Amazonian biogenic volatile organic compounds under global change.

Biogenic volatile organic compounds (BVOCs) play important roles at cellular, foliar, ecosystem and atmospheric levels. The Amazonian rainforest represents one of the major global sources of BVOCs, so its study is essential for understanding BVOC dynamics. It also provides insights into the role of such large and biodiverse forest ecosystem in regional and global atmospheric chemistry and climate. We review the current information on Amazonian BVOCs and identify future research priorities exploring biogenic emissions and drivers, ecological interactions, atmospheric impacts, depositional processes and modifications to BVOC dynamics due to changes in climate and land cover. A feedback loop between Amazonian BVOCs and the trends of climate and land-use changes in Amazonia is then constructed. Satellite observations and model simulation time series demonstrate the validity of the proposed loop showing a combined effect of climate change and deforestation on BVOC emission in Amazonia. A decreasing trend of isoprene during the wet season, most likely due to forest biomass loss, and an increasing trend of the sesquiterpene to isoprene ratio during the dry season suggest increasing temperature stress-induced emissions due to climate change.

C4-like photosynthesis and the effects of leaf senescence on C4-like physiology in Sesuvium sesuvioides (Aizoaceae).

Sesuvium sesuvioides (Sesuvioideae, Aizoaceae) is a perennial, salt-tolerant herb distributed in flats, depressions, or disturbed habitats of southern Africa and the Cape Verdes. Based on carbon isotope values, it is considered a C4 species, despite a relatively high ratio of mesophyll to bundle sheath cells (2.7:1) in the portulacelloid leaf anatomy. Using leaf anatomy, immunocytochemistry, gas exchange measurements, and enzyme activity assays, we sought to identify the biochemical subtype of C4 photosynthesis used by S. sesuvioides and to explore the anatomical, physiological, and biochemical traits of young, mature, and senescing leaves, with the aim to elucidate the plasticity and possible limitations of the photosynthetic efficiency in this species. Assays indicated that S. sesuvioides employs the NADP-malic enzyme as the major decarboxylating enzyme. The activity of C4 enzymes, however, declined as leaves aged, and the proportion of water storage tissue increased while air space decreased. These changes suggest a functional shift from photosynthesis to water storage in older leaves. Interestingly, S. sesuvioides demonstrated CO2 compensation points ranging between C4 and C3-C4 intermediate values, and immunocytochemistry revealed labeling of the Rubisco large subunit in mesophyll cells. We hypothesize that S. sesuvioides represents a young C4 lineage with C4-like photosynthesis in which C3 and C4 cycles are running simultaneously in the mesophyll.

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 (13)CO2 resulted in rapid (<30 min) 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.

Emission of volatile organic compounds after herbivory from Trifolium pratense (L.) under laboratory and field conditions.

Plants emit a wide range of volatile organic compounds in response to damage by herbivores, and many of the compounds have been shown to attract the natural enemies of insect herbivores or serve for inter- and intra-plant communication. Most studies have focused on volatile emission in the laboratory while little is known about emission patterns in the field. We studied the emission of volatiles by Trifolium pratense (red clover) under both laboratory and field conditions. The emission of 24 compounds was quantified in the laboratory, of which eight showed increased emission rates after herbivory by Spodoptera littoralis caterpillars, including (E)-beta-ocimene, the most abundant compound, (Z)-beta-ocimene, linalool, (E)-beta-caryophyllene, (E,E)-alpha-farnesene, 4,8-dimethyl-1,3,7-nonatriene (DMNT), 1-octen-3-ol, and methyl salicylate (MeSA). While most of these compounds have been reported as herbivore-induced volatiles from a wide range of plant taxa, 1-octen-3-ol seems to be a characteristic volatile of legumes. In the field, T. pratense plants with varying herbivore damage growing in established grassland communities emitted only 13 detectable compounds, and the correlation between herbivore damage and volatile release was more variable than in the laboratory. For example, the emission of (E)-beta-ocimene, (Z)-beta-ocimene, and DMNT actually declined with damage, while decanal exhibited increased emission with increasing herbivory. Elevated light and temperature increased the emission of many compounds, but the differences in light and temperature conditions between the laboratory and the field could not account for the differences in emission profiles. Our results indicate that the release of volatiles from T. pratense plants in the field is likely to be influenced by additional biotic and abiotic factors not measured in this study. The elucidation of these factors may be important in understanding the physiological and ecological functions of volatiles in plants.

The relation of H2 S release to SO2 , fumigation of lichens.

Hydrogen sulphide emission in lichens as a response to low concentration SO2 , fumigation was investigated. In an open flow-through system several lichen species were fumigated with 36 ppb SO2 , Two species were also fumigated with higher concentrations (72, 119, 122 and 198 ppb SO2 ,). Hydrogen sulphide emission was monitored concurrently by cryogenic trapping and analysis with gas chromatography. All tested species increased H, S emission significantly in response to fumigation with 36 ppb SO2 . Parmelina tiliacea (L.) Hale and Cladina rangiferina (L.) Wigg. released significantly more H2 S (0.098±0.015 and 0.073±0.013 pmol H2 S g-1 d. wt s-1 , respectively) than Parmelina quercina (Ach.) Hale, Ramalina menziesii Tayl. and Parmelia sulcata Tayl. (0.028 ± 0.01, 0.025±0.014 and 0.023±0.013 pmol H2 S g-1 d. wt s-1 , respectively). Release of H2 S in Hypogymnia physodes was enhanced by increasing SO2 concentrations up to 72 ppb SO2 . No significant difference in H2 S emission in the dark vs. in the light was found. Generally, no correlation was found between photosynthetic activity and H2 S emission for the tested species. Uptake of SO2 was similar for all species, at 24.7 ± 5.6 pmol SO2 g-1 d. wt s-1 in 36 ppb SO2 and increasing at greater SO2 concentrations. Therefore, H2 S-S release represents only 0.11-0.74% of SO2 -S uptake.

Sulfur fertilization and fungal infections affect the exchange of H(2)S and COS from agricultural crops.

The emission of gaseous sulfur (S) compounds by plants is related to several factors, such as the plant S status or fungal infection. Hydrogen sulfide (H(2)S) is either released or taken up by the plant depending on the ambient air concentration and the plant demand for S. On the contrary, carbonyl sulfide (COS) is normally taken up by plants. In a greenhouse experiment, the dependence of H(2)S and COS exchange with ambient air on the S status of oilseed rape (Brassica napus L.) and on fungal infection with Sclerotinia sclerotiorum was investigated. Thiol contents were determined to understand their influence on the exchange of gaseous S compounds. The experiment revealed that H(2)S emissions were closely related to pathogen infections as well as to S nutrition. S fertilization caused a change from H(2)S consumption by S-deficient oilseed rape plants to a H(2)S release of 41 pg g(-1) (dw) min(-1) after the addition of 250 mg of S per pot. Fungal infection caused an even stronger increase of H(2)S emissions with a maximum of 1842 pg g(-1) (dw) min(-1) 2 days after infection. Healthy oilseed rape plants acted as a sink for COS. Fungal infection caused a shift from COS uptake to COS releases. The release of S-containing gases thus seems to be part of the response to fungal infection. The roles the S-containing gases may play in this response are discussed.

The diversification of terpene emissions in Mediterranean oaks: lessons from a study of Quercus suber, Quercus canariensis and its hybrid Quercus afares.

Interspecific gene flow is common in oaks. In the Mediterranean, this process produced geographical differentiations and new species, which may have contributed to the diversification of the production of volatile terpenes in the oak species of this region. The endemic North African deciduous oak Quercus afares (Pomel) is considered to be a stabilized hybrid between the evergreen Quercus suber (L.) and the deciduous Quercus canariensis (Willd.), presumably being monoterpene and isoprene emitters, respectively. In a common garden experiment, we examined the terpene emission capacities, terpene synthase (TPS) activities and nuclear genetic markers in 52 trees of these three oak species. All but one of the Q. suber and Q. canariensis trees were found to be genetically pure, whereas most Q. afares trees possessed a mixed genotype with a predominance of Q. suber alleles. Analysis of the foliar terpene emissions and TPS activities revealed that all the Q. canariensis trees strongly produced isoprene while all the Q. suber trees were strong monoterpene producers. Quercus afares trees produced monoterpenes as well but at more variable and significantly lower rates, and with a monoterpene pattern different than that observed in Q. suber. Among 17 individuals tested, one Q. afares tree emitted only an insignificant amount of terpenes. No mixed isoprene/monoterpene emitter was detected. Our results suggest that the capacity and pattern of volatile terpene production in Algerian Q. afares populations have strongly diverged from those of its parental species and became quantitatively and qualitatively reduced, including the complete suppression of isoprene production.

Root anoxia effects on physiology and emissions of volatile organic compounds (VOC) under short- and long-term inundation of trees from Amazonian floodplains.

Volatile organic compound (VOC) emissions are affected by a variety of biotic and abiotic factors such as light intensity, temperature, CO2 and drought. Another stress factor, usually overlooked but very important for the Amazon region, is flooding. We studied the exchange of VOCs in relation to CO2 exchange and transpiration of 8 common tree species from the Amazonian floodplain forest grown up from seeds using a dynamic enclosure system. Analysis of volatile organics was performed by PTR-MS fast online measurements. Our study confirmed emissions of ethanol and acetaldehyde at the beginning of root anoxia after inundation, especially in less anoxia adapted species such as Vatairea guianensis, but not for Hevea spruceana probably due to a better adapted metabolism. In contrast to short-term inundation, long-term flooding of the root system did not result in any emission of ethanol or/and acetaldehyde. Emission of other VOCs, such as isoprenoids, acetone, and methanol exhibited distinct behavior related to the origin (igapó or várzea type of floodplain) of the tree species. Also physiological activities exhibited different response patterns for trees from igapó or várzea. In general, isoprenoid emissions increased within the course of some days of short-term flooding. After a long period of waterlogging, VOC emissions decreased considerably, along with photosynthesis, transpiration and stomatal conductance. However, even under long-term testing conditions, two tree species did not show any significant decrease or increase in photosynthesis. In order to understand ecophysiological advantages of the different responses we need field investigations with adult tree species.

The missing link in COS metabolism: a model study on the reactivation of carbonic anhydrase from its hydrosulfide analogue.

Carbonic anhydrase (CA) is known to react with carbonyl sulfide, an atmospheric trace gas, whereby H(2)S is formed. It has been shown that, in the course of this reaction, the active catalyst, the His(3)ZnOH structural motif, is converted to its hydrosulfide form: His(3)ZnOH+COS-->His(3)ZnSH+CO(2). In this study, we elucidate the mechanism of reactivation of carbonic anhydrase (CA) from its hydrosulfide analogue by using density functional calculations, a model reaction and in vivo experimental investigation. The desulfuration occurs according to the overall equation His(3)ZnSH+H(2)O right harpoon over left harpoon His(3)ZnOH+H(2)S. The initial step is a protonation equilibrium at the zinc-bound hydrosulfide. The hydrogen sulfide ligand thus formed is then replaced by a water molecule, which is subsequently deprotonated to yield the reactivated catalytic centre of CA. Such a mechanism is thought to enable a plant cell to expel H(2)S or rapidly metabolise it to cysteine via the cysteine synthase complex. The proposed mechanism of desulfuration of the hydrosulfide analogue of CA can thus be regarded as the missing link between COS consumption of plants and their sulfur metabolism.

Soil CO2 efflux in central Amazonia: environmental and methodological effects / Efluxo de CO2 do solo na Amazônia central: efeitos ambiental e metodológico

Soil respiration plays a significant role in the carbon cycle of Amazonian rainforests. Measurements of soil respiration have only been carried out in few places in the Amazon. This study investigated the effects of the method of ring insertion in the soil as well as of rainfall and spatial distribution on CO2 emission in the central Amazon region. The ring insertion effect increased the soil emission about 13-20 percent for sandy and loamy soils during the firsts 4-7 hours, respectively. After rainfall events below 2 mm, the soil respiration did not change, but for rainfall greater than 3 mm, after 2 hours there was a decrease in soil temperature and respiration of about 10-34 percent for the loamy and sand soils, with emissions returning to normal after around 15-18 hours. The size of the measurement areas and the spatial distribution of soil respiration were better estimated using the Shuttle Radar Topographic Mission (SRTM) data. The Campina reserve is a mosaic of bare soil, stunted heath forest-SHF and tall heath forest-THF. The estimated total average CO2 emissions from the area was 3.08±0.8 µmol CO2 m-2 s-1. The Cuieiras reserve is another mosaic of plateau, slope, Campinarana and riparian forests and the total average emission from the area was 3.82±0.76 µmol CO2 m-2 s-1. We also found that the main control factor of the soil respiration was soil temperature, with 90 percent explained by regression analysis. Automated soil respiration datasets are a good tool to improve the technique and increase the reliability of measurements to allow a better understanding of all possible factors driven by soil respiration processes.

Respiração do solo possui um importante papel no ciclo do carbono em florestas tropicais Amazônicas. Entretanto poucas medidas de respiração do solo foram feitas. Neste estudo são apontados os efeitos na metodologia de instalação dos anéis no solo, bem como os efeitos da precipitação e a distribuição espacial da emissão de CO2 na Amazônia central. Os efeitos da inserção de anéis no solo aumentaram de 13 a 20 por cento para o solo arenoso e argiloso, o efeito durou de 4 a 7 horas, respectivamente. Já os efeitos na precipitação, notamos que os eventos abaixo de 2 mm a respiração do solo permaneceu indiferente, mas para precipitação acima de 3 mm, 2 horas depois, houve uma diminuição da temperatura e respiração em 10 a 34 por cento para o solo argilosos e arenosos, retornando a emissão normal após 15 a 18 horas. Para estimar a distribuição espacial da respiração do solo e o tamanho correto das áreas medidas, foram utilizadas as imagens do Shuttle Radar Topographic Mission (SRTM). Considerando que a Reserva de Campina é um mosaico de solo desnudo, floresta alagável de baixa e alta estatura (SHF e THF). A emissão total média de CO2 para a área foi de 3.08±0.8 µmol CO2 m-2 s-1. Já a Reserva do Cuieiras possui outro mosaico de florestas de platôs, encostas, Campinaranas e riparias, sendo a emissão média total desta área foram de 3.82±0.76 µmol CO2 m-2 s-1. Encontramos também que a respiração do solo foi controlada pela temperatura do solo, sendo uma correlação de 90 por cento encontrada pela análise de regressão. Dados obtidos com sistema automático de respiração do solo é uma grande oportunidade de melhoramento da técnica e o aumento da confiança nas medidas em relação aos possíveis fatores que controlam os processos de emissão de CO2 do solo.

Design and field application of an automated cartridge sampler for VOC concentration and flux measurements.

One of the major limitations in advancing the understanding of tropospheric ozone and aerosol generation and developing strategies for their control is the technical ability to accurately measure volatile organic compounds (VOCs). This paper describes the design of a constant flow VOC sampler. The versatile sampler can be used for fully automated concentration and flux measurements of VOCs. The sampler incorporates a microprocessor control unit and provides highly accurate mass flow control and significant ease of operation. Sampling sequences can be programmed directly or by remote control through a PC. All important operational parameters necessary for a complete sampling audit trail are logged. Compact weatherproof housings and low power consumption allow operation at remote sites and locations which are sensitive to disturbances or have restricted access. Inner wetted surfaces of the sampler are constructed from non-contaminating materials that do not sorb or emit VOC, and thus permit the collection of representative samples even in environments with very low VOC concentrations. The cartridge magazine provides a maximum of 20 sequential cartridge samples, which allows for long-term air quality assessments. In the dual channel mode, two samples can be collected simultaneously through two independent sample loops, providing ten sequential sample pairs. This design allows the parallel collection of (a) quality assurance backup samples, (b) samples on two different types of cartridges/sorbents to allow a variety of analyses, or (c) differential samples for flux measurements using enclosure, aerodynamic profile, or relaxed eddy accumulation (REA) methods. Field applications including airplane profile measurements above a tropical rainforest area, as well as gradient and REA measurements over a mid-latitude mixed forest stand are described, and demonstrate the validity and flexibility of the system. In particular, the application of the VOC sampler as an integrated part of a REA system is emphasized.

How does the exchange of one oxygen atom with sulfur affect the catalytic cycle of carbonic anhydrase?

We have extended our investigations of the carbonic anhydrase (CA) cycle with the model system [(H(3)N)(3)ZnOH](+) and CO(2) by studying further heterocumulenes and catalysts. We investigated the hydration of COS, an atmospheric trace gas. This reaction plays an important role in the global COS cycle since biological consumption, that is, uptake by higher plants, algae, lichens, and soil, represents the dominant terrestrial sink for this gas. In this context, CA has been identified by a member of our group as the key enzyme for the consumption of COS by conversion into CO(2) and H(2)S. We investigated the hydration mechanism of COS by using density functional theory to elucidate the details of the catalytic cycle. Calculations were first performed for the uncatalyzed gas phase reaction. The rate-determining step for direct reaction of COS with H(2)O has an energy barrier of deltaG=53.2 kcal mol(-1). We then employed the CA model system [(H(3)N)(3)ZnOH](+) (1) and studied the effect on the catalytic hydration mechanism of replacing an oxygen atom with sulfur. When COS enters the carbonic anhydrase cycle, the sulfur atom is incorporated into the catalyst to yield [(H(3)N)(3)ZnSH](+) (27) and CO(2). The activation energy of the nucleophilic attack on COS, which is the rate-determining step, is somewhat higher (20.1 kcal mol(-1) in the gas phase) than that previously reported for CO(2). The sulfur-containing model 27 is also capable of catalyzing the reaction of CO(2) to produce thiocarbonic acid. A larger barrier has to be overcome for the reaction of 27 with CO(2) compared to that for the reaction of 1 with CO(2). At a well-defined stage of this cycle, a different reaction path can emerge: a water molecule helps to regenerate the original catalyst 1 from 27, a process accompanied by the formation of thiocarbonic acid. We finally demonstrate that nature selected a surprisingly elegant and efficient group of reactants, the [L(3)ZnOH](+)/CO(2)/H(2)O system, that helps to overcome any deactivation of the ubiquitous enzyme CA in nature.