Radiocarbon, stable isotopic compositions and seawater chemical properties of Black Sea core-top sediments and CTD stations

Chloropigments and their derivative pheopigments preserved in sediments can directly be linked to photosynthesis. Their carbon and nitrogen stable isotopic compositions have been shown to be a good recorder of recent and past surface ocean environmental conditions tracing the carbon and nitrogen sources and dominant assimilation processes of the phytoplanktonic community. In this study we report results from combined compound-specific radiocarbon and stable carbon and nitrogen isotope analysis to examine the time-scales of synthesis and fate of chlorophyll-a and its degradation products pheophytin-a, pyropheophytin-a, and 132,173-cyclopheophorbide-a-enol until burial in Black Sea core-top sediments. The pigments are mainly of marine phytoplanktonic origin as implied by their stable isotopic compositions. Pigment ?15N values indicate nitrate as the major uptake substrate but 15N-depletion towards the open marine setting indicates either contribution from N2-fixation or direct uptake of ammonium from deeper waters. Radiocarbon concentrations translate into minimum and maximum pigment ages of approximately 40 to 1200 years. This implies that protective mechanisms against decomposition such as association with minerals, storage in deltaic anoxic environments, or eutrophication-induced hypoxia and light limitation are much more efficient than previously thought. Moreover, seasonal variations of nutrient source, growth period, and habitat and their associated isotopic variability are likely at least as strong as long-term trends. Combined triple isotope analysis of sedimentary chlorophyll and its primary derivatives is a powerful tool to delineate biogeochemical and diagenetic processes in the surface water and sediments, and to assess their precise time-scales.

Iron assimilation by the clam Laternula elliptica from Potter Cove, King Georg Island, Antarctica

Iron stable isotope signatures (d56Fe) in hemolymph (bivalve blood) of the Antarctic bivalve Laternula elliptica were analyzed by Multiple Collector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICP-MS) to test whether the isotopic fingerprint can be tracked back to the predominant sources of the assimilated Fe. An earlier investigation of Fe concentrations in L. elliptica hemolymph suggested that an assimilation of reactive and bioavailable Fe (oxyhydr)oxide particles (i.e. ferrihydrite), precipitated from pore water Fe around the benthic boundary, is responsible for the high Fe concentration in L. elliptica (Poigner et al., 2013, doi:10.1016/j.ecss.2013.10.027). At two stations in Potter Cove (King George Island, Antarctica) bivalve hemolymph showed mean d56Fe values of -1.19 ± 0.34 per mil and -1.04 ± 0.39 per mil, respectively, which is between 0.5 per mil and 0.85 per mil lighter than the pool of easily reducible Fe (oxyhydr)oxides of the surface sediments (-0.3 per mil to -0.6 per mil). This is in agreement with the enrichment of lighter Fe isotopes at higher trophic levels, resulting from the preferential assimilation of light isotopes from nutrition. Nevertheless, d56Fe hemolymph values from both stations showed a high variability, ranging between -0.21 per mil (value close to unaltered/primary Fe(oxyhydr)oxide minerals) and -1.91 per mil (typical for pore water Fe or diagenetic Fe precipitates), which we interpret as a "mixed" d56Fe signature caused by Fe assimilation from different sources with varying Fe contents and d56Fe values. Furthermore, mass dependent Fe fractionation related to physiological processes within the bivalve cannot be ruled out. This is the first study addressing the potential of Fe isotopes for tracing back food sources of bivalves.

Investigations on two sediment cores from the Arctic Ocean

During the "RV Polarstem"-Expedition ARK VIII/2 sediment samples were obtained at the continental slope of NW-Spitsbergen. Detailed sedimentological and geochemical analysis were carried out at two undisturbed box cores (PS2122-1GKG, PS2123-2GKG) as well as two gravity cores (PS2122-1SL, PS2123-2SL). The following parameters were deterrnined: Organic carbon, nitrogen and carbonate contents, hydrogen index, stable isotopes, ice rafted debris, grain-size distribution and biogenic opal. The main objective of this study was the reconstruction of paleoenvironmental changes off the northwest coast of Spitsbergen during the last glacial/interglacial-cycle, i.e., during the last about 128.000 years. The results of the investigations can be summarized as follows: - During isotope stage 1 (Holocene) and 5.5 (Eemian Interglacial), light stable isotopes (d180: 3.4-2 %o; d13C: 0.26-0.5 %o), increased bioturbation, high content of planktonic foraminifera and biogenic opal and low quantity of ice-rafted material, indicate seasonally ice-free conditions along the northwest coast due to the intfluence of the Westspitsbergen Current. - Additionally, the sediment characteristics of the middle of isotope stage 2 (Last Glacial Maximum) and at the end of stage 3 confirms an inflow of warmer Atlantic water. The highest production of planktonic and benthic foraminifera (N. pachyderma sin., Cassidulina teretis) (CaC03: 10 %) may reflect the expansion of the 'Whalers Bay'-Polynya as a result of the influence of the Westspitsbergen Current. Presumably, occasionally open-ice conditions provide sufficient precipitation to buildup the Svalbard/Barents Ice Sheet. - The time intervals for the glacier advances on Svalbard given by Mangerud et al. (1992), can be correlated with increased accumulation of ice-rafted material in the sediments at the northwest coast of Spitsbergen. Especially during isotope stage 4 and at the beginning of the Last Glacial Maximum (isotope stage 2), a drastically increased supply of coarse terrigenous material occurs. The high accumulation rate (0.18-0.21 g/cm**2/ka) of terrigenous organic carbon is indicated by high C/N ratios (until 16) and low hydrogen index (50 mg HC/gC). In constrast to deep sea sediments in the Fram-Strait (Hebbeln 1992), the glacier advance between 118.000 and 108.000 years B.P. ist documented in the continental slope sediments. - At the end of the Weichselian ice age, the deglaciation at the northwest coast starts with a typical melt-water signal in the stables isotope record (d18O: 3.5 %o; d13C: -0.16 %o) and high contents of gravel (6-13 %). The signal can be assigned to an event at the westcoast of Spitsbergen (core NP90-39), dated to 14.500 years B.P. (Andersen et al. 1993).

Nitrite consumption and associated isotope changes during a river flood event in the Elbe river

In oceans, estuaries, and rivers, nitrification is an important nitrate source, and stable isotopes of nitrate are often used to investigate recycling processes (e.g. remineralisation, nitrification) in the water column. Nitrification is a two-step process, where ammonia is oxidised via nitrite to nitrate. Nitrite usually does not accumulate in natural environments, which makes it difficult to study the single isotope effect of ammonia oxidation or nitrite oxidation in natural systems. However, during an exceptional flood in the Elbe River in June 2013, we found a unique co-occurrence of ammonium, nitrite, and nitrate in the water column, returning towards normal summer conditions within 1 week. Over the course of the flood, we analysed the evolution of d15N-[NH4]+ and d15N-[NO2]- in the Elbe River. In concert with changes in suspended particulate matter (SPM) and d15N SPM, as well as nitrate concentration, d15N-NO3 - and d18O-[NO3] -, we calculated apparent isotope effects during net nitrite and nitrate consumption. During the flood event, > 97 % of total reactive nitrogen was nitrate, which was leached from the catchment area and appeared to be subject to assimilation. Ammonium and nitrite concentrations increased to 3.4 and 4.4 µmol/l, respectively, likely due to remineralisation, nitrification, and denitrification in the water column. d15N-[NH4]+ values increased up to 12 per mil, and d15N-[NO2]- ranged from -8.0 to -14.2 per mil. Based on this, we calculated an apparent isotope effect 15-epsilon of -10.0 ± 0.1 per mil during net nitrite consumption, as well as an isotope effect 15-epsilon of -4.0 ± 0.1 per mil and 18-epsilon of -5.3 ± 0.1 per mil during net nitrate consumption. On the basis of the observed nitrite isotope changes, we evaluated different nitrite uptake processes in a simple box model. We found that a regime of combined riparian denitrification and 22 to 36 % nitrification fits best with measured data for the nitrite concentration decrease and isotope increase.

Combining histology, stable isotope analysis and ZooMS collagen fingerprinting to investigate the taphonomic history and dietary behaviour of extinct giant tortoises from the Mare aux Songes deposit on Mauritius

Taphonomic research of bones can provide additional insight into a site's formation and development, the burial environment and ongoing post-mortem processes. A total of 30 tortoise (Cylindraspis) femur bone samples from the Mare aux Songes site (Mauritius)were studied histologically, assessing parameters such as presence and type of microbial alteration, inclusions, staining/infiltrations, the degree of microcracking and birefringence. The absence of microbial attack in the 4200 year old Mare aux Songes bones suggests the animals rapidly entered the soil whole-bodied and were sealed anoxically, although they suffered frombiological and chemical degradation (i.e. pyrite formation/oxidation, mineral dissolution and staining) related to changes in the site's hydrology. Additionally, carbon and nitrogen stable isotopeswere analysed to obtain information on the animals' feeding behaviour. The results show narrowly distributed δ13C ratios, indicating a terrestrial C3 plant-based diet, combined with a wide range in δ15N ratios. This is most likely related to the tortoises' drought-adaptive ability to change their metabolic processes, which can affect the δ15N ratios. Furthermore, ZooMS collagen fingerprinting analysis successfully identified two tortoise species (C. triserrata and C. inepta) in the bone assemblage,which,when combined with stable isotope data, revealed significantly different δ15N ratios between the two tortoise species. As climatic changes around this period resulted in increased aridity in the Mascarene Islands, this could explain the extremely elevated δ15N ratio in our dataset. The endemic fauna was able to endure the climatic changes 4200 years ago, although human arrival in the 17th century changed the original habitat to such an extent that it resulted in the extinction of several species. Fortunately we are still able to study these extinct tortoises due to the beneficial conditions of their burial environment, resulting in excellent bone preservation.

The estuarine geochemical reactivity of Zn isotopes and its relevance for the biomonitoring of anthropogenic Zn and Cd contaminations from metallurgical activities: Example of the Gironde fluvial-estuarine system, France

Zinc stable isotopes measurements by MC-ICP-MS, validated by laboratory intercalibrations, were performed on wild oysters, suspended particles and filtered river/estuarine water samples to provide new constraints for the use of Zn isotopes as environmental tracers. The samples selected were representative of the long range (400 km) transport of metal (Zn, Cd, etc.) contamination from former Zn-refining activities at Decazeville (i.e. δ66Zn > 1 ‰) and its phasing out, recorded during 30 years in wild oysters from the Gironde Estuary mouth (RNO/ROCCH sample bank). The study also addresses additional anthropogenic sources (urban and viticulture) and focuses on geochemical reactivity of Zn in the turbidity gradient and the maximum turbidity zone (MTZ) of the fluvial Gironde Estuary. In this area, dissolved Zn showed a strong removal onto suspended particulate matter (SPM) and progressive enrichment in heavy isotopes with increasing SPM concentrations varying from δ66Zn = -0.02 ‰ at 2 mg/L to +0.90 ‰ at 1310 mg/L. These signatures were attributed to kinetically driven adsorption due to strongly increasing sorption sites in the turbidity gradient and MTZ of the estuary. Oysters from the estuary mouth, contaminated sediments from the Lot River and SPM entering the estuary showed parallel historical evolutions (1979-2010) for Zn/Cd ratios but not for δ66Zn values. Oysters had signatures varying from δ66Zn = 1.43 ‰ in 1983 to 1.18 ‰ in 2010 and were offset by δ66Zn = 0.6 - 0.7 ‰ compared to past (1988) and present SPM from the salinity gradient. Isotopic signatures in river-borne particles entering the Gironde Estuary under contrasting freshwater discharge regimes during 2003-2011 showed similar values (δ66Zn ≈ 0.35 ± 0.03 ‰; 1SD, n=15), i.e. they were neither related to former metal refining activities at least for the past decade nor clearly affected by other anthropogenic sources. Therefore, the Zn isotopic signatures in Gironde oysters reflect the geochemical reactivity of Zn in the estuary rather than signatures of past metallurgical contaminations in the watershed as recorded in contaminated river sediments. The study also shows that the isotopic composition of Zn is strongly fractionated by its geochemical reactivity in the Gironde Estuary, representative of meso-macrotidal estuarine systems.

Assessing land–ocean connectivity via submarine groundwater discharge (SGD) in the Ria Formosa Lagoon (Portugal): combining radon measurements and stable isotope hydrology

Natural radioactive tracer-based assessments of basin-scale submarine groundwater discharge (SGD) are well developed. However, SGD takes place in different modes and the flow and discharge mechanisms involved occur over a wide range of spatial and temporal scales. Quantifying SGD while discriminating its source functions therefore remains a major challenge. However, correctly identifying both the fluid source and composition is critical. When multiple sources of the tracer of interest are present, failure to adequately discriminate between them leads to inaccurate attribution and the resulting uncertainties will affect the reliability of SGD solute loading estimates. This lack of reliability then extends to the closure of local biogeochemical budgets, confusing measures aiming to mitigate pollution. Here, we report a multi-tracer study to identify the sources of SGD, distinguish its component parts and elucidate the mechanisms of their dispersion throughout the Ria Formosa – a seasonally hypersaline lagoon in Portugal. We combine radon budgets that determine the total SGD (meteoric + recirculated seawater) in the system with stable isotopes in water (δ2H, δ18O), to specifically identify SGD source functions and characterize active hydrological pathways in the catchment. Using this approach, SGD in the Ria Formosa could be separated into two modes, a net meteoric water input and another involving no net water transfer, i.e., originating in lagoon water re-circulated through permeable sediments. The former SGD mode is present occasionally on a multi-annual timescale, while the latter is a dominant feature of the system. In the absence of meteoric SGD inputs, seawater recirculation through beach sediments occurs at a rate of  ∼  1.4  ×  106 m3 day−1. This implies that the entire tidal-averaged volume of the lagoon is filtered through local sandy sediments within 100 days ( ∼  3.5 times a year), driving an estimated nitrogen (N) load of  ∼  350 Ton N yr−1 into the system as NO3−. Land-borne SGD could add a further  ∼  61 Ton N yr−1 to the lagoon. The former source is autochthonous, continuous and responsible for a large fraction (59 %) of the estimated total N inputs into the system via non-point sources, while the latter is an occasional allochthonous source capable of driving new production in the system.

Isotopic view of vegetation and carbon and nitrogen cycles in a cerrado ecosystem, southeastern Brazil

Carbon and nitrogen biogeochemical cycles in savannas are strongly regulated by the seasonal distribution of precipitation and pulses of nutrients released during the wetting of the dry soil and are critical to the dynamics of microorganisms and vegetation. The objective of this study was to investigate the spatial and temporal variability of C and N isotope ratios as indicators of the cycling of these elements in a cerrado sensu stricto area, within a protected area in a State Park in the state of São Paulo, Brazil. The foliar δ13C and δ15N values varied from -33.6 to -24.4 ‰ and -2.5 to 4.5 ‰, respectively. The δ13C values showed a consistent relationship with canopy height, revealing the importance of structure of the canopy over the C isotopic signature of the vegetation. Carbon isotopic variations associated with the length of the dry season indicated the importance of recent fixed C to the integrated isotopic signature of the leaf organic C. The studied Cerrado species showed a depleted foliar δ15N, but a wide range of foliar Nitrogen with no difference among canopy heights. However, seasonal variability was observed, with foliar δ15N values being higher in the transition period between dry and rainy seasons. The variation of the foliar C and N isotope ratios presented here was consistent with highly diverse vegetation with high energy available but low availability of water and N.

Land-Water interactions in the amazon

Biogeochemistry is hosting this special thematic issue devoted to studies of land-water interactions, as part of the Large-scale Biosphere-Atmosphere Experiment in Amaznia (LBA). This compilation of papers covers a broad range of topics with a common theme of coupling land and water processes, across pristine and impacted systems. Findings highlighted that hydrologic flowpaths are clearly important across basin size and structure in determining how water and solutes reach streams. Land-use changes have pronounced impacts on flowpaths, and subsequently, on stream chemistry, from small streams to large rivers. Carbon is produced and transformed across a broad array of fluvial environments and wetlands. Surface waters are not only driven by, but provide feedback to, the atmosphere.

Nitrogen availability patterns in white-sand vegetations of Central Brazilian Amazon

Addressing spatial variability in nitrogen (N) availability in the Central Brazilian Amazon, we hypothesized that N availability varies among white-sand vegetation types (campina and campinarana) and lowland tropical forests (dense terra-firme forests) in the Central Brazilian Amazon, under the same climate conditions. Accordingly, we measured soil and foliar N concentration and N isotope ratios (delta(15)N) throughout the campina-campinarana transect and compared to published dense terra-firme forest results. There were no differences between white-sand vegetation types in regard to soil N concentration, C:N ratio and delta(15)N across the transect. Both white-sand vegetation types showed very low foliar N concentrations and elevated foliar C:N ratios, and no significant difference between site types was observed. Foliar delta(15)N was depleted, varying from -9.6 to 1.6aEuro degrees in the white-sand vegetations. The legume Aldina heterophylla had the highest average delta(15)N values (-1.5aEuro degrees) as well as the highest foliar N concentration (2.1%) while the non-legume species had more depleted delta(15)N values and the average foliar N concentrations varied from 0.9 to 1.5% among them. Despite the high variation in foliar delta(15)N among plants, a significant and gradual (15)N-enrichment in foliar isotopic signatures throughout the campina-campinarana transect was observed. Individual plants growing in the campinarana were significantly enriched in (15)N compared to those in campina. In the white-sand N-limited ecosystems, the differentiation of N use seems to be a major cause of variations observed in foliar delta(15)N values throughout the campina-campinarana transect.

Amazon deforestation alters small stream structure, nitrogen biogeochemistry and connectivity to larger rivers

Human activities that modify land cover can alter the structure and biogeochemistry of small streams but these effects are poorly known over large regions of the humid tropics where rates of forest clearing are high. We examined how conversion of Amazon lowland tropical forest to cattle pasture influenced the physical and chemical structure, organic matter stocks and N cycling of small streams. We combined a regional ground survey of small streams with an intensive study of nutrient cycling using (15)N additions in three representative streams: a second-order forest stream, a second-order pasture stream and a third-order pasture stream. These three streams were within several km of each other and on similar soils. Replacement of forest with pasture decreased stream habitat complexity by changing streams from run and pool channels with forest leaf detritus (50% cover) to grass-filled (63% cover) channel with runs of slow-moving water. In the survey, pasture streams consistently had lower concentrations of dissolved oxygen and nitrate (NO(3) (-)) compared with similar-sized forest streams. Stable isotope additions revealed that second-order pasture stream had a shorter NH(4) (+) uptake length, higher uptake rates into organic matter components and a shorter (15)NH(4) (+) residence time than the second-order forest stream or the third-order pasture stream. Nitrification was significant in the forest stream (19% of the added (15)NH(4) (+)) but not in the second-order pasture (0%) or third-order (6%) pasture stream. The forest stream retained 7% of added (15)N in organic matter compartments and exported 53% ((15)NH(4) (+) = 34%; (15)NO(3) (-) = 19%). In contrast, the second-order pasture stream retained 75% of added (15)N, predominantly in grasses (69%) and exported only 4% as (15)NH(4) (+). The fate of tracer (15)N in the third-order pasture stream more closely resembled that in the forest stream, with 5% of added N retained and 26% exported ((15)NH(4) (+) = 9%; (15)NO(3) (-) = 6%). These findings indicate that the widespread infilling by grass in small streams in areas deforested for pasture greatly increases the retention of inorganic N in the first- and second-order streams, which make up roughly three-fourths of total stream channel length in Amazon basin watersheds. The importance of this phenomenon and its effect on N transport to larger rivers across the larger areas of the Amazon Basin will depend on better evaluation of both the extent and the scale at which stream infilling by grass occurs, but our analysis suggests the phenomenon is widespread.

Determination of the geographical origin of Brazilian wines by isotope and mineral analysis

In the present research, we studied wines from three different south Brazilian winemaking regions with the purpose of differentiating them by geographical origin of the grapes. Brazil`s wide territory and climate diversity allow grape cultivation and winemaking in many regions of different and unique characteristics. The wine grape cultivation for winemaking concentrates in the South Region, mainly in the Serra GaA(0)cha, the mountain area of the state of Rio Grande do Sul, which is responsible for 90% of the domestic wine production. However, in recent years, two new production regions have developed: the Campanha, the plains to the south and the Serra do Sudeste, the hills to the southeast of the state. Analysis of isotopic ratios of (18)O/(16)O of wine water, (13)C/(12)C of ethanol, and of minerals were used to characterize wines from different regions. The isotope analysis of delta(18)O of wine water and minerals Mg and Rb were the most efficient to differentiate the regions. By using isotope and mineral analysis, and discrimination analysis, it was possible to classify the wines from south Brazil.

ACCUMULATION AND TRANSLOCATION OF SILICON IN RICE AND BEAN PLANTS USING THE 30SI STABLE ISOTOPE

The 30Si silicon isotope stable was used for assessing the accumulation and translocation of Si in rice and bean plants grown in labeled nutritive solution. The isotopic silicon composition in plant materials was determined by mass spectrometry (IRMS) using the method based on SiF4 formation. Considering the total-Si added into nutritive solutions, the quantity absorbed by plants was near to 51% for rice and 15% for bean plants. The accumulated amounts of Si per plant were about 150g in rice and 8.6g in bean. Approximately 70% of the total-Si accumulated was found in leaves. At presented experimental conditions, the results confirmed that once Si is accumulated in the old parts of rice and bean plant tissues it is not redistributed to new parts, even when Si is not supplied to plants from nutritive solution.

Deuterium Equilibrium Time in Saliva of Newborn Infants

There is an increasing interest about the use of stable isotopes for body composition analysis in pediatrics. To ensure the success of total body water analysis by the deuterium dilution method, it is fundamental to determine the equilibrium tune (plateau) of deuterium in the body fluid studied. Objectives: We report here the equilibration time of deuterium oxide in the saliva of newborns after oral intake of the isotope. Methods: Twenty healthy term newborn infants, 10 males and 10 females, were analyzed. Saliva was collected from each newborn before the oral administration of a 100 mg/kg dose of deuterium oxide (baseline sample) and then at 1-hour intervals for 5 hours after administration. Deuterium enrichment of saliva was determined by isotope ratio mass spectrometry according to the recommendations of the International Atomic Energy Agency. Results: The plateau time of deuterium in saliva occurred 3 hours after oral administration of the stable isotope. Conclusion: These data are essential for further studies on the body composition of newborn infants. To the best of our knowledge, this is the first study regarding the equilibration time of deuterium in the saliva of term newborns. JPGN 48:471-474, 2009.