Reconstruction of source water using the δ18O of tree ring phenylglucosazone: A potential tool in paleoclimate studies

The oxygen isotope ratios of tree ring cellulose have a great potential as proxy for the oxygen isotope ratios of source water, which is related to climate. However, source water isotopic signatures can be masked by plant physiological and biochemical processes during cellulose synthesis. To minimize biochemical effects in the recording of source water, we modified the cellulose molecule to phenylglucosazone, which only has oxygen attached to carbon 3–6 (O_C3–6) of the cellulose glucose moieties, thus eliminating the oxygen attached to carbon 2 of the cellulose glucose moieties (O_C-2). Here we developed a method to use small amounts of inter and intra-annual tree ring cellulose for phenylglucosazone synthesis. Using this new method we tested if the oxygen isotope ratios of source water reconstructed from tree ring phenylglucosazone (δ¹⁸O_sw^PG) and the observed source water (δ¹⁸O_sw^obs) would have a better agreement than those reconstructed from the tree ring cellulose molecule. Annual tree ring samples were obtained from Pinus sylvestris (1997–2003) (Finland) and Picea abies (1971–1992) (Switzerland) and intra-annual tree ring samples were obtained from Pinus radiata (October 2004–March 2006) (New Zealand), each near a meteorological station where precipitation and relative humidity (RH) were measured periodically. The δ¹⁸O of tree ring cellulose and tree ring phenylglucosazone for each of the three species were then used to back calculate the δ¹⁸O of source water according to a previous published empirical equation. As expected, the δ¹⁸O of tree ring phenylglucosazone was superior than cellulose in the reconstruction of source water available to the plant. Deviation between δ¹⁸O_sw^PG and δ¹⁸O_sw^obs was in part correlated with variation in atmospheric relative humidity (RH) which was not observed for the cellulose molecule. We conclude that this new method can be applicable to inter and intra-annual tree ring studies and that the use of the tree ring phenylglucosazone will significantly improve the quality of paleoclimate studies.     

Climatic implications of δ13C and δ18O ratios from C3 and C4 plants growing in a tropical montane habitat in southern India

The stable carbon and oxygen isotope ratios in cellulose of C3 and C4 plants growing on the surface of a montane peat bog in the Nilgiri hills, southern India, were measured. The mean monthly δ¹³C values in cellulose of both C3 and C4 plants are found to be significantly related to rainfall, while the δ¹⁸O values are sensitive to changes in maximum temperature and relative humidity of the region. Further, higher δ¹⁸O values were observed in C4 plants compared to C3 plants, suggesting that C4 plants are probably less sensitive to relative humidity as compared to C3 plants and are able to photosynthesize even during drier conditions. The plant isotope-climate correlations thus established can be used for reconstructing the past temperature and rainfall conditions of the tropics from the isotopic ratios of peat deposits, derived from a mixture of C3 and C4 plants in the region.     

The environmental water of the middle Eocene Arctic: Evidence from δD, δ18O and δ13C within specific compounds

The extensive vertical exposure (> 150 m) of terrestrial sediments on Axel Heiberg Island, which contain thick fossiliferous lignites, presents an exceptional opportunity to follow the establishment and re-establishment of Arctic Metasequoia forests during the middle Eocene. We compared δD values in n-alkanes of chain length 23, 25, 27 and 29 with δ¹⁸O values in phenylglucosazone (P-G) derived from α-cellulose; we also analyzed %-abundance of ferns, gymnosperms and angiosperms using pollen and spores isolated from each lignite. Our results showed that forest composition was altered upon uplift, as gymnosperms became more abundant within the relatively well-drained upland sediments. This was also reflected in the small (1‰), but significant, increase in the δ¹³C value of TOM from lowland to upland environments. However, neither the δD values of n-alkanes nor the δ¹⁸O in P-G were statistically different in the upland sediments, as compared to the lowland sediments; from this we inferred that the oxygen isotope signature of environmental water available to the forests for plant growth was relatively uniform throughout the time of the fossil forests. The δD value of environmental water implied by both n-alkanes and P-G ranged from ? 168 to ? 131% and was considerably enriched compared to all environmental water samples available from the modern Arctic region (< ? 180%). In addition to indicating a warmer Eocene Arctic, subject to meteoric transport patterns different from today's, these results argue against the presence of an Eocene polar ice cap.     

A 215-yr coral δ18O time series from Palau records dynamics of the West Pacific Warm Pool following the end of the Little Ice Age

The West Pacific Warm Pool (WPWP) is a critical region of the global climate system that is closely linked with the El Niño-Southern Oscillation (ENSO). We have generated two monthly resolved coral δ¹⁸O (δ¹⁸O_CRL) records from a key region of the WPWP, the Republic of Palau (7′N, 135′E). The isotopic time series span the years 1793–2008 and 1899–2008. During the period of overlap, the two records are well correlated at interannual and annual periods. Multiple lines of evidence demonstrate a strong ENSO signal in Palau δ¹⁸O_CRL. Our records are consistent with previous investigations of twentieth-century tropical Pacific climate variability. We identify a regionally coherent bi-decadal cycle in the WPWP following the termination of the Little Ice Age. The Palau δ¹⁸O_CRL records show long-term trends towards warming/freshening, suggesting a century scale increase in the strength of the hydrologic cycle associated with the WPWP. Our study represents an important addition to the network of tropical paleo-archives.     

Technical note: some observations on the conversion of dental enamel δ18O(p) values to δ18O(w) to determine human mobility

It has become a widespread practice to convert δ(18)O(p) values measured in human and animal dental enamel to a corresponding value of δ(18)O(w) and compare these data with mapped δ(18)O(w) groundwater or meteoric water values to locate the region where the owner of the tooth lived during the formation of the enamel. Because this is a regression procedure, the errors associated with the predicted δ(18)O(w) values will depend critically on the correlation between the comparative data used to perform the regression. By comparing four widely used regression equations we demonstrate that the smallest 95% error is likely to be greater than ±1% in δ(18)O(w) , and could be as large as ±3.5%. These values are significantly higher than those quoted in some of the recent literature, and measurements with errors at the higher end of this range would render many of the published geographical attributions statistically unsupportable. We suggest that the simplest solution to this situation is to make geographical attributions based on the direct comparison of measured values of δ(18)O(p) rather than on predicted values of δ(18)O(w).     

Sulfonamide inhibition studies of the δ-carbonic anhydrase from the diatom Thalassiosira weissflogii

The δ-carbonic anhydrase (CA, EC 4.2.1.1) TweCA from the marine diatom Thalassiosira weissflogii has recently been cloned, purified and its activity/inhibition with anions investigated. Here we report the first sulfonamide/sulfamate inhibition study of a δ-class CA. Among the 40 such compounds investigated so far, 3-bromosulfanilamide, acetazolamide, ethoxzolamide, dorzolamide and brinzolamide were the most effective TweCA inhibitors detected, with K_Is of 49.6–118 nM. Many simple aromatic sulfonamides as well as dichlorophenamide, benzolamide, topiramate, zonisamide, indisulam and valdecoxib were medium potency inhibitors, (K_Is of 375–897 nM). Saccharin and hydrochlorothiazide were ineffective inhibitors of the δ-class enzyme, with K_Is of 4.27–9.20 μM. The inhibition profile of the δ-CA is very different from that of α-, β- and γ-CAs from different organisms. Although no X-ray crystal structure of this enzyme is available, we hypothesize that as for other CA classes, the sulfonamides inhibit the enzymatic activity by binding to the Zn(II) ion from the δ-CA active site.     

A new δ-lactone from the flowers of Grewia asiatica

The structure of 3, 21, 24 trimethyl-5,7-dihydroxyhentriacontanoic acid δ-lactone, a new δ-lactone, isolated from the flowers of Grewia asiatica has been deduced on the basis of physico-chemical studies.     

Differences in the C age, δC and δO of Holocene tufa and speleothem in the Dinaric Karst

We studied Holocene speleothems and tufa samples collected in numerous caves and rivers in the Dinaric Karst of Croatia, Slovenia, Bosnia and Herzegovina, as well as Serbia and Montenegro. Differences in the formation process of tufa and speleothems are discussed in the context of their isotopic composition (¹⁴C, ¹³C and ¹⁸O), as well as the chemistry of surface water (rivers, lakes) and drip water (in caves). The physical and chemical parameters monitored in the surface water (tufa precipitation) and drip water (speleothem precipitation) show that more stable conditions accompany speleothem rather than tufa formation. This is particularly obvious in the water temperature variations (2-22°C in surface water and 7-12°C in drip water) and in saturation index variation (3-11 in surface water and 1-6 in drip water). The range of ¹⁴C ages recorded by Holocene speleothems (∼12?000 yr) is wider by several thousands years than that of Holocene tufa samples (∼6000 yr). δ¹³C values for tufa samples range from −12‰ to −6‰ and for speleothem samples from −12‰ to +3‰ reflecting higher soil carbon and/or vegetation impact on the process of tufa than on speleothem formation. The differences in δ¹⁸O values of tufa and speleothem samples from different areas reflect different temperature conditions and differing isotopic composition in the water. The study shows that speleothems from the Dinaric Karst can be used as global palaeoclimatic records, whereas tufa records changes in the local palaeoenvironment.     

Wulfeniopsis Hong—A new genus of Scrophulariaceae from Himalaya

While we were investigating the world Veroniceae we found the genus Wulfenia Jacq. discontinuously distributing. W. carinthiaca and W. baldaccii are found in south-eastern Europe and W. orientalis in Turkey and Lebanon, whereas W. amherstiana is a native of W. Himalaya. Such a pattern of distribution, discontinuous between the Mediterranean and W. Himalaya, as far as we know, is hardly frequent. After comparing carefully the specimens from these two places and examining their pollen grains we got the impression that the difference between the plants occuring near the Mediterranean and those in Himalaya is so big that they should no longer be placed in the same genus. It would be necessary, therefore, to describe W. amherstiana as a new and separate genus (we name it Wulfeniopsis Hong). Its corolla is not 2-lipped, but with four lobes (not five) lanceolate, acuminate and erect (not spreading). The stigma is very small, not 2-lobed. Pollen grains are much smaller, with colpi more narrow and lacking of membranes, and their exines are smooth (not reticulate). It’s chromosome numberis 2n = 16 (not 18).     

Biochemical characterization of the δ-carbonic anhydrase from the marine diatom Thalassiosira weissflogii,TweCA

Abstract

Diatom genome sequences clearly reveal the presence of different systems for HCO₃^? uptake. Carbon-concentrating mechanisms (CCM) based on HCO₃^? transport and a plastid-localized carbonic anhydrase (CA, EC 4.2.1.1) appear to be more probable than the others because CAs have been identified in the genome of many diatoms. CAs are key enzymes involved in the acquisition of inorganic carbon for photosynthesis in phytoplankton, as they catalyze efficiently the interconversion between carbon dioxide and bicarbonate. Five genetically distinct classes of CAs exist, α-, β-, γ-, δ- and ζ and all of them are metalloenzymes. Recently we investigated for the first time the catalytic activity and inhibition of the δ-class CA from the marine diatom Thalassiosira weissflogii, named TweCA. This enzyme is an efficient catalyst for the CO₂ hydration and its inhibition profile with sulfonamide/sulfamate and anions have also been investigated. Here, we report the detailed biochemical characterization and chemico-physical properties of the δ-CA of T. weissflogii. The δ-CA encoding gene was cloned and expressed in Artic Express cells and the recombinant protein purified to homogeneity. Interesting to note that TweCA has no intrinsic esterase activity with 4-nitrophenyl acetate (pNpA) as substrate although the phylogenetic analysis showed that δ-CAs are closer to the α-CAs than to the other classes of such enzymes.     

Reconstructing parameters of the FitzHugh–Nagumo system from boundary potential measurements

We consider distributed parameter identification problems for the FitzHugh–Nagumo model of electrocardiology. The model describes the evolution of electrical potentials in heart tissues. The mathematical problem is to reconstruct physical parameters of the system through partial knowledge of its solutions on the boundary of the domain. We present a parallel algorithm of Newton–Krylov type that combines Newton’s method for numerical optimization with Krylov subspace solvers for the resulting Karush–Kuhn–Tucker system. We show by numerical simulations that parameter reconstruction can be performed from measurements taken on the boundary of the domain only. We discuss the effects of various model parameters on the quality of reconstructions. Action Editor: David Terman     

Climatic influences on the evolution of early Homo?

The nature of the human fossil record is less than ideal for the generation of precise correlations between environmental variables and patterns of evolution in specific lineages. Nonetheless, a critical look at what can and cannot be said from individual fossil morphology and the correlation of specific environmental proxies with specific hominin fossils may lead to a greater understanding of the degree of certainty with which we should embrace environmental hypotheses for the evolution of Homo. Climate shifts have been implicated in both the origin of the genus and its dispersal from Africa. Here, I consider three areas in which a climatic influence has been posited to explain evolutionary shifts in the genus Homo: the origin and dispersal of the genus from Africa; geography, climate and body size in early Homo, and the influence of climate-induced sea level rise on morphological isolation in H. erectus. Each of the data sets is far from ideal, and interpretations of each of the data sets are fraught with issues of equifinality. Of the three hypotheses discussed, the clearest link is seen between latitudinal variation (and presumably temperature) and body size in H. erectus. Similarly, climate-induced sea level change seems a reasonable isolating mechanism to explain the pattern of cranial variation in later Asian H. erectus, but the distribution could also reflect incompletely sampled clinal variation. Alternatively, only equivocal support is found for the influence of climate on the differentiation of H. erectus from H. habilis (as proxied by body/brain size scaling), and therefore the dispersal of the genus Homo cannot be as clearly linked to changes in body size and shape as it has been in the past. These preliminary data suggest that an emphasis on understanding local adaptation before looking at global (and specific) level change is critical to elucidating the importance of climatic factors on the evolution of the genus Homo.     

Listening In on the Past: What Can Otolith δ18O Values Really Tell Us about the Environmental History of Fishes?

Oxygen isotope ratios from fish otoliths are used to discriminate marine stocks and reconstruct past climate, assuming that variations in otolith δ¹⁸O values closely reflect differences in temperature history of fish when accounting for salinity induced variability in water δ¹⁸O. To investigate this, we exploited the environmental and migratory data gathered from a decade using archival tags to study the behaviour of adult plaice (Pleuronectes platessa L.) in the North Sea. Based on the tag-derived monthly distributions of the fish and corresponding temperature and salinity estimates modelled across three consecutive years, we first predicted annual otolith δ¹⁸O values for three geographically discrete offshore sub-stocks, using three alternative plausible scenarios for otolith growth. Comparison of predicted vs. measured annual δ¹⁸O values demonstrated >96% correct prediction of sub-stock membership, irrespective of the otolith growth scenario. Pronounced inter-stock differences in δ¹⁸O values, notably in summer, provide a robust marker for reconstructing broad-scale plaice distribution in the North Sea. However, although largely congruent, measured and predicted annual δ¹⁸O values of did not fully match. Small, but consistent, offsets were also observed between individual high-resolution otolith δ¹⁸O values measured during tag recording time and corresponding δ¹⁸O predictions using concomitant tag-recorded temperatures and location-specific salinity estimates. The nature of the shifts differed among sub-stocks, suggesting specific vital effects linked to variation in physiological response to temperature. Therefore, although otolith δ¹⁸O in free-ranging fish largely reflects environmental temperature and salinity, we counsel prudence when interpreting otolith δ¹⁸O data for stock discrimination or temperature reconstruction until the mechanisms underpinning otolith δ¹⁸O signature acquisition, and associated variation, are clarified.     

Combined use of δ¹³C, δ18O and δ15N tracks nitrogen metabolism and genotypic adaptation of durum wheat to salinity and water deficit

? Accurate phenotyping remains a bottleneck in breeding for salinity and drought resistance. Here the combined use of stable isotope compositions of carbon (δ13C), oxygen (δ1?O) and nitrogen (δ1?N) in dry matter is aimed at assessing genotypic responses of durum wheat under different combinations of these stresses. ? Two tolerant and two susceptible genotypes to salinity were grown under five combinations of salinity and irrigation regimes. Plant biomass, δ13C, δ1?O and δ1?N, gas-exchange parameters, ion and N concentrations, and nitrate reductase (NR) and glutamine synthetase (GS) activities were measured. ? Stresses significantly affected all traits studied. However, only δ13C, δ1?O, δ1?N, GS and NR activities, and N concentration allowed for clear differentiation between tolerant and susceptible genotypes. Further, a conceptual model explaining differences in biomass based on such traits was developed for each growing condition. ? Differences in acclimation responses among durum wheat genotypes under different stress treatments were associated with δ13C. However, except for the most severe stress, δ13C did not have a direct (negative) relationship to biomass, being mediated through factors affecting δ1?O or N metabolism. Based upon these results, the key role of N metabolism in durum wheat adaptation to salinity and water stress is highlighted.     

Vegetation recovery alters soil N status in subtropical karst plateau area: Evidence from natural abundance δ15N and δ18O

Plant and Soil - Forest recovery from disturbance can alter soil nitrogen (N) status as a result of complex interactions in plant-soil system. The δ15N and δ18O are indicators that...     

Synthesis of haem cytochrome c prosthetic group from δ-aminolaevulinate by the cell sap from rat liver

To determine whether the prosthetic group of cytochrome c is synthesized and linked to the apoprotein in the cytosol or in connexion with the endoplasmic reticulum, we have studied the incorporation in vitro of delta-amino[(14)C]laevulinate into porphyrin compounds and cytochrome c by the cell sap from rat liver. The radioactive precursor was incorporated into a trichloroacetic acid-precipitable form partially resistant to extractions by acid solvents, suggesting the existence of a fraction covalently linked to protein. The activity was proportional to the amount of protein incubated, did not increase substantially by supplementation with the microsomal fraction and an energy source, and was very low in the pH5 fraction. Addition of increasing amounts of haemin inhibited the incorporation, as with purified delta-aminolaevulinate dehydratase. [(14)C]Protoporphyrin IX was identified by paper chromatography, together with a shoulder running as protohaem IX. The cell sap in the absence of ribosomes was also able to incorporate radioactivity into purified cytochrome c, and the addition of ribosomes significantly enhanced the activity. The precursors of haem c were synthesized in the soluble system by the known haem-synthetic pathway, as shown by the kinetics of labelling of the coproporphyrin, protoporphyrin and haem fractions, and the activities were concentrated in the precipitate obtained between 40 and 60% saturation with (NH(4))(2)SO(4). The presence of ferrochelatase was indicated by the incorporation of (55)Fe into proto- and haemato-haem identified by paper chromatography. It is concluded that the cell sap from rat liver contains the complete set of enzymes for the synthesis from delta-aminolaevulinate of haem c and its linkage to a small pool of free apoprotein c present in soluble form. This suggests that an ancillary pathway of haem synthesis occurs in the cytosol for at least the formation of the prosthetic group, which is linked post-translationally to that pool of apoprotein c synthesized by free polyribosomes.     

Changes of the upwelling rates of nitrate preserved in the δN-signature of sediments and fish scales from the diatomaceous mud belt of Namibia

We investigated one kastencore and multicores taken from the rapidly accumulating diatomaceous muds on the Namibian shelf to trace decadal-scale fluctuations of coastal upwelling by sedimentological, isotopic, geochemical, and paleo ecological methods. One specific objective was to reconstruct the fluctuations of fish populations (indicative of oceanographic and ecological conditions) using the occurrence of fish scales in varved sediment layers and to correlate these fluctuations with paleo environmental conditions. The partly laminated core was dated by ¹⁴C AMS and subsampled at high resolution (1 cm intervals), yielding a resolution of about 3-10 years per sample. The interval for which data are available covers the last 3200 years. The core contains scales of all fish species which are associated with a typical upwelling community: sardines, anchovies, mackerel, jack mackerel, hake and myctophids. Accumulation rates of organic matter and fish scales fluctuated considerably. The variability in abundance and type of fish scales at different depths indicates drastic fluctuations of fish abundance in the Benguela Current during the last 3200 years, as well as changes in community structures. The paleo environmental conditions associated with the different phases of fish population abundance are reflected in the frequency of laminations (indicative of anoxic conditions on the shelf), and by variations of stable isotopes of organic matter. The δ¹⁵N-signature of fish scales from surface sediments shows a ¹⁵N-enrichment of 6‰ related to the average sedimentary δ¹⁵N composition. This indicates that pelagic fish diet was a mixture of 20% algae to 80% zooplankton. We postulate fish scale δ¹⁵N preserves information of the relative nitrate consumption of algae in the upwelling system without any diagenetic imprints. This investigation might become a contribution to the discussion of diagenesis in the δ¹⁵N-signature of bulk sediments.