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Organic carbon (OC) burial in the Antarctic marginal seas is essential for regulating global climate, particularly due to its association with ice shelf retreat. Here, we analyzed total OC (TOC), total nitrogen (TN), radiocarbon isotope, n-alkanes and relative indicators in surface and core sediments from the Ross Sea, West Antarctica. Our aim was to investigate spatial and historical changes in OC sources, and to explore the influencing factors and implications for ice shelf retreat since the last glacial maximum (LGM). Our results revealed distinct spatial patterns of OC sources as indicated by n-alkane indicators in surface sediments. In the Western Ross Sea, n-alkanes predominantly originated from phytoplankton and bacteria, as evidenced by their unimodal distribution, low carbon preference index (CPI) of short-chain n-alkanes (CPIL = 1.41 ± 0.30), and low terrestrial/aquatic ratio (TAR = 0.22 ± 0.14). In the Southwest Ross Sea, n-alkanes were derived from marine algae and terrestrial bryophytes, indicated by bimodal distribution, low ratio of low/high molecular-weight n-alkanes (L/H = 0.62 ± 0.21), low CPI of long-chain n-alkanes (CPIH = 1.18 ± 0.16), and high TAR (1.26 ± 0.66). In contrast, the Eastern Ross Sea exhibited n-alkanes that were a combination of phytoplankton and dust from Antarctic soils and/or leaf waxes from mid-latitude higher plant, as suggested by both unimodal and bimodal distributions, high L/H (1.60 ± 0.58) and CPIH (2.04 ± 0.28), and medium TAR (0.61 ± 0.30). Geologically, during the LGM (27.3 -- 21.0 ka before present (BP)), there was an increased supply of terrestrial OC (TOC/TN = 13.63 ± 1.29, bimodal distribution of n-alkanes with main carbon peaks at nC17/nC19 and nC27). From 21.0 to 8.2 ka BP, as glaciers retreated and temperatures rose, the proportion of marine n-alkanes significantly increased (TOC/TN = 9.09 ± 1.82, bimodal distribution of n-alkanes with main carbon peaks at nC18/nC19 and nC25). From 8.2 ka BP to the present, as the ice shelf continued to retreat to its current position, the marine contribution became dominant (TOC/TN = 8.18 ± 0.51, unimodal distribution of n-alkanes with main carbon peak at nC17/nC18/nC19, and low TAR (0.41 ± 0.32)). This research has significant implications for understanding the variations in Antarctic OC sources and their climatic impacts in the context of accelerated glacier melting. [ABSTRACT FROM AUTHOR]

Over 1/3 of the Earth's human population relies on dryland ecosystems for food and water resources. While these ecosystems are highly sensitive to changes in climate, we lack observational data as to how changes in hydrology influences plant communities. Paleoecological data for southern Arabia show woodland communities transitioned to more dry-adapted herbaceous plants, which suggests rainfall decreased across the Holocene. To assess relationships between hydrology and ecology, we employed leaf wax n-alkane distributions, 513Cwax, and 5Dwax records from rock hyrax (Procavia capensis) middens in Dhofar, Oman. The biomarker properties allowed reconstruction of changes in C3/C4 vegetation and local moisture availability, in tandem with community changes represented by a published pollen record. To constrain interpretations, n-alkane analyses were conducted on herbarium specimens of leaves collected in Dhofar. For the modern specimens, xeric plants typically contained longer homologues than mesic plants. Across the fossil middens (4,038-109 cal yrs BP), the proportions of plant-wax homologues do not show major changes, and thus do not suggest a shift between xeric versus mesic plants. Similarly, 513Cwax values indicate little or no change in the distributions of C3 and C4 vegetation. Limited 5Dwax data from the middens confirm overall drying occurred into the late Holocene, punctuated by a wetter pulse at ~1.6 ka. Taken together, plant wax distributions and isotope data indicate changes in moisture availability across the late Holocene did not alter the structural composition of the plant communities and that the proportion of C3/C4 vegetation remained stable. We infer vegetation changes associated with late Holocene drying involved reshuffling of community composition and not major changes in vegetation structure. Additionally, this study demonstrates that leaf wax n-alkanes from rock hyrax middens provide a method to reconstruct changes in climate and vegetation in dryland ecosystems where other archives are scarce. [ABSTRACT FROM AUTHOR]

Many continental paleoclimate archives originate from wetland sedimentary sequences. While several studies have investigated biomarkers derived from peat-generating vegetation typical of temperate/boreal bogs (e.g., Sphagnum), only scant information is available on emergent plants predominant in temperate/subtropical coastal marshlands, peri-lacustrine and fen environments. Here, we address this gap, focusing on two wetlands in the Mediterranean (Nisí fen and Tenaghi Philippon, Greece). We examined the concentration, homologue distribution, and hydrogen stable isotopic composition (δ[sup 2]H) of leaf wax n-alkanes in 13 fen plant species, their surrounding soil, and surface water during the wet growing season (spring) and the declining water table period (summer). Our findings indicate that local graminoid species primarily contribute to the soil n-alkane signal, with a lesser influence from forbs, likely owing to differences in morphology and vegetation structure. The δ[sup 2]H values of surface and soil water align with local average annual precipitation δ[sup 2]H, reflecting winter-spring precipitation. Consistently, the average δ[sup 2]H of local surface, soil, and lower stem water showed negligible evaporative enrichment, confirming minimal [sup 2]H-fractionation during water uptake. We find that δ[sup 2]H values of source water for wax compound synthesis in local fen plants accurately mirror local annual precipitation. Furthermore, despite differences between leaves and lower stems in n-alkane production rates, their δ[sup 2]H values exhibit remarkable similarity, indicating a shared metabolic substrate, likely originating in leaves. Our net [sup 2]H-fractionation values (i.e., precipitation to leaf n-alkanes) align with those in Chinese highlands and other similar environments, suggesting consistency across diverse climatic zones. Notably, our data reveal a seasonal decrease in the carbon preference index (CPI) in plant samples, indicating wax lipid synthesis changes associated with increased aridity. Additionally, we introduce a new parity isotopic difference index (PID) based on the consistent δ[sup 2]H difference between odd and even n-alkane homologues. The PID demonstrates a strong anticorrelation with plant CPI, suggesting a potential avenue to trace long-term aridity shifts through δ[sup 2]H analysis of odd and even n-alkane homologues in sedimentary archives. While further development of the PID is necessary for broad application, these findings highlight the intricate interplay between plant physiology, environmental parameters, and sedimentary n-alkanes in unravelling past climatic conditions. [ABSTRACT FROM AUTHOR]

Over 1/3 of the Earth’s human population relies on dryland ecosystems for food and water resources. While these ecosystems are highly sensitive to changes in climate, we lack observational data as to how changes in hydrology influences plant communities. Paleoecological data for southern Arabia show woodland communities transitioned to more dry-adapted herbaceous plants, which suggests rainfall decreased across the Holocene. To assess relationships between hydrology and ecology, we employed leaf wax n-alkane distributions, δ13Cwax, and δDwax records from rock hyrax (Procavia capensis) middens in Dhofar, Oman. The biomarker properties allowed reconstruction of changes in C3/C4 vegetation and local moisture availability, in tandem with community changes represented by a published pollen record. To constrain interpretations, n-alkane analyses were conducted on herbarium specimens of leaves collected in Dhofar. For the modern specimens, xeric plants typically contained longer homologues than mesic plants. Across the fossil middens (4,038–109 cal yrs BP), the proportions of plant-wax homologues do not show major changes, and thus do not suggest a shift between xeric versus mesic plants. Similarly, δ13Cwax values indicate little or no change in the distributions of C3 and C4 vegetation. Limited δDwax data from the middens confirm overall drying occurred into the late Holocene, punctuated by a wetter pulse at ∼1.6 ka. Taken together, plant wax distributions and isotope data indicate changes in moisture availability across the late Holocene did not alter the structural composition of the plant communities and that the proportion of C3/C4 vegetation remained stable. We infer vegetation changes associated with late Holocene drying involved reshuffling of community composition and not major changes in vegetation structure. Additionally, this study demonstrates that leaf wax n-alkanes from rock hyrax middens provide a method to reconstruct changes in climate and vegetation in dryland ecosystems where other archives are scarce.

Abstract The aim of this work is to examine the levels, distribution, bases, and hazards of n-alkanes (n-C9 to n-C20) and PAHs in the seawater and sediments around oil production locations in the whole delta region. The variations in the levels of PAHs and n-alkanes in seawater and sediment of the Nile delta coast of the Mediterranean were investigated using GC–MS/MS. The Σn-alkanes residues ranged between 12.05 and 93.51 mg/L (mean: 50.45 ± 17.49 mg/L) and 4.70 to 84.03 µg/g (mean: 31.02 ± 27.995 µg/g) in seawater and sediments, respectively. Total PAHs concentrations ranged between 4.485 and 16.337 μg/L (average: 9.47 ± 3.69 μg/L) and 1.32 to 28.38 ng/g (average 8.61 ± 7.57 ng/g) in seawater and sediment samples, respectively. The CPI (carbon preference index) values fluctuated between 0.62 and 1.72 (seawater) and from 0.234 to 2.175 (sediment), proposing the variation sources of n-alkane in the studied area. PAHs concentrations were lower than the Effective Range Low (ERL) and Effective Range Median (ERM) levels. The Toxic Equivalent Quotient (TEQ) values oscillated between 0.002 and 6.84 ng/L and from 3.72 to 13.48 ng/g for the seawater and sediment samples, respectively. The Ant/(Ant + Phe) ratio in sediment and seawater samples indicated a pyrolytic source while the BaA/(BaA + Chry) ratio indicates petrogenic sources in most of the studied stations.

The aim of this work is to examine the levels, distribution, bases, and hazards of n-alkanes (n-C9 to n-C20) and PAHs in the seawater and sediments around oil production locations in the whole delta region. The variations in the levels of PAHs and n-alkanes in seawater and sediment of the Nile delta coast of the Mediterranean were investigated using GC–MS/MS. The Σn-alkanes residues ranged between 12.05 and 93.51 mg/L (mean: 50.45 ± 17.49 mg/L) and 4.70 to 84.03 µg/g (mean: 31.02 ± 27.995 µg/g) in seawater and sediments, respectively. Total PAHs concentrations ranged between 4.485 and 16.337 μg/L (average: 9.47 ± 3.69 μg/L) and 1.32 to 28.38 ng/g (average 8.61 ± 7.57 ng/g) in seawater and sediment samples, respectively. The CPI (carbon preference index) values fluctuated between 0.62 and 1.72 (seawater) and from 0.234 to 2.175 (sediment), proposing the variation sources of n-alkane in the studied area. PAHs concentrations were lower than the Effective Range Low (ERL) and Effective Range Median (ERM) levels. The Toxic Equivalent Quotient (TEQ) values oscillated between 0.002 and 6.84 ng/L and from 3.72 to 13.48 ng/g for the seawater and sediment samples, respectively. The Ant/(Ant + Phe) ratio in sediment and seawater samples indicated a pyrolytic source while the BaA/(BaA + Chry) ratio indicates petrogenic sources in most of the studied stations. [ABSTRACT FROM AUTHOR]

Simple Summary: Near-infrared spectroscopy (NIRS) has emerged as an accurate and promising alternative to traditional wet chemistry methods in feed and food science. Its applicability extends to estimating concentrations of compounds such as n-alkanes, based on their chemical properties, in various materials, including feed and feces. Analysis of excreta n-alkane patterns can provide insight into the dietary behavior of laying hens, particularly in scenarios where they have access to free-range areas and potentially consume plants from outside sources. Our study attempts to explore extreme cases, such as hens consuming only commercial feed, which result in lower concentrations of n-alkanes in excreta, thus challenging NIRS as a replacement for wet chemistry. Evaluating the accuracy of NIRS in predicting n-alkanes in excreta is critical because of its potential for substantial time and cost savings. Furthermore, it contributes to a deeper understanding of future nutritional strategies for laying hens, particularly in light of external nutritional contributions. N-alkanes offer a promising approach for assessing the nutritional contribution of external sources to the diets of laying hens in free-range production systems. However, traditional laboratory methods, involving extraction, purification and gas chromatographic analysis, are both economically burdensome and time-consuming. Near-infrared spectroscopy (NIRS) is emerging as a viable alternative, with varying degrees of accuracy depending on the chemical nature and concentration of the component of interest. In our research, we focus on the accuracy of NIRS in predicting the concentrations of n-alkanes (C25–C33) in excreta under simulated free-range conditions with two different diets: one containing a commercial feed with minimal n-alkane content and another containing 1% alfalfa on top of the commercial feed. Spectra processing and calibration were tailored for each n-alkane, with NIRS performance influenced by diet type. Notably, plant predictions using NIR-generated data were consistent with laboratory results, despite a slight tendency toward overestimation (3.40% using the NIRS-generated C25-C29-C33 combination versus 2.80% using laboratory analysis). This indicates the potential of NIRS as an efficient tool to assess n-alkanes in excreta of laying hens and, consequently, the nutritional contribution of the free-range environment, providing rapid and cost-effective results. [ABSTRACT FROM AUTHOR]

Simple Summary: Providing better living conditions for laying hens by promoting free-range systems has sparked curiosity about potential alterations in their dietary habits. Understanding these changes can lead to new feeding strategies to meet their nutritional needs. However, this task is challenging due to the inherent complexities of the outdoor environments and variations in plant material breakdown. Our research marks a pioneering step in exploring both qualitative and quantitative methods for assessing plant intake in laying hens using n-alkanes as markers, and demonstrates their viability even at levels of plant material in the diet as low as 1%. It also highlights the need for further research on different sources of n-alkanes, especially in real case studies with different plant and insect species under outdoor conditions. Such studies are essential to provide a deeper understanding of the dietary factors affecting the performance of laying hens in free-range systems. The shift in animal welfare standards towards free-range housing for laying hens in the EU has raised questions about changes in dietary composition. Accurate assessment of outdoor plant material intake is crucial for effective feeding strategies. This study introduces an approach using n-alkanes as markers to determine plant intake in laying hens, involving n-alkane recovery rate assessment, discriminant analysis and linear equation-solving for both qualitative and quantitative assessment, respectively, considering systematic n-alkane combinations. Two diets: a standard commercial diet and a diet incorporating 1% alfalfa were tested. Chemical analyses showed an altered n-alkane profile due to alfalfa inclusion, resulting a recovery rates ranging from 30–44% depending on the n-alkane type and diet. Statistical analysis revealed significant differences in recovery rates among the different alkanes for the same diets and between the diets for the same alkane, together with an interaction between n-alkane carbon chain length and initial concentration in the diet. The method accurately predicted plant inclusion, with a slight overestimation (2.80%) using the combination C25-C29-C33. Accurate qualitative classification of the animals based on fecal n-alkanes profiles was observed. The study successfully demonstrated the utility of n-alkanes for estimating dietary composition, providing a non-invasive approach for future free-range studies. [ABSTRACT FROM AUTHOR]

Many continental paleoclimate archives originate from wetland sedimentary sequences. While several studies have investigated biomarkers derived from peat-generating vegetation typical of temperate/boreal bogs (e.g., Sphagnum), only scant information is available on emergent plants predominant in temperate/subtropical coastal marshlands, peri-lacustrine and fen environments. Here, we address this gap, focusing on two wetlands in the Mediterranean (Nisí fen and Tenaghi Philippon, Greece). We examined the concentration, homologue distribution, and hydrogen stable isotopic composition (δ2H) of leaf wax n-alkanes in 13 fen plant species, their surrounding soil, and surface water during the wet growing season (spring) and the declining water table period (summer). Our findings indicate that local graminoid species primarily contribute to the soil n-alkane signal, with a lesser influence from forbs, likely owing to differences in morphology and vegetation structure. The δ2H values of surface and soil water align with local average annual precipitation δ2H, reflecting winter-spring precipitation. Consistently, the average δ2H of local surface, soil, and lower stem water showed negligible evaporative enrichment, confirming minimal 2H-fractionation during water uptake. We find that δ2H values of source water for wax compound synthesis in local fen plants accurately mirror local annual precipitation. Furthermore, despite differences between leaves and lower stems in n-alkane production rates, their δ2H values exhibit remarkable similarity, indicating a shared metabolic substrate, likely originating in leaves. Our net 2H-fractionation values (i.e., precipitation to leaf n-alkanes) align with those in Chinese highlands and other similar environments, suggesting consistency across diverse climatic zones. Notably, our data reveal a seasonal decrease in the carbon preference index (CPI) in plant samples, indicating wax lipid synthesis changes associated with increased aridity. Additionally, we introduce a new parity isotopic difference index (PID) based on the consistent δ2H difference between odd and even n-alkane homologues. The PID demonstrates a strong anticorrelation with plant CPI, suggesting a potential avenue to trace long-term aridity shifts through δ2H analysis of odd and even n-alkane homologues in sedimentary archives. While further development of the PID is necessary for broad application, these findings highlight the intricate interplay between plant physiology, environmental parameters, and sedimentary n-alkanes in unravelling past climatic conditions.

In Southern Brazil, exotic species as Acacia (A) and Eucalyptus (E) are often planted over native pasturelands and may change bulk soil organic matter (SOM) composition as verified in our previous study with Cambisols (0–5 cm). Here we aimed to follow the impact of seven-year A and E plantation on the composition of the free light- (FLF), occluded light- (OLF) and heavy fraction (HF) of SOM along the soil profile. We hypothesized that A and E may have shifted the molecular composition and carbon (C) stocks (Cs) of SOM fractions, at least at 0–5 cm; with stronger shifts caused by A due to greater E litter recalcitrance. Litter and soil samples (0–20 cm) were collected at A and E and neighboring native pasturelands without A (WA) and without E (WE). Litter, FLF, OLF and HF samples were subjected to C, nitrogen (N), pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS) and lipid biomarkers analysis. In E soil, the Cs of FLF at 0–5 cm (0.5 Mg ha−1) and OLF at 5–10 cm (1.7 Mg ha−1) were 194 and 70 % greater than in WE, whereas in A soil the Cs of OLF at 0–5 cm (0.2 Mg ha−1) was 44 % lower than in WA. Nevertheless, A changed more remarkably the composition of SOM fractions, confirming our hypothesis partially, likely due to greater A litter biodegradability (polysaccharides abundance) compared to E. The contribution of A litter to FLF (0–10 cm) was evidenced by abundance of long chain and the predominance of odd-over-even n-alkanes (particularly >C29), and to OLF (0–20 cm) by the greatest abundance of n-alkanes at C31, resembling A litter. Loss of C and N of OLF in A compared to WA (0–5 cm) was compensated by fresh A litter additions to FLF and OLF and microbial-derived compounds association to soil minerals, equaling soil Cs in A and WA. The lower soil N stock in A compared to WA likely resulted from depletion of occluded microbial-derived N-compounds, supposedly reflecting the breakdown of soil aggregates at forest plantation. The increase of Cs in FLF and OLF of E compared to WE soil was associated with increased abundance of aromatics and n-alkane/alkenes and decrease of fatty acids. Similar patterns of n-alkanes observed for OLF of E and WE soil confirmed the incipient contribution of E litter to OLF. Conversion of these pastures to A and E modifies SOM composition and protection, requiring policies in view of the highly invasive potential and possible negative implications of A and E to native pasture regeneration.

Afforestation has been the dominant land-use change in the Swiss Alps during the last decades which has not only the potential to increase soil organic carbon sequestration, but it has also the potential to alter soil organic matter (SOM) dynamics through the vegetation shift and change in organic matter (OM) input into soils. The effects of afforestation on SOM dynamics, however, are still not fully understood as specific sources of OM and modifications of soil processes influencing decomposition and preservation remain largely unknown on alpine to subalpine slopes. Within this study we aimed to identify the potential sources and the decomposition of OM in a subalpine afforestation chrono-sequence (0–130 years) with Norway spruce (Picea abies L.) on a former pasture by using a multi-proxy molecular marker approach. We observed that leaf-derived OM plays an essential role in the pasture areas, while root-derived OM only plays a minor role in pasture and forest areas. Needle-derived OM represents the dominant source of SOM with increasing forest age, while understory shrubs and moss also contribute to the OM input in younger forest stand ages. However, needle litter and buildup of organic layers and subsequently less input of fresh OM from organic horizons to mineral soil can result in increased OM decomposition in mineral soils rather than contributing to additional SOM stabilization in mineral soils. This was most pronounced in the oldest forest stand (130-year-old) in the investigated afforestation sequence, particularly in deeper soil horizons (10–45 cm). Thereby, our study provides new insights into SOM dynamics following afforestation, especially with respect to the long-term SOM sequestration potential of afforestation of subalpine pasture soils.

Identification and quantification of allochthonous and autochthonous organic carbon (OC) are crucial for the interpretation of burial behaviors of sedimentary OC of shallow lakes under anthropogenic interferences. In this study, we analyzed distribution patterns and δ13C signatures of mid-and long-chain n-alkanes on various types of surface samples from a typically large and shallow Lake Wuliangsu in the Hetao Irrigation District. The results indicate that n-alkanes among submerged macrophytes, emergent plants, and riverine soil show unique distribution patterns and δ13C signatures, supporting the practicability of quantification on OC of these sources by end-member mixing models. Introducing the δ13C values of n-alkanes into the endmember mixing models could effectively reduce the potential error derived from end-member determination on n-alkane distribution patterns and OC degradation. The model results suggest that the riverine sourced OC from the main channel to Lake Wuliangsu has settled down during the southward migration process. Therefore, Lake Wuliangsu serves as an important trap and sink for the allochthonous OC from the Upper Yellow River Reaches. The model results also show a predominate contribution from the autochthonous OC to Lake Wuliangsu (mostly >85%), with open-water areas dominated by submerged macrophytes and the rest of areas by emergent plants, largely modulated by water transparency, water depth, and nutrient concentrations. Together with previously published tetraether results, we further proposed that areas dominated by submerged macrophytes might be more favorable for heterotrophic anaerobic bacteria and methanogenic archaea, largely due to active recycling processes for the labile OC derived from submerged macrophytes. [ABSTRACT FROM AUTHOR]

The “river-sea” geochemical barrier is studied slightly in terms of the variety of pollutants, sedimentation, and degradation. At the same time, problems related to oil pollution, in particular the genesis of hydrocarbons, are almost never covered. This study was dedicated to the origin, concentration, and composition of hydrocarbons in the bottom sediments of the Chernaya River (Black Sea, Crimea) estuarine zone. The features of the marginal filter zone of the river were considered. N-alkanes in the range of C11-C36 were identified in the bottom sediments of the studied water area. It was noted that there was persistent oil pollution (degraded hydrocarbons) in the water area of Sevastopol Bay, adjacent to the confluence of the river. The accumulation of terrestrial material increased as it moved from the river to the sea. The application of various molecular markers displayed the predominately allochthonous origin of the hydrocarbons in the bottom sediments. As a result of the study of molecular markers by using principal component analysis (PCA) and analysis of variance (ANOVA) analysis, three leading factors responsible for hydrocarbon input to the bottom sediments water area were identified. The first one (36.53 % of the total variation) was associated with n-alkanes of natural and anthropogenic input. The second factor (19.52 % variation) was associated with allochthonous organic matter, including petroleum and bacterial destruction. The third factor (10.74 %) was associated with mainly allochthonous routes of organic substances entering the bottom sediments of the water area.

N-alkanes offer a promising approach for assessing the nutritional contribution of external sources to the diets of laying hens in free-range production systems. However, traditional laboratory methods, involving extraction, purification and gas chromatographic analysis, are both economically burdensome and time-consuming. Near-infrared spectroscopy (NIRS) is emerging as a viable alternative, with varying degrees of accuracy depending on the chemical nature and concentration of the component of interest. In our research, we focus on the accuracy of NIRS in predicting the concentrations of n-alkanes (C25–C33) in excreta under simulated free-range conditions with two different diets: one containing a commercial feed with minimal n-alkane content and another containing 1% alfalfa on top of the commercial feed. Spectra processing and calibration were tailored for each n-alkane, with NIRS performance influenced by diet type. Notably, plant predictions using NIR-generated data were consistent with laboratory results, despite a slight tendency toward overestimation (3.40% using the NIRS-generated C25-C29-C33 combination versus 2.80% using laboratory analysis). This indicates the potential of NIRS as an efficient tool to assess n-alkanes in excreta of laying hens and, consequently, the nutritional contribution of the free-range environment, providing rapid and cost-effective results.

The Neogene fluvial–lacustrine sediments of the Tianshui Basin provide records of the interactions among tectonic activity, and climatic and ecological changes on the northeastern Tibetan Plateau (NE TP), from ∼12.4 to 2.6 Ma. We investigated the n-alkane record of a sedimentary sequence from the Tianshui Basin, which reveals shifts in the productivity and sources of n-alkanes. The productivity of n-alkanes doubled many times during ∼4.2–3.2 Ma, accompanied by the increased contribution from aquatic plants; in addition, non-emergent macrophytes occurred sporadically after ∼4.2 Ma but became a significant n-alkane source after ∼3.2 Ma. Changes in the inferred Late Miocene ecology of the region are consistent with the major climate transition in response to global cooling. The oscillations of the types and concentrations of n-alkanes during 4.2–3.2 Ma were likely related to the evolution of the East Asian monsoon (EAM), driven by the tectonic uplift of NE TP and global cooling. The major increase in aquatic plants and biological productivity of this region at ∼3.2 Ma may have been caused by the strengthening of the East Asian summer monsoon (EASM) and the regional tectonic uplift.

The environmental and health risks of n-alkanes and benzene, toluene, ethylbenzene, and xylene (BTEX) in Eze-Iyi River at Isuikwuato oil spill site were evaluated. The water samples (60) were collected from upstream and downstream during the dry and rainy seasons. Concentrations of n-alkanes and BTEX were determined using a gas chromatograph coupled with a flame ionization detector. The percentage recovery of 87.3% and 92.0% was obtained for n-alkanes and BTEX in the water sample. The environmental risk analysis for n-alkanes and BTEX showed 80% of the water samples had a ratio greater than 1 indicating environmental risk in the area. Hydrocarbon source identification using biomarkers indicates that the n-alkane (nC16) dominant during the dry and rainy seasons was from anthropogenic/biogenic source, while nC14 and nC17 were from microbial and marine algae biogenic sources, respectively. The benzene levels in 100% (downstream) and 80% (upstream) of samples in the dry season and 40% (upstream) and 100% (downstream) of samples in the rainy season were above the WHO permissible limit of 0.01 mg/L for drinking water. The health risk index of n-alkanes during the dry season for children (upstream) was greater than 1 signifying adverse health risk. Therefore, consumption of water from the river should be discouraged and routine monitoring by regulatory authorities maintained to checkmate the build-up of BTEX and n-alkanes. [ABSTRACT FROM AUTHOR]

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Abstract In this study, major chemical components of PM2.5 including nitrate, sulfate, organic carbon (OC), and elemental carbon (EC) were measured in Chuncheon, South Korea in May–June, 2021. Average PM2.5 concentration was 16.4±9.7 µg m−3, and OC was the largest contributor of PM2.5 mass concentration. High concentration episodes (HCEs), defined when PM2.5 concentration exceeded 30 µg m−3, were caused by Asian dust, secondary inorganic aerosol (SIA) formation, and primary OC emission. NH4+ was determined to be a limiting factor for SIA formation based on neutralization ratio. There was statistically significant correlation between n-alkanes and PM2.5, and odd alkanes including C27, C29, and C31, which are generally emitted from biogenic sources, were abundant species, suggesting the importance of natural sources over fossil fuel combustion. Polycyclic aromatic hydrocarbons (PAHs) concentrations were significantly lower than those measured at the same sampling site in 2014–2015. Based on the diagnostic ratios of PAHs, vehicular emission, rather than solid fuel emission, were significant for PAHs. Detailed characterization of chemical composition of PM2.5 reported in this study can be of great help in establishing an appropriate abatement policy to reduce PM2.5 concentrations.

Gas injection has emerged over the recent decades as a promising technology to enhance oil recovery in various fields worldwide. The efficiency and success of a gas injection operation can be assessed through a number of vital experimental studies. Interfacial Tension (IFT) between the injected gas and the displacing fluid is a key parameter playing an eminent role in the foregoing studies. The main scope of this work is making a progress in modeling the IFTs between diverse n-alkanes and Methane (CH4), Carbon Dioxide (CO2), and Nitrogen (N2) natural gases. For this purpose, two smart AI-based approaches of Cascaded Feedforward Neural Network (CFNN) and Decision Tree Learning (DT) were used to simultaneously model the IFTs between foregoing immiscible binary systems as a function of pressure, temperature, the gases properties, and the properties of the liquid. Several statistical measures and graphical descriptions were employed to aid the accuracy analysis of the proposed models. Both developed CFNN and DT networks represented desirable close-to-reality predictions in all binary systems. Besides, CFNN established itself as the most robust model for all studies binary systems with RMSE values of 0.5924, 0.5649, and 0.5870 mN/m, and R2 values of 0.9902, 0.9910, and 0.9904 for the train, test, and overall data, respectively.

The climate reconstruction of the Tibetan Plateau, which was called the Third Pole Environment, has been a research hotspot in recent years. However, there are few studies on C3 and C4 plants evolution and it is an area of active debate on whether there are C4 plants existing on the Tibetan Plateau. In this study, the paleoclimate of the Hurleg Lake on the northeastern Tibetan Plateau is reconstructed based on n‐alkane‐induced indicators, while the C4 plant evolution history is established by compound‐specific isotope of long‐chain n‐alkanes since 14.1 cal kyr BP. The response of C4 plant evolution history to climate change on the northeastern margin of the Tibetan Plateau demonstrated that C3 and C4 plants were sensitive to local and global climate change. Solar radiation in summer, insolation‐affected East Asian monsoon, and seasonal climate (including seasonal variation of the solar radiation, temperature, and precipitation) had significant effects on the long‐term growth of C4. On the other hand, factors such as temperature, precipitation, and other potential factors affected the detailed variation of C4 plants in a relatively short‐term. Our finding maintained the existence of C4 plants in the high‐altitude region and indicated that the abundance of C4 plants might increase significantly and the ecological pattern of vegetation on the Tibetan Plateau will change distinctly in the coming warmer climate conditions. Key Points: Paleoclimate and C4 plant evolution on the northeastern Tibetan Plateau since the Last Deglacial were revealedC4 plants on the northeastern Tibetan Plateau were relatively abundant during the Younger Dryas periodInsolation, temperature, East Asian monsoon, and seasonal differences play significant roles in the evolution of C4 plants [ABSTRACT FROM AUTHOR]

Petroleum hydrocarbons are relatively recalcitrant compounds, and as contaminants, they are one of the most serious environmental problems. n-Alkanes are important constituents of petroleum hydrocarbons. Advances in synthetic biology and metabolic engineering strategies have made n-alkane biodegradation more designable and maneuverable for solving environmental pollution problems. In the microbial degradation of n-alkanes, more and more degradation pathways, related genes, microbes, and alkane hydroxylases have been discovered, which provide a theoretical basis for the further construction of degrading strains and microbial communities. In this review, the current advances in the microbial degradation of n-alkanes under aerobic condition are summarized in four aspects, including the biodegradation pathways and related genes, alkane hydroxylases, engineered microbial chassis, and microbial community. Especially, the microbial communities of "Alkane-degrader and Alkane-degrader" and "Alkane-degrader and Helper" provide new ideas for the degradation of petroleum hydrocarbons. Surfactant producers and nitrogen providers as a "Helper" are discussed in depth. This review will be helpful to further achieve bioremediation of oil-polluted environments rapidly. [ABSTRACT FROM AUTHOR]

The aim of this work is to investigate the potential petroleum shales of Dukamaje formation in Sokoto basin for their petroleum potentials. A total of sixteen samples were obtained from different parts of the basin. The samples were subjected to sohxlet extraction to extract the bitumen. The bitumen was subjected to column chromatography and aliphatic and aromatic fractions were collected from each sample by using DCM and n-hexane as solvents. The fractions were subjected to GC/MS analyses with the application of SIM method (selected ion monitoring) which revealed the wide variety of hydrocarbons compounds including n-alkanes, hopanes, sterenes, phenanthrenes, methylphenanthrenes and triaromatic steroids. Interpretation biomarker parameters revealed that the rocks under studies are endowed with organic matter. Also biomarker correlation parameters were employed to compute the quantity of organic matter, type of organic matter, thermal maturity of the organic matter and to assess the depositional environment of the rocks samples. The biomarker parameters indicated that the source organic matter is mostly from marine environment, the depositional condition found to be anoxic reducing condition. The shales are reach in organic matter and the shales are found to be partially matured. [ABSTRACT FROM AUTHOR]

With regard to speed, comfort, and a dense network of destinations, the popularity of air transport is on the rise. For this reason, jet fuel is a commodity with rapidly growing consumption and interesting refinery margins. At the same time, however, it is becoming a focus of attention in terms of reducing negative environmental impacts. As a response to these trends, it will be necessary to coprocess alternative petroleum fractions with sustainable aviation components in oil refineries. Six alternative jet fuel samples of different origin were used to investigate their jet fuel-specific properties, that is, aromatics (from 0 to 59.7 vol%), smoke point (from 12.2 to >50 mm), freezing point (from −49 to <−80 °C) and net specific energy (41.2–43.7 MJ·kg−1), and these properties were compared to standard hydrotreated straight-run Jet A-1 kerosene. The properties of the components studied differed significantly with respect to each other and to the requirements of Jet A-1. Nevertheless, the properties could be well correlated. This provides an opportunity to study possible synergies in blending these components. It was also found that the current methods and instruments used do not always allow a precise determination of the smoke point (>50 mm) and freezing point (<80 °C). [ABSTRACT FROM AUTHOR]

Betaine is a new surfactant with good application prospects in high-temperature and high-salinity reservoirs. The interfacial properties of two kinds of betaine mixtures with a good synergistic effect were evaluated in this paper. On this basis, the effects of temperature-resistant, salt-resistant polymers with different contents of 2-acrylamide-2-methylpropanesulfonic acid (AMPS) on dynamic interfacial tensions (IFTs) against n-alkanes and crude oil were studied. The experimental results show that the IFTs between betaine ASB and n-alkanes can be reduced to ultra-low values by compounding with anionic surfactant petroleum sulfonate (PS) and extended anionic surfactant alkoxyethylene carboxylate (AEC), respectively. ASB@AEC is very oil-soluble with nmin value ≥14, and ASB@PS is relatively water-soluble with nmin value of 10. The water solubility of both ASB@PS and ASB@AEC is enhanced by the addition of water-soluble polymers. The HLB of the ASB@AEC solution becomes better against crude oil after the addition of polymers, and the IFT decreases to an ultra-low value as a result. On the contrary, the antagonistic effect in reducing the IFT can be observed for ASB@PS in the same case. In a word, polymers affect the IFTs of surfactant solutions by regulating the HLB. [ABSTRACT FROM AUTHOR]

Baoji is a medium-sized city in the Guanzhong Plain of northwest China. The compositions of three important organic groups, namely n-alkanes, polycyclic aromatic hydrocarbons (PAHs), and saccharides in atmospheric aerosol with different aerodynamic diameters in power were determined. Both seasonal and daily trends of the target organic chemical groups were demonstrated. The concentration levels of total quantified n-alkanes and saccharides in total suspended particles (TSP) in winter were 541 ± 39 and 651 ± 74 ng·m−3, respectively, much higher than those of the other three seasons. A high total quantified PAHs concentration level of 59.6 ± 6.4 ng·m−3 was also seen in wintertime. n-Alkanes showed a bimodal percent distribution in spring, autumn, and winter. Two peaks were found with the particle sizes of 0.7 μm < Dp < 2.1 μm and 3.3 μm < Dp < 4.7 μm, respectively. In summer, a unimodal was seen with a peak of 4.7 μm < Dp < 5.8 μm. Dehydrated saccharides and PAHs present a unimodal size distribution peaking at the aerodynamic diameters of 0.7 µm < Dp < 2.1 µm. In contrast to glucose and fructose, they mainly exist in the coarse mode particles and have the highest concentrations at aerodynamic diameters of 4.7 µm < Dp < 9.0 µm. The geometric mean diameters (GMD) of n-alkanes and saccharides of the fine particles in winter were higher than in the other seasons. Compared with the data in 2008, the fossil fuel-derived n-alkanes and PAHs in winter decreased by nearly an order of magnitude in 2017. Both the carbon preference index (CPI) of n-alkanes and the diagnostic ratios of PAHs suggest that coal combustion and vehicle exhaust were the major pollution sources of the organic groups in the two decades. It should be noted that the contribution of traffic emissions greatly increased from 2008 to 2017, consistently with a large raise of registered vehicles in Baoji city. The overall results confirm that the control measures conducted by the local government in the recent decade mitigated the air pollution in this city. [ABSTRACT FROM AUTHOR]

Two areas affected by cement plant emissions, in an industrial district of Central Italy, were investigated by foraging honeybees (Apis mellifera ligustica) on the return to their hives, as an in situ biomonitor. The contamination was compared with that of a background reference area on the Central Apennine Mountains, quite far from the contamination sources. At all the sites, the bee colonies were stationary. One hundred seventy-seven compounds belonging to the class of polycyclic aromatic compounds (PACs) were positively identified by gas chromatographic and mass spectrometric techniques. For the first time, the presence of several unusual compounds on bee samples is highlighted. These include polycyclic aromatic sulfur heterocycles (PASHs), 1.55–35.63 ng/g d.w., compounds that, like polycyclic aromatic hydrocarbons (PAHs), 67.50–129.95 ng d.w., are classified as carcinogenic and/or mutagenic. In an attempt to identify the contribution of different and specific sources of these pollutants to the total pollution profile, the composition of aliphatic linear hydrocarbons was also examined. [ABSTRACT FROM AUTHOR]

The data presented in this article relates to the crystallisation of 8 single n-alkanes, C16H34 – C23H48 in representative diesel solvents dodecane and toluene, as well as a mixture of these 8-alkanes with a composition representative of real diesel fuel in the same solvents. For the single alkane systems, the data was collected over a range of 5 concentrations ranging from 0.09 – 0.311xi, depending upon the system, and 4 concentrations for the 8-alkane mixture, 0.1 – 0.5xi. Raw average crystallisation and dissolution points as a function of cooling rate (q) from a polythermal methodology are presented. Along with the equilibrium crystallisation and dissolution temperatures, van't Hoff fitting parameters, relative critical undercooling (uc) values as a function of q as well as the calculated values of KG and αdet.

The shift in animal welfare standards towards free-range housing for laying hens in the EU has raised questions about changes in dietary composition. Accurate assessment of outdoor plant material intake is crucial for effective feeding strategies. This study introduces an approach using n-alkanes as markers to determine plant intake in laying hens, involving n-alkane recovery rate assessment, discriminant analysis and linear equation-solving for both qualitative and quantitative assessment, respectively, considering systematic n-alkane combinations. Two diets: a standard commercial diet and a diet incorporating 1% alfalfa were tested. Chemical analyses showed an altered n-alkane profile due to alfalfa inclusion, resulting a recovery rates ranging from 30–44% depending on the n-alkane type and diet. Statistical analysis revealed significant differences in recovery rates among the different alkanes for the same diets and between the diets for the same alkane, together with an interaction between n-alkane carbon chain length and initial concentration in the diet. The method accurately predicted plant inclusion, with a slight overestimation (2.80%) using the combination C25-C29-C33. Accurate qualitative classification of the animals based on fecal n-alkanes profiles was observed. The study successfully demonstrated the utility of n-alkanes for estimating dietary composition, providing a non-invasive approach for future free-range studies.

The concept of the genus Clinopodium L. has changed considerably since its first description. Most of the currently accepted species of the genus have traditionally been treated as separate genera in the group Satureja sensu lato: Clinopodium L., Calamintha sensu Miller or Moench, and Acinos sensu Miller or Moench. This study aimed to gain a better insight into the species diversity of Clinopodium L. from the Balkans by analyzing the taxa that have traditionally been placed in separate genera. The alkane profile and the micromorphological characteristics of the leaves are analyzed. The leaves are visualized using scanning electron microscopy, and alkanes are isolated using n-hexane as a solvent and analyzed using gas chromatography/mass spectrometry. The alkane profile showed the differentiation of the Acinos-group from the other taxa based on the dominant n-C31, while most of the other taxa contained n-C33 as the dominant alkane. The micromorphological features also showed clear differences between the previously recognized genera, especially in the capitate trichomes. The results showed that micromorphological patterns are highly variable in certain groups of the genus Clinopodium.

The existing combustion kinetic modeling method which aims at developing phenomenological combustion mechanisms characterized by multiple reactions confronts several challenges, including the conflicts between computing resources and mechanism scales during numerical simulation, etc. In order to address these issues, the minimized reaction network method for complex combustion system modeling based on the principle of simultaneous chemical equilibrium is proposed, which is aimed to develop combustion mechanisms with minimal reaction steps under a limited number of species. The concept of mechanism resolution is proposed in this method, and the reaction network with minimal reaction steps under a given mechanism resolution is constructed so that the scale of mechanisms is compressed greatly. Meanwhile, distinguishing from other mechanisms, the reversible form of elementary reactions is adopted and the classical two-parameter (A, Ea) Arrhenius equation fits the rate constants. Typical n-alkanes including n-butane, n-heptane, n-octane, n-decane, n-dodecane and n-hexadecane were taken as examples to indicate the development process of mechanisms and systematic kinetic validations were carried out. Results show that this method leads to very compact mechanisms with satisfactory accuracy, and it eliminates the process of mechanism reduction and is beneficial for mechanism optimization. This method and the derived kinetic mechanisms are hoped to contribute to combustion engineering applications.

Cuticular hydrocarbons (CHCs), the dominant fraction of the insects' epicuticle and the primary barrier to desiccation, form the basis for a wide range of chemical signaling systems. In eusocial insects, CHCs are key mediators of nestmate recognition, and colony identity appears to be maintained through a uniform CHC profile. In the unicolonial Argentine ant Linepithema humile, an unparalleled invasive expansion has led to vast supercolonies whose nestmates can still recognize each other across thousands of miles. CHC profiles are expected to display considerable variation as they adapt to fundamentally differing environmental conditions across the Argentine ant's expanded range, yet this variation would largely conflict with the vastly extended nestmate recognition based on CHC uniformity. To shed light on these seemingly contradictory selective pressures, we attempt to decipher which CHC classes enable adaptation to such a wide array of environmental conditions and contrast them with the overall CHC profile uniformity postulated to maintain nestmate recognition. n-Alkanes and n-alkenes showed the largest adaptability to environmental conditions most closely associated with desiccation, pointing at their function for water-proofing. Trimethyl alkanes, on the other hand, were reduced in environments associated with higher desiccation stress. However, CHC patterns correlated with environmental conditions were largely overriden when taking overall CHC variation across the expanded range of L. humile into account, resulting in conserved colony-specific CHC signatures. This delivers intriguing insights into the hierarchy of CHC functionality integrating both adaptation to a wide array of different climatic conditions and the maintenance of a universally accepted chemical profile.

Abstract The climate reconstruction of the Tibetan Plateau, which was called the Third Pole Environment, has been a research hotspot in recent years. However, there are few studies on C3 and C4 plants evolution and it is an area of active debate on whether there are C4 plants existing on the Tibetan Plateau. In this study, the paleoclimate of the Hurleg Lake on the northeastern Tibetan Plateau is reconstructed based on n‐alkane‐induced indicators, while the C4 plant evolution history is established by compound‐specific isotope of long‐chain n‐alkanes since 14.1 cal kyr BP. The response of C4 plant evolution history to climate change on the northeastern margin of the Tibetan Plateau demonstrated that C3 and C4 plants were sensitive to local and global climate change. Solar radiation in summer, insolation‐affected East Asian monsoon, and seasonal climate (including seasonal variation of the solar radiation, temperature, and precipitation) had significant effects on the long‐term growth of C4. On the other hand, factors such as temperature, precipitation, and other potential factors affected the detailed variation of C4 plants in a relatively short‐term. Our finding maintained the existence of C4 plants in the high‐altitude region and indicated that the abundance of C4 plants might increase significantly and the ecological pattern of vegetation on the Tibetan Plateau will change distinctly in the coming warmer climate conditions.

Leaf cuticular waxes play an important role in reducing evapotranspiration via diffusion. However, the ability of mature trees to regulate the biosynthesis of waxes to changing conditions (e.g., drought, light exposition) remain an open question, especially during the late growing season. This holds also true for one of the most widely distributed trees in Central Europe, the European beech tree (Fagus sylvatica L.). In order to investigate the ongoing formation of wax constituents like alkanes and fatty acids, we conducted a 13CO2 pulse-chase labelling experiment on sun-exposed and shaded branches of a mature beech tree during the late summer 2018. The 13C-label was traced via compound-specific δ13C isotope analysis of n-alkanes and fatty acids to determine the denovo biosynthesis within these compound classes. We did not observe a significant change in lipid concentrations during the late growing season, but we found higher n-alkane concentrations in sun-exposed compared to shaded leaves in August and September. The n-alkane and fatty acid composition showed ongoing modifications during the late growing season. Together with the uptake and following subsequent decrease of the 13C-label, this suggests ongoing de-novo biosynthesis, especially of fatty acids in European beech leaves. Moreover, there is a high variability in the 13C-label among individual branches and between sun-exposed and shaded leaves. At the same time, sun-exposed leaves invest more of the assimilated C into secondary metabolites such as lipids than shaded leaves. This indicates that the investigated mature beech tree could adjust its lipid production and composition in order to acclimate to changes in microclimates within the tree crown and during the investigated period. [ABSTRACT FROM AUTHOR]

Yarrowia lipolytica is a unique, strictly aerobic yeast with the ability to degrade efficiently hydrophobic substrates. In the present work, we evaluated the degrading potential of Yarrowia lipolytica IMUFRJ 50682, isolated from tropical estuarine water in Rio de Janeiro (Brazil), and the possible biomolecules produced during this process. To investigate which crude oil compounds are degraded by Y. lipolytica IMUFRJ 50682, this microorganism was grown in a medium containing Marlim petroleum (19 °API, American Petroleum Institute gravity) at 28 °C and 160 rpm for 5 days. The residual petroleum was submitted to gas chromatograph-mass spectrometric analysis (GC-MS). The chromatographic fingerprints of the residual petroleum were compared with the abiotic control test incubated in the same conditions. Y. lipolytica assimilates high molecular weight hydrocarbons, such as n-alkanes (C11-C19), isoprenoids (pristane and phytane), aromatics with two or three aromatics rings (naphthalene, methylnaphthalenes, dimethylnaphthalenes, trimethylnaphthalenes, phenanthrene, methylphenanthrenes, dimethylphenanthrenes, anthracene). This strain was also capable of consuming more complex hydrocarbons, such as tricyclic terpanes. During this biodegradation, the emulsification index of the culture medium increased significantly, showing that biosurfactant molecules can be produced from this process. Therefore, Y. lipolytica IMUFRJ 50682 showed to be a potential crude oil degrading yeast, which can be used for bioremediation processes and simultaneously produce bioproducts of commercial interest. [ABSTRACT FROM AUTHOR]

Gas injection has emerged over the recent decades as a promising technology to enhance oil recovery in various fields worldwide. The efficiency and success of a gas injection operation can be assessed through a number of vital experimental studies. Interfacial Tension (IFT) between the injected gas and the displacing fluid is a key parameter playing an eminent role in the foregoing studies. The main scope of this work is making a progress in modeling the IFTs between diverse n-alkanes and Methane (CH 4), Carbon Dioxide (CO 2), and Nitrogen (N 2) natural gases. For this purpose, two smart AI-based approaches of Cascaded Feedforward Neural Network (CFNN) and Decision Tree Learning (DT) were used to simultaneously model the IFTs between foregoing immiscible binary systems as a function of pressure, temperature, the gases properties, and the properties of the liquid. Several statistical measures and graphical descriptions were employed to aid the accuracy analysis of the proposed models. Both developed CFNN and DT networks represented desirable close-to-reality predictions in all binary systems. Besides, CFNN established itself as the most robust model for all studies binary systems with RMSE values of 0.5924, 0.5649, and 0.5870 mN/m, and R2 values of 0.9902, 0.9910, and 0.9904 for the train, test, and overall data, respectively. [ABSTRACT FROM AUTHOR]

In this study, major chemical components of PM2.5 including nitrate, sulfate, organic carbon (OC), and elemental carbon (EC) were measured in Chuncheon, South Korea in May-June, 2021. Average PM2.5 concentration was 16.4±9.7 µg m-3, and OC was the largest contributor of PM2.5 mass concentration. High concentration episodes (HCEs), defined when PM2.5 concentration exceeded 30 µg m-3, were caused by Asian dust, secondary inorganic aerosol (SIA) formation, and primary OC emission. NH4 + was determined to be a limiting factor for SIA formation based on neutralization ratio. There was statistically significant correlation between n-alkanes and PM2.5, and odd alkanes including C27, C29, and C31, which are generally emitted from biogenic sources, were abundant species, suggesting the importance of natural sources over fossil fuel combustion. Polycyclic aromatic hydrocarbons (PAHs) concentrations were significantly lower than those measured at the same sampling site in 2014-2015. Based on the diagnostic ratios of PAHs, vehicular emission, rather than solid fuel emission, were significant for PAHs. Detailed characterization of chemical composition of PM2.5 reported in this study can be of great help in establishing an appropriate abatement policy to reduce PM2.5 concentrations. [ABSTRACT FROM AUTHOR]

Wax precipitation inside the pipelines can partially block the oil flow and create serious safety and financial issues for the oil and gas industry. Thermophysical properties of n-alkanes are required to predict wax precipitation and deposition behavior accurately. Several correlations have been proposed based on limited experimental data reported in the literature. This work aims to conduct experiments to collect thermophysical properties for pure n-alkanes with carbon numbers ranging from 17 to 50 using a micro differential scanning calorimeter and validate the available correlations. It was found that a simple correlation that is a function of carbon number or molecular weight could predict the temperature of fusion with reasonable accuracy. However, significant errors were observed with existing correlations to predict the enthalpy of fusion and solid-solid transition, so a correction was proposed for the enthalpy of fusion, and a set of correlations was developed for the enthalpy of solid-solid transition. [ABSTRACT FROM AUTHOR]

Leaf cuticular waxes play an important role in reducing evapotranspiration via diffusion. However, the ability of mature trees to regulate the biosynthesis of waxes to changing conditions (e.g., drought, light exposition) remain an open question, especially during the late growing season. This holds also true for one of the most widely distributed trees in Central Europe, the European beech tree (Fagus sylvatica L.). In order to investigate the ongoing formation of wax constituents like alkanes and fatty acids, we conducted a 13CO2 pulse-chase labelling experiment on sun-exposed and shaded branches of a mature beech tree during the late summer 2018. The 13C-label was traced via compound-specific δ13C isotope analysis of n-alkanes and fatty acids to determine the de-novo biosynthesis within these compound classes. We did not observe a significant change in lipid concentrations during the late growing season, but we found higher n-alkane concentrations in sun-exposed compared to shaded leaves in August and September. The n-alkane and fatty acid composition showed ongoing modifications during the late growing season. Together with the uptake and following subsequent decrease of the 13C-label, this suggests ongoing de-novo biosynthesis, especially of fatty acids in European beech leaves. Moreover, there is a high variability in the 13C-label among individual branches and between sun-exposed and shaded leaves. At the same time, sun-exposed leaves invest more of the assimilated C into secondary metabolites such as lipids than shaded leaves. This indicates that the investigated mature beech tree could adjust its lipid production and composition in order to acclimate to changes in microclimates within the tree crown and during the investigated period.

The research area is located in the Eastern Carpathians, Romania. This region is rich in various formations and indicates significant potential for paleo-environmental reconstruction. The present research was carried out on sediment cores collected at lake Bolătău-Feredeu, Feredeului Mountains (Eastern Carpathians, Romania). Preliminary examination of the sediment confirmed the possibility for data analysis with high temporal resolution. The aim of the research was to clarify and supplement the findings of previous research at this site, to explore the relationships between proxy parameters and to elucidate the cause for the changes. Core dating was carried out using 210Pb and radiocarbon isotopes and indicated that sediment cores span the past 500 years. The research uses a wide range of methodologies, including organic geochemistry with calculated n alkane indices (Phw and Pwax). Based on these proxies, the changes of woody and herbaceous coverage in the catchment can be estimated. Moreover, element concentration, weathering indices and particle size distribution assist to detect climate changes in the catchment area. The data and conclusions yielded by the analysis were compared with the regional modelled temperature profile, based on which five periods were separated. In addition to natural and anthropogenic events, the main factor among the natural processes is the change in annual temperature. Based on the obtained data, several parameters were found to be suitable for monitoring past temperature changes.

A multi-suckling (MS) system for sows and piglets has been developed aiming to improve animal welfare. In this system, large variation in BW gain exists between piglets up to weaning at 9 weeks of age. We aimed to study the causes of variation in BW gain and DM intake of solid feed (DFI) (piglet + sow feed) of piglets during lactation in the MS system. A total of 15 sows and 60 focal piglets across three batches were studied. Individual intake of piglet and sow feed was measured by the dual marker method, and multiple variables were recorded. Multiple linear regression analysis with forward selection was conducted on BW gain and DFI after correcting for piglet sex and batch, using multiple explanatory variables including genetic background, birthweight (BiW), DM feed intake, behaviours and number of skin lesions. These factors jointly explained less than 45 % and 21 % of the variation in BW gain and DFI, respectively. In weeks 2–4, variation in BW gain was mainly explained by BiW (12.0 %) and play and nosing behaviours (7.6 %). In weeks 4–6 and 6–8, it was largely explained by DM intake of piglet feed with 15.1 % and 25.9 %, respectively. Individual variation in DFI in weeks 2–4 was explained by the presence at front and middle teats during suckling bouts (2.9 %), in weeks 4–6 by BiW (9.6 %), and in weeks 6–8 by the number of skin lesions (5.1 %). The unexplained variation in BW gain and DFI warrants further investigation.

The potential of endogenous n-alkane profiling for the assessment of extra virgin olive oils (EVOO) adulteration (blends with cheaper vegetable oils) has been studied by relatively few authors. Analytical methods used for this purpose often involve tedious and solvent-intensive sample preparation prior to analytical determination, making them unattractive. A rapid and solvent-sparing offline solid phase extraction (SPE) gas chromatography (GC) flame ionization detection (FID) method for the determination of endogenous n-alkanes in vegetable oils was, therefore, optimized and validated. The optimized method demonstrated good performance characteristics in terms of linearity (R2 > 0.999), recovery (on average 94%), and repeatability (residual standard deviation, RSD < 11.9%). The results were comparable to those obtained with online high-performance liquid chromatography (HPLC)-GC- FID ( RSD < 5.1%). As an example of an application to prove the potentiality of endogenous n-alkanes in revealing frauds, the data set obtained from 16 EVOO, 9 avocado oils (AVO), and 13 sunflower oils (SFO), purchased from the market, was subjected to statistical analysis and principal component analysis. Two powerful indices, namely (n-C29 + n-C31)/(n-C25 + n-C26) and n-C29/n-C25, were found to reveal the addition of 2% SFO in EVOO and 5% AVO in EVOO, respectively. Further studies are needed to confirm the validity of these promising indices.

The microbial community response to petroleum seepage was investigated in a whole round sediment core (16 cm length) collected nearby natural hydrocarbon seepage structures in the Caspian Sea, using a newly developed Sediment-Oil-Flow-Through (SOFT) system. Distinct redox zones established and migrated vertically in the core during the 190 days-long simulated petroleum seepage. Methanogenic petroleum degradation was indicated by an increase in methane concentration from 8 μM in an untreated core compared to 2300 μM in the lower sulfate-free zone of the SOFT core at the end of the experiment, accompanied by a respective decrease in the δ13C signal of methane from -33.7 to -49.5‰. The involvement of methanogens in petroleum degradation was further confirmed by methane production in enrichment cultures from SOFT sediment after the addition of hexadecane, methylnapthalene, toluene, and ethylbenzene. Petroleum degradation coupled to sulfate reduction was indicated by the increase of integrated sulfate reduction rates from 2.8 SO42-m-2 day-1 in untreated cores to 5.7 mmol SO42-m-2 day-1 in the SOFT core at the end of the experiment, accompanied by a respective accumulation of sulfide from 30 to 447 μM. Volatile hydrocarbons (C2-C6 n-alkanes) passed through the methanogenic zone mostly unchanged and were depleted within the sulfate-reducing zone. The amount of heavier n-alkanes (C10-C38) decreased step-wise toward the top of the sediment core and a preferential degradation of shorter (n-alkanes (>C30) was seen during the seepage. This study illustrates, to the best of our knowledge, for the first time the development of methanogenic petroleum degradation and the succession of benthic microbial processes during petroleum passage in a whole round sediment core.

Using gas chromatography-triple quadrupole tandem mass spectrometry (GC-MS/MS), the soluble organic matter was analyzed for the first time in twenty-two sediment samples from the eastern slopes of the Gongga Mountain, China, at high altitudes between 4,600 and 6,700 m. The C11-C33n-alkanes and C9-C33n-alkan-2-ones were identified in these samples. Both compounds were dominated by odd carbon numbers in the long-chain molecules and contained a maximum of n-C27 or n-C29, indicating that the sediments were predominantly of higher plant origin. However, the short-chain n-alkan-2-ones, with a maximum content of n-C17 or i-C18 (phytone, 6, 10, 14-trimethylpentadecan-2-one), did not show a predominance of odd and even numbers, suggesting that they were predominantly derived from bacteria and algae. Therefore, we suggest that the organic matter in Gongga Mountain comes from three sources, i.e. bacteria, algae, and higher plants. Stable carbon isotope (δ13C) values ranged from −24.6‰ to −27.3‰, indicating that C3 plants were the dominant organic input to the sediments and suggesting a relatively colder and drier depositional environment. However, C4 plants increase sharply at high altitudes of 6,300–6,600 m, suggesting that the paleoclimate of Gongga Mountain became drier and wetter with the increase of altitude.

Seasonal water and sediment samples were collected from the Xiaoqing River estuary and the neighboring sea to study the spatial and temporal distributions, sources and ecological risks of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes. The results showed significant spatial and temporal differences in the concentrations of PAHs and n-alkanes under the influence of precipitation, temperature, and human activities. The concentrations of PAHs in water were lower in the wet season than in the dry season, and those in sediments were higher in the wet season than in the dry season. The concentrations of n-alkanes were higher in the rainy season than in the dry season for both water and sediments. The spatial distributions of PAHs and n-alkanes were estuarine > offshore. The concentration ranges of ∑PAHs in water and sediments were 230.66–599.86 ng/L and 84.51–5548.62 ng/g, respectively, in the wet season and 192.46–8649.55 ng/L and 23.39–1208.92 ng/g, respectively, in the dry season. The proportion of three-ring PAHs in water (57.03% and 78.27% in the wet and dry seasons, respectively) was high, followed by two-ring PAHs (27.31% and 13.59% in the wet and dry seasons, respectively). The proportion of four-ring PAHs was higher in sediments (24.79% and 32.20% in the wet and dry seasons, respectively). The ecological risk of PAHs assessed using the toxicity equivalent quotient and risk quotient was at moderate to moderately high risk levels. The high concentration of n-alkane fraction C16 (611.65–75594.58 ng/L) in the water is indicative of petroleum or other fossil fuel inputs. The main peaks of n-alkanes in river sediments were C27, C29 and C31, indicating higher inputs of plant sources. The sediments in the estuary showed dominance of both short-chain C16 and long-chain C25–C31, indicating a combined input of higher plants and petroleum. The diagnostic ratios of PAHs and n-alkanes indicated that their sources were mainly oil/coal/biomass combustion and petroleum spills attributed to frequent vehicular, vessel and mariculture activities. Given the potential ecological risks of PAHs and n-alkanes in water and sediments, future studies should focus on their bioaccumulation and biotoxicity. [Display omitted] • Ecological risks of ∑PAHs and n-alkanes are medium to high in Xiaoqing River estuary. • Three-ring PAHs in water were dominant at rates of 57.03% in wet and 78.27% in dry. • Four-ring PAHs in sediments were dominant at rates of 24.79% in wet and 32.20% in dry. • High concentrations of n-alkane fraction C16 indicate oil pollution. • PAHs and n-alkanes originate mostly from biomass, coal, and oil combustion. [ABSTRACT FROM AUTHOR]

[Display omitted] • Determination of the specific enthalpy, the specific heat capacity and the heat of transition of six n-alkanes (n = 15 to n = 20), providing very high precision and absolute accuracy and temperature resolution. • Adiabatic scanning calorimetry with very low scanning rates of a few mK/min. • Simultaneous results for the specific heat capacity and the specific enthalpy. • Accurate determination of the heats of transition and enthalpy steps at order–disorder transitions. • Detailed comparison between adiabatic scanning calorimetry and literature results from adiabatic step calorimetry and differential scanning calorimetry. In this work, a Peltier-element-based adiabatic scanning calorimeter was used to investigate, with high-resolution and accuracy, the temperature dependence of the specific heat capacity and specific enthalpy difference of a series of linear alkanes. More specifically, results are reported for the even n-alkanes; namely n-eicosane, n-octadecane, n-hexadecane and for the odd n-alkanes, namely n-nonadecane, n-heptadecane and n-pentadecane. The measurements cover a temperature range from well in the crystalline solid phase across the solid–solid transitions (when present) in to the liquid phase across the melting transition. Accurate transition temperatures and heat of transitions were derived from the direct experimental data in view of the potential use of n-alkanes as phase change materials. [ABSTRACT FROM AUTHOR]

In arid regions, montane lakes are valuable water sources and play important ecological roles. However, recent human-induced inputs of organic pollutants are threatening lake ecology in such regions and becoming a matter of great concern. To investigate pollutant histories and sources, we measured polycyclic aromatic hydrocarbons (PAHs) and n -alkanes in a dated sediment core that spans the last ∼350 years, from montane Lake Issyk-Kul (Kyrgyzstan, Central Asia). Results showed that organic pollutants were delivered to Lake Issyk-Kul in four stages and that their concentrations increased from Stage I (∼1670–1800 CE) to Stage IV (∼2000–2010 CE). Furthermore, we tracked the sources of sedimented PAHs using their ratios combined with n -alkanes data. Ratios of PAHs Ant/(Ant + Phe), Flt/(Flt + Pyr) and Bap/BghiP indicated that inputs during Stage II (∼1800–1970 CE) and Stage III (∼1970–2000 CE) came mainly from high-temperature combustion of coal and vehicle emissions. PAHs in Stage I and Stage IV, however, were mainly derived from low-temperature combustion and petrogenic sources. Diagnostic PAH ratios, combined with the natural n -alkane ratio (NAR＜0) and unresolved complex mixtures (UCM), showed that the sources of PAHs in Stage I were mainly from erosion of bedrock and partly influenced by forest wildfires, different from the source during Stage IV, which was mainly from refined petroleum caused by accidental spills. Our assessment of the contamination history of the lake indicates that toxicity risk to the waterbody from sediment PAHs is low, but recent discharges arising from traffic deserve attention. • History of organic pollutant inputs to a montane lake in arid Central Asia. • PAH sources identified by combined use of PAH ratios and n -alkanes. • TEQ BaP is used to assess toxicity risks and also proved an effective polluted proxy. [ABSTRACT FROM AUTHOR]

The present study determines the levels of n-alkanes in atmospheric wet deposition at an urban site in the Indo-Gangetic Plain, Delhi, during monsoon and non-monsoon periods in 2021. The n-alkane homologs (C 10 –C 33) were determined in wet deposition, which included wet-only and bulk samples. The average total n-alkanes were found to be 56.0 ± 16.7 and 439.4 ± 150.8 μg/L in wet-only samples, whereas, 149.6 ± 46.4 and 454.9 ± 108.4 μg/L in bulk samples during monsoon and non-monsoon periods, respectively. The low molecular weight n-alkanes (C 10 –C 25) exhibited no odd-even predominance in wet-only and bulk depositions during monsoon and non-monsoon periods. However, the high molecular weight n-alkanes (>C 25) showed odd-even predominance during the non-monsoon period. The molecular distribution patterns of n-alkanes indicated possible emissions from bacteria, fossil-fuel combustion, direct volatilization of unburnt fuels, biogenic sources, and other anthropogenic activities. A health risk assessment for n-alkanes revealed the higher susceptibility of children via dermal and oral exposure. The Hazard Index for the exposure of n-alkanes through atmospheric wet deposition was <1, i.e., within the acceptable limit. The Carbon Preference Index (CPI) and wax n-alkanes (WNA)%, supported the prevalence of mixed emission sources with higher contributions from anthropogenic activities. Five sources of n-alkanes were identified using the positive matrix factorization (PMF) model, i.e., gasoline vehicles + fuel evaporation, biogenic, biogenic + diesel exhaust, road dust, and mixed, contributing ∼30 %, 11 %, 26 %, 17 %, and 16 % respectively. The Concentration Weighted Trajectory (CWT) analysis revealed that n-alkanes in wet-only and bulk samples were contributed by different local, regional, and long-range transport of air pollutants. • The first study in the Indian context to investigate n-alkane homologs in wet deposition. • The molecular distribution of n-alkanes suggested their prevalent emissions from anthropogenic and biogenic sources. • The Hazard Index of n-alkanes for exposure through atmospheric wet deposition was within the acceptable limit (<1). • The major sources of n-alkanes were gasoline vehicles, fuel evaporation, biogenic, diesel exhaust, road dust, and mixed. [ABSTRACT FROM AUTHOR]

[Display omitted] • Experimental viscosities for C 6 H 5 I + n -C n at (288.15–308.15) K are reported. • Correlation equations and Bloomfield-Dewan's model have been applied. • The systems studied theoretically are of the type aromatic compound, or C 6 H 12 + n -C n. • A close relationship exists between U V m E (n) and Δ η (n). • The free volume theory describes well η of the solutions. • DISQUAC is used to calculate the residual Gibbs energy in Bloomfield-Dewan's model. Kinematic viscosities were measured for iodobenzene + n -alkane mixtures at (288.15–308.15) K and atmospheric pressure. The corresponding dynamic viscosities (η) were also determined using density data previously obtained in our laboratory. This set of data was employed to calculate Δ η (deviations in absolute viscosity) and quantities of viscous flow. In addition, the correlation equations: McAllister, Grunberg-Nissan, Fang-He, and the Bloomfield-Dewan's model were applied to the systems: iodobenzene, or 1-chloronaphthalene, or 1,2,4-trichlorobenzene, or methyl benzoate or benzene or cyclohexane + n -alkane. It is remarkable that, within the Bloomfield-Dewan's model, residual Gibbs energies were calculated using DISQUAC with interaction parameters available in the literature. From the dependence of U V m E (isochoric molar excess internal energy) and Δ η with n (the number of C atoms of the n -alkane), it is shown that the loss of fluidization of mixtures containing iodobenzene, 1,2,4-trichlorobenzene, or 1-chloronaphthalene when n increases can be ascribed to a decrease, upon mixing, of the number of broken interactions between like molecules. The breaking of correlations of molecular orientations characteristic of longer n -alkanes may explain the decreased negative Δ η values of benzene mixtures with n = 14,16. The replacement, in this type of systems, of benzene by cyclohexane, leads to increased positive Δ η values, probably due to the different shape of cyclohexane. On the other hand, binary mixtures formed by an aromatic polar compound mentioned above and a short n -alkane show large structural effects and large negative Δ η values. From the application of the models, it seems that dispersive interactions are dominant and that size effects are not relevant on η values. The free volume model provides good results for most of the systems considered, since deviations are less than 6% for 20 mixtures from the 29 solutions under study, and only 4 systems show deviations higher than 10%, with a maximum deviation of 15%. Results improve when, within the Bloomfield-Dewan's theory, the contribution to η of the absolute reaction rate model is also considered. [ABSTRACT FROM AUTHOR]