Short- and long-term temporal variations in salinity and the oxygen, carbon and hydrogen isotopic compositions of the Hooghly Estuary water, India

The Hooghly River estuary provides a unique experimental site to understand the effect of monsoonal river discharge on freshwater and seawater mixing. Water samples collected bi-weekly for a duration of 17 months were analyzed for salinity, delta O-18,delta C-13(DIC), as well as delta D to investigate the differential mixing of freshwater and seawater. The differences in salinity and delta O-18 of samples collected during low and high tides on the same day are strongly correlated suggesting a well mixed water column at our sampling site. Low salinity and depleted delta O-18 during monsoon is consistent with increased river discharge as well as high rainfall. We identified different slopes in a delta O-18 versus salinity plot for the estuary water samples collected during monsoon and non-monsoon seasons. This is driven by composition of the freshwater source which is dominated by rainwater during monsoon and rivers during non-monsoon months. Selected delta D analyses of samples indicate that groundwater contributes significantly to the Hooghly Estuary during low rainfall times of the year. delta C-13(DIC) measured in the water recorded low values towards the end of monsoon indicating low productivity (i.e. increased organic respiration) while progressively increasing delta C-13(DIC) values from October till January as well as during some of the pre-monsoon months can be explained by increasing productivity. Very low delta C-13(DIC) (similar to-20%0) suggests involvement of carbon derived from anaerobic oxidation of organics and/or methane with potential contribution from increased anthropogenic water supply. An estimate of seawater incursion into the Hooghly Estuary at different times of the year is obtained by using salinity data in a two-component mixing model. Presence of seawater was found maximum (31-37%) during February till July and lowest (less than or equal to 6%) from September till November. We notice a temporal offset between Ganges River discharge farther upstream at Farakka and salinity variation at the Hooghly Estuary. We believe that this time lag is a result of the physical distance between Farakka and Kakdweep (our sampling location) and put constraints on the travel time of river water during early monsoon. (c) 2012 Published by Elsevier B.V.

On the water-induced critical double point in a polymer solution: the role of isotopic substitution

This paper examines the effect of substitution of water by heavy water in a polymer solution of polystyrene (molecular weight = 13000) and acetone. A critical double point (CDP), at which the upper and the lower partially-miscible regions merge, occurs at nearly the same coordinates as for the system [polystyrene + acetone + water]. The shape of the critical line for [polystyrene + acetone + heavy water] is highly asymmetric. An explanation for the occurrence of the water-induced CDP in [polystyrene + acetone] is advanced in terms of the interplay between contact energy dissimilarity and free-volume disparity of the polymer and the solvent. The question of the possible existence of a one-phase hole in an hourglass phase diagram is addressed in [polystyrene + acetone + water]. Our data exclude such a possibility.

An experimental set-up for carbon isotopic analysis of atmospheric CO2 and an example of ecosystem response during solar eclipse 2010

We present here, an experimental set-up developed for the first time in India for the determination of mixing ratio and carbon isotopic ratio of air-CO2. The set-up includes traps for collection and extraction of CO2 from air samples using cryogenic procedures, followed by the measurement of CO2 mixing ratio using an MKS Baratron gauge and analysis of isotopic ratios using the dual inlet peripheral of a high sensitivity isotope ratio mass spectrometer (IRMS) MAT 253. The internal reproducibility (precision) for the PC measurement is established based on repeat analyses of CO2 +/- 0.03 parts per thousand. The set-up is calibrated with international carbonate and air-CO2 standards. An in-house air-CO2 mixture, `OASIS AIRMIX' is prepared mixing CO2 from a high purity cylinder with O-2 and N-2 and an aliquot of this mixture is routinely analyzed together with the air samples. The external reproducibility for the measurement of the CO2 mixing ratio and carbon isotopic ratios are +/- 7 (n = 169) mu mol.mol(-1) and +/- 0.05 (n = 169) parts per thousand based on the mean of the difference between two aliquots of reference air mixture analyzed during daily operation carried out during November 2009-December 2011. The correction due to the isobaric interference of N2O on air-CO2 samples is determined separately by analyzing mixture of CO2 (of known isotopic composition) and N2O in varying proportions. A +0.2 parts per thousand correction in the delta C-13 value for a N2O concentration of 329 ppb is determined. As an application, we present results from an experiment conducted during solar eclipse of 2010. The isotopic ratio in CO2 and the carbon dioxide mixing ratio in the air samples collected during the event are different from neighbouring samples, suggesting the role of atmospheric inversion in trapping the emitted CO2 from the urban atmosphere during the eclipse.

Seasonal variability of rainfall recorded in growth bands of the Giant African Land Snail Lissachatina fulica (Bowdich) from India

Seasonal rainfall patterns in Bangalore, India, have been reconstructed using stable isotopic ratios in the growth bands of Giant African Land Snail shells. The present study was conducted at Bangalore, India which receives rain during the summer months. The oxygen isotopic record in the rainwater samples collected during different months covering the period of the summer monsoon of the year 2008 is compared with the isotopic ratio in the gastropod growth bands deposited simultaneously. The chronology of the shell growth band is independently established assuming the growth rate observed in a chamber experiment maintaining similar relative humidity and temperature conditions. A consistent pattern observed in the isotopic ratio in the gastropod growth bands and rainwater is demonstrated and provides a novel approach for precipitation reconstruction at seasonal and weekly time scales. This approach of using isotopic ratios in the gastropod growth bands for rainfall can serve as a substitute for filling gaps in rainfall data and for cases where no rain records are available. In addition, they can be used to determine the frequencies and magnitudes of dry spells from the past records. (C) 2013 Elsevier B.V. All rights reserved.

Hydrographical characteristics and oxygen isotopic signatures of water in a coastal environment (Mangalore) along the southeastern Arabian Sea

Coastal marine environments are important links between the continents and the open ocean. The coast off Mangalore forms part of the upwelling zone along the southeastern Arabian Sea. The temperature, salinity, density, dissolved oxygen and stable oxygen isotope ratio (delta O-18) of surface waters as well as those of bottom waters off coastal Mangalore were studied every month from October 2010 to May 2011. The coastal waters were stratified in October and November due to precipitation and runoff. The region was characterised by upwelled bottom waters in October, whereas the region exhibited a temperature inversion in November. The surface and bottom waters presented almost uniform properties from December until April. The coastal waters were observed to be most dense in January and May. Comparatively cold and poorly oxygenated bottom waters during the May sampling indicated the onset of upwelling along the region. delta O-18 of the coastal waters successfully documented the observed variations in the hydrographical characteristics of the Mangalore coast during the monthly sampling period. We also noted that the monthly variability in the properties of the coastal waters of Mangalore was related to the hydrographical characteristics of the adjacent open ocean inferred from satellite-derived surface winds, sea surface height anomaly data and sea surface temperatures.

Sources of major ions and processes affecting the geochemical and isotopic signatures of subsurface waters along a tropical river, Southwestern India

Systematic monitoring of subsurface hydrogeochemistry has been carried out for a period of one year in a humid tropical region along the Nethravati-Gurupur River. The major ion and stable isotope (delta O-18 and delta H-2) compositions are used to understand the hydrogeochemistry of groundwater and its interaction with surface water. In the study, it is observed that intense weathering of source rocks is the major source of chemical elements to the surface and subsurface waters. In addition, agricultural activities and atmospheric contributions also control the major ion chemistry of water in the study area. There is a clear seasonality in the groundwater chemistry, which is related to the recharge and discharge of the hydrological system. On a temporal scale, there is a decrease in major cation concentrations during the monsoon which is a result of dilution of sources from the weathering of rock minerals, and an increase in anion concentrations which is contributed by the atmosphere, accompanied by an increase in water level during the monsoon. The stable isotope composition indicates that groundwater in the basin is of meteoric origin and recharged directly from the local precipitation during the monsoonal season. Soon after the monsoon, groundwater and surface water mix in the subsurface region. The groundwater feeds the surface water during the lean river flow season.

Isotopic fractionation in proteins as a measure of hydrogen bond length

If a deuterated molecule containing strong intramolecular hydrogen bonds is placed in a hydrogenated solvent, it may preferentially exchange deuterium for hydrogen. This preference is due to the difference between the vibrational zero-point energy for hydrogen and deuterium. It is found that the associated fractionation factor (I) is correlated with the strength of the intramolecular hydrogen bonds. This correlation has been used to determine the length of the H-bonds (donor-acceptor separation) in a diverse range of enzymes and has been argued to support the existence of short low-barrier H-bonds. Starting with a potential energy surface based on a simple diabatic state model for H-bonds, we calculate (I) as a function of the proton donor-acceptor distance R. For numerical results, we use a parameterization of the model for symmetric 0-H. ``.0 bonds R. H. McKenzie, Chem. Phys. Lett. 535, 196 (2012)]. We consider the relative contributions of the 0-H stretch vibration, O-H bend vibrations (both in plane and out of plane), tunneling splitting effects at finite temperature, and the secondary geometric isotope effect. We compare our total (I) as a function of R with NMR experimental results for enzymes, and in particular with an earlier model parametrization (D(R), used previously to determine bond lengths. (C) 2015 AIP Publishing LLC.

Stable isotopic signature of Southern Ocean deep water CO2 ventilation

The link between atmospheric CO2 level and ventilation state of the deep ocean is poorly understood due to the lack of coherent observations on the partitioning of carbon between atmosphere and ocean. In this Southern Ocean study, we have classified the Southern Ocean into different zones based on its hydrological features and have binned the variability in latitudinal air-CO2 concentration and its isotopic ratios. Together with air-CO2, we analysed the surface water for the isotopic ratios in dissolved inorganic carbon (DIC). Using the binary mixing approach on the isotopic ratio of atmospheric CO2 and its concentration, we identified the delta C-13 value of source CO2. The isotopic composition of source CO2 was around -9.22 +/- 0.26 parts per thousand for the year 2011 and 2012, while a composition of -13.49 +/- 4.07 parts per thousand was registered for the year 2013. We used the delta C-13 of DIC to predict the CO2 composition in air under equilibrium and compared our estimates with actual observations. We suggest that the degeneration of the DIC in presence of warm water in the region was the factor responsible for adding the CO2 to the atmosphere above. The place of observation coincides with the zone of high wind speed which promotes the process of CO2 exsolution from sea water. (C) 2015 Elsevier Ltd. All rights reserved.

Isotopic and geochemical characterization of invader tilapia fishes from water bodies of West Bengal and Karnataka, India

The otoliths (N = 12) of freshwater invasive species tilapia (Tilapia mossambicus) collected from two water bodies located at Kolkata and Bangalore, India, were analyzed for stable isotopes (delta 18O, delta 14C) and major and trace elements in order to assess the suitability of using otoliths as a tracer of aquatic environmental changes. The stable isotope analysis was done using the dual inlet system of a Finnigan-MAT 253 isotope ratio mass spectrometer (Thermo-Fisher, Bremen, Germany). Concentrations of major and trace elements were determined using a Thermo X-Series II quadrupole mass spectrometer. The stable isotope composition in tilapia otolith samples from Bangalore and Kolkata water bodies are quite good agreeing with that of the respective lake/pond and rain water. Elemental composition revealed in a pattern of Ca > Fe > Na > Sr > K > Ba > Cr > Mg > As > Mn > Zn > Co > Cu > Cd > Pb. The otoliths from Kolkata pond water are more enriched in Ba, Zn, Pb, Mn, Se, Cu, Zn, Cd, and Ni whereas Cr and As were found to be higher in otolith samples from Bangalore lake. The enrichment factor (EF) values of Cr were higher for both the sampling location in comparison with other metals, although all the studied metals exhibited EF values >1. The PCA shows clustering of metals in the otolith which are related either with the metabolic and physiological attributes or waterborne source. The study demonstrated the potential of stable isotope techniques to distinguish otolith specimens from varied climatic zone, while elemental composition recorded the quality of water at both the locations. The role of climate driving the quality of water can be understood by detailed and continuous monitoring of otolith specimens in the future. Future method allows reconstruction of climate and water quality from old specimens from field exposures or museum collection.

Interlaboratory comparison of magnesium isotopic compositions of 12 felsic to ultramafic igneous rock standards analyzed by MC-ICPMS

To evaluate the interlaboratory mass bias for high-precision stable Mg isotopic analysis of natural materials, a suite of silicate standards ranging in composition from felsic to ultramafic were analyzed in five laboratories by using three types of multicollector inductively coupled plasma mass spectrometer (MC-ICPMS). Magnesium isotopic compositions from all labs are in agreement for most rocks within quoted uncertainties but are significantly (up to 0.3 parts per thousand in Mg-26/Mg-24, > 4 times of uncertainties) different for some mafic samples. The interlaboratory mass bias does not correlate with matrix element/Mg ratios, and the mechanism for producing it is uncertain but very likely arises from column chemistry. Our results suggest that standards with different matrices are needed to calibrate the efficiency of column chemistry and caution should be taken when dealing with samples with complicated matrices. Well-calibrated standards with matrix elements matching samples should be used to reduce the interlaboratory mass bias.

Fingerprinting environmental conditions and related stress using stable isotopic composition of rice (Oryza sativa L.) grain organic matter

Sea level rise (SLR) is a primary factor responsible for inundation of low-lying coastal regions across the world, which in turn governs the agricultural productivity. In this study, rice (Oryza sativa L.) cultivated seasonally in the Kuttanad Wetland, a SLR prone region on the southwest coast of India, were analysed for oxygen, hydrogen and carbon isotopic ratios (delta O-18, delta H-2 and delta C-13) to distinguish the seasonal environmental conditions prevalent during rice cultivation. The region receives high rainfall during the wet season which promotes large supply of fresh water to the local water bodies via the rivers. In contrast, during the dry season reduced river discharge favours sea water incursion which adversely affects the rice cultivation. The water for rice cultivation is derived from regional water bodies that are characterised by seasonal salinity variation which co-varies with the delta O-18 and delta H-2 values. Rice cultivated during the wet and the dry season bears the isotopic imprints of this water. We explored the utility of a mechanistic model to quantify the contribution of two prominent factors, namely relative humidity and source water composition in governing the seasonal variation in oxygen isotopic composition of rice grain OM. delta C-13 values of rice grain OM were used to deduce the stress level by estimating the intrinsic water use efficiency (WUEi) of the crop during the two seasons. 1.3 times higher WUE, was exhibited by the same genotype during the dry season. The approach can be extended to other low lying coastal agro-ecosystems to infer the growth conditions of cultivated crops and can further be utilised for retrieving paleo-environmental information from well preserved archaeological plant remains. (c) 2015 Elsevier Ltd. All rights reserved.

Isotopic disequilibrium in Globigerina bulloides and carbon isotope response to productivity increase in Southern Ocean

Oxygen and carbon isotope ratios in planktonic foraminifera Globigerina bulloides collected from tow samples along a transect from the equatorial Indian ocean to the Southern Ocean (45 degrees E and 80 degrees E and 10 degrees N to 53 degrees S) were analysed and compared with the equilibrium delta O-18 and delta C-13 values of calcite calculated using the temperature and isotopic composition of the water column. The results agree within similar to 0.25% for the region between 10 degrees N and 40 degrees S and 75-200 m water depth which is considered to be the habitat of Globigerina bulloides. Further south (from 40 degrees S to 55 degrees S), however, the measured delta O-18 and delta C-13 values are higher than the expected values by similar to 2% and similar to 1% respectively. These enrichments can be attributed to either a `vital effect' or a higher calcification rate. An interesting pattern of increase in the delta C-13(DIC) value of the surface water with latitude is observed between 35 degrees S and similar to 60 degrees S, with a peak at similar to 42 degrees S. This can be caused by increased organic matter production and associated removal. A simple model accounting for the increase in the delta C-13(DIC) values is proposed which fits well with the observed chlorophyll abundance as a function of latitude.