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.

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.

A mass budget of polybrominated diphenyl ethers in San Francisco Bay, CA.

A mass budget of polybrominated diphenyl ethers (PBDEs) in San Francisco Bay is developed as a first step towards understanding the local sources and transport processes controlling PBDE fate in a highly urbanized estuary. Extensive monitoring of PBDEs in estuarine water and sediment, freshwater tributaries, air, and wastewater effluents and sludges were integrated with a mass budget model to provide a synthetic view of these emerging contaminants. The Bay inventories of BDE 47 and BDE 209 in 2006 were estimated to be 33+/-3 kg and 153+/-45 kg, respectively. Empirically derived estimates of annual inputs of BDE 47 and BDE 209 from all quantifiable external sources ranged from 11 to 28 kg/y and 22 to 24 kg/y, respectively. BDE 47 loads were dominated by wastewater while runoff from local tributaries represented the largest contributor to BDE 209 loads. Model results suggest the Bay PBDE inventory is highly sensitive to changes in external loads, with degradation and outflow being the major processes governing PBDE fate. The mass budget presented provides a framework for integrating future monitoring and modeling efforts.

Pyrethroids, pyrethrins, and piperonyl butoxide in sediments by high-resolution gas chromatography/high-resolution mass spectrometry.

A new method for determination of pyrethroids, pyrethrins, and piperonyl butoxide (PBO) by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) was developed for aquatic sediments. The method detection limits for pyrethroids (15 compounds), pyrethrins, and PBO ranged from 0.16 to 1.50 ng/g sediment, which was suitable for detecting these chemicals at environmentally relevant concentrations (low ng/L range) that are toxicologically significant to benthic organisms. Recovery of the analytes from a low level spiked sediment ranged from 89.7% to 135%. Resmethrin showed the lowest recovery at 23.5% and pyrethrins showed the highest recovery at 154%. To confirm the utility of this new method for environmental applications, sediment samples collected from five tributaries of the San Francisco Bay, California were analyzed. Individual pyrethroids were detected in concentrations of up to 17.6 ng/g, while PBO was detected in all sediment samples in concentrations of 0.010-0.215 ng/g. Pyrethrins were not found in the sediment samples.

Polycyclic aromatic hydrocarbons in bivalves from the San Francisco estuary: Spatial distributions, temporal trends, and sources (1993-2001).

Bivalve tissue samples were examined over a range of spatial and temporal scales (1993-2001) to determine PAH distributions, trends, and possible sources. Mussels (Mytilus californianus), oysters (Crassostrea gigas), and clams (Corbicula fluminea) were deployed for three months in the estuary at stations remote from known point source discharges. The range of summation operatorPAH detected in bivalves was oysters 184-6899 microg/kg dry wt (mean 678 microg/kg dry wt), mussels 21-1093 microg/kg dry wt (mean 175 microg/kg dry wt), and clams 78-720 microg/kg dry wt (mean 323 microg/kg dry wt). Linear regression analysis showed no statistically significant (p>0.05) temporal trends in clam and mussel summation operatorPAH at any of the deployment stations or estuary segments. On the other hand, a statistically significant (p<0.05) decreasing trend was found in summation operatorPAH in oysters at the Petaluma River station, and in the North Estuary segment. PAH isomer pair ratios applied as diagnostic indicators suggested that the bioaccumulated PAH were derived primarily from petroleum combustion, with lesser amounts derived from biomass and coal combustion, and unburned petroleum.

Polycyclic aromatic hydrocarbons in the San Francisco Estuary water column: sources, spatial distributions, and temporal trends (1993-2001).

The composition of PAH in surface waters was examined over a range of spatial and temporal scales to determine distributions, trends, and possible sources. Water samples were collected from 1993 to 2001. PAH in organic extracts were analyzed by gas chromatography-mass spectrometry (GC-MS) and 25 individual target PAH summed to get the total PAH concentration in each water sample. The distribution of median total PAH concentration by estuary segments was Extreme South Bay (120 ng l(-1)) > South Bay (49 ng l(-1)) > North Estuary (29 ng l(-1)) > Central Bay (12 ng l(-1)) > Delta (7 ng l(-1)). Overall, total PAH concentrations were significantly higher in the Extreme South Bay compared to all other segments, and the Central Bay and Delta were significantly lower than all other segments (Kruskal-Wallis, H = 157.27, df = 4, p < 0.0005). This distribution reflects the large urbanized and industrialized areas that border the southern portions of the estuary and the less populated and rural areas that surround the Delta. Temporal trend analysis showed a statistically significant temporal trend in total PAH concentration at only one of the 18 sampling stations situated throughout the estuary (San Jose, significant decrease, p = 0.031, r(2) = 0.386, n = 12). PAH isomer pair ratio analysis showed that PAH in estuary waters were derived primarily from combustion of fossil fuels/petroleum (possible PAH source contributors include coal, gasoline, kerosene, diesel, No. 2 fuel oil, and crude oil) and biomass (possible contributors include wood and grasses), with lesser amounts of PAH contributed from direct petroleum input.

Biomass burning as the main source of organic aerosol particulate matter in Malaysia during haze episodes.

The haze episodes that occurred in Malaysia in September-October 1991, August-October 1994 and September-October 1997 have been attributed to suspended smoke particulate matter from biomass burning in southern Sumatra and Kalimantan, Indonesia. In the present study, polar organic compounds in aerosol particulate matter from Malaysia are converted to their trimethylsilyl derivatives and analyzed by gas chromatography-mass spectrometry in order to better assess the contribution of the biomass burning component during the haze episodes. On the basis of this analysis, levoglucosan was found to be the most abundant organic compound detected in almost all samples. The monosaccharides, alpha- and beta-mannose, the lignin breakdown products, vanillic and syringic acids and the minor steroids, cholesterol and beta-sitosterol were also present in some samples. The presence of the tracers from smoke overwhelmed the typical signatures of emissions from traffic and other anthropogenic activities in the urban areas.

Surveillance for previously unmonitored organic contaminants in the San Francisco Estuary.

The San Francisco Estuary Regional Monitoring Program initiated surveillance monitoring to identify previously unmonitored synthetic organic contaminants in the San Francisco Estuary. Organic extracts of water samples were analyzed using gas chromatography-mass spectrometry in full scan mode. The major contaminant classes identified in the samples were fire retardants, pesticides, personal care product ingredients, and plasticizers. Evidence from the literature suggests that some of these contaminants can persist in the environment, induce toxicity, and accumulate in marine biota and in higher food chain consumers. The major sources of these contaminants into the marine environment are the discharge of municipal and industrial wastewater effluents, urban stormwater, and agricultural runoff. As a proactive effort, it is suggested that surveillance studies be used routinely in monitoring programs to identify and prevent potential problem contaminants from harming the marine environment.

Occurrence and sources of triterpenoid methyl ethers and acetates in sediments of the cross-river system, southeast Nigeria.

Pentacyclic triterpenol methyl ethers (PTMEs), germanicol methyl ether (miliacin), 3-methoxyfern-9(11)-ene (arundoin), beta-amyrin methyl ether (iso-sawamilletin), and 3-methoxytaraxer-14-ene (sawamilletin or crusgallin) were characterized in surface sediments of the Cross-River system using gas chromatography-mass spectrometry (GC-MS). Triterpenol esters (mainly alpha- and beta-amyrinyl acetates and hexanoates, and lupeyl acetate and hexanoate) were also found. These distinct compounds are useful for assessing diagenesis that can occur during river transport of organic detritus. Poaceae, mainly Gramineae and Elaeis guineensis higher plant species, are proposed as primary sources for the PTMEs and esters in the sediments. PTMEs are biomarkers of specific higher plant subspecies, while the triterpenol esters are indicators of early diagenetic alteration of higher plant detritus.

Adapting an ambient monitoring program to the challenge of managing emerging pollutants in the San Francisco Estuary.

While over seven million organic and inorganic compounds that have been indexed by the American Chemical Society's Chemical Abstracts Service in their CAS Registry are commercially available, most pollution monitoring programs focus only on those chemical stressors for which regulatory benchmarks exist, and have been traditionally considered responsible for the most significant human and environmental health risks. Until the late 1990s, the San Francisco Estuary Regional Monitoring Program was no exception in that regard. After a thorough external review, the monitoring program responded to the need for developing a pro-active surveillance approach for emerging pollutants in recognition of the fact that the potential for the growing list of widely used chemical compounds to alter the integrity of water is high. We describe (1) the scientific and analytical bases underlying a new surveillance monitoring approach; (2) summarize approaches used and results obtained from a forensic retrospective; (3) present the growing data set on emerging pollutants from surveillance monitoring and related efforts in the San Francisco Bay Area to characterize newly targeted compounds in wastewater streams, sediment, storm water runoff, and biota; and (4) suggest next steps in monitoring program development and applied research that could move beyond traditional approaches of pollutant characterization. Based on the forensic analysis of archived chromatograms and chemical and toxicological properties of candidate compounds, we quantified a variety of synthetic organic compounds which had previously not been targeted for analysis. Flame retardant compounds, pesticides and insecticide synergists, insect repellents, pharmaceuticals, personal care product ingredients, plasticizers, non-ionic surfactants, and other manufacturing ingredients were detected in water, sediment, and/or biological tissue samples. Several of these compounds, especially polybrominated diphenyl ether flame retardants, exhibited concentrations of environmental concern. We also describe environmental management challenges associated with emerging pollutants and how pro-active surveillance monitoring might assist in implementing a more holistic approach to pollution prevention and control before emerging pollutants become a burden on future generations.

Polycyclic aromatic hydrocarbon (PAH) contamination in San Francisco Bay: a 10-year retrospective of monitoring in an urbanized estuary.

Polycyclic aromatic hydrocarbons (PAH) are widespread contaminants in the San Francisco Bay. Several exceedances of water quality criteria raise the possibility that PAH may be impacting aquatic biota. The Regional Monitoring Program for Water Quality in the San Francisco Estuary (RMP) has collected annual monitoring data on PAH in the Bay since 1993. Analysis of Bay water, sediment, and mussel SigmaPAH concentration data showed that there were very few significant (P < 0.05) increasing or decreasing temporal trends in SigmaPAH concentrations in the Bay during the period of 1993-2001. Wet and dry season input of PAH did not show any major influence on water SigmaPAH concentrations over the same period. Based on their relative contribution to the estimated total maximum PAH loading (10,700 kg/yr) into the Bay, the PAH loading pathways are ranked as storm water runoff ( approximately 51%) >tributary inflow ( approximately 28%) >wastewater treatment plant effluent ( approximately 10%) >atmospheric deposition ( approximately 8%) >dredged material disposal ( approximately 2%). The PAH sediment quality threshold of 1000 ng/g, which has been previously suggested by NOAA to protect estuarine fish such as English sole against adverse health effects, was frequently exceeded at individual monitoring stations (11 of the 26 stations exceeded the threshold over 50% of the time). Modeling results have shown that the predominant loss pathway for PAH is degradation in sediments, and unless external loading levels of PAH are controlled, the Bay is not expected to recover rapidly.

Phenols and hydroxy-PAHs (arylphenols) as tracers for coal smoke particulate matter: source tests and ambient aerosol assessments.

Source tests were conducted to analyze and characterize diagnostic key tracers for emissions from burning of coals with various ranks. Ambient aerosol particulate matter was also collected in three areas of China and a background area in Corvallis, OR (U.S.) to confirm the presence of tracers specific for coal smoke. The results showed a series of aliphatic and aromatic hydrocarbons and phenolic compounds, including PAHs and hydroxy-PAHs as the major tracers, as well as a significant unresolved complex mixture (UCM) of compounds. The tracers that were found characteristic of coal combustion processes included hydroxy-PAHs and PAHs. Atmospheric ambient samples from Beijing and Taiyuan, cities where coal is burned in northern China, revealed that the hydroxy-PAH tracers were present during the wintertime, but not in cities where coal is not commonly used (e.g., Guangzhou, South China). Thus, the mass of hydroxy-PAHs can be apportioned to coal smoke and the source strength modeled by summing the proportional contents of EC (elemental carbon), PAHs, UCM and alkanes with the hydroxy-PAHs.

Levels and distribution of polybrominated diphenyl ethers in water, surface sediments, and bivalves from the San Francisco Estuary.

Polybrominated diphenyl ethers (PBDEs) were found in water, surface sediments, and bivalve samples that were collected from the San Francisco Estuary in 2002. sigmaPBDE concentrations in water samples ranged from 3 to 513 pg/ L, with the highest concentrations found in the Lower South Bay (range 103-513 pg/L) region, which receives approximately 26% of the Estuary's wastewater treatment plant effluents. The sigmaPBDEs in sediments ranged from below detection limits to 212 ng/g dry wt, with the highest concentration found at a South Bay station (212 ng/g dry wt), which was up to 3 orders of magnitude higher than other stations. The sigmaPBDE concentrations ranged from 9 to 64 ng/g dry wt in oysters (Crassostrea gigas), from 13 to 47 ng/g dry wt in mussels (Mytilus californianus), and from 85 to 106 ng/g dry wt in clams (Corbicula fluminea). Only three PBDE congeners were detected in bivalves, BDE-47, BDE-99, and BOE-100; these are the most bioaccumulative congeners from the commercial Penta-BDE mixture.