Terpenoids of the Swamp Cypress Subfamily (Taxodioideae), Cupressaceae, an Overview by GC-MS.

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.

Mulinane and Azorellane Diterpenoid Biomarkers by GC-MS from a Representative Apiaceae (Umbelliferae) Species of the Andes.

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 (Δ11,13 and Δ11,14) acids, azorell-13-en-20-oic acid, 13α,14ß-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.

Terpenoid Compositions of Resins from Callitris Species (Cupressaceae).

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.

Enterolactone and other lignan metabolites as taxon-specific markers in modern and ancient woodrat middens.

Diversely sourced degradation products of higher plant lignans were identified in modern and ancient woodrat (Neotoma) middens. The markers indicate extensive chemical modification by intestinal microbial communities of mammals. The observed defunctionalized phenols represent a group of natural products, and their structural elements reveal information about the plant source. The phenols are derived mainly from two precursor types: (1) enterolactone and derivatives from conifer lignans, and (2) 2,3-bis(3'-hydroxybenzyl)butane and related compounds from lignans such as nordihydroguaiaretic acid common in Larrea sp. (e.g. creosote bush).

Solvent-extractable polycyclic aromatic hydrocarbons in biochar: influence of pyrolysis temperature and feedstock.

Despite the increasing agricultural use of biochar as a way of combining the utilization of biomass for energy production with the removal of CO(2) from the atmosphere, it is not known how variations in pyrolysis temperature and feedstock type affect concentration and composition of polycyclic aromatic hydrocarbons (PAHs) that inevitably form and associate with biochar. To close this knowledge gap, we quantified 11 unsubstituted three- to five-ring PAHs as well as alkylated forms of phenanthrene and anthracene in grass and wood chars produced in 100 °C increments across a temperature range (100 to 700 °C). Our results show that solvent-extractable PAH concentrations in biochars produced at heat treatment temperatures (HTTs) of 400 and 500 °C greatly exceed those observed at higher and lower temperature, supporting a low HTT solid-phase formation mechanism operable at temperatures commonly used for industrial biochar production. The maximum extractable yield of 'pyrolytic' unsubstituted PAHs for grass (22 µg g(-1) at HTT = 500 °C) greatly exceeds the value for wood (5.9 µg g(-1)). Moreover, PAH signatures (e.g., total monomethylphenanthrene to phenanthrene ratios, MP/P ~2-3) at intermediate temperatures (400 °C) resemble those of fossil oils rather than that commonly attributed to pyrolytic products. Further research is needed to characterize the PAH evolution in modern pyrolysis reactors and assess the fate of biochar-bound PAHs in soils and sediments. Various commonly applied PAH ratios and indicator compounds show promise as markers for specific feedstock materials and pyrolysis conditions of biochars in environmental systems.

Distributions and sources of polycyclic aromatic hydrocarbons in surface sediments from the Cross River estuary, S.E. Niger Delta, Nigeria.

Polycyclic aromatic hydrocarbon (PAH) analyses of surface sediments from the Cross River estuary by gas chromatography-mass spectrometry indicated natural diagenetically derived PAHs in the upper estuary, with minor and variable amounts of petrogenic and combustion-derived PAHs from human activities (lower estuary). The occurrence of significant amounts of perylene (average 23% of all PAHs) with the diagenetic natural PAHs in the middle estuary bordered by mangrove forests supports its origin from terrestrial organic matter. The natural PAHs represent the highest percentage (average 76%) of the total PAHs in this tropical environment. The traditional geochemical parameters, including the petrogenic PAHs, confirmed trace petroleum contamination in the estuary. Specific PAH ratios such as Fl/Py and Fl/(Fl+Py) also support this source contribution.

Saccharides in atmospheric particulate and sedimentary organic matter: Status overview and future perspectives.

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.

Polycyclic aromatic hydrocarbons in coastal sediments of Southern Terengganu, South China Sea, Malaysia: source assessment using diagnostic ratios and multivariate statistic.

Surface sediments along the Southern Terengganu coast (≤7 km from the coast) were analyzed for polycyclic aromatic hydrocarbons (PAHs). The concentrations of 16 USEPA priority polycyclic aromatic hydrocarbons (ΣPAH16) ranged from 2.59 to 155 ng g-1 and their respective alkylated ranged between 8.80 and 24.90 ng g-1. Traces of acephenanthrylene, benzo[c]phenanthrene, thiophenic PAH, and benzonaphthofuran were identified. PAH diagnostic ratios and cross-plots revealed that these sedimentary PAH compounds are derived mainly from pyrogenic sources, primarily from biomass burning and petroleum combustion residues with minor petrogenic input. The high correlations between pyrogenic PAHs to total PAHs (r >0.73, p <0.5), and the Bap/Bep ratio to total PAHs (r = 0.88, p <0.5), suggest that atmospheric deposition and urban runoff are the main deposition pathways. The concentrations of the PAHs in the southern South China Sea fall in the moderate contamination range of 100-1000 ng g-1.

High concentrations of HgS, MeHg and toxic gas emissions in thermally affected waste dumps from hard coal mining in Poland.

This study aims to provide numerous environmental research approaches to understand the formation of mineral and organic mercury compounds in self-heating coal waste dumps of the Upper Silesian Coal Basin (USCB). The results are combined with environmental and health risk assessments. The mineralogy comprised accessory minerals in the fine fraction of thermally affected waste, i.e., Hg sulfides, most likely cinnabar or metacinnabar. Moreover, other metals, e.g., Pb, Zn and Cu, were found as sulfide forms. Apart from Hg, the ICP-ES/MS data confirmed the high content of Mn, Zn, Pb, Hg, Cr and Ba in these wastes. The high concentration of available Hg resulted in elevated MeHg concentrations in the dumps. There were no correlations or trends between MeHg concentrations and elemental Hg, TS, TOC, and pH. Furthermore, we did not detect microbial genes responsible for Hg methylation. The organic compounds identified in waste and emitted gases, such as organic acids, or free methyl radicals, common in such burn environments, could be responsible for the formation of MeHg. The concentration levels of gases, e.g., benzene, formaldehyde, NH3, emitted by the vents, reached or surpassed acceptable levels numerous times. The potential ecological and human health risks of these dumps were moderate to very high due to the significant influence of the high Hg concentrations.

Composition of organic compounds from low-temperature burning of lignite and their application as tracers in ambient air.

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 ßß-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-, ß-, 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.

Variations in δ13C values of levoglucosan from low-temperature burning of lignite and biomass.

Levoglucosan, an anhydrosaccharide, is commonly used as an organic tracer for biomass burning, but has also been identified from coal smoke particulate matter (PM) including lignites. Here we showed that stable carbon isotope analysis specifically of levoglucosan may be one possible way to determine the relative contributions from coal combustion versus biomass burning sources. PM samples were collected from low-temperature burning/smoldering of Miocene lignites from Poland and basket willow (Salix viminalis L.) representative of biomass. The calculated levoglucosan δ13C values of xylites varied from -23.6 to -21.6‰, while for detritic coal samples they ranged from -24.2 to -23.1‰, with means of -22.7 and -23.7‰, respectively. The calculated levoglucosan δ13C value of basket willow wood was -27.1‰. Values of willow wood mixtures with xylite varied from -25.8 to -23.4‰ (with an increasing proportion of xylite), while values of mixtures of willow and detritic coal ranged from -26.9 to -24.6‰ (with an increasing proportion of detritic coal). The δ13C values for the mixtures changed proportionally to the contents of individual components with R2 = 0.88 and 0.89 for willow with xylite and detritic coal, respectively. The hopanoid distributions characteristic for low-temperature lignite/peat burning, with a predominance of 22R-α,ß-homohopane, ßß-hopanes and hopenes, as well as low or very low values of the homohopane index, were observed in smoke PM from most lignite samples and absent in the basket willow sample. Thus, the relatively high content of hopanes (with the occurrence of 22R-α,ß-homohopane, ßß-hopanes and hopenes) in atmospheric PM samples can be treated as additional tracers of lignite combustion.

Input of organic matter in Brunei Bay, East Malaysia, as indicated by sedimentary steroids and multivariate statistics.

Brunei Bay is one of the most important marine environments of East Malaysia (South China Sea), covering many productive ecosystems with activities including fisheries, tourism, and main shipping lanes for petroleum transfers. Evaluation of the sources and distributions of steroids in the surface sedimentary organic matter was carried out by gas chromatography-mass spectrometry (GC-MS). The concentrations of the total identified sterols (TIS) ranged between 0.81 and 12.69 µg g-1 dry weight, and the total sterones were between 0.11 and 5.66 µg g-1 dry weight. The coprostanol level was comparatively low (<0.10 µg g-1), and the multi-biomarker proxies indicated that the region did not exhibit significant contamination from sewage effluents. Principal component analysis (PCA) revealed the coastal environment of the study area was dominated by allochthonous (mainly terrestrial) organic matter input.

Triterpenoids as major components of the insect-trapping glue of Roridula species.

Roridula dentata and R. gorgonias, two South African plants that were formerly believed to be carnivorous, exhibit an extremely sticky exudate at the tips of secretory trichomes. Unlike the trapping mucilage of Droseraceae, it does not consist of acidic polysaccharides. The Roridula trapping glue was found to be a mutual solution of mainly dihydroxytriterpenoids, instead. All samples contain two isomers of ring A dihydroxyolean-12-enes and dihydroxyurs-12-enes. The difference between the two species is the additional presence of taraxeradiol in the glue of R. gorgonias. The absolute chemical structures of the reported triterpenoids still need confirmation.

Environmental factors controlling the distributions of Botryococcus braunii (A, B and L) biomarkers in a subtropical freshwater wetland.

Here we report the molecular biomarker co-occurrence of three different races of Botryococcus braunii (B. braunii) in the freshwater wetland ecosystem of the Florida Everglades, USA. Thespecific biomarkers include C32-C34 botryococcenes for race B, C27-C32 n-alkadienes and n-alkatrienes for race A, and lycopadiene for race L. The n-alkadienes and n-alkatrienes were present up to 3.1 and 69.5 µg/g dry weight (dw), while lycopadiene was detected in lower amounts up to 3.0 and 1.5 µg/g dw in periphyton and floc samples, respectively. Nutrient concentrations (P and N) did not significantly correlate with the abundances of these compounds. In contrast, n-alkadienes and n-alkatrienes were present in wider diversity and higher abundance in the floc from slough (deeper water and longer hydroperiod) than ridge (shallower water and shorter hydroperiod) locations. n-Alkadienes, n-alkatrienes, and lycopadiene, showed lower δ13C values from -40.0 to -35.5‰, suggesting that the source organisms B. braunii at least partially utilize recycled CO2 (13C depleted) produced from OM respiration rather than atmospheric CO2 (13C enriched) as the major carbon sources.

Analysis of sugars in environmental samples by gas chromatography-mass spectrometry.

Many environmental samples contain complex mixtures of organic compounds with different sources, polarities and reactivities. This study reports a method for the analysis of both polar/water-soluble and apolar organic compounds in several kinds of environmental samples. The analytical method consists of extraction with a mixture of dichloromethane:methanol (2:1, v/v), silylation using BSTFA (N,O-bis-(trimethylsilyl)trifluoroacetamide) and analysis by gas chromatography-mass spectrometry (GC-MS), a common device in chemical and environmental laboratories. Fifty individual sugar standards, including monosaccharides, sugar alcohols, anhydrosugars, disaccharides and trisaccharides, were analyzed for the determination of their fragmentation patterns and retention times. Recoveries (at three concentrations) and limits of detection (LOD) were determined for a standard mixture containing glucose (monosaccharide), sorbitol (sugar alcohol), levoglucosan (anhydrosugar) and sucrose (disaccharide), and they varied from 68 to 119% and 130 to 360 ng mL(-1), respectively. The method was used for the analysis of aerosol particle, soil and sediment samples, and demonstrated its feasibility in detecting not only several important environmental sugars (e.g., glucose, fructose, inositol, mannitol, sorbitol, levoglucosan, sucrose, mycose), but also a large range of organic compound classes from other polar components (e.g., dicarboxylic acids) to apolar compounds such as n-alkanes. Therefore, the analytical method presented here demonstrated its usefulness for a better understanding of sources and transport of various organic compounds in different environmental compartments.

Occurrence and distribution of novel botryococcene hydrocarbons in freshwater wetlands of the Florida Everglades.

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 Potential of Alkyl Amides as Novel Biomarkers and Their Application to Paleocultural Deposits in China.

A series of alkyl amides was detected and identified in the sedimentary record from an archaeological site at Yuchisi, Mengcheng, Anhui, China. The alkyl amides profiles change abruptly at the depth corresponding to the transition between two prehistoric cultures, which also corresponds to an abrupt change in the fatty acid ratio C18:2/C18:0. The different patterns of variation of the longer and shorter chain alkyl amides at the depth of the cultural transition may reflect differences in their response to external environmental changes, as well as different sources. This is the first study of the stratigraphic variation of alkyl amides in sediments, and their first application to assess paleoenvironmental changes. We suggest that alkyl amides may have potential as new biomarkers in archeological and paleoenvironmental studies.

Chemical compositions and characteristics of organic compounds in propolis from Yemen.

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-, ß-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.

Natural product biomarkers as indicators of sources and transport of sedimentary organic matter in a subtropical river.

The sources and transformations of sedimentary organic matter along the Harney River, a representative subtropical river of the Florida Everglades, were assessed using a natural product biomarker approach. Sediment samples were collected from the headwaters to the Continental Shelf, with characteristic vegetation dominated by freshwater marsh species, mangrove (middle to lower estuary), and seagrass as the marine end-member. A peat sample was collected inland. All sample extracts were analyzed by GC-MS as underivatized and as silylated compounds. With these total extract analyses, major compound classes can be defined: n-alkanols, n-alkanoic acids, methyl alkanoates, methyl alpha- and omega-hydroxyalkanoates, triterpenoids, phytosterols and saccharides, with traces of hydrocarbons. In general, the peat sample extract has a different overall composition compared to the sediment extracts. The major differences include distinct carbon number maxima for the lipid series (e.g., C(max)=28 for n-alkanols) probably from sawgrass and periphyton biomass, and predominance of phytosterols (sitosterol and stigmasterol) from higher plant detritus. In contrast, river sediment extracts contain biomarkers predominantly from mangrove-derived organic matter, such as the triterpenoids taraxerol and myricadiol. Significant amounts of saccharides and omega-hydroxyalkanoates are also found. Generally, compound concentrations decrease downstream due to dilution, and alteration of organic compounds from plant waxes and coastal vegetation is obvious in both peat and sediment samples. This is confirmed by the significant low abundance of n-alkanes and n-alkenoic acids due to biodegradation, oxidation of alpha-tocopherol to homophytanic acid gamma-lactone, and presence of traces of dihydrolacunosic acid, a photochemical alteration product of taraxerol.

Seasonal variations in sugar contents and microbial community in a ryegrass soil.

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.