Long-chain Homologues Research Articles

Unveiling the Molecular Characteristics, Origins, and Formation Mechanism of Reduced Nitrogen Organic Compounds in the Urban Atmosphere of Shanghai Using a Versatile Aerosol Concentration Enrichment System.

Reduced nitrogen-containing organic compounds (NOCs) in aerosols play a crucial role in altering their light-absorption properties, thereby impacting regional haze and climate. Due to the low concentration levels of individual NOCs in the air, the utilization of accurate detection and quantification technologies becomes essential. For the first time, this study investigated the diurnal variation, chemical characteristics, and potential formation pathways of NOCs in urban ambient aerosols in Shanghai using a versatile aerosol concentration enrichment system (VACES) coupled with HPLC-Q-TOF-MS. The results showed that NOCs accounted over 60% of identified components of urban organic aerosols, with O/N < 3 compounds being the major contributors (>70%). The predominance of the positive ionization mode suggested the prevalence of reduced NOCs. Higher relative intensities and number fractions of NOCs were observed during nighttime, while CHO compounds showed an opposite trend. Notably, a positive correlation between the intensity of NOCs and ammonium during the nighttime was observed, suggesting that the reaction of ammonium to form imines may be a potential pathway for the formation of reduced NOCs during the nighttime. Seven prevalent types of reduced NOCs in autumn and winter were identified and characterized by an enrichment of CH2 long-chain homologues. These NOCs included alkyl, cyclic, and aromatic amides in CHON compounds, as well as heterocyclic or cyclic amines and aniline homologue series in CHN compounds, which were associated with anthropogenic activities and may be capable of forming light-absorbing chromophores or posing harm to human health. The findings highlight the significant contributions of both primary emissions and ammonium chemistry, particularly amination processes, to the pollution of reduced NOCs in Shanghai's atmosphere.

Geochemical study of the organic matter from the southern part of the Maritsa Iztok Basin

A sequence of carbonaceous mudstones interlayering three lignite seams is characterized by geochemical proxies. The core samples studied came from a borehole drilled in Trojanovo-3 Mine of Maritsa Iztok Basin. The n-alkane molecular composition is dominated by the &gt; C29 long-chain homologues, with a strong “odd” over “even” homologue predominance. In addition to, the prevailing smooth signature of n-alkane distribution attests for one major organic matter source – land-derived higher plants. The sesqui- and di-terpenoid assemblage specifies the prevalence of Cupressaceae, Taxodiaceae, and Podocarpaceae species in the coal-forming mire. The lupane-type triterpenoids registered are a sign for Betulaceae family presence. Biomarkers for herb, macrophyte and algal/bacterial contribution are also recognizable.

The impact of gut bacteria producing long chain homologs of vitamin K2 on colorectal carcinogenesis

Colorectal cancer (CRC) is one of the foremost causes of cancer-related deaths. Lately, a close connection between the course of CRC and the intestinal microbiota has been revealed. Vitamin K2 (VK2) is a bacterially derived compound that plays a crucial role in the human body. Its significant anti-cancer properties may result, inter alia, from a quinone ring possessing a specific chemical structure found in many chemotherapeutics. VK2 can be supplied to our body exogenously, i.e., through dietary supplements or fermented food (e.g., yellow cheese, fermented soybeans -Natto), and endogenously, i.e., through the production of bacteria that constantly colonize the human microbiome of the large intestine.This paper focuses on endogenous K2 synthesized by the most active members of the human gut microbiome. This analysis tested 86 intestinally derived bacterial strains, among which the largest VK2 producers (Lactobacillus, Bifidobacterium, Bacillus) were selected. Moreover, based on the chosen VK2-MK4 homolog, the potential of VK2 penetration into Caco-2 cells in an aqueous environment without the coexistence of fats, pancreatic enzymes, or bile salts has been displayed. The influence of three VK2 homologs: VK2-MK4, VK2-MK7 and VK2-MK9 on apoptosis and necrosis of Caco-2 cells was tested proving the lack of their harmful effects on the tested cells. Moreover, the unique role of long-chain homologs (VK2-MK9 and VK2-MK7) in inhibiting the secretion of pro-inflammatory cytokines such as IL-8 (for Caco-2 tissue) and IL-6 and TNFα (for RAW 264.7) has been documented.

Efficient and fast remediation of soil contaminated by per- and polyfluoroalkyl substances (PFAS) by high-frequency heating

This study presents a novel thermal technology (high-frequency heating, HFH) for the decontamination of soil containing per- and polyfluoroalkyl substances (PFAS) and aqueous film-forming foams (AFFFs). Ultra-fast degradation of short-chain PFAS, long-chain homologs, precursors, legacy PFAS, emerging PFAS was achieved in a matter of minutes. The concentrations of PFAS and the soil type had a negligible impact on degradation efficiency, possibly due to the ultra-fast degradation rate overwhelming potential differences. Under the current HFH experiment setup, we achieved near-complete degradation (e.g., >99.9%) after 1 min for perfluoroalkyl carboxylic acids and perfluoroalkyl ether carboxylic acids and 2 min for perfluoroalkanesulfonic acids. Polyfluoroalkyl precursors in AFFFs were found to degrade completely within 1 min of HFH; no residual cationic, zwitterionic, anionic, or non-ionic intermediate products were detected following the treatment. The gaseous byproducts were considered. Most of gaseous organofluorine products of PFAS at low-and-moderate temperatures disappeared when temperatures reached 890 °C, which is in the temperature zone of HFH. For the first time, we demonstrated minimal loss of PFAS in water during the boiling process, indicating a low risk of PFAS entering the atmosphere with the water vapor. The findings highlight HFH its potential as a promising remediation tool for PFAS-contaminated soils.

B-182 Advantage of Core-Shell Particle Morphology Over Fully Porous HPLC Column for the Analysis of Vitamin K Compounds by LC-MS/MS

Abstract Background Vitamin K’s are a group of structurally similar, fat-soluble compounds. There are two natural forms K1 (Phylloquinone) and K2 (Menaquinone), where the later has short and longer chain homologues called Vitamin K2-MK-4 and Vitamin K2-MK-7 respectively. Due to the extremely hydrophobic nature and poor ionization characteristics of these compounds, LC-MS/MS analysis at low concentrations becomes challenging. In this communication we make parallel comparisons of three HPLC columns packed with fully porous and core-shell particles to showcase the superiority of core-shell columns for sensitive detection of vitamin K analytes by LC-MS/MS. Method We compared fully porous (Gemini and Luna, Phenomenex, Torrance, CA) and core-shell (Kinetex EVO, Phenomenex) C18 columns for this study. All columns evaluated were 50 × 2.1 mm with a 5 μm particle size to maintain low back pressure for the viscous organic modifier utilized. Deionized water and a combination of isopropanol and acetonitrile (1:1; v/v) were used as mobile phase A and B respectively for chromatographic separation. An Agilent 1290 Infinity series LC system was employed with a SCIEX 6500 QTRAP mass spectrometer under APCI for MS detection. Analyst software 1.7.2 used for data analysis. Results The LC-MS/MS method had a 4-minute runtime for chromatographic separation of the analytes including 1.5 min of equilibration time. The comparison data revealed the Gemini C18 column shows some higher selectivity and resolution values, whereas both EVO and Luna C18 columns were somewhat comparable. However, the core-shell EVO C18 column displayed much higher efficiency with narrower and compressed peak widths, which dramatically increased the peak height for all 3 analytes exhibiting the highest signal/noise ratio. Conclusion The core-shell Kinetex 5 μm, EVO C18 column with its unique organo-silica grafting shows much higher efficiency and sensitive detection capability for vitamin K analysis by LC-MS/MS compared to that of conventional fully porous silica particles.

Characteristics of n-alkyl lipids in cultivated Sphagnum and their preservation potential in the topsoil of Sphagnum farmlands in southwest China

Sphagnum, a crucial peat-forming plant, is essential for sustaining the ecosystem and counteracting climate change. In recent years, attempts have been made to cultivate Sphagnum commercially to reduce the environmental impacts of harvesting the natural Sphagnum. However, research on the distribution of lipids in cultivated Sphagnum and their potential for preservation potential in the underlying soil is still limited. This study examined the distribution of n-alkyl lipids and the carbon isotope composition of n-alkanes in both natural and cultivated Sphagnum, as well as the underlying topsoil in southwestern China. Results show that the distributions of n-alkyl lipids in the cultivated Sphagnum are similar to those of the natural Sphagnum in the same region. Additionally, the δ13C values of mid-chain n-alkanes (C23 and C25) in the cultivated Sphagnum are significantly negative compared to those of long-chain homologs (C29 and C31; one-way ANOVA, p < 0.05), indicating that symbiotic methanotrophs are relatively active in the cultivated Sphagnum. Furthermore, the n-fatty acids and n-alkan-2-ones in the topsoil are mainly imported from Sphagnum, while the n-alkanes in the topsoil may originate from both Sphagnum and vascular plants. These findings contribute to a better understanding of the ecological benefits of Sphagnum cultivation and the contribution and fate of Sphagnum-derived carbon in soil profiles.

HYDROCARBON CONTAMINATION IMPACT ON SANDY SOILS WITHIN THE DZUNBAYAN OIL FIELD (EASTERN MONGOLIA)

The data are presented on the particle-size distribution, content of hydrocarbons, n-alkanes in their composition and the number of microorganisms in the soils of Dzunbayan oil production area (Mongolia, the Eastern Gobi desert steppe). The soils studied are characterized by the dominance of sand and fluid fraction (99.50–99.8%) with particles of 2–20 μm. The soils show alkaline reaction (pH 8.2–8.7), they are slightly saline in the control areas and highly saline (water extract salinity 0.13–2.34‰) near the production well. The content of petroleum hydrocarbons (HC) in soils of the study area varied from 9 to 60 mg/kg, with a maximum near the well. The study of the molecular composition of n-alkanes revealed the dominance of long-chain homologues (66.3–79.2% of the total n-alkanes), occurring at various stages of physicochemical and microbiological weathering. According to a number of features, the microbial community of soils is characterized by a high degree of adaptation to the conditions of the arid zone, salinity, and high pH values; at the same time, these conditions limit the development of typical representatives of soil microbiocenoses, i.e., actinomycetes and, to a greater extent, microscopic fungi. The total number of heterotrophic bacteria (HBGs) in the studied soil samples varied within 1.22–3.49 million CFU/g of soil. The proportion of oil-oxidizing bacteria (NOB) was 12.6–18.9% OBA, which corresponded to the high adaptive capacity of the community to hydrocarbons. Specific climatic conditions, features of soil composition, as well as oil with a predominance of heavy paraffin fractions of the Dzunbayan deposit, characterize the low potential ability of soils to self-purify under the oil pollution.

Phytoextraction of per- and polyfluoroalkyl substances (PFAS) by weeds: Effect of PFAS physicochemical properties and plant physiological traits

Phytoextraction is a promising technology that uses plants to remediate contaminated soil. However, its feasibility for per- and polyfluoroalkyl substances (PFAS) and the impact of PFAS properties and plant traits on phytoextraction efficacy remains unknown. In this study, we conducted greenhouse experiment and evaluated the potential of weeds for phytoextraction of PFAS from soil and assessed the effects of PFAS properties and plant traits on PFAS uptake via systematic correlation analyses and electron probe microanalyzer with energy dispersive spectroscopy (FE-EPMA-EDS) imaging. The results showed that 1) phytoextraction can remove 0.04%− 41.4%wt of PFAS from soil, with extracted PFAS primarily stored in plant shoots; 2) Weeds preferentially extracted short-chain PFAS over long-chain homologues from soil. 3) PFAS molecular size and hydrophilicity determined plant uptake behavior, while plant morphological traits, particularly root protein and lipid content, influenced PFAS accumulation and translocation. Although plants with thin roots and small leaf areas exhibited greater PFAS uptake and storage ability, the impact of PFAS physicochemical properties was more significant. 4) Finally, short-chain PFAS were transported quickly upwards in the plant, while uptake of long-chain PFOS was restricted.

Variations of the Level, Profile, and Distribution of PFAS around POSF Manufacturing Facilities in China: An Overlooked Source of PFCA.

The occurrence of per- and polyfluoroalkyl substances (PFAS) was investigated inside two manufacturing facilities in China. Levels, profiles, and spatial distribution of the detected PFAS were found to be distinctly site-specific and influenced by the area's historic function, production structure of the plant, downpour-induced accidental pollution, and variations in the adsorption and transport of compounds. Very high concentrations of PFAS [mainly C4 and C8 perfluoroalkyl sulfonic acids (PFSAs)] were found in topsoil and groundwater from both plants, with the highest values of 4.89 × 106 μg/kg dw and 1.10 × 104 μg/L, respectively. Elevated concentrations of perfluoroalkyl carboxylic acids (PFCAs) in this study were attributed to their unintentional formation during the electrochemical fluorination process, which might be an overlooked source of PFCA. PFAS generally showed decreasing trends from shallow layers to the bottom of the soil core and demonstrated some downward migrations at different soil depths with time, and C4-C8 PFAS presented a deeper seepage than their long-chain homologues. Total organic carbon appeared to be more important for PFAS sorption to the topsoil than to the soil core. Workers were at potential risk of exposure to perfluorooctanesulfonic acid via soil at production and storage related sites. This study provides a critical reference for the systematic control of PFAS pollution around manufacturing facilities and a proof for an overlooked source of PFCA.

Enhanced adsorption of short-chain perfluorobutanoic acid by functionalized periodic mesoporous organosilica: Performance and mechanisms

Removal of short-chain per- and polyfluoroalkyl substances (PFAS) represents a unique challenge in comparison to the long-chain homologs. In this study, a series of functionalized periodic mesoporous organosilica (PMO) materials with tunable molar ratio of fluoroalkyl to amine functional groups were developed and used as platform adsorbents to investigate the adsorption behavior of short-chain PFAS, with a focus on perfluorobutanoic acid (PFBA). Modification with fluoroalkyl group substantially enhanced the adsorption affinity of PFBA with the functionalized PMO materials. Adsorption free energy analysis suggested that although electrostatic interactions were more predominant in PFBA adsorption, modification of PMOs with increased fluoroalkyl group loadings increased the non-electrostatic interactions with PFBA, resulting in more favorable PFBA adsorption. The optimal functionalized PMO showed fast PFBA adsorption kinetics, excellent PFBA removal efficiency in various water chemistry conditions, and can be regenerated and reused for numerous cycles with methanol/water mixture containing 500-mM NH3·H2O as regenerant. Furthermore, the optimal functionalized PMO showed robust performance for the removal of PFAS mixtures under complex natural water matrix. Results of this study suggested the important role of non-electrostatic interactions in enhancing the removal of short-chain PFAS and can provide mechanistic insights into guiding the design of improved adsorbents for PFAS removal.

Different dissipation potential and dietary risk assessment of tristyrylphenol ethoxylates in cowpea ecosystem in China.

Tristyrylphenol ethoxylates (TSPEOn) are widely used as inert ingredients in pesticide formulations in the world. However, the information on the dissipation behavior of different homologs TSPEOn in agro-products is lacking. To investigate the dissipation behavior of TSPEOn, a cowpea field experiment treated with TSPEOn at different doses was carried out in Guangdong province, China. Different 24 TSPEO homologs were all detected in cowpea from the field terminal residue experiments, and the total concentrations of TSPEO homologs in cowpea were 40.0-1,374 μg/kg. The dissipation half-lives of 24 TSPEO homologs in soil were 1.51-2.35 times longer than those in cowpea. The long-chain homologs TSPEOn were dissipated faster than the short-chain homologs TSPEOn, suggesting a homolog-specific degradation of the TSPEOn in the cowpea ecosystem. The characteristic bimodal profiles of TSPEOn (n = 6-29) differing from that of the commercial TSPEOn were observed in the cowpea terminal residues experiment, indicating that the long-chain TSPEOn would degrade to short-chain TSPEOn in cowpea and soil. The acute and chronic dietary exposure risks of ΣTSPEOn in cowpea are within acceptable margins for human consumption across different ages and genders. But the health risks to children should be noticed in future.

Biomarker Records From Eocene Lacustrine Sequence in the Eastern Tibet Plateau and Its Implication for Organic Matter Sources

The Eocene is the initial stage of the Cenozoic global cooling. Compared with the abundant marine records, the continental records of Eocene are scarce. Throughout the Eocene, a series of continuous deposition of gypsum and volcanic tuff-bearing red clastic sediments have developed in the Nangqian Basin (NB). In this work, representative sediments were collected from the NB, and lipid biomarkers and compound-specific carbon isotopes of n-alkanes were analyzed. Based on the robust paleomagnetic age–depth model, from the early to the late Eocene, the compound-specific carbon isotopic compositions (δ13C23 and δ13C25) increased with the sedimentary facies changed. At the same time, the relative proportion of mid-chain length to the long-chain length homologs (Paq) decreased, and the peak carbon number (Cmax) shifted from nC21, nC22 or nC23 to nC16, nC25, nC27, or nC31. We ascribed these variations to the climate drying and water level turning high as indicated by the lithology change from fluvial to lacustrine facies and the terrestrial inputs from neighboring mountain belts in the middle–late Eocene. Moreover, we compared our n-alkane results with other records from the TP and the global sea level and marine benthic δ18O. We found that a nearly synchronous deformation and drying of the eastern TP caused by the India–Asia collision in the early Eocene was closely related to the arid conditions and topographically changed in the northern TP. The climate variations in the Eocene in the NB were mainly controlled by the global climate change and the uplift of the TP and affected by the Paratethys Sea on a long scale.

Effect of burning on the distribution pattern and isotopic composition of plant biomolecules: Implications for paleoecological studies

In fire-prone biomes, the interpretation of paleoecological proxies is subjected to uncertainties since the plant biomarkers/molecules are thermally modified during vegetation fires, and the extent of alterations is yet to be well-constrained, particularly for oxic conditions. Towards this, we performed a series of controlled experiments where leaf samples from C3 (tree and shrub) and C4 (grass) plants were burned under ambient oxygen at temperatures between 200 °C and 500 °C. A topsoil sample was also heated to understand the effect of thermal degradation on organic matter (OM) already present in the soil. Our results show a reduction in the total organic carbon content and leaf wax concentrations which is consistent with the previous studies. We also observed a shift from predominantly long-chain homologues (with odd-over-even in n-alkanes or even-over-odd predominance in n-alkanoic acids; FAs) to balanced distributions with increased mid and short-chain homologues. We observed that the short, mid, and long-chain n-alkanes were mainly formed at the expense of FAs (with losses up to 100%), possibly due to oxygen-rich burning conditions. Burning of plant leaves also affected their stable isotopic compositions. In burned C3 plant leaves (tree and shrub), the bulk carbon isotope values (δ13COM) increased by 1.0–1.4‰, while in C4 grasses, it was 0.4–1.6‰ lower than their unburned counterparts. The changes in the δ13COM values are suggested to be a cumulative product of the kinetic isotope effect and source-driven isotopic fractionation. The carbon isotope values in long-chain n-alkanes (δ13Cn-alk) mostly decreased (up to 4.6‰) in burned C3 and C4 plant leaves due to the isotopic modifications associated with the generation of secondary n-alkanes from FAs. In contrast, the hydrogen isotope values of n-alkanes (δ2Hn-alk) in the burned samples were up to 86‰ higher than their initial values, mainly due to the kinetic isotope effect. Therefore, in biomes susceptible to frequent canopy and litter layer fires, unusually high δ2Hn-alk values coupled with a disproportionate change between δ13Cn-alk and δ2Hn-alk values might indicate pyrogenic OM presence within the soil. We also observed that changes in the n-alkane characteristics due to heating of soil samples were substantially lower than those in plant leaves due to the protected lipid component within organomineral complexes. In summary, we recommend careful consideration and identification of vegetation fire history before using stable isotope-enabled organic proxies for generating paleoecological records.

Bulk and compound-specific \u03b413C and n-alkane indices in a palustrine intermontane record for assessing environmental changes over the past 320\xa0ka: the Padul Basin (Southwestern Mediterranean realm)

Here we provide valuable information about the palaeoenvironmental evolution of Southwestern Mediterranean region during the last ca. 320 ka through a biomarker-based study of the longest continuous continental Quaternary record in the Iberian Peninsula. The n-alkane content and δ13C values of these lipids were measured in 300 samples taken from the uppermost 55 m of the Padul Basin (PB) record. The δ13C signal of long-chain n-alkanes was a reliable proxy for C4/C3 terrestrial vegetation composition in the basin, as emergent macrophytes made a minor contribution to these homologues. In contrast, the δ13C values of C23 and C25 alkanes reflected mainly phases of increasing water level of the lacustrine/palustrine water body since aquatic macrophytes contain a large proportion of these compounds. Low δ13C values were attributed to a marked contribution of plants using the C3 photosynthetic pathway. Intervals with the lowest δ13C values were attributed to an important input of angiosperms, although they could also be explained by changing environmental conditions or environmental stress, as large shifts in δ13C occurred in long-chain homologues typically abundant in terrestrial plants. Shifts in δ13C of medium-chain homologues reflected limited CO2 availability induced by water temperature, salinity, pH, enhanced productivity, low atmospheric pCO2, or stagnant barriers, rather than the abundance of aquatic macrophytes. Our results also suggest enhanced isotopic fractionation during lipid synthesis by aquatic macrophytes within MIS 7 and the Holocene, leading to increased δ13C values of bulk OM and of long-chain n-alkanes. Hence, the δ13C logs were ideal for studying the contribution of aquatic macrophytes to the lipid and isotopic composition of sediments and for the reconstruction of palaeoenvironmental conditions. These results confirmed that C4 plants had a low presence in the PB. Comparison with biomarker analysis and pollen data of the PB and other records of the Southwestern Mediterranean revealed that δ13C values of bulk OM and of long-chain n-alkanes reflected global climatic oscillations during MIS 7 and the episodes Heinrich Events 3, 2, 1 and Younger Dryas.

A ‘Concentrate-&-Destroy’ technology for enhanced removal and destruction of per- and polyfluoroalkyl substances in municipal landfill leachate

Per- and polyfluoroalkyl substances (PFAS) are ubiquitous in landfill leachate due to their widespread applications in various industrial and consumer products. Yet, there has been no cost-effective technology available for treating PFAS in leachate because of the intrinsic persistency of PFAS and the high matrix strength of landfill leachate. We tested a two-step ‘Concentrate-&-Destroy’ technology for treating over 14 PFAS from a model landfill leachate through bench- and pilot-scale experiments. The technology was based on an adsorptive photocatalyst (Fe/TNTs@AC), which was able to selectively adsorb PFAS despite the strong matrix effect of the leachate. Moreover, the pre-concentrated PFAS on Fe/TNTs@AC were effectively degraded under UV, which also regenerates the material. The presence of 0.5 M H2O2 during the photocatalytic degradation enhanced the solid-phase destruction of the PFAS. Fresh Fe/TNTs@AC at a dosage of 10 g/L removed >95% of 13 PFAS from the leachate, 86% after first regeneration, and 74% when reused three times. Fe/TNTs@AC was less effective for PFBA and PFPeA partially due to the transformation of precursors and/or longer-chain homologues into these short-chain PFAS. Pilot-scale tests preliminarily confirmed the bench-scale results. Despite the strong interference from additional suspended solids, Fe/TNTs@AC removed >92% of 18 PFAS in 8 h under the field conditions, and when the PFAS-laden solids were subjected to the UV-H2O2 system, ~84% of 16 PFAS in the solid phase were degraded. The ‘Concentrate-&-Destroy’ strategy appears promising for more cost-effective removal and degradation of PFAS in landfill leachate or PFAS-laden high-strength wastewaters.

Impacts of vegetation and palaeohydrological changes on the n-alkane composition of a Holocene peat sequence from the Upper Vistula Valley (southern Poland)

PurposeThe analysis of n-alkanes in palaeoenvironmental studies of peatlands is mainly limited to ombrogenous peatlands which are a rare feature in the environment. Using n-alkane and plant macrofossil analysis, we have tracked changes in the environment in the valley of a large Central European river. We tested the possibilities for applying such studies to low-moor bogs which are the most commonly occurring type of bog in the world.Materials and methodsRepresentative peat samples were taken from two profiles in a peatland located in the Vistula Valley (southern Poland), and they were analysed for the occurrence and distribution of biomarkers. The distribution of n-alkanes was determined using gas chromatography-mass spectrometry (GC–MS). The botanical composition of the samples was determined by analysis of plant macrofossil remains, and the degree of peat decomposition was also determined.Results and discussionSamples of low-moor peat were characterised by a prevalence of medium- and long-chain n-alkane homologues, which is typical for higher plants. The variable values of the CPI, CPI (25–31), and the C23/C25 ratio have provided information on the stages of formation of the Zapadź bog. The source of n-alkane differentiation is vegetation change related to palaeohydrological dynamics and palaeoenvironmental conditions within the peatland.ConclusionsWe have shown that analysis of n-alkanes can be successfully used in low-moor bogs as a complement to palaeobotanical and palaeozoological methods. The bringing together of these types of research enables changes in the ecosystems of large river valleys to be tracked.

Impact of increasing levels of condensed tannins from sainfoin in the grower–finisher diets of entire male pigs on growth performance, carcass characteristics, and meat quality

Sainfoin is a protein-rich legume with an ideal amino acid profile and therefore could partly replace soybeans in the diets of growing pigs. However, sainfoin also contains a non-negligible amount of condensed tannins (CTs), which can act as antinutritional factors. Bioactive plant compounds, like hydrolysable tannins, have been suggested to be suitable in entire male (EM) production, as they impair the development of accessory sex glands and, by that, reduce boar taint compound levels without negatively impacting growth. It is unknown whether, similar to hydrolysable tannins, CTs from sainfoin reduce the incidence of boar taint without impacting growth performance, carcass traits, and meat quality. For the experiment, 48 Swiss Large White EM were assigned within litter to one of four grower (25–60 kg BW) and finisher (60–105 kg BW) diets supplemented with 0 (T0), 5 (T5), 10 (T10), and 15% (T15) sainfoin meal, respectively. The four diets were designed to be isocaloric and isoproteic. Increasing the dietary sainfoin level had no negative effect on growth performance or the carcass characteristics. Despite leading to a similar feed intake between the treatment groups, increasing the dietary sainfoin levels tended (P ≤ 0.08) to reduce the number of feeder visits but increased the time spent at the feeder as well as the feed intake per visit during the finisher period. By increasing sainfoin intake, the levels of C18:3n-3 and long-chain homologs linearly increased (P < 0.01) in the backfat and intramuscular fat (IMF), whereas in the backfat, but not the IMF, the 18:2n-6 levels decreased (P < 0.01). The latter triggered a greater (P < 0.01) desaturation rate (C18:1n-9/C18:0) of the saturated fatty acids, resulting in a greater (P < 0.01) proportion of monounsaturated fatty acid. Apart from a linear decrease (P = 0.02) in the androstenone levels in the longissimus thoracis (LT), increasing the sainfoin intake had no effect on the level of boar taint in the LT and backfat. As determined by the elevated correlation coefficient, skatole and indole levels, but not androstenone levels, in the adipose tissue seem to be reliable proxies for their respective levels in LT and, therefore, in pork. In conclusion, sainfoin is a suitable homegrown protein source for grower finisher pigs and can be included at up to 15% in the diet to replace 7% of soybean in a diet without producing any noteworthy effects on growth, whereas the impact of CTs on boar taint was limited.

Geochemical Features of Unburned Coal Particles in Fly Ashes from Thermal Power Plants in Bulgaria

Coal combustion in thermal power plants generates huge amounts of solid wastes, including fly ash (FA). The essays of its conversion into value-added products continuously increase. The aim of the study was: (i) to depict organic compounds (if any) present in industrial coal-derived FAs from four thermal power plants (TPPs) in Bulgaria; (ii) to assess the relationship of the compounds present with the feed coals using biomarker proxies; (iii) and, to appreciate biomarkers changes in distribution pattern caused by combustion. Average samples of FAs and samples from electrostatic precipitators of four TPPs feed by different rank coals were analyzed. The study was scheduled in comparison with parent feed coals. The yields of extractable organic matter (EOM) expressed in rel. % were low and comparable, ∼ 0.01%, but normalized to total organic carbon (TOC) depicted some differences. For lower rank coals FAs yields were higher, in the range 10-20 mg/g TOC, all dominated by polar components and an order of magnitude lower for higher rank coal FAs, < 2 mg/g TOC, with considerable portions of neutral compounds. After extensive fractionation of EOM from unburned coal particles in neutral fractions of FAs short chain n-alkanes (nC15-nC19) prevalence was distinguished. The feature was assigned to high temperature of combustion and thermal destruction of long-chain homologues (nC27-nC31). The distribution signatures for low rank coals kept some characteristics of parent coals while in the case of bituminous coal longer homologues were almost absent. The changes in n-alkanes distributions were rank depended and an attempt for explanation by FA particles porosity was done. For organic compounds registered in EOM of coal-derived FAs two provenances are supposed. The first group comes from the feed coals and the second one is formed in combustion processes or has changed distributions under the thermal treatment. Insofar as n-alkanes distribution signature was altered in combustion the origin should rather be assigned to the second group of components.

Assessment of the molecular-level compositional heterogeneity of natural organic matter in bentonites intended for long-term used nuclear fuel storage

Bentonite-rich clays have been chosen as the sealing material in the engineered barrier system of the deep geological repository (DGR) for the long-term storage of used nuclear fuels. Natural organic matter (NOM) found in these bentonites can serve as a source of nutrients for microbial growth. Although high density bentonite does not support microbial activity within its matrix, it is possible that microbial growth will occur at interface of the DGR rock wall and the bentonite; the availability of nutrients is therefore a design consideration. Furthermore, it is unclear if NOM is similar in composition within bentonite samples collected from different locations from the same naturally-occurring clay deposit, or whether NOM chemistry will vary within different batches.Here, we report the detailed geochemical characterisation of different nutrients and NOM in five different MX-80 bentonites from the same location, but collected in different lots. Our results show that total carbon comprises <1% and that organic carbon constitutes less than one-fifth of this total carbon content. Statistical analyses revealed no significant differences in the NOM composition, or the other geochemical characteristics, of these samples. Targeted organic compound analyses indicated a predominance of long-chain homologues in the aliphatic lipids of the bentonites, suggesting that NOM in MX-80 bentonites is primarily terrestrially-derived. We detected nanogram-level variabilities in the concentrations of selected compounds between samples, but these variabilities were not statistically significant. Analysis by solid-state 13C nuclear magnetic resonance (NMR) spectroscopy also showed consistency between the NOM of the different MX-80 samples and a predominance of aliphatic, as well as aromatic compounds, which suggests that the NOM has undergone extensive diagenesis.Overall, all analyses consistently indicated that the NOM composition exhibits low heterogeneity between the different bentonites mined from the same source. These results provide confidence in the potential use of MX-80 as a buffer material for widespread use in DGRs and they build upon past research on the NOM composition of bentonite clays.

Biotransformation of perfluoroalkyl acid precursors from various environmental systems: advances and perspectives.

Perfluoroalkyl acids (PFAAs) are widely used in industrial production and daily life because of their unique physicochemical properties, such as their hydrophobicity, oleophobicity, surface activity, and thermal stability. Perfluorosulfonic acids (PFSAs) and perfluorocarboxylic acids (PFCAs) are the most studied PFAAs due to their global occurrence. PFAAs are environmentally persistent, toxic, and the long-chain homologs are also bioaccumulative. Exposure to PFAAs may arise directly from emission or indirectly via the environmental release and degradation of PFAA precursors. Precursors themselves or their conversion intermediates can present deleterious effects, including hepatotoxicity, reproductive toxicity, developmental toxicity, and genetic toxicity. Therefore, exposure to PFAA precursors constitutes a potential hazard for environmental contamination. In order to comprehensively evaluate the environmental fate and effects of PFAA precursors and their connection with PFSAs and PFCAs, we review environmental biodegradability studies carried out with microbial strains, activated sludge, plants, and earthworms over the past decade. In particular, we review perfluorooctyl-sulfonamide-based precursors, including perfluroooctane sulfonamide (FOSA) and its N-ethyl derivative (EtFOSA), N-ethyl perfluorooctane sulfonamido ethanol (EtFOSE), and EtFOSE-based phosphate diester (DiSAmPAP). Fluorotelomerization-based precursors are also reviewed, including fluorotelomer alcohols (FTOH), fluorotelomer sulfonates (FTSA), and a suite of their transformation products. Though limited information is currently available on zwitterionic PFAS precursors, a preliminary review of data available for 6:2 fluorotelomer sulfonamide betaine (FTAB) was also conducted. Furthermore, we update and refine the recent knowledge on biotransformation strategies with a focus on metabolic pathways and mechanisms involved in the biotransformation of PFAA precursors. The biotransformation of PFAA precursors mainly involves the cleavage of carbon-fluorine (C-F) bonds and the degradation of non-fluorinated functional groups via oxidation, dealkylation, and defluorination to form shorter-chained PFAAs. Based on the existing research, the current problems and future research directions on the biotransformation of PFAA precursors are proposed.