 3-hydroxybutyrate esters found as pheromone components in other members of the Bryocrinae sub-family, and the latter could not be detected in volatiles from N. tenuis and did not elicit EAG responses. Nevertheless, experiments carried out in commercial glasshouses showed that traps baited with a blend of the synthetic pheromone components caught essentially only male N. tenuis, and significantly more than traps baited with octyl hexanoate alone. The latter caught significantly more N. tenuis than unbaited traps which generally caught very few bugs. Traps at plant height caught more N. tenuis males than traps 1 m above or at the base of the plants. The trap catches provided an indication of population levels of N. tenuis and were greatly reduced following an application of insecticide.

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.

Constructing slow-release formulations of herbicide metribuzin using its co-extrusion with biodegradable polyester poly-ε-caprolactone.

Different technologies to prepare long term pesticide forms include polymer coating, preparing composites and encapsulating pesticides in nanoparticles. A simple and low-cost method was proposed to obtain slow-release formulations by co-extrusion of a pesticide with a biodegradable polymer at a temperature above the melting points of both components. A herbicide metribuzin and low-melting polyester poly-ε-caprolactone were chosen for this work. Formulations containing 10%, 20%, and 40% herbicide were prepared. During 7 days of their exposition in water, it was released from 81% to 96% of initially loaded metribuzin; the highest release was detected for 40%-loaded forms. Biodegradation of the constructs and pesticide release were further studied in the model soil. Degradation rates of the specimens increased with an increase in pesticide content, from 9% to 20% over 14 weeks for the 10%/20%-loaded and the 40%-loaded specimens, respectively. The release of metribuzin reached, respectively, 37-38% and 55%. The herbicide content in soil was lower due to its partial degradation in soil; it reached 23-25% and 33%, respectively, from initially loaded into the polymer matrix. Release kinetics of metribuzin in water as in soil best fitted the First-order model. The used approach is promising for obtaining long-term release formulations for soil applications.

Perfluorinated Compounds (PFCs) in Soil of the Pearl River Delta, China: Spatial Distribution, Sources, and Ecological Risk Assessment.

This study investigated the levels, spatial distribution, sources, and ecological risks of 16 perfluorinated compounds (PFCs) in 68 surface soil samples (0-20 cm) from 7 cities in the Pearl River Delta (PRD), China. Sixteen target PFCs, including perfluoroalkyl carboxylic acids (PFCAs, C5-C14, C16, and C18) and perfluoroalkyl sulfonic acids (PFSAs, C4, C6, C8, and C10), were analyzed by high-performance liquid chromatography-negative electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS). Concentrations of total PFCs (∑PFCs) ranged from 2.19 to 98.5 µg kg-1 (dry weight, dw), with an average of 5.97 µg kg-1 dw. Perfluorooctane sulfonate (PFOS) was the dominant PFC, accounting for 23.9% of ∑PFCs. The highest ∑PFCs was found in the soil sample collected from Dongguan with a large number of manufacturing industries. There were no significant differences of ∑PFCs among unban, industrial, and agricultural soils, indicating similar pollution sources in soil of the PRD. More than 70% of ∑PFCs in soil of the PRD could be attributed to the four principal components, represented by PFOS and perfluorooctanoic acid (PFOA), perfluoropentanoic acid (PFPeA) and perfluorohexanoic acid (PFHxA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUdA). Ecological risk assessment indicated that PFOA had low risk to soil plants and animals. However, the risk of PFOS to soil plants was relatively high in some studied regions.

Identification of the Trail Pheromone of the Carpenter Ant Camponotus modoc.

Trail pheromones deposited by ants lead nestmates to food sources. Based on previous evidence that the trail pheromone of the carpenter ant Camponotus modoc originates from the hindgut, our objective in this study was to identify the key component(s) of the pheromone. We collected C. modoc colonies from conifer forests and maintained them in an outdoor enclosure near our laboratory for chemical analyses and behavioral experiments. In gas chromatographic-electroantennographic detection and gas chromatography-mass spectrometric analyses of worker ant hindgut extracts, we identified five candidate components: 2,4-dimethylhexanoic acid, 2,4-dimethyl-5-hexanolide, pentadecane, dodecanoic acid and 3,4-dihydro-8-hydroxy-3,5,7-trimethylisocoumarin. In a series of trail-following experiments, ants followed trails of synthetic 2,4-dimethyl-5-hexanolide, a blend of the five compounds, and hindgut extract over similar distances, indicating that the hexanolide accounted for the entire behavioral activity of the hindgut extract. The hexanolide not only mediated orientation of C. modoc foragers on trails, it also attracted them over distance, indicating a dual function. Further analyses and bioassays with racemic and stereoselectively synthesized hexanolides revealed that the ants produce, and respond to, the (2S,4R,5S)-stereoisomer. The same stereoisomer is a trail pheromone component in several Camponotus congeners, indicating significant overlap in their respective trail pheromone communication systems.

Perfluorohexanoic acid toxicity, part II: Application of human health toxicity value for risk characterization.

Perfluorohexanoic acid (PFHxA) is a short-chain, six-carbon PFAA and is a primary impurity, degradant, and metabolite associated with the short-chain fluorotelomer-based chemistry used in the United States, Europe and Japan today. With the shift towards short-chain PFAA chemistry, uncertainties remain regarding human health risks associated with current exposure levels. Here, we present a critical review and assessment of data relevant to human health risk assessment to today's short-chain PFAA chemistry. Human biomonitoring surveys indicate that PFHxA is infrequently detected in the environment as well as in human serum and urine; however, human health concerns may persist in locations where PFHxA is detected. In a companion paper (Luz et al., 2019) we comprehensively evaluate the available toxicity data for PFHxA, and derive a chronic human health-based reference dose (RfD) for PFHxA of 0.25 mg/kg-day based on benchmark dose modeling of renal papillary necrosis in chronically exposed female rats. In this paper, we apply this RfD in human health-based screening levels calculations, and derive a drinking water lifetime health advisory of 1400 µg/L and a residential groundwater screening level for children of 4000 µg/L. Compared to environmental concentration data, even sites with more elevated concentrations of PFHxA in the environment are at least an order of magnitude lower than these screening levels. Available PFHxA human serum and urine biomonitoring data, used as a biomarker for general population exposure, demonstrates that the general human population exposures to PFHxA are low. Previous estimates of daily intake rates for infants exposed to PFHxA through breast milk, formula, and baby foods (Lorenzo et al., 2016) combined with the most conservative PFHxA peer-reviewed toxicity value (Luz et al., 2019) demonstrate that the margin of safety for PFHxA is high. Therefore, PFHxA and related fluorotelomer precursors currently appear to present negligible human health risk to the general population and are not likely to drive or substantially contribute to risk at sites contaminated with PFAS mixtures. PFHxA may also represent a suitable marker for the safety of fluorotelomer replacement chemistry used today.

Perfluoroalkyl substances (PFASs) in air-conditioner filter dust of indoor microenvironments in Greece: Implications for exposure.

The occurrence of perfluoroalkyl substances (PFASs) was for the first time investigated in various working microenvironments (internet cafes, electronics shops, coffee shops, restaurants, etc.) in Thessaloniki, Greece, using the dust trapped by central air conditioner (A/C) filters. Perfluorooctane sulfonic acid (PFOS) was found in the range from 16 to 227 ng g-1, however it was detectable in only 30% of samples. On the contrary, perfluorohexanoic acid (PFHxA) was found in 85% of samples in the range from 3.6 to 72.5 ng g-1, while 90-95% of samples exhibited perfluorooctanoic acid (PFOA), perfluorodecanoic acid (PFDcA) and perfluorododecanoic acid (PFDoDA) in the range from 10-653 ng g-1, 3.2-7.4 ng g-1 and 3.8-13.1 ng g-1, respectively. The PFAS profile varied largely among the different microenvironment categories suggesting different sources. Estimated daily intakes through dust ingestion were calculated.

A Preliminary Study of Aroma Composition and Impact Odorants of Cabernet Franc Wines under Different Terrain Conditions of the Loess Plateau Region (China).

Due to its appropriate climate characteristics, the Loess Plateau region is considered to be one of the biggest optimal regions for producing high-quality mountain wine in China. However, the complex landform conditions of vineyards are conducive to the formation of mountainous microclimates, which ultimately influence the wine quality. This study aimed to elucidate the influences of three terrain conditions of the Loess Plateau region on the aroma compounds of Cabernet Franc wines by using solid phase microextraction (SPME) with gas chromatography-mass spectrometry (GC-MS). A total of 40, 36 and 35 volatiles were identified and quantified from the flat, lower slope and higher slope vineyards, respectively. Esters were the largest group of volatiles, accounting for 54.6⁻56.6% of total volatiles, followed by alcohols. Wines from the slope lands had the higher levels of aroma compounds than that from flat land. According to their aroma-active values (OAVs), ethyl hexanoate, ethyl octanoate and isoamyl acetate were the most powerful compounds among the eight impact odorants, showing only quantitative but not qualitative differences between the three terrain wines. The shapes of the OAVs for three terrain wines were very similar.

Probiotic supplementation effects on milk fatty acid profile in ewes.

We hypothesised that probiotic feeding would alter the fatty acid (FA) profile of sheep's milk. Sixteen lactating ewes, kept under the same feeding and management practices, were randomly allocated to receive either a control diet or the same diet supplemented with a commercial multi-strain bacterial probiotic. Milk fat FA contents were monitored fortnightly for eight consecutive weeks from 14 d after lambing. Probiotic supplementation increased the contents of butyric and caproic acids in milk fat and had no negative effects on other relevant FA from the human's health point of view (i.e., no differences in branched chain, vaccenic, rumenic and n-3 FA were observed). Under the conditions assayed in the present work, the contents of milk FA originated from rumen microbial metabolism were scantly altered, which suggests that the rumen conversion pathways of FA were not substantially modified by the probiotics.

Effects of carbohydrate/protein ratio on the microstructure and the barrier and sorption properties of wheat starch-whey protein blend edible films.

BACKGROUND: Starch and whey protein isolate and their mixtures were used for making edible films. Moisture sorption isotherms, water vapour permeability, sorption of aroma compounds, microstructure, water contact angle and surface properties were investigated. RESULTS: With increasing protein content, the microstructure changes became more homogeneous. The water vapour permeability increases with both the humidity gradient and the starch content. For all films, the hygroscopicity increases with starch content. Surface properties change according to the starch/whey protein ratio and are mainly related to the polar component of the surface tension. Films composed of 80% starch and 20% whey proteins have more hydrophobic surfaces than the other films due to specific interactions. CONCLUSIONS: The effect of carbohydrate/protein ratio significantly influences the microstructure, the surface wettability and the barrier properties of wheat starch-whey protein blend films. © 2016 Society of Chemical Industry.

Perfluoroalkyl acids (PFAAs) in sediments from rivers of the Pearl River Delta, southern China.

Having been largely used in industrial and household products, perfluoroalkyl acids (PFAAs) appear in environmental and biological systems with prevalence and persistence and have raised great concern in recent years. The present study is aimed at studying concentrations and composition profiles of 16 PFAAs in surface sediments collected from 51 sampling locations in 4 main rivers of the Pearl River Delta, one of the economy-developed areas in China. The total PFAA concentrations (∑ PFAAs) were determined in a wide range of 1.89-15.1 ng g-1 dw (dry weight) with an average concentration to be 3.54 ng g-1 dw. Higher ∑ PFAAs were observed in the downstream of Dongjiang River and the Pearl River, possibly due to the discharge of industrial wastewater. Perfluoropentanoic acid (PFPeA) and perfluorooctane sulfonate (PFOS) were the dominant PFAAs, accounting for 51 to 85% of ∑ PFAAs in 27% of the samples. High PFPeA concentrations in sediments of urban river were scarcely observed in previous studies worldwide. The sources of short-chain perfluoroalkyl carboxylic acids (PFCAs) were significantly different from those of other PFAAs. Preliminary hazard assessment proved negligible for PFOS, perfluorooctanoic acid (PFOA), PFPeA, and perfluorohexanoic acid (PFHxA) concentrations in sediments from rivers of the Pearl River Delta.

Perfluoroalkyl acids (PFAAs) in water and sediment from the coastal regions of Shandong peninsula, China.

Perfluoroalkyl acids (PFAAs) have been observed in various environmental matrices globally in recent years. In this study, the levels, spatial distribution tendencies, and partitioning characteristics of the target 12 PFAAs were investigated in water and sediment from the coastal regions of Shandong peninsula in China, and two sediment core samples were also collected to study the vertical and historical variation of PFAAs. The ranges (means) of total PFAA concentrations were 23.69-148.48 ng/L (76.11 ng/L) in the water and 1.30-11.17 ng/g (5.93 ng/g) in the surface sediment, respectively. Among the target 12 PFAAs, perfluorooctanoic acid (PFOA) was the dominant component in water, followed by perfluorooctane sulfonate (PFOS) and perfluorohexanoic acid (PFHxA). PFOS, perfluoroundecanoic acid, and PFOA were the dominant components in sediment. For their spatial distribution, higher levels of PFAAs were found at the locations close to much developed cities. The PFAA concentrations showed an overall decreasing tendency with depth increase in the two sediment cores, which indicates that the extent of PFAAs pollution is aggravating trend in recent years. Results of the partition coefficient (K d ) show that the compounds with longer carbon chains (C ≥ 7) generally had higher K d values, which suggest that long-chain PFAAs are prone to be adsorbed by sediment. In addition, the Log K d of PFHxA, PFOA, and PFOS were significantly and positively correlated to the salinity of the water. The results of risk assessment suggest appreciable risk of PFAAs to the local ecosystem.

Contribution of precursor compounds to the release of per- and polyfluoroalkyl substances (PFASs) from waste water treatment plants (WWTPs).

Per- and polyfluoroalkyl substances (PFASs) are ubiquitous in sludge and water from waste water treatment plants, as a result of their incorporation in everyday products and industrial processes. In this study, we measured several classes of persistent PFASs, precursors, transformation intermediates, and newly identified PFASs in influent and effluent sewage water and sludge from three municipal waste water treatment plants in Sweden, sampled in 2015. For sludge, samples from 2012 and 2014 were analyzed as well. Levels of precursors in sludge exceeded those of perfluoroalkyl acids and sulfonic acids (PFCAs and PFSAs), in 2015 the sum of polyfluoroalkyl phosphoric acid esters (PAPs) were 15-20ng/g dry weight, the sum of fluorotelomer sulfonic acids (FTSAs) was 0.8-1.3ng/g, and the sum of perfluorooctane sulfonamides and ethanols ranged from non-detected to 3.2ng/g. Persistent PFSAs and PFCAs were detected at 1.9-3.9ng/g and 2.4-7.3ng/g dry weight, respectively. The influence of precursor compounds was further demonstrated by an observed substantial increase for a majority of the persistent PFCAs and PFSAs in water after waste water treatment. Perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorohexane sulfonic acid (PFHxS), and perfluorooctane sulfonic acid (PFOS) had a net mass increase in all WWTPs, with mean values of 83%, 28%, 37% and 58%, respectively. The load of precursors and intermediates in influent water and sludge combined with net mass increase support the hypothesis that degradation of precursor compounds is a significant contributor to PFAS contamination in the environment.

Direct immersion solid-phase microextraction with gas chromatography and mass spectrometry for the determination of specific biomarkers of human sweat in melted snow.

To provide a reliable tool for investigating diffusion processes of the specific components of the human odor 3-hydroxy-3-methylhexanoic acid and 3-methyl-3-sulfanylhexan-1-ol through the snowpack, we developed and optimized an analytical method based on direct immersion solid-phase microextraction followed by gas chromatography with mass spectrometry. Direct immersion solid-phase microextraction was performed using polyacrylate fibers placed in aqueous solutions containing 3-hydroxy-3-methylhexanoic acid and 3-methyl-3-sulfanylhexan-1-ol. After optimization, absorption times of 120 min provided a good balance to shorten the analysis time and to obtain suitable amounts of extractable analytes. The extraction efficiency was improved by increasing the ionic strength of the solution. Although the absolute extraction efficiency ranged between 10 and 12% for 3-hydroxy-3-methylhexanoic acid and 2-3% for 3-methyl-3-sulfanylhexan-1-ol, this method was suitable for analyzing 3-hydroxy-3-methylhexanoic acid and 3-methyl-3-sulfanylhexan-1-ol concentrations of at least 0.04 and 0.20 ng/mL, respectively. The precision of the direct immersion solid-phase microextraction method ranged between 8 and 16%. The variability within a batch of six fibers was 10-18%. The accuracy of the method provided values of 88-95 and 86-101% for 3-hydroxy-3-methylhexanoic acid and 3-methyl-3-sulfanylhexan-1-ol, respectively. The limit of detection (and quantification) was 0.01 ng/mL (0.04 ng/mL) for 3-hydroxy-3-methylhexanoic acid and 0.06 ng/mL (0.20 ng/mL) for 3-methyl-3-sulfanylhexan-1-ol. The signal versus concentration was linear for both compounds (r(2) = 0.973-0.979). The stability of these two compounds showed that 3-hydroxy-3-methylhexanoic acid was more stable in water than 3-methyl-3-sulfanylhexan-1-ol. We applied the method to environmental samples in correspondence with an olfactory target buried previously.

Effect of interfacial composition and crumbliness on aroma release in soy protein/sugar beet pectin mixed emulsion gels.

BACKGROUND: In this study, soy protein isolate/sugar beet pectin (SPI/SBP) emulsion gels were prepared through an enzymatic gelation process. The effects of emulsifier (SBP, SPI or SPI/SBP complex) and emulsification process on the microstructure, texture, breakdown properties and aroma release behavior of resulting emulsion gels were investigated. RESULTS: Oil emulsification by SBP/SPI complex resulted in a higher amount of emulsifier absorbing on the oil-water interface than by SBP and SPI alone, indicating that a more compact interfacial network was formed. Flocculation of oil droplets was observed and corresponding emulsion gels exhibited lower fracture force and strain when the oil was emulsified by SPI and SBP/SPI complex. Moreover, emulsion gels with small droplets produced a greater quantity of small fragments after mastication. However, microstructure did not have a significant effect on breakdown properties of emulsion gels. Headspace gas chromatography analysis showed that the release rate of ethyl butyrate before and after mastication was significantly lower in emulsion gel with more compact network, but the release of aroma compounds with higher hydrophobicity did not show a significant influence of the microstructure and texture of emulsion gel. CONCLUSION: This finding provides a useful application for designing semi-solid foods with desirable flavor perception. © 2016 Society of Chemical Industry.

Faecal metabolite profiling identifies medium-chain fatty acids as discriminating compounds in IBD.

BACKGROUND: Bacteria play a role in the onset and perpetuation of intestinal inflammation in IBD. Compositional alterations may also change the metabolic capacities of the gut bacteria. OBJECTIVE: To examine the metabolic activity of the microbiota of patients with Crohn's disease (CD), UC or pouchitis compared with healthy controls (HC) and determine whether eventual differences might be related to the pathogenesis of the disease. METHODS: Faecal samples were obtained from 40 HC, 83 patients with CD, 68 with UC and 13 with pouchitis. Disease activity was assessed in CD using the Harvey-Bradshaw Index, in UC using the UC Disease Activity Index and in pouchitis using the Pouchitis Disease Activity Index. Metabolite profiles were analysed using gas chromatography-mass spectrometry. RESULTS: The number of metabolites identified in HC (54) was significantly higher than in patients with CD (44, p<0.001), UC (47, p=0.042) and pouchitis (43, p=0.036). Multivariate discriminant analysis predicted HC, CD, UC and pouchitis group membership with high sensitivity and specificity. The levels of medium-chain fatty acids (MCFAs: pentanoate, hexanoate, heptanoate, octanoate and nonanoate), and of some protein fermentation metabolites, were significantly decreased in patients with CD, UC and pouchitis. Hexanoate levels were inversely correlated to disease activity in CD (correlation coefficient=-0.157, p=0.046), whereas a significant positive correlation was found between styrene levels and disease activity in UC (correlation coefficient=0.338, p=0.001). CONCLUSIONS: Faecal metabolic profiling in patients with IBD relative to healthy controls identified MCFAs as important metabolic biomarkers of disease-related changes. TRIAL REGISTRATION NO: NCT 01666717.

Perfluoroalkylated substances in the global tropical and subtropical surface oceans.

In this study, perfluoroalkylated substances (PFASs) were analyzed in 92 surface seawater samples taken during the Malaspina 2010 expedition which covered all the tropical and subtropical Atlantic, Pacific and Indian oceans. Nine ionic PFASs including C6-C10 perfluoroalkyl carboxylic acids (PFCAs), C4 and C6-C8 perfluoroalkyl sulfonic acids (PFSAs) and two neutral precursors perfluoroalkyl sulfonamides (PFASAs), were identified and quantified. The Atlantic Ocean presented the broader range in concentrations of total PFASs (131-10900 pg/L, median 645 pg/L, n = 45) compared to the other oceanic basins, probably due to a better spatial coverage. Total concentrations in the Pacific ranged from 344 to 2500 pg/L (median = 527 pg/L, n = 27) and in the Indian Ocean from 176 to 1976 pg/L (median = 329, n = 18). Perfluorooctanesulfonic acid (PFOS) was the most abundant compound, accounting for 33% of the total PFASs globally, followed by perfluorodecanoic acid (PFDA, 22%) and perfluorohexanoic acid (PFHxA, 12%), being the rest of the individual congeners under 10% of total PFASs, even for perfluorooctane carboxylic acid (PFOA, 6%). PFASAs accounted for less than 1% of the total PFASs concentration. This study reports the ubiquitous occurrence of PFCAs, PFSAs, and PFASAs in the global ocean, being the first attempt, to our knowledge, to show a comprehensive assessment in surface water samples collected in a single oceanic expedition covering tropical and subtropical oceans. The potential factors affecting their distribution patterns were assessed including the distance to coastal regions, oceanic subtropical gyres, currents and biogeochemical processes. Field evidence of biogeochemical controls on the occurrence of PFASs was tentatively assessed considering environmental variables (solar radiation, temperature, chlorophyll a concentrations among others), and these showed significant correlations with some PFASs, but explaining small to moderate percentages of variability. This suggests that a number of physical and biogeochemical processes collectively drive the oceanic occurrence and fate of PFASs in a complex manner.

Short-chain fatty acids (SCFA) in infants' plasma and corresponding mother's milk and plasma in relation to subsequent sensitisation and atopic disease.

BACKGROUND: Short-chain fatty acids (SCFAs) in intestinal contents may influence immune function, while less is known about SCFAs in blood plasma. The aims were to investigate the relation between infants' and maternal plasma SCFAs, as well as SCFAs in mother's milk, and relate SCFA concentrations in infant plasma to subsequent sensitisation and atopic disease. METHODS: Infant plasma (N = 148) and corresponding mother's milk and plasma were collected four months postpartum. Nine SCFA (formic, acetic, propionic, isobutyric, butyric, succinic, valeric, isovaleric, and caproic acid) were analysed by UPLC-MS. At 12 months of age, atopic disease was diagnosed by a pediatric allergologist, and sensitisation was measured by skin prick test. All families participated in the Swedish birth cohort NICE (Nutritional impact on Immunological maturation during Childhood in relation to the Environment). FINDINGS: Infants with sensitisation, atopic eczema, or food allergy had significantly lower concentrations of five, three, and two SCFAs, respectively, in plasma at four months. Logistic regressions models showed significant negative associations between formic, succinic, and caproic acid and sensitisation [ORadj (95% CI) per SD: 0.41 (0.19-0.91); 0.19 (0.05-0.75); 0.25 (0.09-0.66)], and between acetic acid and atopic eczema [0.42 (0.18-0.95)], after adjusting for maternal allergy. Infants' and maternal plasma SCFA concentrations correlated strongly, while milk SCFA concentrations were unrelated to both. Butyric and caproic acid concentrations were enriched around 100-fold, and iso-butyric and valeric acid around 3-5-fold in mother's milk, while other SCFAs were less prevalent in milk than in plasma. INTERPRETATION: Butyric and caproic acid might be actively transported into breast milk to meet the needs of the infant, although mechanistic studies are needed to confirm this. The negative associations between certain SCFAs on sensitisation and atopic disease adds to prior evidence regarding their immunoregulatory potential. FUNDING: Swedish Research Council (Nr. 2013-3145, 2019-0137 and 2023-02217 to A-S.S.), Swedish Research Council for Health, Working Life and Welfare FORTE, Nr 2018-00485 to A.W.), The Swedish Asthma and Allergy Association's Research Fund (2020-0020 to A.S.).