Effect of glucose on aspartic acid racemization

The racemization of aspartic acid in aqueous solution with and without phosphate buffer was found to increase in the presence of d-glucose. This increase in racemization appears to involve the formation of an imine intermediate (Schiff base). Subsequent proton tautomerization leading to the loss of asymmetry during the early stages of melanoidin formation could account for the observed increase in racemization. The racemization reaction did not follow reversible first order kinetics when glucose was added to buffered aspartic acid solution at 80°C; in unbuffered solution reversible first order kinetics were followed up to 624 hr.     

Late Holocene radiocarbon and aspartic acid racemization dating of deep-sea octocorals

Primnoa resedaeformis is a deep-sea gorgonian coral with a two-part skeleton of calcite and gorgonin (a fibrillar protein), potentially containing long-term records of valuable paleo-environmental information. For various reasons, both radiocarbon and U/Th dating of these corals is problematic over the last few centuries. This paper explores aspartic acid racemization dating of the gorgonin fraction in modern and fossil specimens collected from the NW Atlantic Ocean. Radiocarbon dating of the fossil specimen indicates a lifespan of 700 ± 100 years, the longest yet documented for any octocoral. Gorgonin amino acid compositions were identical in the fossil and modern specimens, indicating resistance to organic diagenesis. Similar to bone collagen, the fibrillar protein of gorgonin may impose conformational constraints on the racemization of Asp at low temperatures. The rate of racemization of aspartic acid (d/l-Asp) was similar to previously published results from an 1800 year old anemone (Gerardia). The age equation was: age (years BP 2000 AD) = [(d/l − 0.020 (±.002))/.0011 (±.0001)]² (r² = 0.97, p < .001). The error in an age estimate calculated by d/l-Asp was marginally better than that for ¹⁴C dating over the most recent 50-200 years, although the dating error may be improved by inclusion of more samples over a broader time range. These results suggest that d/l-Asp dating may be useful in augmenting ¹⁴C dating in cases where ¹⁴C calibrations yield two or more intercept ages, or in screening samples for further ¹⁴C or U/Th dating.     

The hydrothermal reaction kinetics of aspartic acid

Experimental data on the hydrothermal reaction kinetics of aspartic acid were acquired using a custom-built spectrophotometric reaction cell which permits in situ observation under hydrothermal conditions. The results of this study indicate that the reaction kinetics of dilute aspartic acid solutions are significantly different depending on the presence or absence of catalytic surfaces such as standard metal alloys. The spectroscopic data presented here represent the first direct observations, in situ and in real time, of an amino acid reacting in a hydrothermal solution. Quantitative kinetic information, including rate constants, concentration versus time profiles, and calculations of the individual component spectra, was obtained from the data using a chemometric approach based on factor analysis/principle component analysis which treats the rate expressions simultaneously as a system of differential algebraic equations (DAE) of index 1. Identification of the products was confirmed where possible by high pressure anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD). The reaction kinetics of aspartic acid under hydrothermal conditions was observed to be highly complex, in contrast to previous studies which indicated almost exclusively deamination. At lower temperatures (120-170 °C), several different reaction pathways were observed, including decarboxylation and polymerization, and the catalytic effects of reactor surfaces on the aspartic acid system were clearly demonstrated. At higher temperatures (above 170 °C), aspartic acid exhibited highly complex behaviour, with evidence indicating that it can simultaneously dimerize and cyclize, deaminate (by up to two pathways), and decarboxylate (by up to two pathways). These higher temperature kinetics were not fully resolvable in a quantitative manner due to the complexity of the system and the constraints of UV spectroscopy. The results of this study provide strong evidence that the reaction kinetics of aspartic acid are very sensitive to parameters such as temperature, reactor materials (i.e., reactive surfaces), and additives, and that previous observations on aspartic acid were specific to the choice of experimental conditions.     

Amino acid racemization in amber-entombed insects: implications for DNA preservation

DNA depurination and amino acid racemization take place at similar rates in aqueous solution at neutral pH. This relationship suggests that amino acid racemization may be useful in accessing the extent of DNA chain breakage in ancient biological remains. To test this suggestion, we have investigated the amino acids in insects entombed in fossilized tree resins ranging in age from <100 years to 130 million years. The amino acids present in 40 to 130 million year old amber-entombed insects resemble those in a modern fly and are probably the most ancient, unaltered amino acids found so far on Earth. In comparison to other geochemical environments on the surface of the Earth, the amino acid racemization rate in amber insect inclusions is retarded by a factor of >10(4). These results suggest that in amber insect inclusions DNA depurination rates would also likely be retarded in comparison to aqueous solution measurements, and thus DNA fragments containing many hundreds of base pairs should be preserved. This conclusion is consistent with the reported successful retrieval of DNA sequences from amber-entombed organisms.     

Aspartic acid racemization in Late Wisconsin Lake Ontario sediments

We have determined aspartic acid racemization and [¹⁴C] ages in sediment from a 17-m piston core recovered from Lake Ontario. This core represents a depositional record extending back into the Late Wisconsin. Total organic radiocarbon ages of the glaciolacustrine lower section of the core are older than the true depositional age. Hence we suggest that these ages do not represent time elapsed since deposition but rather may be up to several thousand years too old due to mixing with ¹⁴C-depleted organic matter and possibly also d-amino acids contained by the glacier and deposited as the glacier receded. Further studies are suggested that might test this hypothesis as well as establish the general applicability of racemization dating to clay sediments.     

Model for large strain consolidation under constant rate of strain

A numerical model, called CCRS1, is presented for one‐dimensional large strain consolidation under constant rate of strain loading conditions. The algorithm accounts for vertical strain, general constitutive relationships, relative velocity of fluid and solid phases, changing compressibility and hydraulic conductivity during consolidation, and an externally applied hydraulic gradient acting across the specimen. Soil compressibility is rate independent, and as such, the current model is most appropriate for less‐structured clays. Verification checks show excellent agreement with analytical and numerical solutions for small and large strain conditions. A series of numeric examples indicates that compressibility and hydraulic conductivity constitutive relationships can have an important effect on constant rate of strain consolidation response. Results also indicate that analytical solutions obtained using small strain theory can be in significant error for large strain conditions with changing coefficient of consolidation. Copyright © 2012 John Wiley & Sons, Ltd.     

Geothermal and other effects on amino acid racemization in selected Deep-Sea Drilling Project cores

Kinetic parameters for the epimerization of isoleucine in multispecific foraminiferal asemblages were used to establish the effects of burial depth and the geothermal gradient on the extent of reaction. It was observed that with a little as thirty meters of burial in a normal thermal regime there were differences between the extent of epimerization measured and that which would have been predicted for thermal equilibrium with bottom water temperatures. As would be expected, these differences are greatest when the heat flow (the geothermal gradient) and/or the sedimentation rates are highest. These effects were observed in most of the DSDP samples studied, and have been used to estimate the average heat flux since the time of sample deposition. Occasional anomalous effects were observed which could not be related to past or present heat flux. These were determined to be due to such geologic occurrences as slumping and reworking or to recent sample contamination. Other problems emerged related to bottom water temperatures including changes over geologic time which are unknown and could not be deduced. Thus, the presence of epimerization anomalies in DSDP cores as noted above limits the effectiveness of amino acid geochronology in such cores, unless these anomalies can be recognized as ab initio.     

Aspartic acid racemization in teeth from Ketef Hinnom,a late Holocene burial cave in Jerusalem: Evidence for reuse

The Ketef Hinnom tombs, lying just outside the walls of the old city of Jerusalem, were carved out of bedrock during the 7th–5th century B.C. Several artefacts dating to the Late Hellenistic Period (ca. 100 B.C.) have also been found within the tombs. Aspartic acid (Asp) racemization in 31 samples of human tooth dentine from these tombs was analyzed in order to evaluate the possible reuse of the tombs during this later period. A range of D/L Asp values was found: a group with values averaging 0.062 and another group averaging 0.043. These D/L values are close to those expected for the two archeological age groups as calculated from (1) the kinetics of Asp racemization as established from experimental studies at higher temperatures and in vivo racemization rates, and (2) the effective annual temperature in the tombs, as measured using the Pallman method. These results thus support the later reuse of the tombs for burials. Several factors contribute to the accuracy of Asp racemization dating, including the age of the individual at death, uncertainties concerning Asp racemization kinetics, and effects of temperature history. © 1999 John Wiley & Sons, Inc.     

Amino acid racemization in mammalian bones and teeth from La Chaise-de-Vouthon (Charente), France

A controlled test of the amino acid dating method as it is currently being applied to bones and teeth was attempted for the time range 100-250 ka, beyond that of ¹⁴C, at the archeological site of La Chaise-de-Vouthon (Charente, France). In Bourgeois-Delaunay, mammal fossils associated with Paleolithic artifacts were collected from layers dated at 101 ± 12 to 114 ± 7 ka by ²³⁰Th/²³⁰ dating of the over- and underlying stalagmitic floors. Racemization ratios for most amino acids were significantly lower than for comparably aged materials from other European sites. Regardless of the rate constants used, most amino acid dates were incorrect. Large associated errors spanned the late Pleistocene, making the dates useless for discriminating archaeological or geological events. Stratigraphic correlations using any tissue were also problematic. Relative interacid ratios varied with age, indicating that diagenetic alteration had affected racemization. Therefore, amino acid relative and absolute dating cannot be accurately applied to mid-Pleistocene bones or teeth.     

Comparison of pumping at constant head and at a constant rate for determining the sustainable yield of a well

Determining the yield of a production well remains one of the main problems in hydrogeological studies. Starting from the results of a 3-year-long monitoring of a continuously exploited well functioning at constant head (i.e., at a variable discharge rate), a new pumping style has been examined using numerical models. The objective is to control the impact of pumping on the aquifer in accordance with the principle of sustainability. Different models were developed in a transient state and were calibrated using discharge data of the well during the recession periods. Successively, the trends of the residual outflow from the aquifer system with the well operating at variable discharge and at constant discharge were simulated. The results indicate that the ratio of the volume of water pumped from the well to the volume of residual outflow is a significant indicator of the sustainability of groundwater withdrawals. Modeling confirms that a constant discharge rate can be derived from the information gained through a preliminary production phase of a well at constant head. This approach appears to be particularly useful when the problem is determining the sustainable yield of a single well from aquifers with low hydraulic diffusivity.     

Measurement of the pure dissolution rate constant of a mineral in water

We present here a methodology, using holographic interferometry, enabling to measure the pure surface reaction rate constant of the dissolution of a mineral in water, unambiguously free from the influence of mass transport. We use that technique to access to this value for gypsum and we demonstrate that it was never measured before but could be deduced a posteriori from the literature results if hydrodynamics is taken into account with accuracy. It is found to be much smaller than expected. This method enables to provide reliable rate constants for the test of dissolution models and the interpretation of in situ measurements, and gives clues to explain the inconsistency between dissolution rates of calcite and aragonite, for instance, in the literature.     

Micromechanism of the diffusion of cement-based grouts in porous media under two hydraulic operating conditions: constant flow rate and constant pressure

Acta Geotechnica - Cement-based grout has been widely used in various civil engineering applications. The diffusion of cement-based grouts in porous media is an important issue in soil sealing and...     

Assessment of integrity and geochronology of archaeological sites using amino acid racemization in land snail shells: Examples from central Texas

Detailed racemization analyses were carried out on samples of the land snail Rabdotus mooreanus from archaeological sites at Fort Hood, in central Texas. D -alloisoleucine/L -isoleucine (A/I) values were determined for 260 individual shells from 29 proveniences, including sites in alluvium, colluvium, and rockshelters, as well as burned rock middens. A/I values show a good correlation with radiocarbon age, and so provide reasonably precise estimates of ages. Analyses indicate the presence of redeposited material in a large number of proveniences. These result from sedimentary processes involved in burial of the sites as well as from later disturbance (aboriginal or recent) of site stratigraphy. Because amino acid racemization analyses are relatively easy to carry out, this method lends itself to very detailed chronostratigraphic analyses of archaeological sites, thus permitting assessment of site integrity and assisting in the interpretation of site formation processes. © 1996 John Wiley & Sons, Inc.     

Bioremediation of acid mine drainage using decomposable plant material in a constant flow bioreactor

Under stagnant conditions, the ability of 15 earth materials (non-lime) including various inorganic 2:1 and 1:1 layer silicates, an amorphous oxide, and two 'whole' soils were tested for their pH-buffering efficiency in an acid mine drainage (AMD) water. The purpose was to decrease AMD acidity to a level where sulfate-reducing bacteria (SRB) placed in it may be activated. Of all materials, a whole soil (a high cation-exchange capacity clayey mollisol containing 40% clay, and 4% soil organic matter) caused the greatest pH increases from 2.5 up to 5.5 units after 10 days in the AMD water. Influent AMD was then ameliorated at various speeds through an SRB driven bioreactor using a 50/50 weight over weight (w/w) combination of the mollisol and ryegrass (MR) as the pH buffer substrate. This substrate combination decreased the SRB acclimatisation period (from 50 days in a previous experiment utilising sludge + ryegrass) to <10 days in the present experiment. After causing pH increases from 2.8 to >6 units in 5 days, the buffer reduced the hydraulic retention time (HRT) of the constant-flow reactor from 12 days at flow speeds of 100 ml/day to 2 days at 25 ml/day, respectively. After 10 days, soluble Fe, Al and sulfate were all decreased >1,800-, >40- and 3-fold, respectively. This was a more efficient performance than the no-flow bioreactor of a previous experiment using sludge + ryegrass. This method of AMD rehabilitation is an alternative for localities that lack cheap sources of calcium compounds for chemical treatment, but have a similar soil type and copious quantities of fresh decomposable plant wastes.     

Solubility and dissolution rate of silica in acid fluoride solutions

We performed 57 batch reactor experiments in acidic fluoride solutions to measure the dissolution rate of quartz. These rate data along with rate data from published studies were fit using multiple linear regression to produce the following non-unique rate law for quartz

where 10^−5.13 < a_HF < 10^1.60, −0.28 < pH < 7.18, and 298 < T < 373 K. Similarly, 97 amorphous silica dissolution rate data from published studies were fit by multiple linear regression to produce the following non-unique rate law for amorphous silica

where 10^−2.37 < a_HF < 10^1.61, −0.32 < pH < 4.76 and 296 < T < 343 K. Regression of the rates versus other combinations of solution species, e.g.  + H⁺, F⁻ + H⁺, HF + , HF + F⁻, or  + F⁻, produced equally good fits. Any of these rate laws can be interpreted to mean that the rate-determining step for silica dissolution in fluoride solutions involves a coordinated attack of a Lewis acid, on the bridging O atom and a Lewis base on the Si atom. This allows a redistribution of electrons from the Si–O bond to form a O–H group and a Si–FH group.     

A dimensional analysis of scaling viscosity and velocity in DEM of constant strain rate tests on asphalt

This paper presents the results from discrete element modelling (DEM) of an idealised (sand) asphalt mixture under constant strain rate (velocity) compressive loading using the Burgers viscoelastic model. Using dimensional analysis it is shown that the effect of scaling applied velocity is the same as that of scaling both viscosities in the Burgers model by the same factor. This has been shown to be the case for a bonded aggregate, and it also has been shown to be applicable even when bond breakage occurs within the sample. This scaling method will be of great benefit in modelling tests on asphalt under different constant strain rates, simply by scaling both viscosities to minimise computational time.     

The stability constant of the UO22+ -humic acid complex

Between pH 3.5 and 7, humic acids form a water-soluble uranyl-humic acid complex with the uranyl ion, UO₂²⁺ (log β₁ = 7.8 ± 0.4 at μ = 0.1). The stability constant of the complex is practically independent of the ionic strength (μ). Experimental results can be explained by the formation of a complex in which every uranyl ion is simultaneously bonded to one phenolic oxygen and one dissociated carboxyl group. The bonding through the phenolic group is considerably stronger than that through carboxylic groups.     

A new method for estimating rate constants for trace gas reactions within stratospheric sulphuric acid aerosol droplets

Uptake of trace gases by (stratospheric aerosol can be significant particularly after large injections of volcanic sulphur. A theoretical scheme is presented to quantify the rate at which trace gases diffuse into these aerosol droplets. Rate constants for 19 trace gases are calculated and it is found that the rates vary from a value of 2.85 × 10^-7s^-1 for CC14 to 8.08 × 10^-7s^-1 for NO. The calculations are characterised by their ease of application and can be incorporated into stratospheric chemical models.     

The method of partial extraction of metals in a constant current electrical field for geochemical exploration

The method of partial extraction of metals (PEM) was invented by a group of Leningrad researchers in the late 60's to early 70's. It is based on the leaching of minerals and rocks under the influence of an electric field, on the migration of metal compounds in this field and on their accumulation in specially equipped receiver-electrodes. The quantity of extracted metals and the speed of accumulation is correlated with the composition of ore bodies and the distance of the sample sites from them. It is possible to use the PEM method for geochemical exploration in areas of thick overburden and for drill logging. The main features of the PEM method are good sensitivity and the possibility of determining the position of maximum concentrations for different metals. A number of techniques for field observations and several examples of their successful applications are described.