Desenvolvimento de um sistema de qualificação de TCA em solução aquosa por voltametria

A garantia da qualidade de produtos alimentares constitui um requisito fundamental no setor alimentar pelo que, na última década se tem assistido à intensificação do desenvolvimento e otimização de processos de controlo. O setor vinícola, em particular, tem essa permanente preocupação em relação à presença de contaminantes que possam conferir ao vinho outras características organoléticas consideradas como defeitos, nomeadamente, o 2,4,6-tricloroanisol (TCA). A presença de TCA no vinho, atribuída à migração a partir de rolhas de cortiça contaminadas com TCA, tem sido apontada como responsável pela ocorrência do referido defeito organolético do vinho, conhecido como “cheiro/gosto a mofo” ou “gosto a rolha”, o qual tem levado a perdas económicas bastante elevadas no setor vinícola mundial. O limite humano para a sua deteção sensorial é inferior a 5 ng/L, pelo que uma concentração reduzida de TCA no vinho é facilmente detetada pelo consumidor. Por este motivo, é de grande relevância para a indústria corticeira, nomeadamente para a indústria de produção de rolhas de cortiça para o engarrafamento de vinho, conseguir identificar a presença deste composto na rolha antes da sua utilização ou ainda nas pranchas de cortiça usadas na produção de rolhas, de modo a poderem ser implementadas medidas corretivas que permitam eliminar ou reduzir o teor de TCA nas mesmas, evitando assim a contaminação futura do vinho engarrafado. Diversas técnicas são utilizadas para detetar a presença do TCA no vinho ou em rolhas, sendo de especial relevância as baseadas em cromatografia gasosa com deteção por espectrometria de massa. Contudo, estas técnicas analíticas capazes de detetar e quantificar níveis de TCA da ordem dos ng/L, são em geral dispendiosas, requerendo equipamentos analíticos caros e pessoal técnico altamente qualificado, não sendo portáteis e por isso dificilmente aplicáveis in-situ, necessitando de um pré-tratamento das amostras complexo com a finalidade de extrair o TCA e concentrá-lo para posterior quantificação. Assim, este procedimento de deteção de TCA, tido como método de referência, não é uma solução economicamente viável para grande parte das pequenas e médias empresas corticeiras, sendo apenas aplicável a um reduzido número de amostras, o que limita a real deteção de contaminações de TCA na cortiça e nas rolhas fabricadas. Neste trabalho, utilizou-se a técnica de voltametria cíclica para detetar TCA na água de cozedura de pranchas de cortiça utilizadas para a produção de rolhas para engarrafamento de vinho. As análises foram realizadas à temperatura ambiente, em menos de 15 minutos, com reduzido uso de solventes orgânicos e sem qualquer pré-tratamento da amostra. A técnica proposta apresenta limites de deteção de 0,31 0,01 ng/L e de quantificação de 0,95 0,05 ng/L inferiores ao limiar de deteção humano. Ensaios realizados em soluções não contaminadas com TCA permitiram quantificar uma concentração de TCA da ordem do referido limite de quantificação (1,0 0,2 ng/L), o que confirma o desempenho satisfatório da metodologia proposta. Por outro lado, o método apresentou uma repetibilidade satisfatória (valores inferiores a 3%) quando aplicado a amostras reais de água de cozedura das pranchas de cortiça obtidas no processo industrial de produção de rolhas. Verificou-se ainda que os teores de TCA nas amostras aquosas determinados pela técnica proposta são concordantes com os obtidos por GC-MS (coeficiente de correlação igual a 0,98), o que confirma a precisão satisfatória da metodologia proposta. Assim, uma vez que esta nova abordagem é um método rápido, de baixo custo, portátil e de fácil utilização, pode ser visto como uma ferramenta alternativa e útil para aplicações industriais in-situ, permitindo a deteção de TCA numa fase inicial da produção de rolhas de cortiça. Esta técnica pode contribuir para a implementação mais eficaz de procedimentos de segregação da cortiça contaminada com o intuito de reduzir ou evitar futuras contaminações de vinho engarrafado com TCA.

(Table 1) Concentration and geological parameters of n-alkanes and n-alkenes in surface sediments from the Gulf of Gabes, Tunisia

Abstract Hydrocarbons in surface sediments were studied quantitatively and qualitatively in 18 stations along the coastline of Gabes Gulf in Tunisia. The results show that the total hydrocarbon levels vary along a wide range from 90 to 1,800 ppm. The GC-MS profiles of aliphatic hydrocarbons vary according to the stations and show that the hydrocarbons were derived from various sources. A special feature prevalent in several stations was identified: aliphatic hydrocarbons with distinctive chemical features. This includes a high abundance of even-numbered n-alkanes (n-C14 - n-C26, maximizing at n-C18, n-C20 and n-C22) and n-alk-1-enes (n-C14:1 - n-C24:1, maximizing at n-C16:1, n-C18:1, n-C20:1 and n-C22:1). This unusual predominance of even-numbered n-alkanes/alkenes is reported for the first time in the Gulf of Gabes and it thus contributes to the information on the rare occurrence of such distributions in the geosphere.

Sedimentology, organic geochemistry, and stable isotopes of core PS2138-1

We studied variations in terrigenous (TOM) and marine organic matter (MOM) input in a sediment core on the northern Barents Sea margin over the last 30 ka. Using a multiproxy approach, we reconstructed processes controlling organic carbon deposition and investigated their paleoceanographic significance in the North Atlantic-Arctic Gateways. Variations in paleo-surface-water productivity are not documented in amount and composition of organic carbon. The highest level of MOM was deposited during 25-23 ka as a result of scavenging on fine-grained, reworked, and TOM-rich material released by the retreating Svalbard/Barents Sea ice sheet during the late Weichselian. A second peak of MOM is preserved because of sorptive protection by detrital and terrigenous organic matter, higher surface-water productivity due to permanent intrusion of Atlantic water, and high suspension load release by melting sea ice during 15.9-11.2 ka.

Lithogenic and biogenic daily and annual particle fluxes on the Lomonosov Ridge of trap LOMO-2

Investigations of lithogenic and biogenic particle fluxes using long-term sediment traps are still very rare in the northern high latitudes and restricted to the arctic marginal seas and sub-arctic regions. Here, for the first time, data on the variability of fluxes of lithogenic matter, carbonate, opal, and organic carbon as well as biomarker composition from the central Arctic Ocean are presented for a one-year period. The study has been carried out on material obtained from a long-term mooring system equipped with two multi-sampling-traps (150 and 1550 m water depth) and deployed on the southern Lomonosov Ridge close to the Laptev Sea continental margin from September 1995 to August 1996. In addition, data from surface-sediments were included in the study to get more information about the flux and sedimentation of organic carbon in this area. Annual fluxes of lithogenic matter, carbonate, opal, and particulate organic carbon are 3.9 g/m**2/y, 0.8 g/m**2/y, 2.6 g/m**2/y, 1.5 g/m**2/y, respectively, at the shallow trap and 11.3 g/m**2/y, 0.5 g/m**2/y, 2.9 g/m**2/y, 1.05 g/m**2/y, respectively, at the deep trap. Both the shallow as well as the deep trap show significant differences in vertical flux values over the year. Higher values were found from mid-July to end of October (total flux of 75-130 mg/m**2/d in the shallow trap and 40-225 mg/m**2/d in the deep trap, respectively). During all other months, fluxes were fairly low in both traps (most total flux values <10 mg/m**2/d1). The interval of increased fluxes can be separated into (1) a mid-July/August maximum caused by increased primary production as documented in high abundances of marine biomarkers and diatoms, and (2) a September/October (absolute) maximum caused by increased influence of Lena river discharge indicated by maximum lithogenic flux and high portions of terrigenous/fluvial biomarkers in both traps. Here, total fluxes in the deep trap were significantly higher than in the shallow trap, suggesting a lateral sediment flux at greater depth. The lithogenic flux data also support the importance of sediment input from the Laptev Sea for the sediment accumulation on the Lomonosov Ridge on geological time scales, as indicated in sedimentary records from this region.

Organic matter based proxies from surface sediments along three transects on the Pakistan continental margin

A valid assessment of selective aerobic degradation on organic matter (OM) and its impact on OM-based proxies is vital to produce accurate environmental reconstructions. However, most studies investigating these effects suffer from inherent environmental heterogeneities. In this study, we used surface samples collected along two meter-scale transects and one longer transect in the northeastern Arabian Sea to constrain initial OM heterogeneity, in order to evaluate selective aerobic degradation on temperature, productivity and alteration indices at the sediment-water interface. All of the studied alteration indices, the higher plant alkane index, alcohol preservation index, and diol oxidation index, demonstrated that they are sensitive indicators for changes in the oxygen regime. Several export production indices, a cholesterol-based stanol/stenol index and dinoflagellate lipid- and cyst-based ratios, showed significant (more than 20%) change only over the lateral oxygen gradients. Therefore, these compounds do not exclusively reflect surface water productivity, but are significantly altered after deposition. Two of the proxies, glycerol dibiphytanyl glycerol tetraether-based TEX86 sea surface temperature indices and indices based on phytol, phytane and pristane, did not show any trends related to oxygen. Nevertheless, unrealistic sea surface temperatures were obtained after application of the TEX86, TEX86L, and TEX86H proxies. The phytol-based ratios were likely affected by the sedimentary production of pristane. Our results demonstrate the selective impact of aerobic organic matter degradation on the lipid and palynomorph composition of surface sediments along a short lateral oxygen gradient and suggest that some of the investigated proxies may be useful tracers of changing redox conditions at the sediment-water interface.

Age determinations, biomarker analyses, and accumulation rates of three sediment cores from the Fram Strait

A reconstruction of Holocene sea ice conditions in the Fram Strait provides insight into the palaeoenvironmental and palaeoceanographic development of this climate sensitive area during the past 8,500 years BP. Organic geochemical analyses of sediment cores from eastern and western Fram Strait enable the identification of variations in the ice coverage that can be linked to changes in the oceanic (and atmospheric) circulation system. By means of the sea ice proxy IP25, phytoplankton derived biomarkers and ice rafted detritus (IRD) increasing sea ice occurrences are traced along the western continental margin of Spitsbergen throughout the Holocene, which supports previous palaeoenvironmental reconstructions that document a general cooling. A further significant ice advance during the Neoglacial is accompanied by distinct sea ice fluctuations, which point to short-term perturbations in either the Atlantic Water advection or Arctic Water outflow at this site. At the continental shelf of East Greenland, the general Holocene cooling, however, seems to be less pronounced and sea ice conditions remained rather stable. Here, a major Neoglacial increase in sea ice coverage did not occur before 1,000 years BP. Phytoplankton-IP25 indices ("PIP25-Index") are used for more explicit sea ice estimates and display a Mid Holocene shift from a minor sea ice coverage to stable ice margin conditions in eastern Fram Strait, while the inner East Greenland shelf experienced less severe to marginal sea ice occurrences throughout the entire Holocene.

Cholesterol and C30 of sediment profile MD90-963

In a deep-sea sediment core recovered from a site lying well above the local lysocline, several organic geochemical proxies, and two different calcite dissolution indicators, are compared in order to evaluate the relationship between calcite dissolution and paleoproductivity over the past three glacial-interglacial cycles. The degree of foraminiferal break-up, and the CaCO3 particle size distribution, both point to significant periods of dissolution every 22 kyr during glacial stages and substages. These dissolution events are concomitant with periods of enhanced primary productivity, as indicated by the abundance of several biomarkers (alkenones, cholesterol, brassicasterol, keto-ol), used here to indicate changes in paleoproductivity. Dissolution fluctuations are highly coherent and in phase with the estimated paleoproductivity variations providing strong evidence that the observed dissolution is due to organic matter remineralization within the sediments rather, than to changes in CO32? concentration in the overlying water column.

Biomarker proxies on ODP Holes 151-912A and 151-912B

A novel and promising biomarker proxy for reconstruction of Arctic sea ice conditions was developed and is based on the determination of a highly branched isoprenoid with 25 carbons (IP25). IP25 records have been restricted to the last 150 kyr BP. We present a biomarker record from Ocean Drilling Program (ODP) Site 912, going back to the Pliocene-Pleistocene boundary and indicating that sea ice of variable extent occurred in the Fram Strait/southern Yermak Plateau area at least since about 2.2 Ma. Furthermore, our data support the idea that a combination of IP25 and open water, phytoplankton biomarker data ("PIP25 index") may give a more reliable and quantitative estimate of past sea ice cover (at least for the study area). The study reveals that the novel IP25/PIP25 biomarker approach has potential for semi-quantitative paleo-sea ice studies covering the entire Quaternary and could motivate further detailed high resolution research on ODP/IODP material using this proxy.

Biomarker distributions in surface sediments from the Kara and Laptev Seas (Arctic Ocean)

Studies of spatial and temporal changes in modern and past sea-ice occurrence may help to understand the processes controlling the recent decrease in Arctic sea-ice cover. Here, we determined concentrations of IP25, a novel biomarker proxy for sea ice developed in recent years, phytoplankton-derived biomarkers (brassicasterol and dinosterol) and terrigenous biomarkers (campesterol and ß-sitosterol) in the surface sediments from the Kara and Laptev seas to estimate modern spatial (seasonal) sea-ice variability and organic-matter sources. C25-HBI dienes and trienes were determined as additional paleoenvironmental proxies in the study area. Furthermore, a combined phytoplankton-IP25 biomarker approach (PIP25 index) is used to reconstruct the modern sea-ice distribution more quantitatively. The terrigenous biomarkers reach maximum concentrations in the coastal zones and estuaries, reflecting the huge discharge by the major rivers Ob, Yenisei and Lena. Maxima in phytoplankton biomarkers indicating increased primary productivity were found in the seasonally ice-free central part of the Kara and Laptev seas. Neither IP25 nor PIP25, however, show a clear and simple correlation with satellite sea-ice distribution in our study area due to the complex environmental conditions in our study area and the transportation process of sea-ice diatom in the water column. Differences in the diene/IP25 and triene/IP25 ratios point to different sources of these HBIs and different environmental conditions. The diene/IP25 ratio seems to correlate positively with sea-surface temperature, while negatively with salinity distributions.

Total organic carbon, bitumen ratio, hopane and sterane parameters of ODP Sites 128-798 and 128-799

Notable compositional changes of organic matter are observed below the silica transition zone in thermally immature sediments. The increase of bitumen ratio, and hopane and sterane isomerization parameters indicate an acceleration of the kinetics of the chemical reactions which transform the organic matter. This phenomenon is probably due to the numerous mineral and textural changes induced by the transformation of amorphous biogenic silica into crystalline authigenic silica.