(Table S1) Stable oxygen isotopic values and Mg/Ca ratios of Globigerinoides ruber w from sediment core AAS9_21

Variations in sea surface temperature (SST), d18O of sea water (?18Ow), and salinity were reconstructed for the past 68 ka using a sediment core (AAS9/21) from the eastern Arabian Sea (EAS) in order to understand the changes in evaporation and precipitation associated with the monsoon system. The Mg/Ca-derived SST record varies by ~4°C; it shows that marine isotope stage (MIS) 4 was warmer than MIS 3, that the Last Glacial Maximum was 4°C cooler than the present, and that there was a 2°C increase within the Holocene. MIS 4 records higher d18Ow and salinity values than MIS 2, suggesting variable flow of low-salinity Bay of Bengal flow into the EAS during glacial periods. The transition from MIS 4 to MIS 3 was marked with a conspicuous shift from higher to lower d18Ow values, which reflects a decrease in the evaporation-precipitation budget in the EAS, perhaps due to the strengthening of southwest monsoon. Monsoon reconstructions based on d18Ow reveal that monsoon-driven precipitation was higher during MIS 3 and MIS 1 and was lower during MIS 2 and MIS 4. This is consistent with earlier monsoon reconstructions based on upwelling indices from the western Arabian Sea. However, the amplitude of monsoon fluctuations derived through upwelling indices and d18Ow varies significantly, which may indicate spatial variability of monsoon rainfall.

Mineralogical, geochemical and magnetic signatures of surface sediments from the Canadian Beaufort Shelf and Amundsen Gulf (Canadian Arctic)

Mineralogical, geochemical, magnetic, and siliciclastic grain-size signatures of 34 surface sediment samples from the Mackenzie-Beaufort Sea Slope and Amundsen Gulf were studied in order to better constrain the redox status, detrital particle provenance, and sediment dynamics in the western Canadian Arctic. Redox-sensitive elements (Mn, Fe, V, Cr, Zn) indicate that modern sedimentary deposition within the Mackenzie-Beaufort Sea Slope and Amundsen Gulf took place under oxic bottom-water conditions, with more turbulent mixing conditions and thus a well-oxygenated water column prevailing within the Amundsen Gulf. The analytical data obtained, combined with multivariate statistical (notably, principal component and fuzzy c-means clustering analyses) and spatial analyses, allowed the division of the study area into four provinces with distinct sedimentary compositions: (1) the Mackenzie Trough-Canadian Beaufort Shelf with high phyllosilicate-Fe oxide-magnetite and Al-K-Ti-Fe-Cr-V-Zn-P contents; (2) Southwestern Banks Island, characterized by high dolomite-K-feldspar and Ca-Mg-LOI contents; (3) the Central Amundsen Gulf, a transitional zone typified by intermediate phyllosilicate-magnetite-K-feldspar-dolomite and Al-K-Ti-Fe-Mn-V-Zn-Sr-Ca-Mg-LOI contents; and (4) mud volcanoes on the Canadian Beaufort Shelf distinguished by poorly sorted coarse-silt with high quartz-plagioclase-authigenic carbonate and Si-Zr contents, as well as high magnetic susceptibility. Our results also confirm that the present-day sedimentary dynamics on the Canadian Beaufort Shelf is mainly controlled by sediment supply from the Mackenzie River. Overall, these insights provide a basis for future studies using mineralogical, geochemical, and magnetic signatures of Canadian Arctic sediments in order to reconstruct past variations in sediment inputs and transport pathways related to late Quaternary climate and oceanographic changes.

Palynological counts (dinoflagellate cysts) and foraminiferal geochemistry (d18O, d18C, Mg/Ca) of the Pliocene-Pleistocene transition in the North Atlantic

The position of the North Atlantic Current (NAC) during the intensification of Northern Hemisphere glaciation (iNHG) has been evaluated using dinoflagellate cyst assemblages and foraminiferal geochemistry from a ~260 kyr interval straddling the base of the Quaternary System from two sites: eastern North Atlantic Deep Sea Drilling Project Site 610 in the path of the present NAC and central North Atlantic Integrated Ocean Drilling Program Site U1313 in the subtropical gyre. Stable isotope and foraminiferal Mg/Ca analyses confirm cooling near the marine isotope stage (MIS) G7-G6 transition (2.74 Ma). However, a continued dominance of the dinoflagellate cyst Operculodinium centrocarpum sensu Wall and Dale (1966) indicates an active NAC in the eastern North Atlantic for a further 140 kyr. At MIS 104 (~2.60 Ma), a profound dinoflagellate cyst assemblage turnover indicates NAC shutdown in the eastern North Atlantic, implying elevated atmospheric pressure over the Arctic and a resulting shift in the westerlies that would have driven the NAC. These findings challenge recent suggestions that there was no significant southward shift of the NAC or the Arctic Front during iNHG, and reveal a fundamental climatic reorganization near the base of the Quaternary.

Measurement results of d18O, Mg/Ca, and Ti/Ca of sediment cores GeoB10042-1 and GeoB10043-3

The advection of relatively fresh Java Sea water through the Sunda Strait is presently responsible for the low-salinity "tongue" in the eastern tropical Indian Ocean with salinities as low as 32 per mil. The evolution of the hydrologic conditions in the eastern tropical Indian Ocean since the last glacial period, when the Sunda shelf was exposed and any advection via the Sunda Strait was cutoff, and the degree to which these conditions were affected by the Sunda Strait opening are not known. Here we have analyzed two sediment cores (GeoB 10042-1 and GeoB 10043-3) collected from the eastern tropical Indian Ocean off the Sunda Strait that cover the past ~40,000?years. We investigate the magnitude of terrigenous supply, sea surface temperature (SST), and seawater d18O (d18Osw) changes related to the sea level-driven opening of the Sunda Strait. Our new spliced records off the Sunda Strait show that during the last glacial, average SST was cooler and d18Osw was higher than elsewhere in the eastern tropical Indian Ocean. Seawater d18O decreased ~0.5 per mil after the opening of the Sunda Strait at ~10 kyr B.P. accompanied by an SST increase of 1.7°C. We suggest that fresher sea surface conditions have persisted ever since due to a continuous transport of low-salinity Java Sea water into the eastern tropical Indian Ocean via the Sunda Strait that additionally increased marine productivity through the concomitant increase in terrigenous supply.

ROCK OUTCROPS IN THE CANADIAN SHIELD: AN INVESTIGATION OF CONTAMINANT TRANSPORT FROM SURFACE SOURCES IN FRACTURED ROCK AQUIFERS

Flow, recharge and transport dynamics in fractured rock aquifers with low lying rock outcrops is a largely unexplored area of study in hydrogeology. The purpose of this thesis is to examine these topics in an agricultural area in Eastern Ontario. The study consists of a regional scale groundwater quality study, an infiltration experiment that considers bacteria transport from the ground surface to a well, and a numerical modelling study that tests the parameters that affect surface infiltration of a tracer from a rock outcrop to a deeper horizontal fracture. In the water quality study, approximately 65% of the samples contained total coliform, 16% contained E. coli, and 1% contained nitrate-N at greater than 5 mg/L. Occurrence of E. coli increased when considering seasonality, where wells were drilled on rock outcrops, and for shallow well intervals. Nitrate-N did not occur above the Guidelines for Canadian Drinking Water Quality (Health Canada, 2012) of 10 mg/L. Rapid arrival times were observed in the infiltration study for both the microspheres (30 minutes) and a dye tracer (45 minutes) in a well approximately 6.0 m in horizontal and 2.8 m in vertical distance from the tracer source. Transport velocities were approximately 38.9 m/day for the dye tracer and 115.2 m/day for the colloidal tracer. Results of the model runs indicate that overburden can provide an effective protective layer to transport in fractures, that high groundwater velocities occur in larger fracture apertures and higher gradients dilute tracer concentrations, and that lower groundwater velocities occur with smaller fracture apertures and lower gradients result in elevated tracer concentrations. Lower rainfall rates, larger fracture apertures, early tracer time, larger gradients, and lower water levels maintained unsaturated conditions for longer time periods such that tracer transport was delayed until saturated conditions were attained. The overall heterogeneity of this aquifer environment creates a source water protection conundrum where the water quality is generally good, while transport can occur very quickly in proximity to rock outcrops and in areas with limited overburden.

Swellable polymer films containing Au nanoparticles for point-of-care therapeutic drug monitoring using surface-enhanced Raman spectroscopy

Large (10 × 10 cm) sheets of surface-enhanced Raman spectroscopy (SERS) active polymer have been prepared by stabilising metal nanoparticle aggregates within dry hydroxyethylcellulose (HEC) films. In these films the aggregates are protected by the polymer matrix during storage but in use they are released when aqueous analyte droplets cause the films to swell to their gel form. The fact that these "Poly-SERS" films can be prepared in bulk but then cut to size and stored in air before use means that they provide a cost effective and convenient method for routine SERS analysis. Here we have tested both Ag and Au Poly-SERS films for use in point-of-care monitoring of therapeutic drugs, using phenytoin as the test compound. Phenytoin in water could readily be detected using Ag Poly-SERS films but dissolving the compound in phosphate buffered saline (PBS) to mimic body fluid samples caused loss of the drug signal due to competition for metal surface sites from Cl^- ions in the buffer solution. However, with Au Poly-SERS films there was no detectable interference from Cl^- and these materials allowed phenytoin to be detected at 1.8 mg L^-1, even in PBS. The target range of detection of phenytoin in therapeutic drug monitoring is 10-20 mg L^-1. With the Au Poly-SERS films, the absolute signal generated by a given concentration of phenytoin was lower for the films than for the parent colloid but the SERS signals were still high enough to be used for therapeutic monitoring, so the cost in sensitivity for moving from simple aqueous colloids to films is not so large that it outweighs the advantages which the films bring for practical applications, in particular their ease of use and long shelf life.

Ultrasound and microwave assisted extraction of ergosterol from Agaricus bisporus L.: optimization through response surface methodology

There is scientific evidence demonstrating the benefits of mushrooms ingestion due to their richness in bioactive compounds such as mycosterols, in particular ergosterol [I]. Agaricus bisporus L. is the most consumed mushroom worldwide presenting 90% of ergosterol in its sterol fraction [2]. Thus, it is an interesting matrix to obtain ergosterol, a molecule with a high commercial value. According to literature, ergosterol concentration can vary between 3 to 9 mg per g of dried mushroom. Nowadays, traditional methods such as maceration and Soxhlet extraction are being replaced by emerging methodologies such as ultrasound (UAE) and microwave assisted extraction (MAE) in order to decrease the used solvent amount, extraction time and, of course, increasing the extraction yield [2]. In the present work, A. bisporus was extracted varying several parameters relevant to UAE and MAE: UAE: solvent type (hexane and ethanol), ultrasound amplitude (50 - 100 %) and sonication time (5 min-15 min); MAE: solvent was fixed as ethanol, time (0-20 min), temperature (60-210 •c) and solid-liquid ratio (1-20 g!L). Moreover, in order to decrease the process complexity, the pertinence to apply a saponification step was evaluated. Response surface methodology was applied to generate mathematical models which allow maximizing and optimizing the response variables that influence the extraction of ergosterol. Concerning the UAE, ethanol proved to be the best solvent to achieve higher levels of ergosterol (671.5 ± 0.5 mg/100 g dw, at 75% amplitude for 15 min), once hexane was only able to extract 152.2 ± 0.2 mg/100 g dw, in the same conditions. Nevertheless, the hexane extract showed higher purity (11%) when compared with the ethanol counterpart ( 4% ). Furthermore, in the case of the ethanolic extract, the saponification step increased its purity to 21%, while for the hexane extract the purity was similar; in fact, hexane presents higher selectivity for the lipophilic compounds comparatively with ethanol. Regarding the MAE technique, the results showed that the optimal conditions (19 ± 3 min, 133 ± 12 •c and 1.6 ± 0.5 g!L) allowed higher ergosterol extraction levels (556 ± 26 mg/100 g dw). The values obtained with MAE are close to the ones obtained with conventional Soxhlet extraction (676 ± 3 mg/100 g dw) and UAE. Overall, UAE and MAE proved to he efficient technologies to maximize ergosterol extraction yields.

Flowers of Gomphrena globosa L. as an alternatve source of betacyanins: optimization of the extraction using response surface methodology

Betacyanins are betalain pigments that display a red-violet colour which have been reported to be three times stronger than the red-violet dye produced by anthocyanins [1]. The applications of betacyanins cover a wide range of matrices, mainly as additives or ingredients in the food industry, cosmetics, pharmaceuticals and livestock feed. Although, being less commonly used than anthocyanins and carotenoids, betacyanins are stable between pH 3 to 7 and suitable for colouring in low acid matrices. In addition, betacyanins have been reported to display interesting medicinal character as powerful antioxidant and chemopreventive compounds either in vitro or in vivo models [2]. Betacyanins are obtained mainly from the red beet of Beta vulgaris plant (between I 0 to 20 mg per I 00 g pulp) but alternative primary sources are needed [3]. In addition, independently of the source used, the effect of the variables that affect the extraction of betacyanins have not been properly described and quantified. Therefore, the aim of this study was to identifY and optimize the conditions that maximize betacyanins extraction using the tepals of Gomphrena globosa L. flowers as an alternative source. Assisted by the statistical technique of response surface methodology, an experimental design was developed for testing the significant explanatory variables of the extraction (time, temperature, solid-liquid ratio and ethanolwater ratio). The identification was performed using high-performance liquid chromatography coupled with a photodiode array detector and mass spectrometry with electron spray ionization (HPLC-PDAMS/ ESI) and the response was measured by the quantification of these compounds using HPLC-PDA. Afterwards, a response surface analysis was performed to evaluate the results. The major betacyanin compounds identified were gomphrenin 11 and Ill and isogomphrenin IJ and Ill. The highest total betacyanins content was obtained by using the following conditions: 45 min of extraction. time, 35•c, 35 g/L of solid-liquid ratio and 25% of ethanol. These values would not be found without optimizing the conditions of the betacyanins extraction, which moreover showed contrary trends to what it has been described in the scientific bibliography. More specifically, concerning the time and temperature variables, an increase of both values (from the common ones used in the bibliography) showed a considerable improvement on the betacyanins extraction yield without displaying any type of degradation patterns.

Optimization of ultrasound-assisted extraction to obtain mycosterols from Agaricus bisporus L. by response surface methodology and comparison with conventional Soxhlet extraction

Ergosterol, a molecule with high commercial value, is the most abundant mycosterol in Agaricus bisporus L. To replace common conventional extraction techniques (e.g. Soxhlet), the present study reports the optimal ultrasound-assisted extraction conditions for ergosterol. After preliminary tests, the results showed that solvents, time and ultrasound power altered the extraction efficiency. Using response surface methodology, models were developed to investigate the favourable experimental conditions that maximize the extraction efficiency. All statistical criteria demonstrated the validity of the proposed models. Overall, ultrasound-assisted extraction with ethanol at 375 W during 15 min proved to be as efficient as the Soxhlet extraction, yielding 671.5 ± 0.5mg ergosterol/100 g dw. However, with n-hexane extracts with higher purity (mg ergosterol/g extract) were obtained. Finally, it was proposed for the removal of the saponification step, which simplifies the extraction process and makes it more feasible for its industrial transference.

The impact of tides and waves on near-surface suspended sediment concentrations in the English Channel

Numerous ecological problems of continental shelf ecosystems require a refined knowledge of the evolution of suspended sediment concentrations (SSC). The present investigation focuses on the spatial and temporal variabilities of near-surface SSC in coastal waters of the English Channel (western Europe) by exploiting numerical predictions from the Regional Ocean Modeling System ROMS. Extending previous investigations of ROMS performances in the Channel, this analysis refines, with increased spatial and temporal resolutions, the characterization of near-surface SSC patterns revealing areas where concentrations are highly correlated with evolutions of tides and waves. Significant tidal modulations of near-surface concentrations are thus found in the eastern English Channel and the French Dover Strait while a pronounced influence of waves is exhibited in the Channel Islands Gulf. Coastal waters present furthermore strong SSC temporal variations, particularly noticeable during storm events of autumn and winter, with maximum near-surface concentrations exceeding 40 mg l−1 and increase by a factor from 10 to 18 in comparison with time-averaged concentrations. This temporal variability strongly depends on the granulometric distribution of suspended sediments characterized by local bi-modal contributions of silts and sands off coastal irregularities of the Isle of Wight, the Cotentin Peninsula and the southern Dover Strait.

Assessment of surface temperatures of buffalo bulls (Bubalus bubalis) raised under tropical conditions using infrared thermography.

O presente trabalho visou avaliar as temperaturas superficiais de diferentes regiões anatômicas de búfalos ao longo do tempo, por meio da termografia infravermelha, e correlacioná-las a índices bioclimatológicos de conforto térmico. O ensaio foi realizado em região de clima tropical úmido (Afi de Köppen), de abril a agosto. Dez touros (n=10) foram avaliados a cada 25 dias (manhã: seis-nove horas; tarde: 12-15h), quanto à frequência respiratória (FR), temperatura retal (TR) e imagens termográficas da órbita ocular (ORB), flanco direito (FLd), flanco esquerdo (FLe) e escroto (ESC). Os dados climatológicos foram ininterruptamente monitorados, e calculados o índice de temperatura e umidade (ITU) e o índice de conforto de Benezra (ICB). O ITU foi ?78, com diferença entre turnos (P<0,05). Já o ICB variou de 1,96 a 2,25 e apresentou diferenças ao longo dos meses e entre turnos (P<0,05). As temperaturas observadas foram de TR=38,2±0,5ºC, ORB=36,1±0,8ºC, FLd=33,5±2,5ºC, FLe=35,4±1,7ºC e ESC=33,3±1,1ºC, as quais variaram significativamente ao longo dos meses e entre turnos (P<0,05). O ITU apresentou correlações positivas com ORB (0,72), FLd (0,77), FLe (0,75) e ESC (0,41) (P<0,0001). A temperatura máxima de ORB apresentou a maior correlação com a TR (0,58; P<0,0001). Portanto, as temperaturas superficiais dos animais sofrem interferências das variações climáticas e se elevam ao longo do dia, devido à variação nos índices de conforto térmico; a temperatura máxima de ORB foi o parâmetro mais condicionado à temperatura retal. Também, as oscilações de temperatura de superfície de ORB, FLd, FLe e ESC podem ser aferidas em bubalinos com o uso da termografia infravermelha, de modo preciso e não invasivo.

Assessment of surface temperatures of buffalo bulls (Bubalus bubalis) raised under tropical conditions using infrared thermography.

O presente trabalho visou avaliar as temperaturas superficiais de diferentes regiões anatômicas de búfalos ao longo do tempo, por meio da termografia infravermelha, e correlacioná-las a índices bioclimatológicos de conforto térmico. O ensaio foi realizado em região de clima tropical úmido (Afi de Köppen), de abril a agosto. Dez touros (n=10) foram avaliados a cada 25 dias (manhã: seis-nove horas; tarde: 12-15h), quanto à frequência respiratória (FR), temperatura retal (TR) e imagens termográficas da órbita ocular (ORB), flanco direito (FLd), flanco esquerdo (FLe) e escroto (ESC). Os dados climatológicos foram ininterruptamente monitorados, e calculados o índice de temperatura e umidade (ITU) e o índice de conforto de Benezra (ICB). O ITU foi ?78, com diferença entre turnos (P<0,05). Já o ICB variou de 1,96 a 2,25 e apresentou diferenças ao longo dos meses e entre turnos (P<0,05). As temperaturas observadas foram de TR=38,2±0,5ºC, ORB=36,1±0,8ºC, FLd=33,5±2,5ºC, FLe=35,4±1,7ºC e ESC=33,3±1,1ºC, as quais variaram significativamente ao longo dos meses e entre turnos (P<0,05). O ITU apresentou correlações positivas com ORB (0,72), FLd (0,77), FLe (0,75) e ESC (0,41) (P<0,0001). A temperatura máxima de ORB apresentou a maior correlação com a TR (0,58; P<0,0001). Portanto, as temperaturas superficiais dos animais sofrem interferências das variações climáticas e se elevam ao longo do dia, devido à variação nos índices de conforto térmico; a temperatura máxima de ORB foi o parâmetro mais condicionado à temperatura retal. Também, as oscilações de temperatura de superfície de ORB, FLd, FLe e ESC podem ser aferidas em bubalinos com o uso da termografia infravermelha, de modo preciso e não invasivo.

Annual crop rotation of tropical pastures with no-till soil as affectedby lime surface application.

Soil acidity and low natural fertility are the main limiting factors for grain production in tropical regionssuch as the Brazilian Cerrado. The application of lime to the surface of no-till soil can improve plant nutrition, dry matter production, crop yields and revenue. The present study, conducted at the Lageado Experimental Farm in Botucatu, State of São Paulo, Brazil, is part of an ongoing research project initi-ated in 2002 to evaluate the long-term effects of the surface application of lime on the soil?s chemical attributes, nutrition and kernel/grain yield of peanut (Arachis hypogaea), white oat (Avena sativa L.) and maize (Zea mays L.) inter cropped with palisade grass (Urochloa brizantha cv. Marandu), as well as the forage dry matter yield of palisade grass in winter/spring, its crude protein concentration, estimated meat production, and revenue in a tropical region with a dry winter during four growing seasons. The experiment was designed in randomized blocks with four replications. The treatments consisted of four rates of lime application (0, 1000, 2000 and 4000 kg ha−1), performed in November 2004. The surface application of limestone to the studied tropical no-till soil was efficient in reducing soil acidity from the surface down to a depth of 0.60 m and resulted in greater availability of P and K at the soil surface. Ca and Mg availability in the soil also increased with the lime application rate, up to a depth of 0.60 m. Nutrient absorption was enhanced with liming, especially regarding the nutrient uptake of K, Ca and Mg by plants.Significant increases in the yield components and kernel/grain yields of peanut, white oat and maize were obtained through the surface application of limestone. The lime rates estimated to achieve the maximum grain yield, especially in white oat and maize, were very close to the rates necessary to increase the base saturation of a soil sample collected at a depth of 0?0.20 m to 70%, indicating that the surface liming of 2000 kg ha−1is effective for the studied tropical no-till soil. This lime rate also increases the forage dry matter yield, crude protein concentration and estimated meat production during winter/spring in the maize-palisade grass inter cropping, provides the highest total and mean net profit during the four growing seasons, and can improve the long-term sustainability of tropical agriculture in the Brazilian Cerrado.