Pyrolysis-Gas Chromatography/Mass Spectrometry of Soil Organic Matter Extracted from a Brazilian Mangrove and Spanish Salt Marshes

The soil organic matter (SOM) extracted under different vegetation types from a Brazilian mangrove (Pai Matos Island, Sao Paulo State) and from three Spanish salt marshes (Betanzos Ria and Corrubedo Natural Parks, Galicia, and the Albufera Natural Park, Valencia) was investigated by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The chemical variation was larger in SOM from the Spanish marshes than in the SOM of the Brazilian mangroves, possibly because the marshes included sites with both tidal and nontidal variation, whereas the mangrove forest underwent just tidal variation. Thus, plant-derived organic matter was better preserved under permanently anoxic environments. Moreover, given the low number of studied profiles and sedimentary-vegetation sequences in both areas, depth trends remain unclear. The chemical data also allow distinction between the contributions of woody and nonwoody vegetation inputs. Soil organic matter decomposition was found to cause: (i) a decrease in lignin contents and a relative increase in aliphatics; (ii) an increase in short-chain aliphatics at the expense of longer ones; (iii) a loss of odd-over-even dominance in alkanes and alkenes; and (iv) an increase in microbial products, including proteins, sterols, short-chain fatty acids, and alkanes. Pyrolysis-gas chromatography/mass spectrometry is a useful tool to study the behavior and composition of SOM in wetland environments such as mangroves and salt marshes. Additional profiles need to be studied for each vegetation type, however, to improve the interpretability of the chemical data.

Natural antioxidants protecting irradiated beef burgers from lipid oxidation

The effect of butylated hydroxytoluene/butylated hydroxyanisole blend (BHT/BHA), and rosemary and oregano extracts, added individually or in combination, on lipid oxidation and fatty acid composition was investigated on irradiated frozen beef burgers. Irradiation treatment was carried out using a (60)CO semi-industrial irradiator at doses of 6, 7 and 8 kGy, and then the treated meat samples were stored at -20 degrees C for 90 days. Lipid oxidation and fatty acid composition of beef samples were evaluated by measurement of TBARS and gas chromatography, respectively. The results of the experiment showed that rosemary extract, applied alone and in combination with either BHT/BHA or oregano extracts was more effective in maintaining a low oxidation level in the samples compared to oregano extract used individually or in combination with BHT/BHA. Results also showed no significant differences (p > 0.05) in fatty acid composition in all analyzed samples, although some changes in terms of decreased PUFA and MUFA, beside of slight increase of SFA content were observed. However, these differences do not correlate positively neither with the irradiation dose nor the type of antioxidant. Thus, there is a potential application of these spices as natural antioxidants in irradiated meats. (C) 2009 Elsevier Ltd. All rights reserved.

Effects of natural antioxidants on the lipid profile of electron beam-irradiated beef burgers

The purpose of this study was to assess the efficacy of rosemary and oregano extracts in avoiding oxidative changes in beef burgers, and to evaluate the fatty acid profile of these products after electron beam exposition. Extracts, individually or in combination, were added to beef burgers and compared to synthetic antioxidants commonly used in food (butylated hydroxytoluene, butylated hydroxyanisole). The ground beef were submitted to electron beam irradiation at doses of 0, 3.5 and 7 kGy, and stored for 90 days. At regular time intervals, lipid oxidation and fatty acid composition were evaluated through measurement of thiobarbituric acid-reactive substances (TBARS) and gas chromatography, respectively. The results indicate that, although the irradiation process triggers an increase in the lipid oxidation ratio expressed by TBARS values, great changes in the fatty acid profiles were not observed; instead, they continued to present characteristics very similar to that of non-irradiated beef. Thus, as irradiation doses of up to 7 kGy for frozen meat can make foods safe from foodborne pathogens, natural antioxidants derived from spices are able to reduce and avoid lipid changes that may cause a deterioration of the sensory quality of these foods, and these natural extracts offer a good choice for replacing synthetic additives.

Nest temperature and respiratory gases during natural incubation in the broad-shelled river turtle, Chelodina expansa (Testudinata : Chelidae)

Temperature was monitored in three natural nests, and oxygen and carbon dioxide partial pressure monitored in one natural nest of the broad-shelled river turtle, Chelodina expansa, throughout incubation. Nest temperature decreased after nest construction in autumn, remained low during winter and gradually increased in spring to a maximum in summer. In a nest where temperature was recorded every hour, temperature typically fluctuated through a 2 degrees C cycle on a daily basis throughout the entire incubation period, and the nest always heated faster than it cooled. Oxygen and carbon dioxide partial pressures in this nest were similar to soil oxygen and carbon dioxide partial pressures for the first 5 months of incubation, but nest respiratory gas tensions deviated from the surrounding soil over the last three months of incubation. Nest respiratory gas tensions were not greatly different from those in the atmosphere above the ground except after periods of rain. After heavy rain during the last 3 months of incubation the nest became moderately hypoxic (P-O2 similar to 100 Torr) and hypercapnic (P-CO2 similar to 50 Torr) for several successive days. These short periods of hypoxia and hypercapnia were not lethal.

Factors controlling the origin of gas in Australian Bowen Basin coals

Open system pyrolysis (heating rate 10 degrees C/min) of coal maturity (vitrinite reflectance, VR) sequence (0.5%, 0.8% and 1.4% VR) demonstrates that there are two stages of thermogenic methane generation from Bowen Basin coals. The first and major stage shows a steady increase in methane generation maximising at 570 degrees C, corresponding to a VR of 2-2.5%. This is followed by a less intense methane generation which has not as yet maximised by 800 degrees C (equivalent to VR of 5%). Heavier (C2+) hydrocarbons are generated up to 570 degrees C after which only the C-1 (CH4, CO and CO2) gases are produced. The main phase of heavy hydrocarbon generation occurs between 420 and 510 degrees C. Over this temperature range,methane generation accounts for only a minor component, whereas the wet gases (C-2-C-5) are either in equal abundance or are more abundant by a factor of two than the liquid hydrocarbons. The yields of non-hydrocarbon gases CO2 and CO are greater then methane during the early stages of gas generation from an immature coal, subordinate to methane during the main phase of methane generation after which they are again dominant. Compositional data for desorbed and produced coal seam gases from the Bowen show that CO2 and wet gases are a minor component. This discrepancy between the proportion of wet gas components produced during open system pyrolysis and that observed in naturally matured coals may be the result of preferential migration of wet gas components, by dilution of methane generated during secondary cracking of bitumen, or kinetic effects associated with different activations for production of individual hydrocarbon gases. Extrapolation of results of artificial pyrolysis of the main organic components in coal to geological significant heating rates suggests that isotopically light methane to delta(13)C of -50 parts per thousand can be generated. Carbon isotope depletions in C-13 are further enhanced, however, as a result of trapping of gases over selected rank levels (instantaneous generation) which is a probable explanation for the range of delta(13)C values we have recorded in methane desorbed from Bowen Basin coals (-51 +/- 9 parts per thousand). Pervasive carbonate-rich veins in Bowen Basin coals are the product of magmatism-related hydrothermal activity. Furthermore, the pyrolysis results suggest an additional organic carbon source front CO2 released at any stage during the maturation history could mix in varying proportions with CO2 from the other sources. This interpretation is supported by C and O isotopic ratios, of carbonates that indicate mixing between magmatic and meteoric fluids. Also, the steep slope of the C and O isotope correlation trend suggests that the carbonates were deposited over a very narrow temperature interval basin-wide, or at relatively high temperatures (i.e., greater than 150 degrees C) where mineral-fluid oxygen isotope fractionations are small. These temperatures are high enough for catagenic production of methane and higher hydrocarbons from the coal and coal-derived bitumen. The results suggests that a combination of thermogenic generation of methane and thermodynamic processes associated with CH4/CO2 equilibria are the two most important factors that control the primary isotope and molecular composition of coal seam gases in the Bowen Basin. Biological process are regionally subordinate but may be locally significant. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

Gas-phase dissociation of 1,4-naphthoquinone derivative anions by electrospray ionization tandem mass spectrometry

Gas-phase dissociation pathways of deprotonated 1,4-naphthoquinone (NQ) derivatives have been investigated by electrospray ionization tandem mass spectrometry (ESI-MS/MS). The major decomposition routes have been elucidated on the basis of quantum chemical calculations at the B3LYP/6-31+G(d,p) level. Deprotonation sites have been indicated by analysis of natural charges and gas-phase acidity. NQ anions underwent an interesting reaction under collision-induced dissociation conditions, which resulted in the radical elimination of the lateral chain, in contrast with the even-electron rule. Possible pathways have been suggested, and their mechanisms have been elucidated on the basis of Gibbs energy and enthalpy values for the anions previously described at each pathway. Copyright (C) 2009 John Wiley & Sons, Ltd.

Natural abundance of stable carbon and nitrogen isotopes in Cannabis sativa reflects growth conditions

Stable carbon and nitrogen isotope signatures (delta C-13 and delta N-15) of Cannabis sativa were assessed for their usefulness to trace seized Cannabis leaves to the country of origin and to source crops by determining how isotope signatures relate to plant growth conditions. The isotopic composition of Cannabis examined here covered nearly the entire range of values reported for terrestrial C-3 plants. The delta C-13 values of Cannabis from Australia, Papua New Guinea and Thailand ranged from -36 to -25 parts per thousand, and delta N-15 values ranged from -1.0 to 15.8 parts per thousand. The stable isotope content did not allow differentiation between Cannabis originating from the three countries, but delta C-13 values of plantation-grown Cannabis differed between well-watered plants (average delta C-13 of -30.0 parts per thousand) and plants that had received little irrigation (average delta C-13 of -26.4 parts per thousand). Cannabis grown under controlled conditions had delta C-13 values of -32.6 and -30.6 parts per thousand with high and low water supply, respectively. These results indicate that water availability determines leaf C-13 in plants grown under similar conditions of light, temperature and air humidity. The delta C-13 values also distinguished between indoor- and outdoor-grown Cannabis; indoor- grown plants had overall more negative delta C-13 values (average -31.8 parts per thousand) than outdoor-grown plants (average -27.9 parts per thousand). Contributing to the strong C-13-depletion of indoor- grown plants may be high relative humidity, poor ventilation and recycling of C-13-depleted respired CO2. Mineral fertilizers had mostly lower delta N-15 values (-0.2 to 2.2 parts per thousand) than manure-based fertilizers (7.6 to 22.7 parts per thousand). It was possible to link delta N-15 values of fertilizers associated with a crop site to soil and plant delta N-15 values. The strong relationship between soil, fertilizer, and plant delta N-15 suggests that Cannabis delta N-15 is determined by the isotopic composition of the nitrogen source. The distinct delta N-15 values measured in Cannabis crops make delta N-15 an excellent tool for matching seized Cannabis with a source crop. A case study is presented that demonstrates how delta C-13 and delta N-15 values can be used as a forensic tool.

Diving behaviour of two Australian bimodally respiring turtles, Rheodytes leukops and Emydura macquarii, in a natural setting

Time-depth recorders were used to investigate the diving performance and behaviour of two bimodally respiring turtle species, Rheodytes leukops and Emydura niacquarii, known to have a high and low reliance on aquatic respiration, respectively. Significant differences in diving performance between R. leukops and E. macquarii were observed in the number of dives/day (39.3 +/- 5.38 vs 112.2 +/- 11.73 dives/day; mean +/- SE), mean dive length (33.1 +/- 7.33 min vs 9.6 +/- 2.26 min) and maximum dive length (623 +/- 104.74 min vs 67.1 +/- 8.14 min), respectively. Differences in diving performance between R. leukops and E macquarii are attributed to the species' reliance (or lack thereof) upon aquatic respiration. Rheodytes leukops displayed a weak bimodal pattern of increased surfacing frequency in the early morning (05:00-07:00) and late afternoon (14:00-18:00), while E. macquarii displayed a strong bimodal pattern of elevated surfacing frequency over similar time periods. Daily patterns of increased surfacing frequency for both species failed to correlate with fluctuating aquatic Po-2 levels or water temperature, and may instead be explained by the heightened activity levels of both species during twilight.

Geographic variation of natural products of tropical nudibranch Asteronotus cespitosus

Extracts of the dorid nudibranch Asteronotus cespitosus from two geographically separate regions of Australia and from the Philippines were compared using thin-layer, high-performance liquid and gas chromatography and H-1 NMR analysis. Halogenated metabolites were detected in all mollusk specimens. The major component detected in digestive tissue of specimens from the Great Barrier Reef in northeastern Australia was 4,6-dibromo2-(2',4'-dibromophenoxy)phenol (1), with minor amounts of 3,5-dibromo-2(3',5'-dibromo-20-methoxyphenoxy)phenol (2). In a specimen collected from northwestern Australia, only 3,5-dibromo-2-(3',5'-dibromo-2'-methoxyphenoxy)phenol was found. The specimen from the Philippines contained 2,3,4,5-tetrabromo-6-(2'-bromophenoxy) phenol (3) together with a novel chlorinated pyrrolidone (4). In addition, the sesquiterpenes dehydroherbadysidolide (5) and spirodysin (6) were detected in the digestive organs and mantle tissue of the nudibranchs from the Great Barrier Reef and from the Philippines, whereas these chemicals were not found in the specimen from northwestern Australia. All of the chemicals (1-3,5, and 6) have previously been isolated from the sponge Dysidea herbacea, as have chlorinated metabolites related to 4. This is the first time the characteristic halogenated metabolites that typify Dysidea herbacea have been reported from a carnivorous mollusk, which implies a dietary origin as opposed to de novo synthesis.

Sponge halogenated natural products found at parts-per-million levels in marine mammals

Several unknown, abundant brominated compounds (BCs) were recently detected in the blubber of dolphins and other marine mammals from Queensland (northeast Australia). The BC were interpreted as potential natural products due to the lack of anthropogenic sources for these compounds. This study investigated whether some of the BCs accumulated by diverse marine mammal species are identical with natural BCs previously isolated from sponges (Dysidea sp.) living in the same habitat. Isolates from sponges and mollusks (Asteronotus cespitosus) were compared with the signals detected in the mammals' tissue. Mass spectra and gas chromatography retention times on four different capillary columns of the isolates from sponges and mammals were identical in all respects. This proves that the chemical name of the compound previously labeled BC-2 is 4,6-dibromo-2-(2'-dibromo)phenoxyanisole and that the chemical name of BC-11 is 3,5-dibromo-2-(3',5'-dibromo-2'-methoxy)phenoxyanisole. Using a quantitative reference solution of BC-2, we established that the concentrations of the brominated metabolies found in the marine mammals are frequently >1 mg/kg. The highest concentration (3.8 mg/kg), found in a sample of pygmy sperm whale (Kogia breviceps), indicates that BC-2 is a bioaccumulative, natural organohalogen compound. This is supported by the concentrations of the BCs in our samples being equal to the highest concentrations of anthropogenic BCs in any environmental sample. The quantitative determination of BC-2 in blubber of marine mammals from Africa and the Antarctic suggests that BC-2 is wide-spread. These results are direct proof that marine biota can produce persistent organic chemicals that accumulate to substantial concentrations in higher trophic organisms.

Seasonal changes in the diving performance of the bimodally respiring freshwater turtle Rheodytes leukops in a natural setting

The objective of this study was to investigate how seasonally fluctuating environmental conditions influence the diving performance of the highly aquatic, bimodally respiring turtle Rheodytes leukops in a natural setting. Over four consecutive seasons (Austral autumn 2000 to summer 2001), the diving behaviour of adult turtles was recorded via pressure-sensitive time-depth recorders within Marlborough Creek, central Queensland, Australia. Short surfacing intervals recorded for R. leukops in winter suggest that the species utilizes aquatic respiration as an overwintering strategy to prevent the development of a metabolic acidosis during the long inactive dives observed during the season. As water temperature increases and aquatic P-O 2 decreases, R. leukops switches from facultative to obligate air-breathing, presumably because of the increased metabolic cost associated with aquatic respiration under summer conditions. Increases in mean surfacing time from winter to spring and summer are attributed to seasonal changes in behaviour possibly associated with foraging rather than to the physiological state of the turtle, given that no difference in median surfacing time among seasons was observed.

Surto de toxoplasmose em um seminário de Bragança Paulista (Estado de São Paulo): aspectos clínicos, sorológicos e epidemiológicos

Nove casos de toxoplasmose adquirida comprovada (forma linfoglandular), ocorridos em um Seminário de Bragança Paulista, motivaram uma investigação clínica e sorológica. De acôrdo com os dados assim obtidos, pelo menos 30 pessoas (em um total de 81) apresentavam toxoplasmose na ocasião. Ao todo, foram realizadas 314 reações de Sabin-Feldman e de imunofluorescência indireta. O inquérito sorológico pela prova do corante extendeu-se também a algumas espécies animais da localidade. Em vista das limitações relativas à investigação epidemiológica, foi possível apenas a colocação de várias hipóteses, nada se podendo concluir quanto aos aspectos epidemiológicos do surto. Registrando, pela primeira vez, na literatura médica esta ocorrência, os autores alertam para a possibilidade dêstes surtos em instituições fechadas ou zona rural. Insistem na necessidade de pesquisas mais profundas, em situações similares, para o reconhecimento das fontes de infecção e mecanismos de transmissão, a despeito das dificuldades decorrentes dos escassos conhecimentos sôbre a história natural da toxoplasmose e do ciclo biológico do parasita.

Aspectos ecológicos da tripanossomose americana: I - observações sôbre o Panstrongylus megistus e suas relações com focos naturais da infecção, em área urbana da cidade de São Paulo, Brasil

São relatadas as investigações que levaram a efeito o encontro de foco natural da Tripanossomose Americana, na área ocupada pelo bairro denominado Chácara Flora, na cidade de São Paulo. Esse foco conta com o concurso do triatomíneo Panstrongylus megistus, de gambás Didelphis marsupialis e de ratos domésticos da espécie Rattus norvegicus. A presença destes últimos permite admitir maior aproximação da infecção no sentido do ambiente humano. O encontro de um espécimen adulto fêmea de P. megistus sugando ativamente o homem dentro da habitação, aliado à revisão da literatura, permite supor que não se trata de subespécie ecológica. A presença de diferenças essenciais de comportamento no norte e sul do Brasil, no estado atual dos conhecimentos, seria resultante, preponderantemente, da ação de fatôres ambientais, entre os quais, as condições climáticas.

Aspectos ecológicos da tripanossomose americana: V- observações sobre colonização espontânea de triatomíneos silvestres em ecótopos artificiais, com especial referência ao Triatoma sordida

Relatam-se os resultados obtidos com investigações destinadas a detectar o poder invasivo de triatomíneos silvestres em relação a ecótopos artificiais. Estes foram representados por galinheiros experimentais instalados em áreas habitadas por populações extradomiciliares de Triatoma sordida e T. arthurneivai. Ambos revelaram tendência invasiva, mas a capacidade de colonização no ambiente artificial só foi demonstrada pelo primeiro. As colônias obtidas de T. sordida monstraram-se bastante estáveis de acordo com a permanência da população silvestre. A presença desta última foi periodicamente detectada graças à idealização e emprego de artefatos que servissem de esconderijos tipo "calha". As observações no ambiente natural confirmam a ação favorável que as alterações nele introduzidas exercem sobre a densidade desse triatomíneo. Assim sendo, é de se prever que ele venha a invadir e ocupar com relativa rapidez os nichos ecológicos domiciliares deixados vagos pela eliminação de outros triatomíneos.

Hábitos alimentares, infecção natural e distribuição de triotomíneos domiciliados na região nordeste do Brasil

São apresentadas as informações obtidas no inquérito triatomíneo levado a efeito na região nordeste do Brasil. As características biogeográficas incluem a presença de áreas semi-áridas da caatinga e amplas faixas transicionais com outras feições paisagísticas. Entre estas foram incluídas as da floresta tropical atlântica e as inclusões florestadas mais extensas. No período de 1975 a 1980 foram examinados 15.342 triotomíneos coletados no ambiente domiciliar, visando detectar as presenças de sangue ingerido e de infecção natural por Trypanosoma tipo cruzi. O conteúdo intestinal foi submetido a reações com antisoros para homem, cão, gato, roedor (Kattus), marsupial (Didelphis) e ave (Gallus). Por ordem de freqüência, as espécies encontradas foram Triatoma pseudomaculada (40,6%), Panstrongylus megistus (19,7%), Triatoma brasiliensis e T. sordida (ambos com 14,3%), Rhodnius nasutus (6,1%) e Triatoma infestans (1,1%); além de em algumas outras raras. A presença de sangue foi detectada em 42,4% e a infecção em 3,4% desse total de espécimens examinados. Observou-se elevada mobilidade alimentar, com coeficientes gerais de 54,8% para ave e 30,0% para homem. Em nível específico pôde determinar apreciável grau de antropofilia em P. megistus e, em menor intensidade, em T. brasiliensis. Por sua vez, T. infestans mostrou-se altamente antropófilo. Observou-se apreciável ornitofilia em T. pseudomaculata e T. sordida, com elevada intensidade em R. nasutus. Por outro lado, a presença de sangue humano em espécimens capturados no peridomicílio indicou a ocorrência de freqüente mobilidade espacial, com exceção de T. infestans que não mostrou evidências de abandonar o domicílio. A tendência à domiciliação, além desta, revelou-se apreciável em P. megistus, moderada em T. brasiliensi, T. pseudomaculata, T. sordida e praticamente nula em R. nasutus. A distribuição geográfica confirmou o caráter autóctone de T. brasiliensis, T. pseudomaculata e R. nasutus em relação à caatinga, e do P. megistus em relação às regiões florestais atlânticas e de inclusão. Este último revelou caráter invasivo no que concerne à caatinga, enquanto T. infestans e T. sordida mostraram o mesmo aspecto quanto à região nordeste como um todo. Os resultados permitem concluir que, na transmissão regional epidemiologicamente significante da tripanossomíase americana, desempenha papel relevante o P. megistus, em primeiro lugar, e o T. brasiliensis, em segundo. Dependendo de fatores vários, provavelmente da densidade, poderão atuar secundariamente nesse sentido o T. pseudomaculata e o T. sordida. Quanto à T. infestans, a sua presença, em número reduzido, representa, no momento, risco apenas potencial. O controle rotineiro, mediante a desinsetização domiciliar, deverá fornecer bons resultados no que concerne à interrupção da transmissão. Todavia a reinfestação, pelo menos do peridomicílio, deverá provavelmente continuar. E isso em virtude de focos extradomiciliares que fornecem espécimens com tendência à colonização no ambiente humano. É de se prever que ela se fará a custa do P. megistus nas áreas florestais atlânticas e de inclusão e de T. brasiliensis, T. pseudomaculata e R. nasutus nas áreas da caatinga. A vigilância epidemiológica deverá pois levar em conta esses aspectos e tender a aumentar sua eficiência pela continuidade das pesquisas.