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1.
Amino acid racemization (AAR) is widely used as a cost-effective method to date molluscs in time-averaging and taphonomic studies, but it has not been attempted for echinoderms despite their paleobiological importance and distinct biomineralization. Here we demonstrate the applicability of AAR geochronology for dating Holocene Peronella peronii (Echinodermata: Echinoidea) collected from Sydney Harbour (Australia). Using standard HPLC methods we determined the extent of AAR in 74 Peronella tests and performed replicate analyses on 23 tests. Replicate analyses from the outer edge of 23 tests spanning the observed range of D/L values yielded median coefficients of variation <4% for Asp, Glu, and Phe D/L values, which is comparable to the analytical precision. Correlations between THAA D/L values across 178 independently prepared subsamples of 74 individuals are also very high (Spearman ρ ≥ 0.95) for these three amino acids. The ages of 20 individuals spanning the observed range of D/L values were determined using 14C analyses, and Bayesian model averaging was used to determine the best AAR age model. Only three models fit to Glu D/L contributed to the final averaged age model. Modeled ages ranged from 14 to 5496 years, and the median 95% confidence interval for the 54 AAR ages was ±29% of the modelled age. In comparison, the median 2σ confidence interval for nine graphite target 14C ages was ±8% of the median age estimate and the median 2σ confidence interval for 20 carbonate target 14C ages was ±26% of the median age estimate. Overall Peronella yield high-quality D/L values and appear to be a good target for AAR geochronology. 相似文献
2.
It has been nearly three decades since the last systematic interlaboratory comparison of amino acid racemization (AAR) measurements among active laboratories. The advent of new methods and improved instrumentation for existing techniques requires that these comparisons be conducted more frequently than has occurred. The present study represents a first step in this process. Five homogeneous liquid samples were distributed to six participating laboratories that use one or more of the following analytical methods: Ion-exchange liquid chromatography (IEx), Reverse-phase liquid chromatography (RP), or Gas chromatography (GC). The five samples have been used in previous formal or informal interlaboratory comparisons: three are Pleistocene mollusk samples, two are Pleistocene eggshell samples. Use of homogeneous liquids eliminated variables involved in the majority of the sample preparative steps (sample cleaning, hydrolysis, desalting), so any observed variability between laboratories can be attributed to instrumental factors or possible small effects associated with the hydration procedures employed prior to instrumental analysis. Although most results indicate good agreement (within 10%) for all amino acid d/l values, there are some notable exceptions for certain amino acids or certain samples. For the five amino acids that are most commonly used in geochronological applications (Asx, Glx, Leu, Val, and A/I), inter-method comparisons reported here provide quantitative regressions that can be used when results from one method are compared with those from another. 相似文献
3.
A variety of mathematical expressions that describe changes over time (t) in the extent of amino acid racemisation (AAR, expressed as the ratio of d- to l-amino acid isomers or epimers) have been used in Quaternary geochronology. The integrated rate equation was first used to estimate fossil age from D/L but its geochronological utility is disadvantaged by uncertainties regarding the conformity of AAR in fossil protein to apparent reversible first-order kinetics for the entire reaction history. ‘Non-linear’ models have subsequently been used to relate D/L to t. The logarithmic equation successfully applied to Atlantic Coastal Plain research has not achieved widespread application, perhaps due to the regional calibration required if sensitivity to temperature is to be modelled, or the difficulties encountered when extending the model to include fossils with D/L<0.1. Success producing a linear correlation between D/L transformed with a power function and t has seen this approach emerge as one of the most commonly applied in AAR geochronology in recent years. Like parabola curve fitting, which has been applied to trends in D/L versus t in a variety of fossils and geographic settings, power transformations may not be suitable for geochronological modelling during the latter stages of amino acid diagenesis. Several studies have demonstrated the utility of simple and contingent linear equations for relating D/L to t. Future research should aim to reduce reliance on independent calibration and explore the geochronological benefits of AAR in pools other than the total hydrolysable amino acids. 相似文献
4.
Sediments deposited during glacial-interglacial cycles through the Early to Mid-Pleistocene in the North Sea are chronologically poorly constrained. To contribute to the chronology of these units, amino acid racemization (AAR) and strontium (Sr) isotope analyses have been performed on samples from four shallow borings and one oil well along a transect in the northern North Sea. D/L Asp (aspartic acid) values obtained through reverse-phase liquid chromatography in the benthic foraminiferal species Elphidium excavatum is focused on because of consistent results and a good stratigraphic distribution of this benthic species. For the Early Pleistocene, an age model for the well 16/1–8, from the central part of the northern North Sea based on Sr ages allows for dating of the prograding wedges filling the pre-Quaternary central basin. A regional calibration curve for the racemization of Asp in Elphidium excavatum is developed using published ages of radiocarbon-dated samples and samples associated with the previously identified Bruhnes/Matuyama (B/M) paleomagnetic boundary and a Sr age from this study. Based on all the available geochronological evidence, samples were assigned to marine oxygen isotope stages (MIS) with uncertainties on the order of 10–70 ka.Sr ages suggest a hiatus of <2 million years (Ma) possibly due to non-deposition or low sedimentation between the Utsira Formation (Pliocene) and the Early Pleistocene. An increase in sedimentation rates around 1.5 ± 0.07 Ma (∼MIS 51) may partly be due to sediment supply from rivers from the south-east and partly due to the extension of ice sheet around 1.36 ± 0.07 Ma from the Norwegian coast to the central North Sea. A possible basin-wide glaciation occurred around 1.1 Ma (∼ MIS 32) (upper regional unconformity/top of unit Q4 in this study), resulting in erosion and regional unconformity. Two interglacials in the Norwegian Channel have been dated: the Radøy Interglacial to 1.07 ± 0.01 Ma (possibly MIS 31, the ‘super interglacial’), and the Norwegian Trench Interglacial to 0.50 ± 0.02 Ma (possibly MIS 13). A massive till unit identified at the same stratigraphic level in all shallow borings may partly represent an extensive MIS 12 glaciation. This study shows that the combined use of amino acid racemization data and Sr isotope chronology can refine the chronological ambiguities of Quaternary North Sea sediments related partly to the impact of glacial processes. 相似文献
5.
The taxonomy of the land-snail genus Cerion, and the relevance of hundreds of shell forms to phylogenetic and evolutionary processes has been the subject of much discussion over the past few decades. Fundamental to understanding evolutionary trends is the independent confirmation of the age, biostratigraphic, and chronostratigraphic order of a comprehensive set of fossil forms. Amino acid racemization (AAR) is a geochronological tool applicable to dating living and fossil Cerion shells. The extent of racemization of aspartic acid (Asp D/L) and glutamic acid (Glu D/L) were determined for 507 Cerion shells dating between the early last interglaciation (marine isotope stage (MIS) 5e, c. 125 ka) and the present from the Bahamas. The AAR data based on Cerion support the established morphostratigraphic succession of deposits younger than MIS 5e and provide greater resolution, particularly for biostratigraphic successions of Holocene age. Age models were constructed for Asp and Glu using D/L values paired with 14C ages and historical collection dates from 23 Cerion shells. In addition to the relative-age time series, the Holocene age models developed from D/L Glu and Asp apply to the last 7 ka and geographically within the central Bahamas. In two case studies, large numbers of AAR-generated ages provide insights into the age structure of accretionary soils and rates and age constraints on evolutionary processes related to Cerion land snails. 相似文献
6.
Amino acid racemization (AAR) is a geochronological method that uses the ratio of D- to L-configurations in optically active amino acids from carbonate fossils to determine the time elapsed since the death of an organism. Although AAR techniques have been widely applied to foraminiferal tests, there have been limited dedicated assessments of the potential of isolating a bleach-resistant, intra-crystalline fraction of proteins to improve the reliability of AAR in this biomineral system. In this study, we evaluate the effect of two oxidative pre-treatments (hydrogen peroxide and bleach) on amino acid concentrations and D/L values in sub-modern benthic foraminifers (Ammonia spp. and Haynesina germanica) and well-preserved mid Holocene and mid Pleistocene planktic foraminifers (Pulleniatina obliquiloculata, Globorotalia truncatulinoides, and Globorotalia tumida). The oxidative pre-treatments successfully reduced the amino acid content of the foraminiferal tests to a residual fraction, and with the exception of Ammonia spp., neither pre-treatment substantially affected the relative proportion of individual amino acids. The bleaching pre-treatment does not consistently alter D/L values when compared to peroxide pre-treatment, but it does tend to reduce the subsample variability in D/L values, albeit only to a small degree in an inconsistent fashion. Therefore, we recommend that a relatively weak oxidative pre-treatment with 3% hydrogen peroxide is sufficient for foraminifera-based AAR applications. 相似文献
7.
The deep-sea environment is among the most stable on Earth, making it well suited for amino acid geochronology. Foraminifera with calcareous tests are distributed across the World Ocean and are often recovered in sufficient abundance from sediment cores to derive robust mean amino acid D/L values of multiple replicates from each stratigraphic level. The extent of racemization (D/L) can be compared with independent age control, which in most cases is based on correlation with global marine oxygen-isotope stages and radiocarbon ages from the same stratigraphic levels. In this study, we report the results of amino acid racemization analysis of multiple foraminifera species from well-dated sediment cores taken from the Pacific, Atlantic, and Arctic oceans. The composite of results analyzed to date (179 samples, each composed of an average of 8.6 subsamples = 1531 analyses) show that D/L values generally increase systematically down core, and are similar for samples of comparable ages from different deep-sea sites. Previously published equations that relate D/L values of aspartic and glutamic acids to post-depositional temperature and sample age for Pulleniatina obliquiloculata generally conform to the D/L trends for species analyzed in this study. Laboratory heating experiments were used to quantify the difference in the rate of racemization between P. obliquiloculata and other taxa. For example, aspartic acid in P. obliquiloculata racemizes an average of 12–16% faster than in the common high-latitude species, Neogloboquadrina pachyderma (s). Apparently, the unexpectedly high D/L values previously reported for N. pachyderma (s) older than 35 ka from the Arctic Ocean cannot be attributed to taxonomic effects. 相似文献
8.
Identifying outliers and assessing the accuracy of amino acid racemization measurements for geochronology: I. Age calibration curves 总被引：1，自引：1，他引：0
Numerical ages derived from amino acid racemization (AAR) geochronology are typically based on calibration curves that relate the extent of AAR to the age of independently dated specimens. Here, we compare options for developing calibration curves and quantifying age uncertainties using AAR data from 481 late Holocene shells, and AMS 14C analyses of 36 shells of four molluscan taxa (Ethalia, Natica, Tellina, and Turbo) collected from shallow sediment cores from a back-reef lagoon of the central Great Barrier Reef. The four taxa differed substantially in the quality of their geochronogical results. Explicitly including data from specimens alive at the time of collection improves calibration curves, but weighting numerical ages based on their uncertainty has no effect. Calibration curve statistics do not adequately assess calibration uncertainty. The relation between ages inferred from different amino acids is recommended for identifying aberrant specimens and quantifying the uncertainty of inferred ages. For this study, the AAR ages based on two amino acids (aspartic acid and glutamic acid) exceed 200 yr or 20% of their mean inferred age in 15% of the specimens. Once these were removed, the mean age error (1σ) for individual specimens based on two amino acids analyzed in duplicate subsamples ranged from 53 to 142 yr for Tellina and Turbo, respectively, or about a 30% age error for these relatively young shells. This compares favorably with analytical errors estimated at 50 yr or 5%. The presence of notable outliers undetectable using data from single amino acids emphasizes the importance of analyzing multiple amino acids. 相似文献
9.
Jeffrey L. Bada 《Earth and Planetary Science Letters》1981,55(2):292-298
Investigation of amino acid racemization in fossil bones and teeth from the Olduvai Gorge region, Tanzania, indicates that aspartic acid racemization can be used to date samples which are less than ～80,000–100,000 years old in this area. In older samples, significant secondary aspartic acid is apparently present and thus these samples have lower than expectedD/L aspartic acid ratios. Isoleucine in older samples, however, is apparently syngenetic with the samples, so the epimerization of isoleucine to alloisoleucine can be used with certain limitations to date fossil bones and teeth from the older stratigraphic sections in the Olduvai region. 相似文献
10.
The inter- and intra-crystalline fractions of Patella vulgata limpets recovered from archaeological sites in Northern Spain (covering Neolithic, Mesolithic, Magdalenian, Solutrean, and Aurignacian periods) were examined for amino acid composition and racemisation over time. The calcitic apex and rim areas of the shells were found to probably be composed of similar proteins, as the D/L values and amino acids were comparable and varied in the same way with increasing age; however, the mineral structures present in these areas differed. The aragonitic intermediate part of the shell showed a distinctly different amino acid composition and mineral structure. The main protein leaching from the inter-crystalline fraction occurred within the first 6000 yr after the death of the organism. In contrast, the intra-crystalline fraction — comprised of a different protein composition than the inter-crystalline fraction — appeared to behave as a closed system for at least 34 ka, as reflected by the lack of a significant decrease in the amino acid content; however, changes in the amino acid percentages occurred during this period. The concentration of aspartic acid remained almost constant with age both in inter- and intra-crystalline proteins, and its contribution to the total amino acid content increased with age at the expense of other amino acids such as glutamic acid, serine, glycine and alanine. Temperature is thought to play a key role in the amino acid racemisation of P. vulgata and could explain why in the localities belonging to the Gravettian and Solutrean period, which formed during relatively cold conditions, D/L values were similar to those detected in shells from sites formed during the Magdalenian. 相似文献
11.
In this study we compare the organic geochemistry of fossil and modern Glycymeris shells. Amino acids were preserved within the shells. The amino acid content of the shells was similar at all the sites studied. Amino acid racemization and epimerization of Glycymeris shells are suitable techniques for dating Pleistocene raised marine deposits. As reported in other studies, we found that isoleucine epimerization analysis has a greater capacity to discriminate between sites of different age than glutamic acid and aspartic acid. However, particular constraints regarding the use of amino acid dating concern intrashell variability, so to avoid divergent results, it is necessary to sample the same part of the shell, namely the complex cross lamellar region near the umbo. The dating of high-energy coastal marine deposits calls for extensive field work in order to ensure the collection of a large number of samples in order to obtain robust results and reject spurious values. Shell accumulations on the shore-line are conditioned by several factors. The high coefficients of variation for epimerization values and their distribution pattern can be attributed mainly to time-linked taphonomical processes (time-averaging) that gave rise to the shell-bearing bed. However, reworking from former highstand sea level deposits, which usually occupy higher topographic levels, is not a common occurrence. Therefore, as a result of time-averaging and post-depositional processes, it is difficult to identify substages in stacked shell beds in raised beach deposits belonging to the same marine oxygen isotope stage by means of amino acid racemization/epimerization. 相似文献
12.
A radiocarbon-calibrated aminochronology, based on the bivalve Mulinia lateralis, is presented for Chesapeake Bay core MD03-2661, a 25 m piston core drilled near Kent Island (38°53.21′N; 76°23.89′W) during the 2003 USGS Marion-Dufresne cruise. Three separate approaches were used to calibrate amino acid racemization (AAR) data for aspartic acid with radiocarbon data. For the first approach, a direct or paired analysis calibration incorporated eight articulated specimens, thereby allowing for the application of AAR and radiocarbon analysis of the same specimen and effectively eliminating both intrashell variability and time averaging as factors in the calibration. A second direct approach relied on valves that were bilaterally split to facilitate both AAR and radiocarbon dating, thus effectively eliminating time averaging effects from this calibration. For the third indirect approach, nine independent radiocarbon dates were combined with 129 Asx D/L ratios from the same core depths to produce an indirect calibration model, from which intershell variability and time averaging could be estimated. Variability in AAR ratios was recognized from a myriad of sources, including analytical error, intrashell variability, inherent variability, time averaging, and contamination. The majority of this variability was controlled for through experimental design or by the application of these three independent calibration approaches. The direct calibration of articulated shells and the indirect calibration yielded virtually identical age models, well within their respective 95% confidence intervals. This study establishes an aminostratigraphic reference section for the Holocene record of the Chesapeake Bay and demonstrates the usefulness of multiple calibration approaches and the potential utility of AAR for future studies of sedimentary processes and chronologies in the bay. 相似文献
13.
The most extensive terrestrial outcrops of glacial and glaciomarine deposits in the Eastern Canadian Arctic are exposed in sea cliffs along the Clyde Foreland and Qivitu Peninsula of Baffin Island. Collectively known as the Clyde Foreland Formation (CFF), these stacked deposits record at least seven glacial advances. Despite having been the focus of numerous investigations spanning nearly 50 years, no numerical chronological framework for the age of the deposits has been established. Previous studies relied on biostratigraphy and amino acid racemization (AAR) geochronology and postulated that the oldest units were Late Pliocene to Mid-Pleistocene in age. In this paper, we use a cosmogenic radionuclide isochron approach to determine a minimum age for the burial of a paleosol preserved within the CFF. Abundant palynomorphs in the paleosol are dominated by cool-climate taxa. Combining the paleosol burial age with a compilation of published and new CFF AAR data for marine bivalves Hiatella arctica and Mya truncata, we statistically define seven CFF aminozones and develop a piecewise isoleucine AAR calibration model for Baffin Island. From this, we estimate the minimum age of each aminozone, although the propagation of errors through all calculations produces large uncertainties for each age estimate. The youngest three CFF units, known as the Kogalu, Kuvinilk, and Cape Christian members, were most likely deposited during glaciations in the Mid- to Late-Pleistocene. The paleosol formed prior to 1.15 ± 0.20 Ma, and the underlying aminozones represent sedimentation during Early Pleistocene or latest Pliocene glaciations and record early advances of Laurentide ice across Baffin Island. 相似文献
14.
Identifying outliers and assessing the accuracy of amino acid racemization measurements for geochronology: II. Data screening 总被引：1，自引：1，他引：0
Amino acid racemization (AAR) is a cost-effective method for dating the large numbers of specimens required for time-averaging studies. Because the aim of time-averaging studies is to determine the structure of the age distribution, any data screening must be done cautiously and systematically. Methods to quantitatively assess the quality of AAR data and to identify aberrant specimens are under-developed. Here we examine a variety of screening criteria for identifying outliers and determining the suitability of specimens for numerical dating including: high serine concentrations (modern contamination), covariance of aspartic acid (Asp) and glutamic acid (Glu) concentrations (diagenetic influences), replication of measurements (specimen heterogeneity), and the relation between Asp and Glu d/l values (internal consistency). This study is based on AAR analyses of 481 late Holocene shells of four molluscan taxa (Ethalia, Natica, Tellina, and Turbo) collected from shallow sediment cores from the central Great Barrier Reef. Different outliers are flagged by the different screening criteria, and 6% of specimens were found to be unsuitable for time-averaging analyses based on screening the raw AAR data. We recommend a hybrid approach for identifying outliers and specimens for numerical dating. 相似文献
15.
The composition of bound amino acids was studied in selected types of green and blue-green plankton algae by means of a new elaborated method, using paper chromatography at the triple development of the chromatogram in the set-up: butanol: acetic acid: water at the rate of 4 : 1 : 5. Algologically and bacterially pure cultures of the green algae Ankistrodesmus falcatus, Haematococcus pluvialis, Chlorella pyrenoidosa, Pediastrum boryanum, Scendesmus obliquus and of the blue-green algae Anacystis nidulans, Microcystis pulverea and Microcystis aeruginosa were cultivated in inorganic and in organic medium. The contents of amino acids in green algae were qualitatively and quantitatively evaluated in relation to their physiologic condition (phase of logarithmic growth, phase of stagnation) and to the method of nutrition. The results were compared with the contents of amino acids in blue-green algae obtained in monocultures from freshwater at blue-green algae water blooms. The composition of bound amino acids was studied in selected types of green and blue-green plankton algae by means of a new elaborated method, using paper chromatography at the triple development of the chromatogram in the set-up: butanol: acetic acid: water at the rate of 4 : 1 : 5. Algologically and bacterially pure cultures of the green algae Ankistrodesmus falcatus, Haematococcus pluvialis, Chlorella pyrenoidosa, Pediastrum boryanum, Scendesmus obliquus and of the blue-green algae Anacystis nidulans, Microcystis pulverea and Microcystis aeruginosa were cultivated in inorganic and in organic medium. The contents of amino acids in green algae were qualitatively and quantitatively evaluated in relation to their physiologic condition (phase of logarithmic growth, phase of stagnation) and to the method of nutrition. The results were compared with the contents of amino acids in blue-green algae obtained in monocultures from freshwater at blue-green algae water blooms. The following amino acids were found in the organismus of primary production: alanine, aspartic acid, arginine, cysteine, glutamic acid, histidine, isoleucine, leucine, lysine, proline, serine and glycine, threonine, tryptophane, tyrosine and valine. The following amino acids were predominant from the quantitative aspect: glutamic acid, threonine and serine and glycine. The composition of amino acids in green algae cultivated in an inorganic medium did not differ significantly from cultures cultivated in an organic medium. Differences in the quantitative composition of the individual amino acids were ascertained with green algae in relation to their physiologic condition. 相似文献
16.
John W. Magee Gifford H. Miller Nigel A. Spooner Danielle G. Questiaux Malcolm T. McCulloch Peter A. Clark 《Quaternary Geochronology》2009,4(2):84-92
A whole emu egg, with infilling sediment believed to be coeval with egg laying and burial, was found in late Pleistocene lunette sediments near Lake Eyre, central Australia. The stratigraphic context and initial amino acid racemization (AAR) results suggested an age between 25 ka and 35 ka, ideal for a multiple cross-dating comparison. The sediment infilling the egg provided material for luminescence dating that minimized problems of association. Age estimations from AAR, 14C and U series methods were obtained from the eggshell and optically stimulated luminescence (OSL) of the infilling sediment. All methods agreed within their respective dating uncertainties confirming the utility of all four methods. They indicate an age for the emu egg of 31.24 ± 0.34 ka. 相似文献
17.
High-temperature isothermal heating of biominerals has commonly been used to artificially accelerate protein degradation in order to extrapolate kinetic parameters to the lower temperatures experienced in vivo and in the burial environment. It is not easy to test the accuracy of these simulations due to the difficulty of finding samples of known age held at a known temperature. We compare protein degradation in the intra-crystalline organic matrix of heated (80 °C, 110 °C, and 140 °C) massive Porites sp. coral to that directly measured in the skeleton of colonies growing at ∼26 °C and deposited over the last five centuries. This provides the opportunity to critically evaluate the underlying assumption that high-temperature experiments accurately mimic degradation processes and kinetics occurring in a ‘naturally aged’ biomineral. In all samples the intra-crystalline protein fraction was isolated and the L- and D- concentration of multiple amino acids measured using reverse-phase high-performance liquid chromatography (RP-HPLC). There was no evidence of a failure of the closed system in the high-temperature experiments (assessed by X-ray diffraction, thermogravimetric analyses and determination of leached amino acid concentration). We compared conventional methods for estimation of kinetic parameters with a new ‘model-free’ approach that makes no assumptions regarding the underlying kinetics of the system and uses numerical optimisation to estimate relative rate differences. The ‘model-free’ approach generally produced more reliable estimates of the observed rates of racemization in ‘naturally aged’ coral, although rates of hydrolysis (as estimated from the release of free amino acids) were usually over-estimated. In the amino acids for which we were able to examine both racemization and hydrolysis (aspartic acid/asparagine, glutamic acid/glutamine and alanine), it was clear that hydrolysis was less temperature sensitive than racemization, which may account for the differences in degradation patterns observed between the ‘naturally aged’ coral and high-temperature data. It is clearly important to estimate the individual temperature dependence of each of the parallel reactions. 相似文献
18.
Occurrence of Industrial Chemicals (HPS, BPS, and SPS) in Surface Water The paper gives the results of water examinations for different phenylsulfonamides. Random samples taken every month between May 1999 and August 2000 from surface water out of the river Rhine (kilometer 838), the river Ruhr (Mülheim Styrum) and the river Emscher (Oberhausen center) were tested for the corrosion inhibiting agent 6‐[methyl(phenylsulfonyl)amino]‐hexanoic acid (HPS) as well as its metabolites 4‐[methyl‐(phenylsulfonyl)amino]‐butanoic acid (BPS) and sarkosin‐N‐(phenylsulfonyl) (SPS). Furthermore, the sewage plant effluents of two municipal wastewater treatment plants from the rural area were also included in the monitoring program. The analytical method includes solid‐phase extraction (SPE), a derivatization step as well as gas chromatography mass spectrometry (GC‐MS). SPS is regularly found in all investigated surface waters, but only occasionally in the effluents of the two rural sewage plants. The median values for SPS amount to 0.09 μg/L in the river Rhine, 0.60 μg/L in the river Ruhr, and 0.70 μg/L in the river Emscher. BPS can only be found in the river Ruhr (median value: 0.08 μg/L) and in the river Emscher (median value: 0.41 μg/L). HPS was regularly found in a surface water for the first time. This substance can be detected in the Emscher through the whole measurement period. The median value for HPS amounts to 1.78 μg/L. Aditionally, the validation characteristics of an alternative analytical method including solid‐phase microextraction (SPME) is worked out. The fully automated process includes an on‐fiber methylation step and the GC‐MS. The repeatability standard deviation of the process amounts to RSD < 12%. Detection limits between 0.07 and 0.70 μg/L are achieved. 相似文献
19.
The reductive amination of low‐molecular‐weight saccharides, uronic acids, and amino sugars, followed by a separation of the derivates by means of ion‐pair chromatography or RP‐HPLC, offers an interesting alternative to HPAEC‐PAD for the environmental analysis of these compounds. Under this aspect various potential amination reagents, i.e., p‐amino‐benzoic acid (p‐AMBA), p‐AMBA propyl ester, 1‐aminopyrene, 2‐(2‐aminophenyl)indole, and 4‐aminoazobenzene, were tested with regard to the formation of derivates and to the chromatographic properties of the formed derivates. p‐AMBA, p‐AMBA propyl ester and 4‐aminoazobenzene proved to be especially suited, because they facilitate the amination of all carbohydrate reference components together with a complete separation and sensible detection (detection limits < 0.5 mg/L) of the derivates. Mainly the following elution sequence was ascertained: amino sugars (hexosamines) / disaccharide(s) / monosaccharides (hexoses) / hexuronic acid(s) / N‐acetyl‐D‐glucosamine. Detection limits down to 0.1 μmol/L were realized using p‐AMBA as reagent, facilitating the determination of the target compounds in landfill leachates and lysimeter percolates. Applying the p‐AMBA propyl ester for derivatization, chromatographic interferences with weakly retained derivates and the coelution of the reagent with its galactosamine derivate can be avoided, since the ester elutes after its derivates unlike p‐AMBA itself. 相似文献
20.
Jordon Bright Darrell S. Kaufman Steven L. Forman William C. McIntosh Jim I. Mead Arturo Baez 《Quaternary Geochronology》2010,5(6):631-643
A recently discovered Bison-bearing fossil locality at Térapa, Sonora, Mexico, had previously been dated to 440 ± 130 ka using whole rock 40Ar/39Ar on a basalt flow that impounds the deposit. This age is considerably older than the accepted age of about 240–160 ka for the migration of Bison into greater North America. The Térapa deposit also contains a mixture of fossils from extralimital or extinct tropical animals and temperate animals. Constraining the age of the deposit is critical to interpret the paleontologic and paleoclimatologic implications of this unique Sonoran fossil locality. Three additional geochronological methods have been applied to this deposit (infrared stimulated luminescence (IRSL), amino acid racemization (AAR), and radiocarbon) and the data from the original 40Ar/39Ar age were revisited. The IRSL data suggest that the impounding basalt flow and the sediments that abut it were emplaced 43 ka ago and that the oldest sediments were deposited shortly after. Two radiocarbon ages suggest the fossiliferous sediments were emplaced by 42 ka. Effective diagenetic temperatures inferred from the AAR results, combined with AAR data from a similar-age deposit in southern Arizona, are in accordance with the 40–43 ka age estimates. For the AAR results to corroborate the 40Ar/39Ar age, the effective diagenetic temperature for the area would need to be approximately 3 °C, which is unrealistically low for northern Mexico. The new geochronological results suggest the Térapa deposit and fossils are 40–43 ka old. The anomalously old 40Ar/39Ar age for the impounding basalt is probably the result of low 40Ar* concentrations and inherited 40Ar. 相似文献