Human breathable air in a Mediterranean forest: characterization of monoterpene concentrations under the canopy

Monoterpenes have been identified as potential determinants of the human health effects induced by forest exposure. The present study characterizes the total monoterpene concentrations at nose height in a Mediterranean Holm oak forest located in North-East Iberian Peninsula during the annual emission peak (summer and autumn: June to November) using a Proton Transfer Reaction–Mass Spectrometry (PTR-MS). Results show a strong variability of the total monoterpene concentrations in season and daytime. The concentration peak appears during July and August. These two months displayed two average maxima in their diel cycles: One during early morning (from 6:00 to 8:00, 0.30 ppbv for July and 0.41 ppbv for August) and another one at early afternoon (from 13:00 to 15:00, 0.27 ppbv during July and 0.32 ppbv during August). Monoterpene concentrations were strongly related with the temperature (exponentially) and solar radiation (rectangular hyperbolic relationship). The concentrations registered here are similar or higher than in previous ex situ studies showcasing the effects of forests on human health. These findings provide relevant data for the scientific and healthcare community by improving the understanding of monoterpene dynamics at nose height and suggesting further research on the effects of forests on human health, particularly in the Mediterranean region.The research leading to these results has received funding from “la Caixa” Foundation. Furthermore, this study was supported by the Spanish Government Grant CGL2013-48074-P, the Catalan Government grant SGR 2017-1005, the European Research Council Synergy grant ERC-2013-SyG 610028 IMBALANCE-P

Unexpected seasonality in quantity and composition of Amazon rainforest air reactivity

The hydroxyl radical (OH) removes most atmospheric pollutants from air. The loss frequency of OH radicals due to the combined effect of all gas-phase OH reactive species is a measureable quantity termed total OH reactivity. Here we present total OH reactivity observations in pristine Amazon rainforest air, as a function of season, time-of-day and height (0-80 m). Total OH reactivity is low during wet (10s-1) and high during dry season (62s-1). Comparison to individually measured trace gases reveals strong variation in unaccounted for OH reactivity, from 5 to 15% missing in wet-season afternoons to mostly unknown (average 79%) during dry season. During dry-season afternoons isoprene, considered the dominant reagent with OH in rainforests, only accounts for ∼20% of the total OH reactivity. Vertical profiles of OH reactivity are shaped by biogenic emissions, photochemistry and turbulent mixing. The rainforest floor was identified as a significant but poorly characterized source of OH reactivity

Emissions of putative isoprene oxidation products from mango branches under abiotic stress

Although several per cent of net carbon assimilation can be re-released as isoprene emissions to the atmosphere by many tropical plants, much uncertainty remains regarding its biological significance. In a previous study, we detected emissions of isoprene and its oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) from tropical plants under high temperature/light stress, suggesting that isoprene is oxidized not only in the atmosphere but also within plants. However, a comprehensive analysis of the suite of isoprene oxidation products in plants has not been performed and production relationships with environmental stress have not been described. In this study, putative isoprene oxidation products from mango (Mangifera indica) branches under abiotic stress were first identified. High temperature/light and freeze-thaw treatments verified direct emissions of the isoprene oxidation products MVK and MACR together with the first observations of 3-methyl furan (3-MF) and 2-methyl-3-buten-2-ol (MBO) as putative novel isoprene oxidation products. Mechanical wounding also stimulated emissions of MVK and MACR. Photosynthesis under 13CO2 resulted in rapid (<30min) labelling of up to five carbon atoms of isoprene, with a similar labelling pattern observed in the putative oxidation products. These observations highlight the need to investigate further the mechanisms of isoprene oxidation within plants under stress and its biological and atmospheric significance. © 2013 The Author

Diel and seasonal changes of biogenic volatile organic compounds within and above an Amazonian rainforest

The Amazonian rainforest is a large tropical ecosystem, which is one of the last pristine continental terrains. This ecosystem is ideally located for the study of diel and seasonal behaviour of biogenic volatile organic compounds (BVOCs) in the absence of local human interference. In this study, we report the first atmospheric BVOC measurements at the Amazonian Tall Tower Observatory (ATTO) site, located in central Amazonia. A quadrupole proton-transfer-reaction mass spectrometer (PTR-MS), with seven ambient air inlets, positioned from near ground to about 80 m (0.05, 0.5, 4, 24, 38, 53 and 79 m above the forest floor), was deployed for BVOC monitoring. We report diel and seasonal (February-March 2013 as wet season and September 2013 as dry season) ambient mixing ratios for isoprene, monoterpenes, isoprene oxidation products, acetaldehyde, acetone, methyl ethyl ketone (MEK), methanol and acetonitrile. Clear diel and seasonal patterns were observed for all compounds. In general, lower mixing ratios were observed during night, while maximum mixing ratios were observed during the wet season (February-March 2013), with the peak in solar irradiation at 12:00 LT (local time) and during the dry season (September 2013) with the peak in temperature at 16:00 LT. Isoprene and monoterpene mixing ratios were the highest within the canopy with a median of 7.6 and 1 ppb, respectively (interquartile range (IQR) of 6.1 and 0.38 ppb) during the dry season (at 24 m, from 12:00 to 15:00 LT). The increased contribution of oxygenated volatile organic compounds (OVOCs) above the canopy indicated a transition from dominating forest emissions during the wet season (when mixing ratios were higher than within the canopy), to a blend of biogenic emission, photochemical production and advection during the dry season when mixing ratios were higher above the canopy. Our observations suggest strong seasonal interactions between environmental (insolation, temperature) and biological (phenology) drivers of leaf BVOC emissions and atmospheric chemistry. Considerable differences in the magnitude of BVOC mixing ratios, as compared to other reports of Amazonian BVOC, demonstrate the need for long-term observations at different sites and more standardized measurement procedures, in order to better characterize the natural exchange of BVOCs between the Amazonian rainforest and the atmosphere. © Author(s) 2015

Intra- and interannual changes in isoprene emission from central Amazonia

Isoprene emissions are a key component in biosphere-atmosphere interactions, and the most significant global source is the Amazon rainforest. However, intra- and interannual variations in biological and environmental factors that regulate isoprene emission from Amazonia are not well understood and, thereby, are poorly represented in models. Here, with datasets covering several years of measurements at the Amazon Tall Tower Observatory (ATTO) in central Amazonia, Brazil, we (1) quantified canopy profiles of isoprene mixing ratios across seasons of normal and anomalous years and related them to the main drivers of isoprene emission - solar radiation, temperature, and leaf phenology; (2) evaluated the effect of leaf age on the magnitude of the isoprene emission factor (Es) from different tree species and scaled up to canopy with intra- and interannual leaf age distribution derived by a phenocam; and (3) adapted the leaf age algorithm from the Model of Emissions of Gases and Aerosols from Nature (MEGAN) with observed changes in Es across leaf ages. Our results showed that the variability in isoprene mixing ratios was higher between seasons (max during the dry-to-wet transition seasons) than between years, with values from the extreme 2015 El Niño year not significantly higher than in normal years. In addition, model runs considering in situ observations of canopy Es and the modification on the leaf age algorithm with leaf-level observations of Es presented considerable improvements in the simulated isoprene flux. This shows that MEGAN estimates of isoprene emission can be improved when biological processes are mechanistically incorporated into the model.This research was supported by the German Federal Ministry of Education and Research, BMBF funds 01LB1001A; Brazilian Ministry of Science, Technology, Innovation and Communication; FINEP/MCTIC contract 01.11.01248.00); UEA; FAPEAM; LBA/INPA; and SDS/CEUC/RDS-Uatumã. It was also supported by grant nos. NSF-PRFB-1711997 and NSF-1754163. The article processing charges for this open-access publication were covered by the Max Planck Society.Peer reviewe

The Amazon Tall Tower Observatory (ATTO): Overview of pilot measurements on ecosystem ecology, meteorology, trace gases, and aerosols

The Amazon Basin plays key roles in the carbon and water cycles, climate change, atmospheric chemistry, and biodiversity. It has already been changed significantly by human activities, and more pervasive change is expected to occur in the coming decades. It is therefore essential to establish long-term measurement sites that provide a baseline record of present-day climatic, biogeochemical, and atmospheric conditions and that will be operated over coming decades to monitor change in the Amazon region, as human perturbations increase in the future. The Amazon Tall Tower Observatory (ATTO) has been set up in a pristine rain forest region in the central Amazon Basin, about 150 km northeast of the city of Manaus. Two 80 m towers have been operated at the site since 2012, and a 325 m tower is nearing completion in mid-2015. An ecological survey including a biodiversity assessment has been conducted in the forest region surrounding the site. Measurements of micrometeorological and atmospheric chemical variables were initiated in 2012, and their range has continued to broaden over the last few years. The meteorological and micrometeorological measurements include temperature and wind profiles, precipitation, water and energy fluxes, turbulence components, soil temperature profiles and soil heat fluxes, radiation fluxes, and visibility. A tree has been instrumented to measure stem profiles of temperature, light intensity, and water content in cryptogamic covers. The trace gas measurements comprise continuous monitoring of carbon dioxide, carbon monoxide, methane, and ozone at five to eight different heights, complemented by a variety of additional species measured during intensive campaigns (e.g., VOC, NO, NO2, and OH reactivity). Aerosol optical, microphysical, and chemical measurements are being made above the canopy as well as in the canopy space. They include aerosol light scattering and absorption, fluorescence, number and volume size distributions, chemical composition, cloud condensation nuclei (CCN) concentrations, and hygroscopicity. In this paper, we discuss the scientific context of the ATTO observatory and present an overview of results from ecological, meteorological, and chemical pilot studies at the ATTO site. © Author(s) 2015

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Abstract Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

Within-canopy sesquiterpene ozonolysis in Amazonia

Populärvetenskaplig sammanfattning: En mycket reaktiv spårgas i Amazonas. Växter släpper ut flyktiga organiska ämnen, som är mycket viktiga eftersom de släpps ut i stora mängder och påverkar tillverkningen av aerosoler, förändrar luftkvaliteten och fungerar som kommunikation mellan växter och herbivorer. Det här arbetet presenterar uppmätningar av sesquiterpener, vilka är flyktiga organiska partiklarna inom gruppen isoprenoider, de har de största utsläpps grupperna. Sesquiterpener är mycket reaktiva och finns därför i väldigt små koncentrationer, därför har det inte varit möjligt att mäta dem tidigare. Här presenteras de första mätningarna av sesquiterpener i ett flux torn i en central amazon region, detta låter oss se sesquiterpenernas roll i trädkronorna. För att få mätningarna användes en ’Proton Transfer Reaction Mass Spectrometer’ som har insläpp på olika höjder från 2 till 40 meter. Vårt resultat tyder på att sesquiterpenerna är invert relaterade till ozon, eftersom sesquiterpenerna visar höga koncentrationer under natten, och ozon visar höga koncentrationer under dagen. Därför, i Amazonas, är sesquiterpenernas koncentration bestämda av ozon, vilket är deras sink, eftersom sesquiterpener försvinner från systemet som en följd av deras reaktion med ozonet. Detta medför att en serie av möjlig feedback mekanismer för klimatet förklaras, men det behövs många fler undersökningar för att man ska kunna bekräfta alla dessa processer.Sesquiterpenes are highly reactive terpenoids produced by vegetation and may serve many important biological functions such as acting as antioxidants and as semiochemicals (chemicals acting as messengers within or between species). Once emitted to the atmosphere, by reacting with oxidants like ozone and contributing to secondary organic aerosol formation, the emission of sesquiterpenes from vegetation may have significant impacts on radiation balance and precipitation dynamics. Although it is known that sesquiterpenes have short atmospheric lifetimes of a few minutes, analytical difficulties stemming from low concentrations, high reactivities, and high “stickiness” have so far prevented the detailed characterization of within-canopy sources and sinks. Therefore little is known about sesquiterpene emissions and chemistry within canopies. This study presents the first ambient air profile observations of rapid sesquiterpene ozonolysis reactions obtained during the BrazilianAir 2010 field campaign in Central Amazonia, from September 2010 to February 2011. Our results show that sesquiterpene concentrations followed a very different pattern compared to isoprene and monoterpenes, by peaking at night instead of during the day and peaking near the ground instead of within the canopy. Furthermore, their concentrations were inversely related with ozone, suggesting that sesquiterpene concentrations were more strongly determined by ozonolysis rather than by emissions, which is further corroborated by experiments done in Biosphere 2, Arizona, where no oxidation was taking place and sesquiterpenes followed the same diurnal pattern as isoprene and monoterpenes. These observations suggest rapid ozonolysis reactions within the canopy which strongly determine sesquiterpene concentrations in both time and space. Moreover, calculated sesquiterpene ozonolysis rates peaked during midday at a height of ca. 20m above ground, suggesting that they are mainly determined by the high ozone concentrations during the day. We conclude that ambient concentrations of sesquiterpenes are not necessarily low because of low plant emissions, but rather high ozonolysis rates which were unaccounted for in previous ambient air studies. Our findings should help to better understand the environmental and biological controls on the dynamics of chemical emission, loss, and transport of highly reactive species like sesquiterpenes within canopies and their potential biological and atmospheric impacts. In particular, our observations suggest that the fraction of emitted sesquiterpenes lost within the canopy to ozonolysis could be large and that this process reduces ozone concentrations thereby providing plants protection against exogenous reactive oxygen species

Real-time carbon allocation into biogenic volatile organic compounds (BVOCs) and respiratory carbon dioxide (CO2) traced by PTR-TOF-MS, 13CO2 laser spectroscopy and 13C-pyruvate labelling.

Our understanding of biogenic volatile organic compound (BVOC) emissions improved substantially during the last years. Nevertheless, there are still large uncertainties of processes controlling plant carbon investment into BVOCs, of some biosynthetic pathways and their linkage to CO2 decarboxylation at central metabolic branching points. To shed more light on carbon partitioning during BVOC biosynthesis, we used an innovative approach combining δ13CO2 laser spectroscopy, high-sensitivity proton-transfer-reaction time-of-flight mass spectrometry and a multiple branch enclosure system in combination with position-specific 13C-metabolite labelling. Feeding experiments with position-specific 13C-labelled pyruvate, a central metabolite of BVOC synthesis, enabled online detection of carbon partitioning into 13C-BVOCs and respiratory 13CO2. Measurements of trace gas emissions of the Mediterranean shrub Halimium halimifolium revealed a broad range of emitted BVOCs. In general, [2-13C]-PYR was rapidly incorporated into emitted acetic acid, methyl acetate, toluene, cresol, trimethylbenzene, ethylphenol, monoterpenes and sesquiterpenes, indicating de novo BVOC biosynthesis of these compounds. In contrast, [1-13C]-pyruvate labelling substantially increased 13CO2 emissions in the light indicating C1-decarboxylation. Similar labelling patterns of methyl acetate and acetic acid suggested tightly connected biosynthetic pathways and, furthermore, there were hints of possible biosynthesis of benzenoids via the MEP-pathway. Overall, substantial CO2 emission from metabolic branching points during de novo BVOC biosynthesis indicated that decarboxylation of [1-13C]-pyruvate, as a non-mitochondrial source of CO2, seems to contribute considerably to daytime CO2 release from leaves. Our approach, combining synchronised BVOC and CO2 measurements in combination with position-specific labelling opens the door for real-time analysis tracing metabolic pathways and carbon turnover under different environmental conditions, which may enhance our understanding of regulatory mechanisms in plant carbon metabolism and BVOC biosynthesis

Drought affects carbon partitioning into volatile organic compound biosynthesis in Scots pine needles

Summary The effect of drought on the interplay of processes controlling carbon partitioning into plant primary and secondary metabolisms, such as respiratory CO2 release and volatile organic compound (VOC) biosynthesis, is not fully understood. To elucidate the effect of drought on the fate of cellular C sources into VOCs vs CO2, we conducted tracer experiments with 13CO2 and position-specific 13C-labelled pyruvate, a key metabolite between primary and secondary metabolisms, in Scots pine seedlings. We determined the stable carbon isotope composition of leaf exchanged CO2 and VOC. Drought reduced the emission of the sesquiterpenes α-farnesene and β-farnesene but did not affect 13C-incorporation from 13C-pyruvate. The labelling patterns suggest that farnesene biosynthesis partially depends on isopentenyl diphosphate crosstalk between chloroplasts and cytosol, and that drought inhibits this process. Contrary to sesquiterpenes, drought did not affect emission of isoprene, monoterpenes and some oxygenated compounds. During the day, pyruvate was used in the TCA cycle to a minor degree but was mainly consumed in pathways of secondary metabolism. Drought partly inhibited such pathways, while allocation into the TCA cycle increased. Drought caused a re-direction of pyruvate consuming pathways, which contributed to maintenance of isoprene and monoterpene production despite strongly inhibited photosynthesis. This underlines the importance of these volatiles for stress tolerance.This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (ERC consolidator grant VOCO2 #647008). The authors are also grateful to Monika Eiblmeier for technical assistance in GC-MS/IRMS analyses, Michael Rienks for logistical help and Manizha Khakimova for gardening the plants.Peer reviewe