Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component ...of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar radiation and by acting as cloud condensation nuclei. The quantitative assessment of such climate effects remains hampered by a number of factors, including an incomplete understanding of how biogenic VOCs contribute to the formation of atmospheric secondary organic aerosol. The growth of newly formed particles from sizes of less than three nanometres up to the sizes of cloud condensation nuclei (about one hundred nanometres) in many continental ecosystems requires abundant, essentially non-volatile organic vapours, but the sources and compositions of such vapours remain unknown. Here we investigate the oxidation of VOCs, in particular the terpene α-pinene, under atmospherically relevant conditions in chamber experiments. We find that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours. These vapours form at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally.
A new non-invasive and potentially inexpensive frontier in the diagnosis of cancer relies on the detection of volatile organic compounds (VOCs) in exhaled breath samples. Breath can be sampled and ...analyzed in real-time, leading to fascinating and cost-effective clinical diagnostic procedures. Nevertheless, breath analysis is a very young field of research and faces challenges, mainly because the biochemical mechanisms behind the cancer-related VOCs are largely unknown. In this review, we present a list of 115 validated cancer-related VOCs published in the literature during the past decade, and classify them with respect to their "fat-to-blood" and "blood-to-air" partition coefficients. These partition coefficients provide an estimation of the relative concentrations of VOCs in alveolar breath, in blood and in the fat compartments of the human body. Additionally, we try to clarify controversial issues concerning possible experimental malpractice in the field, and propose ways to translate the basic science results as well as the mechanistic understanding to tools (sensors) that could serve as point-of-care diagnostics of cancer. We end this review with a conclusion and a future perspective.
A compendium of all the volatile organic compounds (VOCs) emanating from the human body (the volatolome) is for the first time reported. 1840 VOCs have been assigned from breath (872), saliva (359), ...blood (154), milk (256), skin secretions (532) urine (279), and faeces (381) in apparently healthy individuals. Compounds were assigned CAS registry numbers and named according to a common convention where possible. The compounds have been grouped into tables according to their chemical class or functionality to permit easy comparison. Some clear differences are observed, for instance, a lack of esters in urine with a high number in faeces. Careful use of the database is needed. The numbers may not be a true reflection of the actual VOCs present from each bodily excretion. The lack of a compound could be due to the techniques used or reflect the intensity of effort e.g. there are few publications on VOCs from blood compared to a large number on VOCs in breath. The large number of volatiles reported from skin is partly due to the methodologies used, e.g. collecting excretions on glass beads and then heating to desorb VOCs. All compounds have been included as reported (unless there was a clear discrepancy between name and chemical structure), but there may be some mistaken assignations arising from the original publications, particularly for isomers. It is the authors' intention that this database will not only be a useful database of VOCs listed in the literature, but will stimulate further study of VOCs from healthy individuals. Establishing a list of volatiles emanating from healthy individuals and increased understanding of VOC metabolic pathways is an important step for differentiating between diseases using VOCs.
Breath analysis is a young field of research with its roots in antiquity. Antoine Lavoisier discovered carbon dioxide in exhaled breath during the period 1777-1783, Wilhelm (Vilém) Petters discovered ...acetone in breath in 1857 and Johannes Müller reported the first quantitative measurements of acetone in 1898. A recent review reported 1765 volatile compounds appearing in exhaled breath, skin emanations, urine, saliva, human breast milk, blood and feces. For a large number of compounds, real-time analysis of exhaled breath or skin emanations has been performed, e.g., during exertion of effort on a stationary bicycle or during sleep. Volatile compounds in exhaled breath, which record historical exposure, are called the 'exposome'. Changes in biogenic volatile organic compound concentrations can be used to mirror metabolic or (patho)physiological processes in the whole body or blood concentrations of drugs (e.g. propofol) in clinical settings-even during artificial ventilation or during surgery. Also compounds released by bacterial strains like Pseudomonas aeruginosa or Streptococcus pneumonia could be very interesting. Methyl methacrylate (CAS 80-62-6), for example, was observed in the headspace of Streptococcus pneumonia in concentrations up to 1420 ppb. Fecal volatiles have been implicated in differentiating certain infectious bowel diseases such as Clostridium difficile, Campylobacter, Salmonella and Cholera. They have also been used to differentiate other non-infectious conditions such as irritable bowel syndrome and inflammatory bowel disease. In addition, alterations in urine volatiles have been used to detect urinary tract infections, bladder, prostate and other cancers. Peroxidation of lipids and other biomolecules by reactive oxygen species produce volatile compounds like ethane and 1-pentane. Noninvasive detection and therapeutic monitoring of oxidative stress would be highly desirable in autoimmunological, neurological, inflammatory diseases and cancer, but also during surgery and in intensive care units. The investigation of cell cultures opens up new possibilities for elucidation of the biochemical background of volatile compounds. In future studies, combined investigations of a particular compound with regard to human matrices such as breath, urine, saliva and cell culture investigations will lead to novel scientific progress in the field.
The chemical signatures of volatile organic compounds (VOCs) in humans can be utilized for point-of-care (POC) diagnosis. Apart from toxic exposure studies, VOCs generated in humans can provide ...insights into one’s healthy and diseased metabolic states, acting as a biomarker for identifying numerous diseases noninvasively. VOC sensors and the technology of e-nose have received significant attention for continuous and selective monitoring of various physiological and pathophysiological conditions of an individual. Noninvasive detection of VOCs is achieved from biomatrices of breath, sweat and saliva. Among these, detection from sweat and saliva can be continuous in real-time. The sensing approaches include optical, chemiresistive and electrochemical techniques. This article provides an overview of such techniques. These, however, have limitations of reliability, precision, selectivity, and stability in continuous monitoring. Such limitations are due to lack of sensor stability and complexity of samples in a multivariate environment, which can lead to false readings. To overcome selectivity barriers, sensor arrays enabling multimodal sensing, have been used with pattern recognition techniques. Stability and precision issues have been addressed through advancements in nanotechnology. The use of various forms of nanomaterial not only enhance sensing performance, but also plays a major role in detection on a miniaturized scale. The rapid growth in medical Internet of Things (IoT) and artificial intelligence paves a pathway for improvements in human theranostics.
We tested the ability of 14 strains of Trichoderma to emit volatile compounds that decreased or stopped the growth of Phytophthora infestans. Volatile organic compounds (VOCs) emitted from ...Trichoderma strains designated T41 and T45 inhibited the mycelial growth of P. infestans grown on a laboratory medium by 80 and 81.4%, respectively, and on potato tubers by 93.1 and 94.1%, respectively. Using the DNA sequence analysis of the translation elongation factor region, both Trichoderma strains were identified as Trichoderma atroviride. VOCs emitted by the strains were analyzed, and 39 compounds were identified. The most abundant compounds were 3-methyl-1-butanol, 6-pentyl-2-pyrone, 2-methyl-1-propanol, and acetoin. Electron microscopy of the hyphae treated with T. atroviride VOCs revealed serious morphological and ultrastructural damages, including cell deformation, collapse, and degradation of cytoplasmic organelles. To our knowledge, this is the first report describing the ability of Trichoderma VOCs to suppress the growth of the late blight potato pathogen.
The biocontrol activity and chemical composition of the volatile organic compounds (VOCs) produced by Pseudomonas chlororaphis subsp. aureofaciens SPS-41 were investigated. The VOCs inhibited ...mycelial growth and spore germination in Ceratocystis fimbriata, which causes black rot disease in sweet potato tuber roots (TRs) and showed wide-spectrum antifungal activity against several plant pathogenic fungi. A microscopic examination of C. fimbriata cells suggested morphological changes and a loss of cellular contents. Different inoculation strategies significantly affected the antifungal activity of the VOCs. In the volatile profile of SPS-41, the most abundant compound, 3-methyl-1-butanol, followed by phenylethyl alcohol and 2-methyl-1-butanol showed strong inhibition toward C. fimbriata. The weight loss rate and disease severity of the TRs were significantly reduced in response to the VOCs emitted by SPS-41. The results suggest that the VOCs produced by P. chlororaphis subsp. aureofaciens SPS-41 might constitute an attractive biological fumigant for controlling black rot disease in sweet potato TRs.
•The SPME/GC–MS analysis of wheat organic volatiles was implemented.•158 VOCs, of which 98 never found before in wheat kernels, were identified.•Pedoclimatic conditions were the highest source of ...variability in VOCs profile.•Selected VOCs permitted to discriminate among wheats cultivated in different areas.•Selected VOCs permitted to discriminate between durum and common wheat.
Food volatile organic compounds (VOCs) analysis is a useful tool in authentication and classification processes, but, to date, the analysis of wheat VOCs is still little explored. In this study a method of analysis based on solid phase microextraction coupled with gas chromatography-mass spectrometry was optimized by testing different types of fibers, sample preparation methods and amounts, extraction temperatures and times, desorption times and oven programs. The analysis was applied to six wheat cultivars harvested in different areas, and permitted to identify 158 VOCs, of which 98 never found before. A principal component analysis performed on the dataset showed that the area of cultivation accounted for the highest source of variability. Partial least squares analysis permitted to correctly classify wheats based on their cultivation area and species, and to identify the most discriminant VOCs. These results are promising for the study of the influence of geographical origin on wheat quality.
Atmospheric oxidation is a key phenomenon that connects atmospheric chemistry with globally challenging environmental issues, such as climate change, stratospheric ozone loss, acidification of soils ...and water, and health effects of air quality. Ozone, the hydroxyl radical and the nitrate radical are generally considered to be the dominant oxidants that initiate the removal of trace gases, including pollutants, from the atmosphere. Here we present atmospheric observations from a boreal forest region in Finland, supported by laboratory experiments and theoretical considerations, that allow us to identify another compound, probably a stabilized Criegee intermediate (a carbonyl oxide with two free-radical sites) or its derivative, which has a significant capacity to oxidize sulphur dioxide and potentially other trace gases. This compound probably enhances the reactivity of the atmosphere, particularly with regard to the production of sulphuric acid, and consequently atmospheric aerosol formation. Our findings suggest that this new atmospherically relevant oxidation route is important relative to oxidation by the hydroxyl radical, at least at moderate concentrations of that radical. We also find that the oxidation chemistry of this compound seems to be tightly linked to the presence of alkenes of biogenic origin.
Tropospheric ozone (O.sub.3) and peroxyacetyl nitrate (PAN) are both photochemical pollutants harmful to the ecological environment and human health. In this study, measurements of O.sub.3 and PAN as ...well as their precursors were conducted from May to July 2019 at Nam Co station (NMC), a highly pristine high-altitude site in the southern Tibetan Plateau (TP), to investigate how distinct transport processes and photochemistry contributed to their variations. Results revealed that, despite highly similar diurnal variations with steep morning rises and flat daytime plateaus that were caused by boundary layer development and downmixing of free-tropospheric air, day-to-day variations in O.sub.3 and PAN were in fact controlled by distinct physicochemical processes. During the dry spring season, air masses rich in O.sub.3 were associated with high-altitude westerly air masses that entered the TP from the west or the south, which frequently carried high loadings of stratospheric O.sub.3 to NMC. During the summer monsoon season, a northward shift of the subtropical jet stream shifted the stratospheric downward entrainment pathway also to the north, leading to direct stratospheric O.sub.3 entrainment into the troposphere of the northern TP, which traveled southwards to NMC within low altitudes via northerly winds in front of ridges or closed high pressures over the TP. Westerly and southerly air masses, however, revealed low O.sub.3 levels due to the overall less stratospheric O.sub.3 within the troposphere of low-latitude regions. PAN, however, was only rich in westerly or southerly air masses that crossed over polluted regions such as northern India, Nepal or Bangladesh before entering the TP and arriving at NMC from the south during both spring and summer. Overall, the O.sub.3 level at NMC was mostly determined by stratosphere-troposphere exchange (STE), which explained 77 % and 88 % of the observed O.sub.3 concentration in spring and summer, respectively. However, only 0.1 % of the springtime day-to-day O.sub.3 variability could be explained by STE processes, while 22 % was explained during summertime. Positive net photochemical formation was estimated for both O.sub.3 and PAN based on observation-constrained box modeling. Near-surface photochemical formation was unable to account for the high O.sub.3 level observed at NMC, nor was it the determining factor for the day-to-day variability of O.sub.3 . However, it was able to capture events with elevated PAN concentrations and explain its day-to-day variations. O.sub.3 and PAN formation were both highly sensitive to NO.sub.x levels, with PAN being also quite sensitive to volatile organic compound (VOC) concentrations. The rapid development of transportation networks and urbanization within the TP may lead to increased emissions and loadings in NO.sub.x and VOCs, resulting in strongly enhanced O.sub.3 and PAN formation in downwind pristine regions, which should be given greater attention in future studies.
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