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The fractIons of dichloromethane extracts of leaves from andiroba (Carapa guianensis - Meliaceae), caapi (Banisteriopsis caapi - Malpighiaceae), cocoa (Theobroma cacao - Sterculiaceae), Brazil nut (Bertholletia excelsa - Lecytidaceae), cupuaçu (Theobroma grandiflorum - Sterculiaceae), marupá (Simaruba amara - Simaroubaceae) and rubber tree (Hevea brasiliensis - Euphorbiaceae), were analyzed by HT-HRGC and HT-HRGC-MS. Esters of homologous series of fatty acids and long chain alcohols, phytol, amyrines and tocopherols were characterized. The characterization of the compounds was based mainly in mass spectra data and in addition by usual spectrometric data (¹H and 13C NMR, IR).

The occurrence of Cunninghamia chaneyi from the middle Miocene sediments of the former Lake Clarkia in Northern Idaho is the last known occurrence of this genus in the geologic record of North America. Cunninghamia chaneyi has been reported on the basis of foliar branches from the Oligocene Rujada, Lyons and Bridgecreek floras of Oregon and the Oligocene Gumboot flora of southwestern Washington. These resemble the extant C. lanceolata. The C. marquettii from the Haynes Creek flora of east central Idaho more closely resembles C. konishii. Both C. protokonishii from the middle Miocene of Japan and C. europaea from the later Miocene of Poland also resemble C. konishii. The C. miocenica that has been described from the Oligocene and Miocene of central Europe is thought to be intermediate between the two extant species. The Clarkia Cunninghamia chaneyi is represented at four localities by well preserved compressions and impressions of foliar branches, rarely single needles, seed cones and pollen cone fascicles. The foliar branches are similar to those found beneath arboretum trees of C. lanceolata. The needles are lightly smaller in both width and length than those of the extant species. The size of the cones and cone fascicles of the fossils is identical to that of the extant C. lanceolata. However the shape of the cone bracts, the reduced cone scales and the seed attachment scars are some what different from that of the extant species. Most significantly, stomatal bands on the fossil species are half as wide as those on the extant species. The excellent preservation allowed analysis of extractable chemical compounds from foliar branches and cones of Cunninghamia chaneyi from Clarkia. Several mono-, sesqui- and diterpenoids have been identified in the extracts. The sesquiterpenoid pattern is similar to that described from the resin of C. miocenica from Central Europe.

The excellent preservation of plant macrofossils of the Miocene Clarkia flora, Emerald Creek, Idaho, USA, allowed the analysis of the extractable chemical compounds of five fossil conifer species. Foliar branches and cones of Cunninghamia chaneyi, Glyptostrobus oregonensis and Taxodium dubium (Taxodiaceae) and foliar branches of Metasequoia occidentalis (Taxodiaceae) and Calocedrus sp. (Cupressaceae) have been extracted with organic solvents, and the extracts have been analyzed as is and derivatized using gas chromatography-mass spectrometry. Generally, the extracts from foliar branches and cones of the same species showed similar extract patterns while the extracts from different species yielded different extract compositions. Several sesqui- and diterpenoids that probably originate from the resins have been identified. Most of the terpenoids have been degraded during diagenesis, but some compounds have been preserved unaltered. An aliphatic alcohol, n-nonacosan- 10-ol, that occurs in the waxes of extant conifers was present in the foliage of all investigated fossil conifers. Furthermore, all conifer species contained the diterpenoids ferruginol and 6,7-dihydroferruginol which are known from extant species of Cupressaceae, Taxodiaceae and Podocarpaceae. The fossil conifer species showed characteristic diterpenoid patterns which in part match the compounds that have been found in related extant species. In Taxodium dubium some terpenoids (sugiol, ferruginol methylether, isochamaecydine) have been identified which also occur in extant T. distichum. Glyptostrobus oregonensis contains terpenoids similar to Taxodium dubium, but lacks ferruginol methylether. Cunninghamia chaneyi is characterized by two diterpenoids (hinokiol, hinokione) that have also been identified in the extracts of extant C. lanceolata. Specific terpenoids have not been observed in the foliar branches of Metasequoia occidentalis. Extracts of Calocedrus sp. (Cupressaceae) contain totarol which is known from numerous extant species of Cupressaceae and Podocarpaceae, but has been described only from one species of the Taxodiaceae (Cryptomeria).

In order to evaluate hydrocarbon inputs to Crater Lake from anthropogenic and natural sources, samples of water, aerosol, surface slick and sediment were collected and analyzed by gas chromatography-mass spectrometry (GC-MS) for determination of their aliphatic and aromatic hydrocarbon concentrations and compositions. Results show that hydrocarbons originate from both natural (terrestrial plant waxes and algae) and anthropogenic (petroleum use) sources and are entering the lake through direct input and atmospheric transport. The concentrations of petroleum hydrocarbons range from low to undetectable. The distributions and abundances of n-alkanes, polycyclic aromatic hydrocarbons (PAH) and unresolved complex mixture (UCM) from petroleum are similar for all surface slick sampling sites. The estimated levels of PAH in surface slicks range from 7–9 ng/m2 which are low. Transport of petroleum-derived hydrocarbons from the lake surface has resulted in their presence in some sediments, particularly near the boat operations mooring (total petroleum HC = 1440 µg/kg, dry wt. compared to naturally derived n-alkanes, 240 µg/kg, dry wt.). The presence of biomarkers such as the tricyclic terpanes, hopanes and steranes in shallow sediments further confirms petroleum input from boat traffic. In the deep lake sediments, petroleum hydrocarbon concentrations were very low (16 µg/kg, dry wt.). Very low concentrations of PAH were detected in shallow sediments (17–40 µg/kg at 5 m depth near the boat operations) and deep sediments (3–15 µg/kg at 580 m depth). The individual PAH concentrations in sediments (µg/kg or ppb range) are at least three orders of magnitude less than reported threshold effects levels (mg/kg or ppm range, test amphipod Hyalella azteca). Therefore, no adverse effects are expected to occur in benthic biota exposed to these sediments. Boating activities are leaving a detectable level of petroleum in surface waters and lake sediments but these concentrations are very low. [ABSTRACT FROM AUTHOR]

The resins bled from stems and in seed cones and leaves of Cryptomeria japonica, Glyptostrobus pensilis, Taxodium distichum, and T. mucronatum were characterized to provide an overview of their major natural product compositions. The total solvent extract solutions were analyzed as the free and derivatized products by gas chromatography-mass spectrometry to identify the compounds, which comprised minor mono- and sesquiterpenoids, and dominant di- and triterpenoids, plus aliphatic lipids (e.g., n-nonacosan-10-ol). Ferruginol, 7α-p-cymenylferruginol, and chamaecydin were the major characteristic markers for the Taxodioideae conifer subfamily. The mass spectrometric data can aid polar compound elucidation in environmental, geological, archeological, forensic and pharmaceutical studies. [ABSTRACT FROM AUTHOR]

The environmental fate of conifer resins and their natural product compounds as mixtures is of importance for source, alteration, and transport studies. The compound compositions of resins of the common Callitris species (Cupressaceae) based on gas chromatography-mass spectrometry have not been reported. Results show that diterpenoids were the most abundant components and callitrisic acid was present in the resin extracts of all Callitris species analyzed. Significant amounts of 4-epi-pimaric and sandaracopimaric acids, with lesser communic, ozic, and lambertianic acids, were also in the mixtures. Phenolic diterpenoids, for example, ferruginol, hinokiol, were found in trace quantities in some samples. Thus, callitrisic acid and 4-epi-pimaric acid are the characteristic diterpenoids of Callitris species that are amenable to molecular biomarker analyses in geological or environmental applications. [ABSTRACT FROM AUTHOR]

Saccharides are omnipresent compounds in terrestrial and marine ecosystems. Since the 2000s, their role in environmental and geochemical studies has significantly increased, but only anhydrosaccharides (mainly levoglucosan) have been reviewed. Here we present the wider knowledge about saccharides in organic matter of aerosols, bottom sediments, soils, dust, and sedimentary rocks. The main purpose here is to characterize the possible sources of saccharides, as well as sacharol formation, seasonal variability, and the possible applications in environmental and paleoenvironmental interpretations. Different saccharide sources were designated, including biomass burning, and particulate matter such as pollen, spores, lichen, and fungi, as well as polysaccharide decomposition as possible inputs of monosaccharides. The main focus was on the most common saccharides encountered in environmental samples and sedimentary rocks. These are the mono- and disaccharides glucose, fructose, sucrose, and trehalose, and sacharols arabitol and mannitol. The anhydrosaccharides levoglucosan, mannosan, and galactosan were evaluated as ancient wildfire indicators and industrialization tracers found in lacustrine sediments starting from Pleistocene to contemporary deposits. However, other anhydrosaccharides like xylosan and arabinosan were also found as products of fossil wood burning. These anhydrosaccharides have the potential to be further tracers of hemicellulose burning. Additional recommendations are proposed for future research, including environmental and paleoenvironmental topics that need to be addressed., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Levoglucosan, a product from thermal decomposition of cellulose, is widely known as an organic tracer of biomass burning, but has also been reported from coal smoke particulate matter (PM) including lignites. This study provides direct evidence that levoglucosan is generated not only during low-temperature burning/smoldering of xylite, but also from other lignite types including detritic and detroxylitic brown coals from Poland. Moreover, only trace amounts of mannosan and galactosan have been detected in PM of lignite smoke. The hopanes in lignite smoke PM comprise the thermodynamically unstable ββ-hopanes and hopenes, with values of the homohopane index 22S/(22S + 22R) ranging from 0.02 to 0.12. This is characteristic for immature organic matter, and combined with the presence of anhydrosaccharides can be used as tracers for lignite combustion in ambient air. Furthermore, almost all Miocene lignite smoke PM samples contain α-, β-, γ-, and δ-tocopherols, and prist-1-ene. This is the first report of the occurrence of all four tocopherol isomers in the geological record (in lignite extracts) and in lignite smoke PM samples. Lower α-tocopherol is observed for the lignite burn-test samples than in the corresponding lignite extracts, probably due to partial chain degradation to prist-1-ene during combustion., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Extracts of bled resin from Azorella compacta , of the Azorelloideae family from the Andes (>4000 m), were analyzed by gas chromatography-mass spectrometry. The mass spectra of the dominant compounds of the resin and its hydrogenation products were documented. The most abundant compounds were oxygenated diterpenoids, namely mulinadien-20-oic (Δ 11,13 and Δ 11,14 ) acids, azorell-13-en-20-oic acid, 13α,14β-dihydroxymulin-11-en-20-oic acid, and azorellanol, with a group of azorellenes and mulinadienes. The mass spectra of the novel diterpenoid hydrocarbons with the azorellane and mulinane skeletons were also presented. This study documents the molecular diversity of these diterpenoid classes, and could be of great utility for future organic geochemical, environmental, archeological, pharmaceutical, and forensic chemistry studies.

Propolis is a gummy material made by honeybees for protecting their hives from bacteria and fungi. The main objective of this study is to determine the chemical compositions and concentrations of organic compounds in the extractable organic matter (EOM) of propolis samples collected from four different regions in Yemen. The propolis samples were extracted with a mixture of dichloromethane and methanol and analyzed by gas chromatography-mass spectrometry (GC-MS). The results showed that the total extract yields ranged from 34% to 67% (mean = 55.5 ± 12.4%). The major compounds were triterpenoids (254 ± 188 mg g -1 , mainly α-, β-amyryl and dammaradienyl acetates), n-alkenes (145 ± 89 mg g -1 ), n-alkanes (65 ± 29 mg g -1 ), n-alkanoic acids (40 ± 26 mg g -1 ), long chain wax esters (38 ± 25 mg g -1 ), n-alkanols (8 ± 3 mg g -1 ) and methyl n-alkanoates (6 ± 4 mg g -1 ). The variation in the propolis chemical compositions is apparently related to the different plant sources. The compounds of these propolis samples indicate that they are potential sources of natural bio-active compounds for biological and pharmacological applications.

Soil particles contain a variety of natural and anthropogenic organic components, and in urban areas can be considered as local collectors of pollutants. Surface soil samples were taken from ten urban areas in Riyadh during early winter of 2007. They were extracted with dichloromethane-methanol mixture and the extracts were analyzed by gas chromatography-mass spectrometry. The major compounds were unresolved complex mixture (UCM), plasticizers, n-alkanes, carbohydrates, n-alkanoic acids, hopanes, n-alkanols, and sterols. Vegetation detritus was the major natural source of organic compounds (24.0 ± 15.7%) in samples from areas with less human activities and included n-alkanes, n-alkanoic acids, n-alkanols, sterols and carbohydrates. Vehicular emission products and discarded plastics were the major anthropogenic sources in the soil particles (53.3 ± 21.3% and 22.7 ± 10.7%, respectively). The anthropogenic tracers were UCM, plasticizers, n-alkanes, hopanes and traces of steranes. Vegetation and human activities control the occurrence and distribution of natural and anthropogenic extractable organic matter in this arid urban area., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

A series of mono-methylalkanes (MMAs) with carbon numbers from C10 to C23 and C29 were detected in freshwater wetlands of the Everglades. A decrease in concentration and molecular complexity was observed in the order from periphyton and floc, to surface soil and deeper soil horizons. These compounds were present in varying amounts up to 27 μg gdw(-1) in periphyton, 74 μg gdw(-1) in floc, 1.8 μg gdw(-1) in surface soil, <0.03 μg gdw(-1) in deeper soils (12-15 cm). A total of 46 MMAs, including three iso and three anteiso-alkanes, were identified. Compound specific carbon isotopes values were determined for some dominant MMAs, and suggest that they originate from microbial sources, including cyanobacteria. Potential decarboxylation from fatty acids could also potentially contribute to the MMAs detected. Early diagenetic degradation was suggested to affect the accumulation of MMAs in soils and further studies are needed to address their applications as biomarkers., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The reactivity of higher plant derived 3-oxy-triterpenoids to sunlight was investigated using a series of pure reference standards both under simulated and real solar exposure. The majority of the exposed compounds showed reactivity to light, particularly to simulated sunlight and among others generated seco-derivatives. While photochemical processes have been suggested for the formation of such compounds, their abundances in some sediments have often been assumed to be the result of diagenetic reworking of parent triterpenoids. Analyses of mangrove leaf waxes, an important known source of taraxerol in coastal ecosystems, showed the presence of the 3,4-seco-derivative dihydrolacunosic acid, which could represent an important biotic source for des-A-triterpenoid precursors to such sediments, and is unrelated to aquatic organic matter diagenesis.

A high abundance of isoprenoid hydrocarbons, the botryococcenes, with carbon numbers from 32 to 34 were detected in the Florida Everglades freshwater wetlands. These compounds were present in varying amounts up to 106microg/gdw in periphyton, 278microg/gdw in floc, and 46microg/gdw in soils. Their structures were determined based on comparison to standards, interpretation of their mass spectra and those of their hydrogenation products, and comparison of Kovats indexes to those reported in the literature. A total of 26 cyclic and acyclic botryococcenes with 8 skeletons were identified, including those with fewer degrees of unsaturation, which are proposed as early diagenetic derivatives from the natural products. This is the first report that botryococcenes occur in the Everglades freshwater wetlands. Their potential biogenetic sources from green algae and cyanobacteria were examined, but neither contained botryococcenes. Thus, the source implication of botryococcenes in this ecosystem needs further study.

The relationship among sugar concentrations, microbial community and physical variables (precipitation and soil temperature) was investigated in a ryegrass soil from January 2004 to January 2005. Mono- and disaccharide sugars were extracted using a mixture of dichloromethane and methanol and analyzed as their TMS derivatives by GC-MS. Changes in microbial community were assessed using phospholipid and neutral lipid fatty acids (PLFA and NLFA, respectively) analysis. The results of a one-year study showed that the seasonal variability of sugar contents found in the soil samples is mainly related to biomass or nutritional status of the fungal community. The increase in sucrose and fructose exudation by plant roots in the beginning of the growing season (early spring) may be responsible for the highest fungal biomass amount (PLFAs) observed in this study. Fungal storage lipid abundances (NLFAs) peaked in summer, during the same period that the highest concentrations of mannitol and trehalose were detected. This is consistent with these two sugars being stress-induced fungal metabolites, produced due to the low soil moisture observed during this season. In contrast, bacterial community growth seems to be more dependent on plant substrate than on physical variables, since the strongest decrease in bacterial biomass amounts (PLFAs) was found after cutting of the ryegrass field in early July.