Lipase catalyzed reactions of aliphatic and arylaliphatic carbonic acid esters

Symmetrical dialkyl carbonates and dibenzyl carbonates reacted with various nucleophiles in the presence of Candida antarctica lipase B in organic solvents. For example, reaction of dibutyl and dibenzyl carbonate with an alcohol gave a mixture of the mono- and disubstituted products. Aminolysis, however, afforded only the carbamates, without subsequent reaction to the ureum derivatives. The reaction rates were rather low compared with carboxylic esters; the reactivity increased in the order dimethyl相似文献   

Formation of organic products in self-radiolyzed calcium carbonate

Summary Calcium carbonate labeled with carbon-14 was self-irradiated by means of the -decay of its carbon-14. A number of products containing one or two carbon atoms were identified by high performance liquid chromatography. Formic and oxalic acids were produced in relatively high yields, while glyoxylic, glycolic, and acetic acids, as well as formaldehyde and methanol, were formed in lower yields. These results support the suggestion that carbonates subjected to ionizing radiation could have been a source of carbon for organic synthesis on the primitive earth.     

The effects of liming an Adirondack lake watershed on downstream water chemistry

Calcite treatment of chronically acidic lakes has improved fish habitat, but the effects on downstream water quality have not previously been examined. In this study, the spatial and temporal effects of watershed CaCO₃ treatment on the chemistry of a lake outlet stream in the Adirondack Mountains of New York were examined. Before CaCO₃ treatment, the stream was chronically acidic. During spring snowmelt before treatment, pH and acid-neutralizing capacity (ANC) in the outlet stream declined, and NO ₃ ^– and inorganic monomeric aluminum (Al_IM) concentrations increased sharply. During that summer, SO ₄ ^– and NO ₃ ^– concentrations decreased downstream, and dissolved organic carbon (DOC) concentrations and ANC increased, in association with the seasonal increase in decomposition of organic matter and the attendant SO ₄ ^– -reduction process. A charge-balance ANC calculation closely matched measured downstream changes in ANC in the summer and indicated that SO ₄ ^– reduction was the major process contributing to summer increases in ANC. Increases in Ca²⁺ concentration and ANC began immediately after CaCO₃ application, and within 3 months, exceeded their pretreatment values by more than 130 eq/L. Within 2 months after treatment, downstream decreases in Ca²⁺ concentration, ANC, and pH, were noted. Stream mass balances between the lake and the sampling site 1.5 km downstream revealed that the transport of all chemical constituents was dominated by conservative mixing with tributaries and ground water; however, non-conservative processes resulted in significant Ca²⁺ losses during the 13-month period after CaCO₃ treatment. Comparison of substrate samples from the buffered outlet stream with those from its untreated tributaries showed that the percentage of cation-exchange sites occupied by Ca²⁺ as well as non-exchangeable Ca, were higher in the outlet-stream substrate than in tributary-stream substrate. Mass-balance data for Ca²⁺ H⁺, Al_IM, and DOC revealed net downstream losses of these constituents and indicated that a reasonable set of hypothesized reactions involving Al_IM, HCO ₃ ^– , Ca²⁺, SO ₄ ^– NO ₃ ^– , and DOC could have caused the measured changes in stream acid/base chemistry. In the summer, the sharp decrease in ANC continued despite significant downstream decreases in SO₄ ^2– concentrations. After CaCO₃ treatment, reduction of SO ₄ ^– was only a minor contributor to ANC changes relative to those caused by Ca²⁺ dilution from acidic tributaries and acidic ground water, and Ca²⁺ interactions with stream substrate.     

Stable-isotope studies on the collagenic and hydroxylapatite components of fossils: Palaeoecological implications

Collagenic material has been extracted and analysed for stable carbon- and nitrogen-isotope ratios from Henschke Cave, a Late Pleistocene fossil locality, South Australia. The carnivore Thylacoleo carnifex most likely consumed omnivores ( Parameles spp.) with a palaeodiet of C₃ plant material under a forest canopy, which was also recorded in the herbivores analysed ( Macropus spp., Sthenurus spp. and Diprotodon spp.). A forested environment supports previous interpretations of extant fauna and their modern habitats. The presence of negative nitrogen-isotope ratios in herbivores has been interpreted as non-diagenetic on the basis of carbon/nitrogen ratios and amino acid spectra, and in fact may be indicative of acidic soils. Analyses on bone and enamel carbonate hydroxylapatite from the same species support the conclusion that bone is unreliable for palaeoecological and palaeoclimatological research. However, bone carbonate hydroxylapatite may prove valuable in assessing the extent of isotopic fractionation during diagenesis. A review of carbon-isotope analyses on fossil collagenic material and enamel carbonate hydroxylapatite suggests a carnivore-herbivore boundary. The application of this boundary in palaeoecological research requires further investigation. Future palaeoecological research on fossils needs to incorporate stable-isotope analyses on the carbonate hydroxylapatite and collagenic components of fossils.     

The Ocruranus–Eohalobia group of small shelly fossils from the Lower Cambrian of Yunnan

Lower Cambrian phosphorite samples from Maotianshan, Yunnan Province, South China, yielded a variety of small shelly fossils. Sclerites of the second pre-trilobite faunal assemblage of Meishucun, the Paragbborilus-Siphogonuchites–Lapworthella association of Nemakit–Daldynian to Tommotían age, were dominant. They comprise previously unknown spine-bearing specimens of Ocruranus finial Liu, 1979, and new morphotypes of Eohalobia diandongensis Jiang, 1982. Well-preserved sclerites reveal a laminated, composite fine structure with marginal, incremental growth. Each lamella consists of radial series of minute growth elements. The shells are phosphatically preserved, but micropetrographic evidence from drill-core samples indicates calcium carbonate as primary shell material. In the light of this new evidence, Ocruranus–Eohalobia group fossils are interpreted as parts of coeloscleritophoran scleritomes.     

Calcification in aquatic plants

Abstract. The CaCO₃ deposits of aquatic plants may be intra-, inter- and extracellular. Calcification is mainly the result of photosynthetic CO₂ or HCO⁻₃ assimilation. This raises the local pH and CO²⁻₃ concentration resulting from shifts in the dissolved inorganic carbon equilibrium, due to either net CO₂ depletion as in Halimeda or localized OH⁻ efflux (or H⁺ influx) as in Chara. The plant cell wall may be important in CaCO₃ nucleation by acting as an epitaxial substratum or template, or by creating a microenvironment enriched in Ca²⁺ compared to Mg²⁺. Hypotheses on the reason for the lack of calcification in many aquatic plants are presented.     

Les Rhynchonelles du Bathonien du domaineprovencal: Liaison entre l'installation des peuplements et les modalités de la transgression bathonienne dans les Alpes-Maritimes

In the Maritime Alps, the Middle and Upper Bathoniancorresponds to a transgressive episode on the Provençal platform. The advancement of the marine invasion is very noticeable between Grasse and Antibes. The sediment shows the existence of a shallow marine environment in which benthic organisms were predominant.The deposits are at first varied: marly layers withbivalves (burrowers for the most part) and calcareous layers with monospecific populations of brachiopods (Burmirhynchia mediterranea nov. sp. in a calm environment, and B. turgidaBuckman in a more turbulent environment).The deposits then become uniform and show theexistence of very shallows environments: B. decorata kiliani nov. subsp. is the only representative of macrofauna in the micritic limestones that can be attributed to the Upper Bathonian.The Rhynchonellids, as on the other Bathonian carbonateplatforms of Western Europe, seem to be the only organisms likely to stay alive and proliferate in the specific environments in which entirely carbonate sediments are deposited in shallow water. Due to their relationships to those existing in other platforms, the species described in this article permit the clarification of biostratigraphic correlations.     

CARBONIC ANHYDRASE AND CARBON FIXATION IN COCCOLITHOPHORIDS1

Rates of carbon fixation in coccolithophorids in culture, unlike many other algae, are carbon limited at ambient levels of dissolved inorganic carbon (DIC). Apparently, plants often rely on activity of carbonic anhydrase (CA) to raise the level of CO₂ in cells and achieve carbon saturation. However, CA activities in the coccolithophorids, Coccolithus (= Emiliania) huxleyi Lohmann and Hymenomonas (=Cricosphaera) carterae Braarud, were either not detectable or very low compared to activities in other systems, including other algae, higher plants, and representative animals. Furthermore, additions of CA to medium with 2 mM DIC at pH 8.1 resulted in nearly 30% enhancement of photosynthesis, but not coccolith formation. Although carbon fixation in coccolithophorids can be suppressed by the CA inhibitor acetazolamide, studies of CaCO₃ nucleation revealed a non-specific effect of the inhibitor. Using a 30 min assay based on pH decreases accompanying loss of dissolved. CO₃^2-, inhibition of crystal formation in the absence of CA at 1 mM acetazolamide was demonstrated for decalcified crab carapace, a tissue with which normal CaCo₃ deposition in vitro has been shown. The results suggest only a minor role for CA in coccolithophorids.     

Effects of acid irrigation and liming on two clones of Norway spruce

Summary The effect of acid irrigation on the growth of rooted cuttings ofPicea abies (L.) Karst, was investigated in a pot experiment lasting 3 years. It involved two clones of Norway spruce, H 253 Bogstad I and H 254 Bogstad II. Irrigation water of pH 5.4, 4.0, 3.0 and 2.5 was used. Liming was included in the experiment.After the experimental period, the plants of all treatments were growing reasonably well. However, those plants irrigated at pH 2.5 were slightly discoloured. The plant mortality was only 3% throughout the experiment, and was not connected to acid irrigation. The limiting growth factor was N. All other nutrient elements measured in the plants were close to optimal concentration. Plants irrigated at pH 2.5, and to some extent at pH 3, contained excessively high concentrations of Al, t-S and SO₄. The total amount of Ca, Fe and Mn taken up by the plants decreased with increasing soil acidity. The increased growth of clone H 254 relative to H 253, produces a corresponding impression on soil characteristics. Soil acidity is governed by acid irrigation and CaCO₃ application, but the clonal effects are also of importance. Norway spruce appears to be tolerant to Al concentrations as high as 50 mmol/kg in the needles.