A first assessment of the sources of isoprene and monoterpene emissions from a short-rotation coppice Eucalyptus gunnii bioenergy plantation in the UK

Eucalyptus gunnii is a fast-growing, cold-tolerant tree species endemic to Tasmania that is suitable for growing as short-rotation coppice (SRC) plantations in the UK. Fast growing eucalypts such as E. gunnii could potentially deliver higher biomass yields with a superior calorific value for the domestic bioenergy market than other SRC plantation species such as willow or poplar. However, eucalypts are known emitters of biogenic volatile organic compounds (BVOC) like isoprene and monoterpenes. These compounds contribute to the formation of atmospheric pollutants such as ozone and secondary organic aerosols. An assessment of the sources of BVOCs during the lifecycle of a UK E. gunnii SRC plantation found the mean standardised emissions of isoprene and total monoterpenes from branches of juvenile foliage to be 7.50 μg C gdw−1 h−1 and 1.30 μg C gdw−1 h−1, respectively. The predominant monoterpene emitted was cis-β-ocimene. Isoprene emissions from the forest floor were extremely low but monoterpene emissions peaked at 50 μg C m−2 h−1. α-Pinene and d-limonene were the major components of the monoterpene emissions, with higher emissions correlated to the abundance of leaf litter. Both the magnitude and composition of monoterpene emissions from the forest floor varied during the SRC plantation life cycle, with the coppiced and regrowth stands of eucalyptus producing less emissions. The woodchip produced at harvesting emitted only trace levels of isoprene but substantial monoterpene emissions, up to 90 μg C m−2 h−1, predominately eucalyptol. Harvesting and resulting biomass chips may provide a short-lived concentrated source of BVOCs in winter at SRC plantations. Modelled annual emissions using MEGAN 2.1 (canopy emissions only) suggest that BVOC emissions from a UK E. gunnii SRC plantation are most abundant in summer, and that modelled annual isoprene and total monoterpenes emissions could be around 6.9 kg C ha−1 and 2.4 kg C ha−1 respectively, for a young plantation. Based on the very limited data, the per-hectare E. gunnii isoprene emissions are smaller than estimates for other SRC/SRF plantation species in the UK; the per-hectare monoterpene emissions are in the span of estimates for other plantation species

Red-bed bleaching in a CO2 storage analogue: insights from Entrada Sandstone fracture-hosted mineralization

Improving our ability to predict the interactions between CO2 and reservoir rocks at geological time scales is of key importance if carbon capture and storage (CCS) is to have a role in climate-change mitigation, particularly in the light of likely regulatory requirements. Understanding and identifying the relevant geological processes over long time scales can be obtained only at natural-analogue sites. At one such site, in the Salt Wash Graben area of Utah, USA, widespread bleaching affects the Middle Jurassic red-bed “wet dune” Entrada Sandstone. Previous work has proposed a genetic link between the bleaching and spatially concomitant recent and modern CO2-rich fluids. The results presented here challenge some of the previous models and come from a detailed petrographic examination of mineralized fractures in the Entrada Sandstone that are centered in vertical extensions to the bleaching. These fractures typically contain complex mineralization assemblages. Pyrite was a paragenetically early phase, identifiable from common pseudomorphs of mixed iron oxides and oxyhydroxides that rarely contain relict pyrite. The pyrite contains up to 3 wt% arsenic. The volume of fracture-adjacent bleached sandstone is sufficient to have been the source of iron for the pyrite originally present in the fracture. The pyrite pseudomorphs occur at the center of fracture- and pore-filling cements that comprise intergrowths of hematite–goethite–jarosite–gypsum, an assemblage that suggests that their formation resulted from the oxidative alteration of pyrite, a genetic link supported by the arsenic present in the iron-bearing minerals. The presence of jarosite and proximal removal of earlier, sandstone-hosted carbonates are consistent with, and indicative of, the low-pH conditions associated with pyrite oxidation reactions. Calcite- and gypsum-cemented fractures crosscut, and contain fragments of, the pyrite-pseudomorphic and -oxidation assemblages, proving that they postdate pyrite formation and its subsequent oxidation, and that pyrite oxidation was not a result of modern weathering reactions. In outcrop, some calcite- and gypsum-cemented fractures link with travertine deposits associated with the modern and recent CO2-rich fluids. The mineral assemblages observed here, and the paragenetic sequence that we have inferred, suggest that the fracture-associated bleaching patterns result from the fracture-fed movement of sulfur-bearing reducing fluids, with hydrogen sulfide the most likely bleaching agent. We conclude that bleaching adjacent to fractures is not genetically related to modern CO2-bearing fluids despite the spatial relationship. The bleaching was already present when the modern fluids utilized the same fracture-based fluid pathways. We suggest that the more widespread regional bleaching formed contemporaneously with the fracture bleaching and followed similar mechanisms. This study highlights the complexity of interpreting analogue sites and the importance of using field and petrographic observations to unravel textures and events that are juxtaposed spatially but not temporally

Isoprene and monoterpene emissions from alder, aspen and spruce short rotation forest plantations in the UK

An expansion of bioenergy has been proposed to help reduce fossil-fuel greenhouse gas emissions, and short-rotation forestry (SRF) can contribute to this expansion. However, SRF plantations could also be sources of biogenic volatile organic compound (BVOC) emissions, which can impact atmospheric air quality. In this study, emissions of isoprene and 11 monoterpenes from the branches and forest floor of hybrid aspen, Italian alder and Sitka spruce stands in an SRF field trial in central Scotland were measured during two years (2018–2019) and used to derive emission potentials for different seasons. Sitka spruce was included as a comparison as it is the most extensive plantation species in the UK. Winter and spring emissions of isoprene and monoterpenes were small compared to those in summer. Sitka spruce had a standardised mean emission rate of 15 µgCg−1h−1 for isoprene in the dry and warm summer of 2018 – more than double the emissions in 2019. However, standardised mean isoprene emissions from hybrid aspen were similar across both years, approximately 23 µgCg−1h−1, and standardised mean isoprene emissions from Italian alder were very low. Mean standardised total monoterpene emissions for these species followed a similar pattern of higher standardised emissions in the warmer year: Sitka spruce emitting 4.5 and 2.3 µgCg−1h−1 for 2018 and 2019, aspen emitting 0.3 and 0.09 µgCg−1h−1, and Italian alder emitting 1.5 and 0.2 µgCg−1h−1, respectively. In contrast to these foliage emissions, the forest floor was only a small source of monoterpenes, typically 1 or 2 orders of magnitude lower than foliage emissions on a unit of ground area basis. Estimates of total annual emissions from each plantation type per hectare were derived using the MEGAN 2.1 model. The modelled total BVOC (isoprene and monoterpenes) emissions of SRF hybrid aspen plantations were approximately half those of Sitka spruce for plantations of the same age. Italian alder SRF emissions were 20 times smaller than from Sitka spruce. The expansion of bioenergy plantations to 0.7 Mha has been suggested for the UK to help achieve net-zero greenhouse gas emissions by 2050. The model estimates show that, with such an expansion, total UK BVOC emissions would increase between <1 % and 35 %, depending on the tree species planted. Whereas increases might be small on a national scale, regional increases might have a larger impact on local air quality

Assessment of the impact of CO 2 storage in sandstone formations by experimental studies and geochemical modeling: the case of the Mesohellenic Trough, NW Greece

Representative sandstone samples from Mesohellenic Trough (NW Greece) were selected to investigate the geochemical reactions that occur when they come in contact with CO2 under representative in-situ conditions (T = 70 °C, P = 150 bar, 6 months reaction in batch experiments). Those sandstones consisted of predominant calcite and quartz, with lesser amounts of feldspars, chlorite, ankerite, dolomite, kaolinite, montmorillonite and muscovite. After reaction with CO2, the brine became acidic and was enriched in cations as a result of mineral dissolution. Minor mineralogical changes were observed that involved: a) the dissolution of carbonate minerals and b) the incongruent dissolution of chlorite to form clays and silica. The results related to these, have been linked with geochemical modelling using the PHREEQC code. Simulation results for a 10 ka time period predicted that chlorite was expected to dissolve completely within 100 years, leading to boehmite growth and increasing the mass of dolomite. Feldspars were expected to react at a later stage in the reaction sequence. Sensitivity tests were run to access the effect of various adjustable parameters on the outcome results. The geochemical experiments and modelling lend support to the view that Pentalofos and Tsotyli sandstone formations of the Mesohellenic Trough are suitable for the long-term storage of CO2 produced in the neighbouring lignite-fired power plants, at least in terms of mineralogy and geochemistry

Simulating impacts on UK air quality from net-zero forest planting scenarios

The UK proposes additional bioenergy plantations and afforestation as part of measures to meet net-zero greenhouse gas emissions, but species and locations are not yet decided. Different tree species emit varying amounts of isoprene and monoterpene volatile organic compounds that are precursors to ozone and secondary organic aerosol (SOA) formation, the latter of which is a component of PM2.5. The forest canopy also acts as a depositional sink for air pollutants. All these processes are meteorologically influenced. We present here a first step at coupling information on tree species planting suitability and other planting constraints with data on UK-specific BVOC emission rates and tree canopy data to simulate via the WRF-EMEP4UK high spatial resolution atmospheric chemistry transport model the impact on UK air quality of four potential scenarios. Our ‘maximum planting’ scenarios are based on planting areas where yields are predicted to be ≥50 % of the maximum from the Ecological Site Classification Decision Support System (ESC-DSS) for Eucalyptus gunnii, hybrid aspen (Populus tremula), Italian alder (Alnus cordata) and Sitka spruce (Picea sitchensis). The additional areas of forest in our scenarios are 2.0 to 2.7 times current suggestions for new bioenergy and afforestation landcover in the UK. Our planting scenarios increase UK annual mean surface ozone concentrations by 1.0 ppb or 3 % relative to the baseline landcover for the highest BVOC emitting species (e.g., E. gunni). Increases in ozone reach 2 ppb in summer when BVOC emissions are greatest. In contrast, all the additional planting scenarios lead to reductions in UK annual mean PM2.5 – ranging from -0.2 µg m-3 (-3 %) for Sitka spruce to -0.5 µg m-3 (-7 %) for aspen – revealing that PM2.5 deposition to the additional forest canopy area more than offsets additional SOA formation. Relative decreases in annual mean PM2.5 are greater than the relative increases in annual mean ozone. Reductions in PM2.5 are least in summer, coinciding with the period of maximum monoterpene emissions. Although only a first step in evaluating the impact of increased forest plantation on UK air quality, our study demonstrates the need for locally relevant data on landcover suitability, emissions and meteorology in model simulations

Chiral monoterpenes reveal forest emission mechanisms and drought responses

Monoterpenes (C10H16) are emitted in large quantities by vegetation to the atmosphere (>100 TgC year−1), where they readily react with hydroxyl radicals and ozone to form new particles and, hence, clouds, affecting the Earth’s radiative budget and, thereby, climate change1,2,3. Although most monoterpenes exist in two chiral mirror-image forms termed enantiomers, these (+) and (−) forms are rarely distinguished in measurement or modelling studies4,5,6. Therefore, the individual formation pathways of monoterpene enantiomers in plants and their ecological functions are poorly understood. Here we present enantiomerically separated atmospheric monoterpene and isoprene data from an enclosed tropical rainforest ecosystem in the absence of ultraviolet light and atmospheric oxidation chemistry, during a four-month controlled drought and rewetting experiment7. Surprisingly, the emitted enantiomers showed distinct diel emission peaks, which responded differently to progressive drying. Isotopic labelling established that vegetation emitted mainly de novo-synthesized (−)-α-pinene, whereas (+)-α-pinene was emitted from storage pools. As drought progressed, the source of (−)-α-pinene emissions shifted to storage pools, favouring cloud formation. Pre-drought mixing ratios of both α-pinene enantiomers correlated better with other monoterpenes than with each other, indicating different enzymatic controls. These results show that enantiomeric distribution is key to understanding the underlying processes driving monoterpene emissions from forest ecosystems and predicting atmospheric feedbacks in response to climate change

Note: CO2-mineral dissolution experiments using a rocking autoclave and a novel titanium reaction cell

A novel titanium reaction cell has been constructed for the study of water-rock-CO2 reactions. The reaction cell has been used within a direct-sampling rocking autoclave and offers certain advantages over traditional “flexible gold/titanium cell” approaches. The main advantage is robustness, as flexible cells are prone to rupture on depressurisation during gas-rich experiments. The reaction cell was tested in experiments during an inter-laboratory comparison study, in which mineral kinetic data were determined. The cell performed well during experiments up to 130 °C and 300 bars pressure. The data obtained were similar to those of other laboratories participating in the study, and also to previously published dat

Leaf-level metabolic changes in response to drought affect daytime CO2 emission and isoprenoid synthesis pathways

In the near future, climate change will cause enhanced frequency and/or severity of droughts in terrestrial ecosystems, including tropical forests. Drought responses by tropical trees may affect their carbon use, including production of volatile organic compounds (VOCs), with implications for carbon cycling and atmospheric chemistry that are challenging to predict. It remains unclear how metabolic adjustments by mature tropical trees in response to drought will affect their carbon fluxes associated with daytime CO2 production and VOC emission. To address this gap, we used position-specific 13C-pyruvate labeling to investigate leaf CO2 and VOC fluxes from four tropical species before and during a controlled drought in the enclosed rainforest of Biosphere 2 (B2). Overall, plants that were more drought-sensitive had greater reductions in daytime CO2 production. Although daytime CO2 production was always dominated by non-mitochondrial processes, the relative contribution of CO2 from the tricarboxylic acid cycle tended to increase under drought. A notable exception was the legume tree Clitoria fairchildiana R.A. Howard, which had less anabolic CO2 production than the other species even under pre-drought conditions, perhaps due to more efficient refixation of CO2 and anaplerotic use for amino acid synthesis. The C. fairchildiana was also the only species to allocate detectable amounts of 13C label to VOCs and was a major source of VOCs in B2. In C. fairchildiana leaves, our data indicate that intermediates from the mevalonic acid (MVA) pathway are used to produce the volatile monoterpene trans-β-ocimene, but not isoprene. This apparent crosstalk between the MVA and methylerythritol phosphate pathways for monoterpene synthesis declined with drought. Finally, although trans-β-ocimene emissions increased under drought, it was increasingly sourced from stored intermediates and not de novo synthesis. Unique metabolic responses of legumes may play a disproportionate role in the overall changes in daytime CO2 and VOC fluxes in tropical forests experiencing drought