Browsing by Subject "CHEMICAL-COMPOSITION"

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  • Qi, Lu; Vogel, Alexander L.; Esmaeilirad, Sepideh; Cao, Liming; Zheng, Jing; Jaffrezo, Jean-Luc; Fermo, Paola; Kasper-Giebl, Anne; Dällenbach, Kaspar; Chen, Mindong; Ge, Xinlei; Baltensperger, Urs; Prevot, Andre S. H.; Slowik, Jay G. (2020)
    The aerosol mass spectrometer (AMS), combined with statistical methods such as positive matrix factorization (PMF), has greatly advanced the quantification of primary organic aerosol (POA) sources and total secondary organic aerosol (SOA) mass. However, the use of thermal vaporization and electron ionization yields extensive thermal decomposition and ionization-induced fragmentation, which limit chemical information needed for SOA source apportionment. The recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) provides mass spectra of the organic aerosol fraction with a linear response to mass and no thermal decomposition or ionization-induced fragmentation. However, the costs and operational requirements of online instruments make their use impractical for long-term or spatially dense monitoring applications. This challenge was overcome for AMS measurements by measuring re-nebulized water extracts from ambient filter samples. Here, we apply the same strategy for EESI-TOF measurements of 1 year of 24 h filter samples collected approximately every fourth day throughout 2013 at an urban site. The nebulized water extracts were measured simultaneously with an AMS. The application of positive matrix factorization (PMF) to EESI-TOF spectra resolved seven factors, which describe water-soluble OA: less and more aged biomass burning aerosol (LABB(EESI) and MABB(EESI), respectively), cigarette-smoke-related organic aerosol, primary biological organic aerosol, biogenic secondary organic aerosol, and a summer mixed oxygenated organic aerosol factor. Seasonal trends and relative contributions of the EESI-TOF OA sources were compared with AMS source apportionment factors, measured water-soluble ions, cellulose, and meteorological data. Cluster analysis was utilized to identify key factor-specific ions based on PMF. Both LABB and MABB contribute strongly during winter. LABB is distinguished by very high signals from C6H10O5 (levoglucosan and isomers) and C8H12O6, whereas MABB is characterized by a large number of CxHyOz and CxHyOzN species of two distinct populations: one with low H : C and high O : C and the other with high H : C and low O : C. Two oxygenated summertime SOA sources were attributed to terpene-derived biogenic SOA, a major summertime aerosol source in central Europe. Furthermore, a primary biological organic aerosol factor was identified, which was dominated by plant-derived fatty acids and correlated with free cellulose. The cigarette-smoke-related factor contained a high contribution of nicotine and high abundance of organic nitrate ions with low m/z.
  • Hussein, Tareq; Juwhari, Hassan; Al Kuisi, Mustafa; Alkattan, Hamza; Lahlouh, Bashar; Al-Hunaiti, Afnan (2018)
    In this study, we analyzed the concentrations of accumulation and coarse modes measured during November 2013–July 2017 at an urban background site in Amman, Jordan. The concentrations showed distinct seasonal variations with high concentrations with a monthly average higher than 100 cm−3 and 1.5 cm−3, respectively, for accumulation and coarse modes during the winter and low concentrations with a monthly average less than 40 cm−3 and 1–1.5 cm−3, respectively, for accumulation and coarse modes during the summer. Sand and dust storms (SDS) affected the coarse mode during the early spring whereas local dust re-suspension affected them during the autumn. The gravimetric analysis confirmed the seasonal variation of the calculated particulate mass concentration but suggested that the assumption of spherical particles and unit density is not always proper. The ATR-FTIR analysis of selected filters revealed that aerosols in the background atmosphere of Amman are a mixture of locally emitted (fossil fuel combustion) and local/regional dust. Based on the 24-h average of the calculated PM10, the pollution standard index (PSI) revealed that about 81% of the days were either good or moderate air quality conditions. About 71% of the days were below the 24-h PM10 limit value according to the Jordanian air quality standards (120 μg m−3).
  • Xavier, Carlton; Rusanen, Anton; Zhou, Putian; Chen, Dean; Pichelstorfer, Lukas; Pontus, Roldin; Boy, Michael (2019)
    In this study we modeled secondary organic aerosol (SOA) mass loadings from the oxidation (by O-3, OH and NO3) of five representative biogenic volatile organic compounds (BVOCs): isoprene, endocyclic bond-containing monoterpenes (alpha-pinene and limonene), exocyclic double-bond compound (beta-pinene) and a sesquiterpene (beta-caryophyllene). The simulations were designed to replicate an idealized smog chamber and oxidative flow reactors (OFRs). The Master Chemical Mechanism (MCM) together with the peroxy radical autoxidation mechanism (PRAM) were used to simulate the gas-phase chemistry. The aim of this study was to compare the potency of MCM and MCM + PRAM in predicting SOA formation. SOA yields were in good agreement with experimental values for chamber simulations when MCM + PRAM was applied, while a stand-alone MCM underpredicted the SOA yields. Compared to experimental yields, the OFR simulations using MCM + PRAM yields were in good agreement for BVOCs oxidized by both O-3 and OH. On the other hand, a stand-alone MCM underpredicted the SOA mass yields. SOA yields increased with decreasing temperatures and NO concentrations and vice versa. This highlights the limitations posed when using fixed SOA yields in a majority of global and regional models. Few compounds that play a crucial role (> 95% of mass load) in contributing to SOA mass increase (using MCM + PRAM) are identified. The results further emphasized that incorporating PRAM in conjunction with MCM does improve SOA mass yield estimation.
  • Perttila, Sini; Jalava, Taina; Rinne, Marketta; Viana, Gabriel Da Silva; Valaja, Jarmo (2021)
    The apparent (AID) and standardised (SID) ileal amino acid digestibilities in wheat, soybean meal and rapeseed meal were determined with Ross 308 broiler chicken (n = 64) using the slaughter technique with chromium mordanted straw as an indigestible marker. The recovery of endogenous amino acids at the distal ileum was determined with protein-free diet and it was used to calculate the SID digestibilities of the studied feed ingredients. The mean amino acid AID and SID were higher in soybean meal and wheat than in rapeseed meal (p
  • Rinta-Kanto, J. M.; Pehkonen, K.; Sinkko, H.; Tamminen, M. V.; Timonen, S. (2018)
    In this study, the abundance and composition of prokaryotic communities associated with the inner tissue of fruiting bodies of Suillus bovinus, Boletus pinophilus, Cantharellus cibarius, Agaricus arvensis, Lycoperdon perlatum, and Piptoporus betulinus were analyzed using culture-independent methods. Our findings indicate that archaea and bacteria colonize the internal tissues of all investigated specimens and that archaea are prominent members of the prokaryotic community. The ratio of archaeal 16S rRNA gene copy numbers to those of bacteria was >1 in the fruiting bodies of four out of six fungal species included in the study. The largest proportion of archaeal 16S rRNA gene sequences belonged to thaumarchaeotal classes Terrestrial group, Miscellaneous Crenar-chaeotic Group (MCG), and Thermoplasmata. Bacterial communities showed characteristic compositions in each fungal species. Bacterial classes Gammaproteobacteria, Actinobacteria, Bacilli, and Clostridia were prominent among communities in fruiting body tissues. Bacterial populations in each fungal species had different characteristics. The results of this study imply that fruiting body tissues are an important habitat for abundant and diverse populations of archaea and bacteria.
  • Booyens, Wanda; Beukes, Johan P.; Van Zyl, Pieter G.; Ruiz-Jimenez, Jose; Kopperi, Matias; Riekkola, Marja-Liisa; Josipovic, Miroslav; Vakkari, Ville; Laakso, Lauri (2019)
    A recent paper reported GCxGC-TOFMS analysis used for the first time in southern Africa to tentatively characterise and semi-quantify 1000 organic compounds in aerosols at Welgegund - a regional background atmospheric monitoring station. Ambient polar organic aerosols characterised are further explored in terms of temporal variations, as well as the influence of meteorology and sources. No distinct seasonal pattern was observed for the total number of polar organic compounds tentatively characterised and their corresponding semi-quantified concentrations (sum of the normalised response factors, Sigma NRFs). However, the total number of polar organic compounds and Sigma NRFs between late spring and early autumn seemed relatively lower compared to the period from mid-autumn to mid-winter, while there was a period during late winter and early spring with significantly lower total number of polar organic compounds and Sigma NRFs. Relatively lower total number of polar organic compounds and corresponding Sigma NRFs were associated with fresher plumes from a source region relatively close to Welgegund. Meteorological parameters indicated that wet removal during late spring to early autumn also contributed to lower total numbers of polar organics and associated Sigma NRFs. Increased anticyclonic recirculation and more pronounced inversion layers contributed to higher total numbers of polar organic species and Sigma NRFs from mid-autumn to mid-winter, while the influence of regional biomass burning during this period was also evident. The period with significantly lower total number of polar organic compounds and Sigma NRFs was attributed to fresh open biomass burning plumes occurring within proximity of Welgegund, consisting mainly of volatile organic compounds and non-polar hydrocarbons. Multiple linear regression substantiated that the temporal variations in polar organic compounds were related to a combination of the factors investigated in this study.
  • Asmala, E.; Autio, R.; Kaartokallio, H.; Pitkanen, L.; Stedmon, C. A.; Thomas, D. N. (2013)
  • Carbone, S.; Onasch, T.; Saarikoski, S.; Timonen, H.; Saarnio, K.; Sueper, D.; Ronkko, T.; Pirjola, L.; Häyrinen, A.; Worsnop, D.; Hillamo, R. (2015)
    A method to detect and quantify mass concentrations of trace metals on soot particles by the Aerodyne soot-particle aerosol mass spectrometer (SP-AMS) was developed and evaluated in this study. The generation of monodisperse Regal black (RB) test particles with trace amounts of 13 different metals (Na, Al, Ca, V, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Sr and Ba) allowed for the determination of the relative ionization efficiency of each metal relative to black carbon (RIEmeas). The observed RIEmeas/RIEtheory values were larger than unity for Na, Rb, Ca, Sr and Ba due to thermal surface ionization (TSI) on the surface of the laser-heated RB particles. Values closer to unity were obtained for the transition metals Zn, Cu, V and Cr. Mn, Fe, and Ni presented the lowest RIEmeas/RIEtheory ratios and highest deviation from unity. The latter discrepancy is unexplained; however it may be related to problems with our calibration method and/or the formation of metal complexes that were not successfully quantified. The response of the metals to the laser power was investigated and the results indicated that a minimum pump laser current of 0.6 A was needed in order to vaporize the metals and the refractory black carbon (rBC). Isotopic patterns of metals were resolved from high-resolution mass spectra, and the mass-weighted size distributions for each individual metal ion were obtained using the high-resolution particle time-of-flight (HR-PToF) method. The RIEmeas values obtained in this study were applied to the data of emission measurements in a heavy-fuel-oil-fired heating station. Emission measurements revealed a large number of trace metals, including evidence for metal oxides and metallic salts, such as vanadium sulfate, calcium sulfate, iron sulfate and barium sulfate, which were identified in the SP-AMS high-resolution mass spectra. SP-AMS measurements of Ba, Fe, and V agreed with ICP-MS analyzed filter samples within a factor of 2 when emitted rBC mass loadings were elevated.
  • Hao, Liqing; Garmash, Olga; Ehn, Mikael; Miettinen, Pasi; Massoli, Paola; Mikkonen, Santtu; Jokinen, Tuija; Roldin, Pontus; Aalto, Pasi; Yli-Juuti, Taina; Joutsensaari, Jorma; Petäjä, Tuukka; Kulmala, Markku; Lehtinen, Kari E. J.; Worsnop, Douglas R.; Virtanen, Annele (2018)
    Characterizing aerosol chemical composition in response to meteorological changes and atmospheric chemistry is important to gain insights into new particle formation mechanisms. A BAECC (Biogenic Aerosols - Effects on Clouds and Climate) campaign was conducted during the spring 2014 at the SMEAR II station (Station for Measuring Forest Ecosystem-Aerosol Relations) in Finland. The particles were characterized by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). A PBL (planetary boundary layer) dilution model was developed to assist interpreting the measurement results. Right before nucleation events, the mass concentrations of organic and sulfate aerosol species were both decreased rapidly along with the growth of PBL heights. However, the mass fraction of sulfate aerosol of the total aerosol mass was increased, in contrast to a decrease for the organic mass fraction. Meanwhile, an increase in LVOOA (low-volatility oxygenated organic aerosol) mass fraction of the total organic mass was observed, in distinct comparison to a reduction of SVOOA (semi-volatile OOA) mass fraction. Our results demonstrate that, at the beginning of nucleation events, the observed sulfate aerosol mass was mainly driven by vertical turbulent mixing of sulfate-rich aerosols between the residual layer and the newly formed boundary layer, while the condensation of sulfuric acid (SA) played a minor role in interpreting the measured sulfate mass concentration. For the measured organic aerosols, their temporal profiles were mainly driven by dilution from PBL development, organic aerosol mixing in different boundary layers and/or partitioning of organic vapors, but accurate measurements of organic vapor concentrations and characterization on the spatial aerosol chemical composition are required. In general, the observed aerosol particles by AMS are subjected to joint effects of PBL dilution, atmospheric chemistry and aerosol mixing in different boundary layers. During aerosol growth periods in the nighttime, the mass concentrations of organic aerosols and organic nitrate aerosols were both increased. The increase in SVOOA mass correlated well with the calculated increase in condensed HOMs' (highly oxygenated organic molecules) mass. To our knowledge, our results are the first atmospheric observations showing a connection between increase in SVOOA and condensed HOMs during the nighttime.
  • Kapp, Karmen; Orav, Anne; Roasto, Mati; Raal, Ain; Püssa, Tõnu; Vuorela, Heikki; Tammela, Päivi; Vuorela, Pia (2020)
    Mint flavorings are widely used in confections, beverages, and dairy products. For the first time, mint flavoring composition of mint candies and food supplements (n=45), originating from 16 countries, as well as their antibacterial properties, was analyzed. The flavorings were isolated by Marcussons type micro-apparatus and analyzed by GC-MS. The total content of the mint flavoring hydrodistilled extracts was in the range of 0.01-0.9%. The most abundant compounds identified in the extracts were limonene, 1,8-cineole, menthone, menthofuran, isomenthone, menthol and its isomers, menthyl acetate. The antimicrobial activity of 13 reference substances and 10 selected mint flavoring hydrodistilled extracts was tested on Escherichia coli and Staphylococcus aureus by broth dilution method. Linalool acetate and (-)-carvone, as most active against both bacteria, had the lowest MIC (90) values. (+)-Menthyl acetate, (-)-menthyl acetate, and limonene showed no antimicrobial activity. Three of the tested extracts had antimicrobial activity against E. coli and 8 extracts against S. aureus . Their summary antimicrobial activity was not always in concordance with the activities of respective reference substances.
  • Äijälä, Mikko; Dällenbach, Kaspar; Canonaco, Francesco; Heikkinen, Liine; Junninen, Heikki; Petäjä, Tuukka; Kulmala, Markku; Prevot, Andre S. H.; Ehn, Mikael (2019)
    The interactions between organic and inorganic aerosol chemical components are integral to understanding and modelling climate and health-relevant aerosol physicochemical properties, such as volatility, hygroscopicity, light scattering and toxicity. This study presents a synthesis analysis for eight data sets, of non-refractory aerosol composition, measured at a boreal forest site. The measurements, performed with an aerosol mass spectrometer, cover in total around 9 months over the course of 3 years. In our statistical analysis, we use the complete organic and inorganic unit-resolution mass spectra, as opposed to the more common approach of only including the organic fraction. The analysis is based on iterative, combined use of (1) data reduction, (2) classification and (3) scaling tools, producing a data-driven chemical mass balance type of model capable of describing site-specific aerosol composition. The receptor model we constructed was able to explain 83 +/- 8% of variation in data, which increased to 96 +/- 3% when signals from low signal-to-noise variables were not considered. The resulting interpretation of an extensive set of aerosol mass spectrometric data infers seven distinct aerosol chemical components for a rural boreal forest site: ammonium sulfate (35 +/- 7% of mass), low and semi-volatile oxidised organic aerosols (27 +/- 8% and 12 +/- 7 %), biomass burning organic aerosol (11 +/- 7 %), a nitrate-containing organic aerosol type (7 +/- 2 %), ammonium nitrate (5 +/- 2 %), and hydrocarbon-like organic aerosol (3 +/- 1 %). Some of the additionally observed, rare outlier aerosol types likely emerge due to surface ionisation effects and likely represent amine compounds from an unknown source and alkaline metals from emissions of a nearby district heating plant. Compared to traditional, ionbalance-based inorganics apportionment schemes for aerosol mass spectrometer data, our statistics-based method provides an improved, more robust approach, yielding readily useful information for the modelling of submicron atmospheric aerosols physical and chemical properties. The results also shed light on the division between organic and inorganic aerosol types and dynamics of salt formation in aerosol. Equally importantly, the combined methodology exemplifies an iterative analysis, using consequent analysis steps by a combination of statistical methods. Such an approach offers new ways to home in on physicochemically sensible solutions with minimal need for a priori information or analyst interference. We therefore suggest that similar statisticsbased approaches offer significant potential for un- or semi-supervised machine-learning applications in future analyses of aerosol mass spectrometric data.
  • Epie, Kenedy E.; Artigas, Olga M.; Santanen, Arja; Mäkelä, Pirjo S. A.; Stoddard, Frederick L. (2018)
    The biomass potential of eight high yielding maize cultivars was studied in the sub-boreal climate of southern Finland. The effects of harvest date on lignin and sugar production, biomass yield, mineral element composition, bioenergy potential and soil nutrient management were determined in two years. The eight maize cultivars produced 17.6-33.3 t ha(-1) of biomass. The ear fraction contained 50-60% of the biomass, and ash and mineral element composition of the plant fractions were significantly different (p <0.001), with more ash, Ca and S in the above-ear fractions of the plants than in the mid-stalk portions, whereas the C:N ratio was highest in the lower stalk. Cultivars with less lignin content produced more fermetable sugars. Despite the relatively cool growing conditions and short season of the sub-boreal region, maize has potential for use as biomass, for biofuel or other uses. The crop can be fractioned into ear and stalk, with the lower 20 cm of stalk left in the field to maintain soil organic matter content.
  • Berg, Björn (2018)
    Decomposition of foliar litter may be complete or proceed at a progressively lower rate to become zero and a limit value for decomposition may be estimated. Limit values for decomposition have been found to range from 100% accumulated mass loss to 42%, resulting in 'stable' fractions of 0 and 58%, respectively. A limit value does not necessarily mean a complete stop in decomposition but litter mass loss may proceed at a very low rate. An asymptotic function is used to estimate limit value/stable fraction, separating a readily decomposed and a stable residue. The stabilized litter fraction defined as (100 - limit value)/100 may be used for estimating the accumulation rate of stable carbon (C) in organic layers.
  • Duplissy, J.; Merikanto, J.; Franchin, A.; Tsagkogeorgas, G.; Kangasluoma, J.; Wimmer, D.; Vuollekoski, H.; Schobesberger, S.; Lehtipalo, K.; Flagan, R. C.; Brus, D.; Donahue, N. M.; Vehkamäki, H.; Almeida, J.; Amorim, A.; Barmet, P.; Bianchi, F.; Breitenlechner, M.; Dunne, E. M.; Guida, R.; Henschel, H.; Junninen, H.; Kirkby, J.; Kürten, A.; Kupc, A.; Määttänen, A.; Makhmutov, V.; Mathot, S.; Nieminen, T.; Onnela, A.; Praplan, A. P.; Riccobono, F.; Rondo, L.; Steiner, G.; Tome, A.; Walther, H.; Baltensperger, U.; Carslaw, K. S.; Dommen, J.; Hansel, A.; Petäjä, T.; Sipilä, M.; Stratmann, F.; Vrtala, A.; Wagner, P. E.; Worsnop, D. R.; Curtius, J.; Kulmala, M. (2016)
    We report comprehensive, demonstrably contaminant-free measurements of binary particle formation rates by sulfuric acid and water for neutral and ion-induced pathways conducted in the European Organization for Nuclear Research Cosmics Leaving Outdoor Droplets chamber. The recently developed Atmospheric Pressure interface-time of flight-mass spectrometer was used to detect contaminants in charged clusters and to identify runs free of any contaminants. Four parameters were varied to cover ambient conditions: sulfuric acid concentration (10(5) to 10(9)molcm(-3)), relative humidity (11% to 58%), temperature (207K to 299K), and total ion concentration (0 to 6800ionscm(-3)). Formation rates were directly measured with novel instruments at sizes close to the critical cluster size (mobility size of 1.3nm to 3.2nm). We compare our results with predictions from Classical Nucleation Theory normalized by Quantum Chemical calculation (QC-normalized CNT), which is described in a companion paper. The formation rates predicted by the QC-normalized CNT were extended from critical cluster sizes to measured sizes using the UHMA2 sectional particle microphysics model. Our results show, for the first time, good agreement between predicted and measured particle formation rates for the binary (neutral and ion-induced) sulfuric acid-water system. Formation rates increase with RH, sulfuric acid, and ion concentrations and decrease with temperature at fixed RH and sulfuric acid concentration. Under atmospheric conditions, neutral particle formation dominates at low temperatures, while ion-induced particle formation dominates at higher temperatures. The good agreement between the theory and our comprehensive data set gives confidence in using the QC-normalized CNT as a powerful tool to study neutral and ion-induced binary particle formation in atmospheric modeling.
  • Cai, Xiaoqing; Lin, Ziwen; Penttinen, Petri; Li, Yongfu; Li, Yongchun; Luo, Yu; Yue, Tian; Jiang, Peikun; Fu, Weijun (2018)
    Converting natural forests to plantations would markedly change soil physiochemical and biological properties, as a consequence of changing plant vegetative coverage and management practices. However, the effects of such land-use change on the soil nutrient pools and related enzymes activities still remain unclear. The aim of this study was to explore the effects of conversion from natural evergreen broadleaf forests to Moso bamboo plantations on the pool sizes and forms of soil N, P and K, microbial biomass, and nutrient cycling related enzyme activities. Soil samples from four adjacent evergreen broadleaf forest-Moso bamboo plantation pairs were collected from a subtropical region in Zhejiang Province, China. The soil organic C (SOC), total N (TN), total P (TP) and total K (TK) concentrations and stocks and different N, P and K forms were measured, and the microbial biomass C (MBC), microbial biomass N (MBN), microbial biomass P (MBP) and four soil enzymes (protease, urease, acid phosphatase and catalase) were determined. The results showed that converting broadleaf forests to Moso bamboo plantations decreased the concentration and stock of SOC but increased those of TK in both soil layers (0-20 and 20-40 cm), and such land-use change increased the concentration and stock of TN and TP only in the 0-20 cm soil layer (P <0.05). This land-use conversion increased the concentrations of NH4+-N, NO3- N, resin-Pi, NaHCO3-P-1, NaOH-P-i, HCl-P-i, available K and slowly available K, but decreased the concentrations of water-soluble organic nitrogen (WSON), NaHCO3-P-o and NaOH-P-o (P <0.05). Further, this land-use change decreased the microbial biomass and activities of protease, urease, acid phosphatase and catalase (P <0.05). In addition, the acid phosphatase activity correlated positively with the concentrations of MBP and NaHCO3-P-o, and the activities of urease and protease correlated positively with the concentrations of MBN and WSON (P <0.01). To conclude, converting natural broadleaf forests to Moso bamboo plantations had positive effects on soil inorganic N, P and K pools, and negative effects on soil organic N and P pools, and on N- and P-cycling related enzyme activities. Therefore, management practices that increase organic nutrient pools and microbial activity are needed to be developed to mitigate the depletion of organic nutrient pools after the land-use conversion.
  • Varnai, Aniko; Costa, Thales H. F.; Faulds, Craig B.; Milagres, Adriane M. F.; Siika-aho, Matti; Ferraz, Andre (2014)
    Background: Sugar cane internodes can be divided diagonally into four fractions, of which the two innermost ones are the least recalcitrant pith and the moderately accessible pith-rind interface. These fractions differ in enzymatic hydrolyzability due to structural differences. In general, cellulose hydrolysis in plants is hindered by its physical interaction with hemicellulose and lignin. Lignin is believed to be linked covalently to hemicellulose through hydroxycinnamic acids, forming a compact matrix around the polysaccharides. Acetyl xylan esterase and three feruloyl esterases were evaluated for their potential to fragment the lignocellulosic network in sugar cane and to indirectly increase the accessibility of cellulose. Results: The hydrolyzability of the pith and pith-rind interface fractions of a low-lignin-containing sugar cane clone (H58) was compared to that of a reference cultivar (RC). Acetyl xylan esterase enhanced the rate and overall yield of cellulose and xylan hydrolysis in all four substrates. Of the three feruloyl esterases tested, only TsFaeC was capable of releasing p-coumaric acid, while AnFaeA and NcFaeD released ferulic acid from both the pith and interface fractions. Ferulic acid release was higher from the less recalcitrant clone (H58)/fraction (pith), whereas more p-coumaric acid was released from the clone (RC)/fraction (interface) with a higher lignin content. In addition, a compositional analysis of the four fractions revealed that p-coumaroyl content correlated with lignin, while feruloyl content correlated with arabinose content, suggesting different esterification patterns of these two hydroxycinnamic acids. Despite the extensive release of phenolic acids, feruloyl esterases only moderately promoted enzyme access to cellulose or xylan. Conclusions: Acetyl xylan esterase TrAXE was more efficient in enhancing the overall saccharification of sugar cane, compared to the feruloyl esterases AnFaeA, TsFaeC, and NcFaeD. The hydroxycinnamic acid composition of sugar cane fractions and the hydrolysis data together suggest that feruloyl groups are more likely to decorate xylan, while p-coumaroyl groups are rather linked to lignin. The three different feruloyl esterases had distinct product profiles on non-pretreated sugar cane substrate, indicating that sugar cane pith could function as a possible natural substrate for feruloyl esterase activity measurements. Hydrolysis data suggest that TsFaeC was able to release p-coumaroyl groups esterifying lignin.
  • Koski, Tuuli-Marjaana; Kalpio, Marika; Laaksonen, Toni; Sirkiä, Päivi; Kallio, Heikki P.; Yang, Baoru; Linderborg, Kaisa M.; Klemola, Tero (2017)
    The evolutionary purpose of a fleshy fruit is to attract seed dispersers and get the seeds dispersed by frugivorous animals. For this reason, fruits should be highly rewarding to these mutualists. However, insect herbivory can alter plant reproductive success e.g. by decreasing fruit yield or affecting the attractiveness of the fruits to mutualistic seed dispersers. Under natural conditions, we tested the effects of experimental larval-defoliation on berry ripening and consumption of a non-cultivated dwarf shrub, the bilberry (Vaccinium myrtillus L.), which produces animal-dispersed berries with high sugar and anthocyanin concentration. Bilberry ramets with high fruit yield were most likely to have their berries foraged, indicating that frugivores made foraging choices based on the abundance of berries. Moreover, the probability for berries being foraged was the lowest for non-defoliated ramets that grew adjacent to larval-defoliated ramets, even though larval-defoliation did not affect the biochemical composition (total concentrations of anthocyanins, sugars and organic acids) or the probability of ripening of berries. We hypothesise that the lower probability for berries being foraged in these ramets may be a consequence of rhizome- or volatile-mediated communication between ramets, resulting in a priming effect of the herbivore defence and lower attractiveness of the non-defoliated ramets.
  • Myllys, Nanna; Ponkkonen, Tuomo; Chee, Sabrina; Smith, James (2020)
    The role of an oxidation product of trimethylamine, trimethylamine oxide, in atmospheric particle formation is studied using quantum chemical methods and cluster formation simulations. Molecular-level cluster formation mechanisms are resolved, and theoretical results on particle formation are confirmed with mass spectrometer measurements. Trimethylamine oxide is capable of forming only one hydrogen bond with sulfuric acid, but unlike amines, trimethylamine oxide can form stable clusters via ion-dipole interactions. That is because of its zwitterionic structure, which causes a high dipole moment. Cluster growth occurs close to the acid:base ratio of 1:1, which is the same as for other monoprotic bases. Enhancement potential of trimethylamine oxide in particle formation is much higher than that of dimethylamine, but lower compared to guanidine. Therefore, at relatively low concentrations and high temperatures, guanidine and trimethylamine oxide may dominate particle formation events over amines.
  • Taipale, Sami J.; Vuorio, Kristiina; Aalto, Sanni L.; Peltomaa, Elina; Tiirola, Marja (2019)
    Eutrophication (as an increase in total phosphorus [TP]) increases harmful algal blooms and reduces the proportion of high-quality phytoplankton in seston and the content of ω-3 long-chain polyunsaturated fatty acids (eicosapentaenoic acid [EPA] and docosahexaenoic acid [DHA]) in fish. However, it is not well-known how eutrophication affects the overall nutritional value of phytoplankton. Therefore, we studied the impact of eutrophication on the production (as concentration; μg L−1) and content (μg mg C−1) of amino acids, EPA, DHA, and sterols, i.e., the nutritional value of phytoplankton in 107 boreal lakes. The lakes were categorized in seven TP concentration categories ranging from ultra-oligotrophic (50 μg L−1). Phytoplankton total biomass increased with TP as expected, but in contrast to previous studies, the contribution of high-quality phytoplankton did not decrease with TP. However, the high variation reflected instability in the phytoplankton community structure in eutrophic lakes. We found that the concentration of amino acids increased in the epilimnion whereas the concentration of sterols decreased with increasing TP. In terms of phytoplankton nutritional value, amino acids, EPA, DHA, and sterols showed a significant quadratic relationship with the lake trophic status. More specifically, the amino acid contents were the same in the oligo- and mesotrophic lakes, but substantially lower in the eutrophic lakes (TP > 35 μg L−1/1.13 μmol L−1). The highest EPA and DHA content in phytoplankton was found in the mesotrophic lakes, whereas the sterol content was highest in the oligotrophic lakes. Based on these results, the nutritional value of phytoplankton reduces with eutrophication, although the contribution of high-quality algae does not decrease. Therefore, the results emphasize that eutrophication, as excess TP, reduces the nutritional value of phytoplankton, which may have a significant impact on the nutritional value of zooplankton, fish, and other aquatic animals at higher food web levels.
  • Fanourgakis, George S.; Kanakidou, Maria; Nenes, Athanasios; Bauer, Susanne E.; Bergman, Tommi; Carslaw, Ken S.; Grini, Alf; Hamilton, Douglas S.; Johnson, Jill S.; Karydis, Vlassis A.; Kirkevag, Alf; Kodros, John K.; Lohmann, Ulrike; Luo, Gan; Makkonen, Risto; Matsui, Hitoshi; Neubauer, David; Pierce, Jeffrey R.; Schmale, Julia; Stier, Philip; Tsigaridis, Kostas; van Noije, Twan; Wang, Hailong; Watson-Parris, Duncan; Westervelt, Daniel M.; Yang, Yang; Yoshioka, Masaru; Daskalakis, Nikos; Decesari, Stefano; Gysel-Beer, Martin; Kalivitis, Nikos; Liu, Xiaohong; Mahowald, Natalie M.; Myriokefalitakis, Stelios; Schrodner, Roland; Sfakianaki, Maria; Tsimpidi, Alexandra P.; Wu, Mingxuan; Yu, Fangqun (2019)
    A total of 16 global chemistry transport models and general circulation models have participated in this study; 14 models have been evaluated with regard to their ability to reproduce the near-surface observed number concentration of aerosol particles and cloud condensation nuclei (CCN), as well as derived cloud droplet number concentration (CDNC). Model results for the period 2011-2015 are compared with aerosol measurements (aerosol particle number, CCN and aerosol particle composition in the submicron fraction) from nine surface stations located in Europe and Japan. The evaluation focuses on the ability of models to simulate the average across time state in diverse environments and on the seasonal and short-term variability in the aerosol properties. There is no single model that systematically performs best across all environments represented by the observations. Models tend to underestimate the observed aerosol particle and CCN number concentrations, with average normalized mean bias (NMB) of all models and for all stations, where data are available, of -24 % and -35 % for particles with dry diameters > 50 and > 120 nm, as well as -36 % and -34 % for CCN at supersaturations of 0.2 % and 1.0 %, respectively. However, they seem to behave differently for particles activating at very low supersaturations (<0.1 %) than at higher ones. A total of 15 models have been used to produce ensemble annual median distributions of relevant parameters. The model diversity (defined as the ratio of standard deviation to mean) is up to about 3 for simulated N-3 (number concentration of particles with dry diameters larger than 3 nm) and up to about 1 for simulated CCN in the extra-polar regions. A global mean reduction of a factor of about 2 is found in the model diversity for CCN at a supersaturation of 0.2 % (CCN0.2) compared to that for N-3, maximizing over regions where new particle formation is important. An additional model has been used to investigate potential causes of model diversity in CCN and bias compared to the observations by performing a perturbed parameter ensemble (PPE) accounting for uncertainties in 26 aerosol-related model input parameters. This PPE suggests that biogenic secondary organic aerosol formation and the hygroscopic properties of the organic material are likely to be the major sources of CCN uncertainty in summer, with dry deposition and cloud processing being dominant in winter. Models capture the relative amplitude of the seasonal variability of the aerosol particle number concentration for all studied particle sizes with available observations (dry diameters larger than 50, 80 and 120 nm). The short-term persistence time (on the order of a few days) of CCN concentrations, which is a measure of aerosol dynamic behavior in the models, is underestimated on average by the models by 40 % during winter and 20 % in summer. In contrast to the large spread in simulated aerosol particle and CCN number concentrations, the CDNC derived from simulated CCN spectra is less diverse and in better agreement with CDNC estimates consistently derived from the observations (average NMB -13 % and -22 % for updraft velocities 0.3 and 0.6 m s(-1), respectively). In addition, simulated CDNC is in slightly better agreement with observationally derived values at lower than at higher updraft velocities (index of agreement 0.64 vs. 0.65). The reduced spread of CDNC compared to that of CCN is attributed to the sublinear response of CDNC to aerosol particle number variations and the negative correlation between the sensitivities of CDNC to aerosol particle number concentration (partial derivative N-d/partial derivative N-a) and to updraft velocity (partial derivative N-d/partial derivative w). Overall, we find that while CCN is controlled by both aerosol particle number and composition, CDNC is sensitive to CCN at low and moderate CCN concentrations and to the updraft velocity when CCN levels are high. Discrepancies are found in sensitivities partial derivative N-d/partial derivative N-a and partial derivative N-d/partial derivative w; models may be predisposed to be too "aerosol sensitive" or "aerosol insensitive" in aerosol-cloud-climate interaction studies, even if they may capture average droplet numbers well. This is a subtle but profound finding that only the sensitivities can clearly reveal and may explain intermodel biases on the aerosol indirect effect.