Strong isoprene emission response to temperature in tundra vegetation.

Emissions of biogenic volatile organic compounds (BVOCs) are a crucial component of biosphere-atmosphere interactions. In northern latitudes, climate change is amplified by feedback processes in which BVOCs have a recognized, yet poorly quantified role, mainly due to a lack of measurements and concomitant modeling gaps. Hence, current Earth system models mostly rely on temperature responses measured on vegetation from lower latitudes, rendering their predictions highly uncertain. Here, we show how tundra isoprene emissions respond vigorously to temperature increases, compared to model results. Our unique dataset of direct eddy covariance ecosystem-level isoprene measurements in two contrasting ecosystems exhibited Q10 (the factor by which the emission rate increases with a 10 °C rise in temperature) temperature coefficients of up to 20.8, that is, 3.5 times the Q10 of 5.9 derived from the equivalent model calculations. Crude estimates using the observed temperature responses indicate that tundra vegetation could enhance their isoprene emissions by up to 41% (87%)-that is, 46% (55%) more than estimated by models-with a 2 °C (4 °C) warming. Our results demonstrate that tundra vegetation possesses the potential to substantially boost its isoprene emissions in response to future rising temperatures, at rates that exceed the current Earth system model predictions.

Pelagibacter metabolism of diatom-derived volatile organic compounds imposes an energetic tax on photosynthetic carbon fixation.

Volatile organic compounds (VOCs) produced by phytoplankton are molecules with high vapor pressures that can diffuse across cell membranes into the environment, where they become public goods. VOCs likely comprise a significant component of the marine dissolved organic carbon (DOC) pool utilized by microorganisms, but they are often overlooked as growth substrates because their diffusivity imposes analytical challenges. The roles of VOCs in the growth of the photoautotrophic diatom Thalassiosira pseudonana and heterotrophic bacterium Pelagibacter sp. HTCC1062 (SAR11) were examined using co-cultures and proton-transfer reaction time-of-flight mass spectrometry. VOCs at 82 m/z values were produced in the cultures, and the concentrations of 9 of these m/z values changed in co-culture relative to the diatom monoculture. Several of the m/z values were putatively identified, and their metabolism by HTCC1062 was confirmed by measuring ATP production. Diatom carbon fixation rates in co-culture with HTCC1062 were 20.3% higher than the diatom monoculture. Removal of VOCs from the T. pseudonana monoculture using a hydrocarbon trap caused a similar increase in carbon fixation (18.1%). These results show that a wide range of VOCs are cycled in the environment, and the flux of VOCs from phytoplankton to bacterioplankton imposes a large and unexpected tax on phytoplankton photosynthesis.

Understanding Trends in Pesticide Volatilization from Agricultural Fields Using the Pesticide Loss via Volatilization Model.

The Pesticide Loss via Volatilization model was developed to predict and understand pesticide volatilization rates from a planted agricultural field. The model allows the user to adjust the properties of the pesticide, various soil and plant descriptors, and climatic conditions. A useful output from the model is the 24 h cumulative percentage volatilization (CPV24h) loss. The model was validated by comparing modeled CPV24h values to measured ones compiled from the literature. Sensitivity analysis showed that the plant intercept fraction (%I), leaf area index (LAI), and leaf height (hleaf) strongly affect volatilization rates of plant- and soil-sorbed pesticides whereas LAI, hleaf, and the percent of water on the plant surface strongly affect more water-soluble pesticides. The model showed that most pesticides volatilize more readily from plants than from soil and that volatilization rates vary significantly for certain pesticides (but not all) when applied to plants at different growth stages and for different species of plants. Results are displayed on chemical space diagrams to paint a clear picture of how CPV24h varies for chemicals with different properties under different conditions.

Implications of Bioremediation of Polycyclic Aromatic Hydrocarbon-Contaminated Soils for Human Health and Cancer Risk.

Bioremediation uses soil microorganisms to degrade polycyclic aromatic hydrocarbons (PAHs) into less toxic compounds and can be performed in situ, without the need for expensive infrastructure or amendments. This review provides insights into the cancer risks associated with PAH-contaminated soils and places bioremediation outcomes in a context relevant to human health. We evaluated which bioremediation strategies were most effective for degrading PAHs and estimated the cancer risks associated with PAH-contaminated soils. Cancer risk was statistically reduced in 89% of treated soils following bioremediation, with a mean degradation of 44% across the B2 group PAHs. However, all 180 treated soils had postbioremediation cancer risk values that exceeded the U.S. Environmental Protection Agency (USEPA) health-based acceptable risk level (by at least a factor of 2), with 32% of treated soils exceeding recommended levels by greater than 2 orders of magnitude. Composting treatments were most effective at biodegrading PAHs in soils (70% average reduction compared with 28-53% for the other treatment types), which was likely due to the combined influence of the rich source of nutrients and microflora introduced with organic compost amendments. Ultimately, bioremediation strategies, in the studies reviewed, were unable to successfully remove carcinogenic PAHs from contaminated soils to concentrations below the target cancer risk levels recommended by the USEPA.

Understanding and Predicting the Fate of Semivolatile Organic Pesticides in a Glacier-Fed Lake Using a Multimedia Chemical Fate Model.

Melting glaciers release previously ice-entrapped chemicals to the surrounding environment. As glacier melting accelerates under future climate warming, chemical release may also increase. This study investigated the behavior of semivolatile pesticides over the course of one year and predicted their behavior under two future climate change scenarios. Pesticides were quantified in air, lake water, glacial meltwater, and streamwater in the catchment of Lake Brewster, an alpine glacier-fed lake located in the Southern Alps of New Zealand. Two historic-use pesticides (endosulfan I and hexachlorobenzene) and three current-use pesticides (dacthal, triallate, and chlorpyrifos) were frequently found in both air and water samples from the catchment. Regression analysis indicated that the pesticide concentrations in glacial meltwater and lake water were strongly correlated. A multimedia environmental fate model was developed for these five chemicals in Brewster Lake. Modeling results indicated that seasonal lake ice cover melt, and varying contributions of input from glacial melt and streamwater, created pulses in pesticide concentrations in lake water. Under future climate scenarios, the concentration pulse was altered and glacial melt made a greater contribution (as mass flux) to pesticide input in the lake water.

Influence of Temperature, Relative Humidity, and Soil Properties on the Soil-Air Partitioning of Semivolatile Pesticides: Laboratory Measurements and Predictive Models.

Soil-air partition coefficient (Ksoil-air) values are often employed to investigate the fate of organic contaminants in soils; however, these values have not been measured for many compounds of interest, including semivolatile current-use pesticides. Moreover, predictive equations for estimating Ksoil-air values for pesticides (other than the organochlorine pesticides) have not been robustly developed, due to a lack of measured data. In this work, a solid-phase fugacity meter was used to measure the Ksoil-air values of 22 semivolatile current- and historic-use pesticides and their degradation products. Ksoil-air values were determined for two soils (semiarid and volcanic) under a range of environmentally relevant temperature (10-30 °C) and relative humidity (30-100%) conditions, such that 943 Ksoil-air measurements were made. Measured values were used to derive a predictive equation for pesticide Ksoil-air values based on temperature, relative humidity, soil organic carbon content, and pesticide-specific octanol-air partition coefficients. Pesticide volatilization losses from soil, calculated with the newly derived Ksoil-air predictive equation and a previously described pesticide volatilization model, were compared to previous results and showed that the choice of Ksoil-air predictive equation mainly affected the more-volatile pesticides and that the way in which relative humidity was accounted for was the most critical difference.

An improved screening tool for predicting volatilization of pesticides applied to soils.

Pesticide volatilization and vapor drift can have adverse effects on nontarget, sensitive ecosystems and human health. Four approaches for pesticide volatilization screening based on Fick's Law were investigated. In each approach, vapor pressures or environmentally relevant partition coefficients were used to describe pesticide behavior in an agricultural field system and to predict 24-h cumulative percentage volatilization (CPV(24h)) losses. The multiphase partitioning approach based on soil-air (K(soil-air)) and water-air (K(water-air)) partition coefficients was found to most accurately model literature-reported pesticide volatilization losses from soils. Results for this approach are displayed on chemical space diagrams for sets of hypothetical K(soil-air) and K(water-air) combinations under different temperature, relative humidity, and soil organic carbon conditions. The CPV(24h) increased with increasing temperature and relative humidity and with decreasing soil organic carbon content. Pesticides and the conditions under which the greatest volatilization losses exist were easily identified using this visual screening technique.

Volatile responses of dwarf birch to mimicked insect herbivory and experimental warming at two elevations in Greenlandic tundra.

Plants release a complex blend of volatile organic compounds (VOCs) in response to stressors. VOC emissions vary between contrasting environments and increase with insect herbivory and rising temperatures. However, the joint effects of herbivory and warming on plant VOC emissions are understudied, particularly in high latitudes, which are warming fast and facing increasing herbivore pressure. We assessed the individual and combined effects of chemically mimicked insect herbivory, warming, and elevation on dwarf birch (Betula glandulosa) VOC emissions in high-latitude tundra ecosystems in Narsarsuaq, South Greenland. We hypothesized that VOC emissions and compositions would respond synergistically to warming and herbivory, with the magnitude differing between elevations. Warming increased emissions of green leaf volatiles (GLVs) and isoprene. Herbivory increased the homoterpene, (E)-4,8-dimethyl-1,3,7-nonatriene, emissions, and the response was stronger at high elevation. Warming and herbivory had synergistic effects on GLV emissions. Dwarf birch emitted VOCs at similar rates at both elevations, but the VOC blends differed between elevations. Several herbivory-associated VOC groups did not respond to herbivory. Harsher abiotic conditions at high elevations might not limit VOC emissions from dwarf birch, and high-elevation plants might be better at herbivory defense than assumed. The complexity of VOC responses to experimental warming, elevation, and herbivory are challenging our understanding and predictions of future VOC emissions from dwarf birch-dominated ecosystems.

Impacts of elevation on plant traits and volatile organic compound emissions in deciduous tundra shrubs.

The northernmost regions of our planet experience twice the rate of climate warming compared to the global average. Despite the currently low air temperatures, tundra shrubs are known to exhibit high leaf temperatures and are increasing in height due to warming, but it is unclear how the increase in height will affect the leaf temperature. To study how temperature, soil moisture, and changes in light availability influence the physiology and emissions of climate-relevant volatile organic compounds (VOCs), we conducted a study on two common deciduous tundra shrubs, Salix glauca (separating males and females for potential effects of plant sex) and Betula glandulosa, at two elevations in South Greenland. Low-elevation Salix shrubs were 45% taller, but had 37% lower rates of net CO2 assimilation and 63% lower rates of isoprene emission compared to high-elevation shrubs. Betula shrubs showed 40% higher stomatal conductance and 24% higher glandular trichome density, in the low-elevation valley, compared to those from the high-elevation mountain slope. Betula green leaf volatile emissions were 235% higher at high elevation compared to low elevation. Male Salix showed a distinct VOC blend and emitted 55% more oxygenated VOCs, compared to females, possibly due to plant defense mechanisms. In our light response curves, isoprene emissions increased linearly with light intensity, potentially indicating adaptation to strong light. Leaf temperature decreased with increasing Salix height, at 4 °C m-1, which can have implications for plant physiology. However, no similar relationship was observed for B. glandulosa. Our results highlight that tundra shrub traits and VOC emissions are sensitive to temperature and light, but that local variations in soil moisture strongly interact with temperature and light responses. Our results suggest that effects of climate warming, alone, poorly predict the actual plant responses in tundra vegetation.

Bidirectional Exchange of Biogenic Volatile Organic Compounds in Subarctic Heath Mesocosms During Autumn Climate Scenarios.

Biogenic volatile organic compound (BVOC) flux dynamics during the subarctic autumn are largely unexplored and have been considered insignificant due to the relatively low biological activity expected during autumn. Here, we exposed subarctic heath ecosystems to predicted future autumn climate scenarios (ambient, warming, and colder, dark conditions), changes in light availability, and flooding, to mimic the more extreme rainfall or snowmelt events expected in the future. We used climate chambers to measure the net ecosystem fluxes and bidirectional exchange of BVOCs from intact heath mesocosms using a dynamic enclosure technique coupled to a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS). We focused on six BVOCs (methanol, acetic acid, acetaldehyde, acetone, isoprene, and monoterpenes) that were among the most dominant and that were previously identified in arctic tundra ecosystems. Warming increased ecosystem respiration and resulted in either net BVOC release or increased uptake compared to the ambient scenario. None of the targeted BVOCs showed net release in the cold and dark scenario. Acetic acid exhibited significantly lower net uptake in the cold and dark scenario than in the ambient scenario, which suggests reduced microbial activity. Flooding was characterized by net uptake of the targeted BVOCs and overruled any temperature effects conferred by the climate scenarios. Monoterpenes were mainly taken up by the mesocosms and their fluxes were not affected by the climate scenarios or flooding. This study shows that although autumn BVOC fluxes on a subarctic heath are generally low, changes in future climate may strongly modify them.

Greenland Ice Sheet Surfaces Colonized by Microbial Communities Emit Volatile Organic Compounds.

Volatile organic compounds (VOCs) are emitted by organisms for a range of physiological and ecological reasons. They play an important role in biosphere-atmosphere interactions and contribute to the formation of atmospheric secondary aerosols. The Greenland ice sheet is home to a variety of microbial communities, including highly abundant glacier ice algae, yet nothing is known about the VOCs emitted by glacial communities. For the first time, we present VOC emissions from supraglacial habitats colonized by active microbial communities on the southern Greenland ice sheet during July 2020. Emissions of C5-C30 compounds from bare ice, cryoconite holes, and red snow were collected using a push-pull chamber active sampling system. A total of 92 compounds were detected, yielding mean total VOC emission rates of 3.97 ± 0.70 µg m-2 h-1 from bare ice surfaces (n = 31), 1.63 ± 0.13 µg m-2 h-1 from cryoconite holes (n = 4), and 0.92 ± 0.08 µg m-2 h-1 from red snow (n = 2). No correlations were found between VOC emissions and ice surface algal counts, but a weak positive correlation (r = 0.43, p = 0.015, n = 31) between VOC emission rates from bare ice surfaces and incoming shortwave radiation was found. We propose that this may be due to the stress that high solar irradiance causes in bare ice microbial communities. Acetophenone, benzaldehyde, and phenylmaleic anhydride, all of which have reported antifungal activity, accounted for 51.1 ± 11.7% of emissions from bare ice surfaces, indicating a potential defense strategy against fungal infections. Greenland ice sheet microbial habitats are, hence, potential sources of VOCs that may play a role in supraglacial microbial interactions, as well as local atmospheric chemistry, and merit future research efforts.

Identification of polar transformation products and high molecular weight polycyclic aromatic hydrocarbons (PAHs) in contaminated soil following bioremediation.

Bioremediation is a technique commonly used to reduce the toxicity associated with polycyclic aromatic hydrocarbons (PAHs) in contaminated soils. However, the efficacy of bioremedial applications is evaluated based on the removal of a subset of parent (or unsubstituted) PAHs and does not incorporate toxic polar transformation products or the more mutagenic high molecular weight PAHs (MW≥302amu or MW302-PAHs). Previously, an effects-directed analysis approach was used to assess the effect of bioremediation on the toxicity of a coal tar-contaminated soil. Increased genotoxicity and developmental toxicity was measured postbioremedation in the more polar soil extract fractions, as compared to the less polar fractions where the targeted PAHs eluted, and could not be attributed to the 88 target PAHs analyzed for (including selected oxygen-containing PAHs). In this study, comprehensive two-dimensional gas chromatography time-of-flight and liquid chromatography quadrupole time-of-flight mass spectrometry were used to characterize transformation products in the soil extract fractions identified as toxic, previously. Additionally, the degradation of 12MW302-PAHs, picene (MW=278) and coronene (MW=300) were evaluated following bioremediation. Non-targeted analysis resulted in the tentative identification of 10 peaks with increased intensity postbioremediation (based on mass spectral library matching and fragmentation patterns from >5000 candidate peaks in the soil extracts). Several of these compounds contained oxygen, suggesting they would be relatively polar. MW302-PAHs were not significantly degraded during bioremediation, suggesting that the carcinogenic potential associated with these PAHs might remain unchanged. The results of this study suggest that polar transformation products, and MW302-PAHs, should be considered for realistic risk assessment of bioremediated soils.

Concentrations, gas-particle distributions, and source indicator analysis of brominated flame retardants in air at Toolik Lake, Arctic Alaska.

Brominated flame-retardants (BFRs) can be released from consumer products, resulting in accumulation in the surrounding environment and/or long-range transport to remote environments. We evaluated concentration changes in a suite of BFRs, including 13 polybrominated diphenyl ethers (PBDEs) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), in air at Toolik Lake, Arctic Alaska during the Northern Hemisphere summer of 2013. A high-volume active air sampler was used to collect 2 day integrated samples at the field station and three flow-through air samplers were used to collect 18 day integrated samples along a transect extending away from the field station. The BDE congeners associated with the penta-BDE commercial mixture (BDE-47, -99, and -100) were the most frequently detected BFRs and were found at concentrations consistent with those reported at other Arctic sites. Gas-particle distributions were influenced by temperature and correlations between gas-phase concentrations and temperature suggested that either volatilization from local sources or re-emission from secondary sources (that is, re-volatilization of BFRs that had migrated northwards from distant sources) was important for the lower-brominated BFRs during the warmer months. Source indicator analysis suggested no single dominant geographic source of BFRs while results from the flow-through samplers indicated that the field station itself was not a significant source of BFRs.

The abundant marine bacterium Pelagibacter simultaneously catabolizes dimethylsulfoniopropionate to the gases dimethyl sulfide and methanethiol.

Marine phytoplankton produce ∼10(9) tonnes of dimethylsulfoniopropionate (DMSP) per year(1,2), an estimated 10% of which is catabolized by bacteria through the DMSP cleavage pathway to the climatically active gas dimethyl sulfide(3,4). SAR11 Alphaproteobacteria (order Pelagibacterales), the most abundant chemo-organotrophic bacteria in the oceans, have been shown to assimilate DMSP into biomass, thereby supplying this cell's unusual requirement for reduced sulfur(5,6). Here, we report that Pelagibacter HTCC1062 produces the gas methanethiol, and that a second DMSP catabolic pathway, mediated by a cupin-like DMSP lyase, DddK, simultaneously shunts as much as 59% of DMSP uptake to dimethyl sulfide production. We propose a model in which the allocation of DMSP between these pathways is kinetically controlled to release increasing amounts of dimethyl sulfide as the supply of DMSP exceeds cellular sulfur demands for biosynthesis.