Seasonal variations in chemical composition and stable isotopes of farmed and wild Brazilian freshwater fish

This study examined variations in the Fulton condition factor, chemical composition, and stable isotopes of carbon and nitrogen in the Brazilian freshwater fish cachara (Pseudoplatystoma fasciatum), comparing farmed and wild fish in different seasons. Values for energy, protein, moisture, and Fulton's condition factor were higher for farmed than for wild fish in the rainy season, indicating better nutritional quality; however, these differences were not observed in the dry season. Likewise, we found significant enhancement of delta(15)N in farmed fish in the rainy season but not in the dry season, whereas enhancement of delta(13)C was observed in both seasons. The combined measurement of delta(13)C and delta(15)N provided traceability under all conditions. Our findings show that stable isotope analysis of C and N can be used to trace cachara origin, and that seasonal variations need to be considered when applying chemical and isotopic authentication of fish and fish products. (C) 2010 Elsevier Ltd. All rights reserved.

Measurement of total body water (TBW) and total energy expenditure (TEE) using stable isotopes

Understanding the relationship between diet, physical activity and health in humans requires accurate measurement of body composition and daily energy expenditure. Stable isotopes provide a means of measuring total body water and daily energy expenditure under free-living conditions. While the use of isotope ratio mass spectrometry (IRMS) for the analysis of 2H (Deuterium) and 18O (Oxygen-18) is well established in the field of human energy metabolism research, numerous questions remain regarding the factors which influence analytical and measurement error using this methodology. This thesis was comprised of four studies with the following emphases. The aim of Study 1 was to determine the analytical and measurement error of the IRMS with regard to sample handling under certain conditions. Study 2 involved the comparison of TEE (Total daily energy expenditure) using two commonly employed equations. Further, saliva and urine samples, collected at different times, were used to determine if clinically significant differences would occur. Study 3 was undertaken to determine the appropriate collection times for TBW estimates and derived body composition values. Finally, Study 4, a single case study to investigate if TEE measures are affected when the human condition changes due to altered exercise and water intake. The aim of Study 1 was to validate laboratory approaches to measure isotopic enrichment to ensure accurate (to international standards), precise (reproducibility of three replicate samples) and linear (isotope ratio was constant over the expected concentration range) results. This established the machine variability for the IRMS equipment in use at Queensland University for both TBW and TEE. Using either 0.4mL or 0.5mL sample volumes for both oxygen-18 and deuterium were statistically acceptable (p>0.05) and showed a within analytical variance of 5.8 Delta VSOW units for deuterium, 0.41 Delta VSOW units for oxygen-18. This variance was used as “within analytical noise” to determine sample deviations. It was also found that there was no influence of equilibration time on oxygen-18 or deuterium values when comparing the minimum (oxygen-18: 24hr; deuterium: 3 days) and maximum (oxygen-18: and deuterium: 14 days) equilibration times. With regard to preparation using the vacuum line, any order of preparation is suitable as the TEE values fall within 8% of each other regardless of preparation order. An 8% variation is acceptable for the TEE values due to biological and technical errors (Schoeller, 1988). However, for the automated line, deuterium must be assessed first followed by oxygen-18 as the automated machine line does not evacuate tubes but merely refills them with an injection of gas for a predetermined time. Any fractionation (which may occur for both isotopes), would cause a slight elevation in the values and hence a lower TEE. The purpose of the second and third study was to investigate the use of IRMS to measure the TEE and TBW of and to validate the current IRMS practices in use with regard to sample collection times of urine and saliva, the use of two TEE equations from different research centers and the body composition values derived from these TEE and TBW values. Following the collection of a fasting baseline urine and saliva sample, 10 people (8 women, 2 men) were dosed with a doubly labeled water does comprised of 1.25g 10% oxygen-18 and 0.1 g 100% deuterium/kg body weight. The samples were collected hourly for 12 hrs on the first day and then morning, midday, and evening samples were collected for the next 14 days. The samples were analyzed using an isotope ratio mass spectrometer. For the TBW, time to equilibration was determined using three commonly employed data analysis approaches. Isotopic equilibration was reached in 90% of the sample by hour 6, and in 100% of the sample by hour 7. With regard to the TBW estimations, the optimal time for urine collection was found to be between hours 4 and 10 as to where there was no significant difference between values. In contrast, statistically significant differences in TBW estimations were found between hours 1-3 and from 11-12 when compared with hours 4-10. Most of the individuals in this study were in equilibrium after 7 hours. The TEE equations of Prof Dale Scholler (Chicago, USA, IAEA) and Prof K.Westerterp were compared with that of Prof. Andrew Coward (Dunn Nutrition Centre). When comparing values derived from samples collected in the morning and evening there was no effect of time or equation on resulting TEE values. The fourth study was a pilot study (n=1) to test the variability in TEE as a result of manipulations in fluid consumption and level of physical activity; the magnitude of change which may be expected in a sedentary adult. Physical activity levels were manipulated by increasing the number of steps per day to mimic the increases that may result when a sedentary individual commences an activity program. The study was comprised of three sub-studies completed on the same individual over a period of 8 months. There were no significant changes in TBW across all studies, even though the elimination rates changed with the supplemented water intake and additional physical activity. The extra activity may not have sufficiently strenuous enough and the water intake high enough to cause a significant change in the TBW and hence the CO2 production and TEE values. The TEE values measured show good agreement based on the estimated values calculated on an RMR of 1455 kcal/day, a DIT of 10% of TEE and activity based on measured steps. The covariance values tracked when plotting the residuals were found to be representative of “well-behaved” data and are indicative of the analytical accuracy. The ratio and product plots were found to reflect the water turnover and CO2 production and thus could, with further investigation, be employed to identify the changes in physical activity.

Determination of coastal ground and surface water processes and character by use of hydrochemistry and stable isotopes, Fraser Coast, Queensland

This study was part of an integrated project developed in response to concerns regarding current and future land practices affecting water quality within coastal catchments and adjacent marine environments. Two forested coastal catchments on the Fraser Coast, Australia, were chosen as examples of low-modification areas with similar geomorphological and land-use characteristics to many other coastal zones in southeast Queensland. For this component of the overall project, organic , physico-chemical (Eh, pH and DO), ionic (Fe2+, Fe3+), and isotopic (ä13CDIC, ä15NDIN ä34SSO4) data were used to characterise waters and identify sources and processes contributing to concentrations and form of dissolved Fe, C, N and S within the ground and surface waters of these coastal catchments. Three sites with elevated Fe concentrations are discussed in detail. These included a shallow pool with intermittent interaction with the surface water drainage system, a monitoring well within a semi-confined alluvial aquifer, and a monitoring well within the fresh/saline water mixing zone adjacent to an estuary. Conceptual models of processes occurring in these environments are presented. The primary factors influencing Fe transport were; microbial reduction of Fe3+ oxyhydroxides in groundwaters and in the hyporheic zone of surface drainage systems, organic input available for microbial reduction and Fe3+ complexation, bacterial activity for reduction and oxidation, iron curtain effects where saline/fresh water mixing occurs, and variation in redox conditions with depth in ground and surface water columns. Data indicated that groundwater seepage appears a more likely source of Fe to coastal waters (during periods of low rainfall) via tidal flux. The drainage system is ephemeral and contributes little discharge to marine waters. However, data collected during a high rainfall event indicated considerable Fe loads can be transported to the estuary mouth from the catchment.

Hydrothermal rare earth elements mineralization in the Barra do Itapirapua carbonatite, southern Brazil: behaviour of selected trace elements and stable isotopes (C, O)

The Bura do Itapira pua carbonatite is located in southern Brazil and belongs to the Cretaceous Ponta Grossa alkaline-carbonatitic province related to the opening of the South Atlantic. The carbonatite complex is emplaced in Proterozoic granites and is mainly composed of plutonic magnesio- to ferrocarbonatite, with smaller amounts of subvolcanic magnesiocarbonatite. Hydrothermal alteration of the carbonatite has led to the formation of quartz, apatite, fluorite, rue earth fluorocarbonates, barite and sulfides in variable proportions. Trace element data, delta(13)C and delta(18)O are presented here, with the aim of better understanding the geochemical nature of hydrothermal alteration related to rare earth elements (REE) mineralization. The non-overprinted plutonic carbonatite shows the lowest REE contents, and its primitive carbon and oxygen stable isotopic composition places it in the field of primary igneous carbonatites. Two types of hydrothermally overprinted plutonic carbonatites can be distinguished based on secondary minerals and geochemical composition. Type I contains mainly quartz, rare earth fluorocarbonates and apatite as hydrothermal secondary minerals, and has steep chondrite normalized REE patterns, with Sigma(REE+Y) of up to 3 wt.% (i.e., two orders of magnitude higher than in fresh plutonic samples). In contrast, the Type II overprint contains apatite, fluorite and barite as dominant hydrothermal minerals, and is characterized by heavy REE enrichment relative to the fresh samples, with flat chondrite normalized REE patterns. Carbon and oxygen stable isotope ratios of Types I and II are elevated (delta(18)O + 8 to + 12 parts per thousand; delta(13)C - 6 to - 2 parts per thousand) relative to the fresh samples. Hydrothermally overprinted carbonatites exposed to weathering show even higher delta(18)O values (delta(18)O 13 to 25 parts per thousand) but no additional REE enrichment. The subvolcanic carbonatite has anomalously high delta(13)C of up to + 1 parts per thousand, which suggests crustal contamination through interaction with carbonate-bearing metasediments. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Biological, physical and chemical properties at the Subtropical Shelf Front Zone in the SW Atlantic Continental Shelf

The physical aspects of the Subtropical Shelf Front (STSF) for the Southwest Atlantic Continental Shelf were previously described. However, only scarce data on the biology of the front is available in the literature. The main goal of this paper is to describe the physical, chemical and biological properties of the STSF found in winter 2003 and summer 2004. A cross-section was established at the historically determined location of the STSF. Nine stations were sampled in winter and seven in summer. Each section included a series of conductivity-temperature-depth (CTD) stations where water samples from selected depths were filtered for nutrient determination. Surface samples were taken for chlorophyll a (Chl-a) determination and plankton net tows carried out above and below the pycnocline. Results revealed that winter was marked by an inner-shelf salinity front and that the STSF was located on the mid-shelf The low salinity waters in the inner-shelf indicated a strong influence of freshwater, with high silicate (72 mu M), suspended matter (45 mg l(-1)), phosphate (2.70 mu M) and low nitrate (1.0 mu M) levels. Total dissolved nitrogen was relatively high (22.98 mu M), probably due to the elevated levels of organic compound contribution close to the continental margin. Surface Chl-a concentration decreased from coastal well-mixed waters, where values up to 8.0 mg m(-3) were registered, to offshore waters. Towards the open ocean, high subsurface nutrients values were observed, probably associated to South Atlantic Central Waters (SACW). Zooplankton and ichthyoplankton abundance followed the same trend; three different groups associated to the inner-, mid- and outer-shelf region were identified. During summer, diluted waters extended over the shelf to join the STSF in the upper layer; the concentration of inorganic nutrients decreased in shallow waters; however, high values were observed between 40 and 60 m and in deep offshore waters. Surface Chl-a ranged 0.07-1.5 mg m(-3); winter levels were higher. Three groups of zoo and ichthyoplankton, separated by the STSF, were also identified. Results of the study performed suggest that the influence of freshwater was stronger during winter and that abundance distribution of Chl-a, copepods and ichthyoplankton was related to the Plata Plume Waters (PPW), rather than to the presence of the STSF. During summer, when the presence of freshwater decreases, plankton interactions seem to take place in the STSF. (C) 2008 Elsevier Ltd. All rights reserved.

Production, radiochemical separation and chemical coupling of radioactive arsenic isotopes to synthesize radiopharmaceuticals for molecular imaging

Noninvasive molecular-imaging technologies are playing a keyrole in drug discovery, development and delivery. Positron Emission Tomography (PET) is such a molecular imaging technology and a powerful tool for the observation of various diseases. However, it is limited by the availability of agents with high selectivity to the target and a physical half-life of the used positron emitting nuclide which matches the biological half-life of the observed process. For the long lasting enrichment of antibodies in tumor tissue few suitable isotopes for PET imaging are currently available. The element arsenic provides a range of isotopes, which could be used for diagnosis and also for endoradiotherapy. This work describes the development of radiochemical separation procedures to separate arsenic isotopes in no-carrier-added (nca) purity from reactor or cyclotron irradiated targets, the development and evaluation of a labeling chemistry to attach these separated arsenic isotopes to monoclonal antibodies, the in vitro and in vivo evaluation of antibodies labeled with radioactive arsenic isotopes and the molecular imaging using small animal PET.

Paleoclimate and Amerindians: Evidence from stable isotopes and atmospheric circulation

Two Amerindian demographic shifts are attributed to climate change in the northwest plains of North America: at ≈11,000 calendar years before present (yr BP), Amerindian culture apparently split into foothills–mountains vs. plains biomes; and from 8,000–5,000 yr BP, scarce archaeological sites on the open plains suggest emigration during xeric “Altithermal” conditions. We reconstructed paleoclimates from stable isotopes in prehistoric bison bone and relations between weather and fractions of C4 plants in forage. Further, we developed a climate-change model that synthesized stable isotope, existing qualitative evidence (e.g., palynological, erosional), and global climate mechanisms affecting this midlatitude region. Our isotope data indicate significant warming from ≈12,400 to 11,900 yr BP, supporting climate-driven cultural separation. However, isotope evidence of apparently wet, warm conditions at 7,300 yr BP refutes emigration to avoid xeric conditions. Scarcity of archaeological sites is best explained by rapid climate fluctuations after catastrophic draining of the Laurentide Lakes, which disrupted North Atlantic Deep Water production and subsequently altered monsoonal inputs to the open plains.

Physical, chemical, biological and ecotoxicological properties of wastewater discharged from Davis Station, Antarctica

The properties and toxicity of untreatedwastewater at Davis Station, East Antarctica,were investigated to inform decisions regarding the appropriate level of treatment for local discharge purposes and more generally, to better understand the risk associated with dispersal and impact of wastewaters in Antarctica. Suspended solids, nutrients (nitrogen, phosphorus), biological oxygen demand (BOD), metals, organic contaminants, surfactants and microbiological load were measured at various locations throughout the wastewater discharge system. Wastewater quality and properties varied greatly between buildings on station, each ofwhich has separate holding tanks. Nutrients, BOD and settleable solid levelswere higher than standard municipal wastewaters. Microbiological loads were typical of untreated wastewater. Contaminants detected in the wastewater included metals and persistent organic compounds, mainly polybrominated diphenyl ethers (PBDEs). The toxicity of wastewater was also investigated in laboratory bioassays using two local Antarctic marine invertebrates, the amphipod Paramoera walkeri and the microgastropod Skenella paludionoides. Animals were exposed to a range of wastewater concentrations from3% to 68% (test 1) or 63% (test 2) over 21 days with survival monitored daily. Significant mortality occurred in all concentrations of wastewater after 14 to 21 days, and at higher concentrations (50–68% wastewater) mortality occurred after only one day. Results indicate that the local receiving marine environment at Davis Station is at risk from existing wastewater discharges, and that advanced treatment is required both to remove contaminants shown to cause toxicity to biota, as well as to reduce the environmental risks associated with non-native micro-organisms in wastewater.

Do stable isotopes in carbonate cement of Mio-Pleistocene Himalayan sediments record paleoecological and paleoclimatic changes?

Non-pedogenic carbonates, such as carbonate cement and nodules in the sandstones, are quite common in the terrestrial geological record. Unlike pedogenic carbonates, their stable isotope ratios lack investigations for paleo-climatic reconstructions. The present investigation therefore, explores the possibility of use of stable isotope studies of non-pedogenic carbonates from the Mb-Pleistocene Siwalik Group of sediments exposed in the Ramnagar sub-basin of the NW Himalaya. Petrographic studies reveal the dominance of micrite fabric in carbonate nodules both of pedogenic and non-pedogenic samples irrespective of specific stratigraphic unit However, calcite as cement in the sandstones shows the dominance of micrite fabric in the younger in age sediments. Seventy-two non-pedogenic carbonate samples from the carbonate nodules and cement in the Siwalik sandstones, ranging in age between similar to 1 Ma and 12.2 Ma, were analyzed for delta C-13 and delta O-18 values. The delta C-13 values vary from -24.77 parts per thousand to -1.1 parts per thousand and delta O-18 values vary from -15.34 parts per thousand to -7.81 parts per thousand. Pedogenic and non-pedogenic carbonates ranging in age between similar to 1 Ma and 6 Ma have largely similar delta C-13 values and the range of delta C-13 values indicate the dominance of C-4 type of vegetation. However, unlike pedogenic carbonates which showed the dominance of C-3 type of vegetation pre- 7 Ma on the basis of delta C-13 -depleted isotopic values (Singh et al., 2011), delta C-13 values are largely enriched in the corresponding aged non-pedogenic carbonates revealing no information on specific type of vegetation. Likewise, paleoprecipitational reconstructions from delta O-18 values in pedogenic carbonates showed a progressive increase in aridity from similar to 12 Ma to recent excluding short term increases in rainfall/monsoon intensity at around 10 Ma, 5 Ma, and 1.8 Ma (Singh et al., 2012). On the contrary, such reconstructions are not possible from the delta O-18 values of non-pedogenic carbonates and indeed the delta O-18 values of non-pedogenic carbonates are largely depleted to as much as 6 parts per thousand from the corresponding pedogenic carbonates. Such differences in delta C-13 and delta O-18 values of non-pedogenic carbonates from pedogenic carbonates are primarily due to the dependence of the former on groundwater conditions responsible for precipitating carbonate. Further, a comparison of isotopic values between non-pedogenic and pedogenic carbonates can be interpreted that post-6 Ma and pre-6 Ma non-pedogenic carbonates were largely formed by shallow and deep groundwater conditions respectively. The result of these investigative studies therefore, suggests that the stable delta C-13 and delta O-18 values of non-pedogenic carbonates, unlike the pedogenic carbonates and irrespective of nature of calcite fabric, showed their little importance in paleoclimatic and paleoecological reconstructions. (C) 2014 Elsevier B.V. All rights reserved.