共查询到20条相似文献，搜索用时 812 毫秒
1.
Remediation of U-contaminated sites relies upon thermodynamic speciation calculations to predict U(VI) movement in the subsurface. However, reliability and applicability of geochemical speciation and reactive transport models may be limited by determinate (model) errors and random (uncertainty) errors in the equilibrium speciation calculations. This study examines propagated uncertainty in two types of subsurface calculations: I. Dissolved U(VI) speciation based on measured analytical constraints and solution phase equilibria and II. Overall U(VI) speciation which combined the dissolved phase equilibria with previously published adsorption reactions. Three levels of uncertainty, instrumental uncertainty, temporal variation and spatial variation across a site, were investigated using first-derivative sensitivity calculations and Monte Carlo simulations. Dissolved speciation calculations were robust, with minimal amplification of uncertainty and normal output distributions. The most critical analytical constraints in the dissolved system are pH, DIC, total U and total Ca, with some effect from dissolved . When considering adsorption equilibria, calculations were robust with respect to adsorbed U(VI) concentration prediction, but bimodal distributions of dissolved U(VI) concentrations were observed in simulations with background levels of total U(VI) and higher (spatial and temporal variability) estimates of input uncertainty. Consequently, sorption model predictions of dissolved U(VI) may not be robust with respect these higher levels of uncertainty. 相似文献
2.
Abstract ‘Peak’metamorphic carbon isotope fractionations between calcite and graphite (ΔCal–Gr) in marbles and calc-silicates from the Cucamonga granulite terrane (San Gabriel Mountains, California) range from 3.48 to 2.90%. The data are used to test three previously published calibrations of the calcite–graphite carbon isotope thermometer. An empirical calibration of the calcite–graphite carbon isotope thermometer gives temperatures of 700–750°C; a theoretical–experimental calibration of the system gives temperatures of 760°–870°C; an experimental calibration gives temperatures of 870–1300°C. Temperatures calculated using the empirical calibration are in agreement with those calculated from garnet-based cation exchange thermometry when uncertainty is considered. Temperatures calculated using the theoretical–experimental calibration overlap the upper range of cation exchange thermometry temperatures and range to 50°C higher. The experimental calibration yields temperatures from 50 to 480°C higher than those from cation exchange thermometry. Moreover, temperatures from the experimental calibration are also inconsistent with mineral and melt equilibria in the granulite phase assemblage. Despite the better agreement between cation exchange thermometry and the empirical calibration of the calcite–graphite system, temperatures calculated using the theoretical–experimental calibration may be real peak metamorphic temperatures. If retrograde diffusion partially reset garnet-based cation exchange thermometers by c. 50°C, then the cation exchange temperatures are consistent with those from the theoretical–empirical calibration. Thermometric evidence from biotite dehydration melting equilibria is consistent with either the empirical calibration if melting was fluid-present, or the theoretical–experimental calibration if melting was fluid-absent. 相似文献
3.
Method of Data Reduction and Uncertainty Estimation for Platinum-Group Element Data Using Inductively Coupled Plasma-Mass Spectrometry 总被引：1，自引：0，他引：1
A data reduction method is described for determining platinum-group element (PGE) abundances by inductively coupled plasma-mass spectrometry (ICP-MS) using external calibration or the method of standard addition. Gravimetric measurement of volumes, the analysis of reference materials and the use of procedural blanks were all used to minimise systematic errors. Internal standards were used to correct for instrument drift. A linear least squares regression model was used to calculate concentrations from drift-corrected counts per second (cps). Furthermore, mathematical manipulations also contribute to the uncertainty estimates of a procedure. Typical uncertainty estimate calculations for ICP-MS data manipulations involve: (1) Carrying standard deviations from the raw cps through the data reduction or (2) calculating a standard deviation from multiple final concentration calculations. It is demonstrated that method 2 may underestimate the uncertainty estimate of the calculated data. Methods 1 and 2 do not typically include an uncertainty estimate component from a regression model. As such models contribute to the uncertainty estimates affecting the calculated data, an uncertainty estimate component from the regression must be included in any final error calculations. Confidence intervals are used to account for uncertainty estimates from the regression model. These confidence intervals are simpler to calculate than uncertainty estimates from method 1, for example. The data reduction and uncertainty estimation method described here addresses problems of reporting PGE data from an article in the literature and addresses both precision and accuracy. The method can be applied to any analytical technique where drift corrections or regression models are used. 相似文献
4.
Generalized computer methods are developed for inferring details of the formation of cosmochemical systems. Compositions of ideal gas mixtures existing in equilibrium with multicomponent solid and liquid phases are calculated. A comparison of computed results with experimental data is made for the ternary system MgO-FeO-SiO2. While the ideal-solution approximation is shown to be inaccurate in dealing with the silicate melts, in a system where there are only solids and gas, the stable phases and compositions can be accurately calculated. A model system containing the elements H, O, Si, Mg, S, C, Cl and F is investigated over a range of compositions involving the gas and ten solid phases, to show the power of the technique in dealing with complex gas-solid equilibria. Systems close to cosmic composition are next considered, both with and without iron. When present, most of the iron is computed to be in the metallic state with little going into pyroxene or olivine solid solutions. At low hydrogen concentration and low temperature, troilite becomes the stable iron-bearing phase. The calculated equilibrium concentrations are very sensitive to the assumed ratio of magnesium to silicon. The computational method described is easily applied to complex systems of solids and gases and represents an important tool with which to investigate cosmochemical systems. 相似文献
5.
化学测量中不确定度的计算方法——不确定度连续传递模型计算示例 总被引：2，自引：0，他引：2
不确定度连续传递模型的基本步骤为：①对标准曲线的各点进行不确定度评定,给出各点的标准不确定度;②对标准曲线各点的响应值进行多次测定,得出其平均值和标准不确定度;③以这2个标准不确定度为权重进行拟合,得出双误差拟合方程和标准不确定度的计算公式;④计算标准曲线各点与其校准点的差值,并将其转换成标准不确定度;⑤将以上4项按不确定度传播规律计算总不确定度。实际测量时, ①、②、④步用插值法算得。通过一个实例比较了不同拟合方法间结果的差别,说明了运用X、Y的相对误差作为权重的直线拟和,再加上“不确定度连续传递模型”算得的测量不确定度更为合理。 相似文献
6.
不确定度连续传递模型的基本步骤为：①对标准曲线的各点进行不确定度评定,给出各点的标准不确定度;②对标准曲线各点的响应值进行多次测定,得出其平均值和标准不确定度;③以这2个标准不确定度为权重进行拟合,得出双误差拟合方程和标准不确定度的计算公式;④计算标准曲线各点与其校准点的差值,并将其转换成标准不确定度;⑤将以上4项按不确定度传播规律计算总不确定度。实际测量时, ①、②、④步用插值法算得。通过一个实例比较了不同拟合方法间结果的差别,说明了运用X、Y的相对误差作为权重的直线拟和,再加上“不确定度连续传递模型”算得的测量不确定度更为合理。 相似文献
7.
Assessment of widely used methods to derive depositional ages from detrital zircon populations 总被引：1，自引：0，他引：1
The calculation of a maximum depositional age(MDA)from a detrital zircon sample can provide insight into a variety of geological problems.However,the impact of sample size and calculation method on the accuracy of a resulting MDA has not been evaluated.We use large populations of synthetic zircon dates(N≈25,000)to analyze the impact of varying sample size(n),measurement uncertainty,and the abundance of neardepositional-age zircons on the accuracy and uncertainty of 9 commonly used MDA calculation methods.Furthermore,a new method,the youngest statistical population is tested.For each method,500 samples of n synthetic dates were drawn from the parent population and MDAs were calculated.The mean and standard deviation of each method ove r the 500 trials at each n-value(50-1000,in increments of 50)were compa red to the known depositional age of the synthetic population and used to compare the methods quantitatively in two simulation scenarios.The first simulation scenario varied the proportion of near-depositional-age grains in the synthetic population.The second scenario varied the uncertainty of the dates used to calculate the MDAs.Increasing sample size initially decreased the mean residual error and standard deviation calculated by each method.At higher n-values(>~300 grains),calculated MDAs changed more slowly and the mean resid ual error increased or decreased depending on the method used.Increasing the p roportion of near-depositional-age grains and lowering measurement uncertainty decreased the number of measurements required for the calculated MDAs to stabilize and decreased the standard deviation in calculated MDAs of the 500 samples.Results of the two simulation scenarios show that the most successful way to increase the accuracy of a calculated M DA is by acquiring a large number of low-uncertainty measurements(300300)approach is used if the calculation of accurate MDAs are key to research goals.Other acquisition method s,such as high-to moderate-precision measurement methods(e.g.,1%-5%,2σ)acquiring low-to moderate-n datasets(50300).Additionally,they are most susceptible to producing erroneous MDAs due to contamination in the field or laboratory,or through disturbances of the youngest zircon’s U-Pb systematics(e.g.,lead loss).More conservative methods that still produce accurate MDAs and are less susceptible to contamination or lead loss include:youngest grain cluster at 1σunce rtainty(YGC 1σ),youngest grain clusterat 2σuncertainty(YGC 2σ),and youngest statistical population(YSP).The ages calculated by these methods may be more useful and appealing when fitting calculated MDAs in to pre-existing chronostratigraphic frameworks,as they are less likely to be younger than the true depositional age.From the results of our numerical models we illustrate what geologic processes(i.e.,tectonic or sedimentary)can be resolved using MDAs derived from strata of different ages. 相似文献
8.
Contributions to Mineralogy and Petrology - Low pressure phase equilibria for natural mafic systems may be calculated utilizing empirically derived single component distribution coefficients and... 相似文献
9.
Pamela G. Doctor 《Engineering Geology》1989,26(4):411-429
Sensitivity and uncertainty analyses methods for computer models are being applied in performance assessment modeling in the geologic high-level radioactive-waste repository program. The models used in performance assessment tend to be complex physical/chemical models with large numbers of input variables. There are two basic approaches to sensitivity and uncertainty analyses: deterministic and statistical. The deterministic approach to sensitivity analysis involves numerical calculation or employs the adjoint form of a partial differential equation to compute partial derivatives; the uncertainty analysis is based on Taylor series expansions of the input variables propagated through the model to compute means and variances of the output variable. The statistical approach to sensitivity analysis involves a response surface approximation to the model with the sensitivity coefficients calculated from the response surface parameters; the uncertainty analysis is based on simulation. The methods each have strengths and weaknesses. 相似文献
10.
导数换算作为常用的位场数据处理手段具有重要的物理意义。由于实际测量误差和噪声的影响,波数域导数换算存在计算过程不稳定、求导结果精度差的问题。为了降低噪声干扰,提高导数计算精度,提出了在波数域常规导数算子基础上附加Chebyshev低通滤波器的任意阶导数换算方法。通过分析该滤波器的滤波特性,并结合位场异常径向平均功率谱曲线特征,确定了Chebyshev低通滤波法的滤波参数,减少了人为因素对求导结果的干扰。二度体和三度体模型试验表明,与其他3种方法(常规FFT(fast Fourier transformation)法、向上延拓法和ISVD(integrated second vertical derivative)法)相比,该方法计算的导数与理论值的均方根误差最小,求导结果精度较高。在虎林盆地布格重力异常数据处理中,利用该方法计算的垂向二阶导数受噪声干扰小,结果可靠性较高,依此划分出的8条大断裂和11条小断裂在以往研究中均得到证实。 相似文献
11.
Equilibrium-kinetic model of water-rock interaction 总被引：1，自引：0，他引：1
A computer model was developed for chemical interaction in water-rock systems. The model is based on the concept of partial
equilibrium [1] and combines the calculation of chemical equilibria in multicomponent systems with accounting for the kinetics
of the congruent dissolution of minerals as a function of pH (zeroth order kinetic reactions). The development of the process
in time is simulated as a series of sequential partial equilibria, and the bulk chemical composition of the system is calculated
at each time step from the chemical composition of aqueous solution at the beginning of the step and masses of minerals dissolved
during time Δt. The dissolution rates of individual minerals are calculated at each time step for the given temperature, current pH value,
and the degree of solution saturation with respect to minerals. Variations in the surface area of minerals due to precipitation
and dissolution are accounted for. Model application is exemplified by the calculation of chemical equilibria in the water-granite
system. The model may be useful for understanding the character of low-temperature interactions in water-rock systems under
stagnant conditions, in particular, the multistage development of groundwater chemistry, interaction of liquid radioactive
waste injected into underground repositories, etc. 相似文献
12.
Katy A. Boon Peter Rostron Michael H. Ramsey 《Geostandards and Geoanalytical Research》2011,35(3):353-367
In the assessment of potentially contaminated land, the number of samples and the uncertainty of the measurements (including that from sampling) are both important factors in the planning and implementation of an investigation. Both parameters also effect the interpretation of the measurements produced, and the process of making decisions based upon those measurements. However, despite their importance, previously there has been no method for assessing if an investigation is fit‐for‐purpose with respect to both of these parameters. The Whole Site Optimised Contaminated Land Investigation (WSOCLI) method has been developed to address this issue, and to allow the optimisation of an investigation with respect to both the number of samples and the measurement uncertainty, using an economic loss function. This function was developed to calculate an ‘expectation of (financial) loss’, incorporating costs of the investigation itself, subsequent land remediation, and potential consequential costs. To allow the evaluation of the WSOCLI method a computer program ‘OCLISIM’ has been developed to produce sample data from simulated contaminated land investigations. One advantage of such an approach is that as the ‘true’ contaminant concentrations are created by the program, these values are known, which is not the case in a real contaminated land investigation. This enables direct comparisons between functions of the ‘true’ concentrations and functions of the simulated measurements. A second advantage of simulation for this purpose is that the WSOCLI method can be tested on many different patterns and intensities of contamination. The WSOCLI method performed particularly well at high sampling densities producing expectations of financial loss that approximated to the true costs, which were also calculated by the program. WSOCLI was shown to produce notable trends in the relationship between the overall cost (i.e., expectation of loss) and both the number of samples and the measurement uncertainty, which are: (a) low measurement uncertainty was optimal when the decision threshold was between the mean background and the mean hot spot concentrations. (b) When the hot spot mean concentration is equal to or near the decision threshold, then mid‐range measurement uncertainties were optimal. (c) When the decision threshold exceeds the mean of the hot spot, mid‐range measurement uncertainties were optimal. The trends indicate that the uncertainty may continue to rise if the difference between hot spot mean and the decision threshold increases further. (d) In any of the above scenarios, the optimal measurement uncertainty was lower if there is a large geochemical variance (i.e., heterogeneity) within the hot spot. (e) The optimal number of samples for each scenario was indicated by the WSOCLI method, and was between 50 and 100 for the scenarios considered generally; although there was significant noise in the predictions, which needs to be addressed in future work to allow such conclusions to be clearer. 相似文献
13.
目前,测流不确定度通过误差试验或通过经验数值来确定,但这些方式存在着工作量大或不确定估计不足等局限性。为解决此问题,对基于实测数据和统计理论的插值方差估计法在不同测流条件下进行了验证,选取白河、襄阳和沙洋3个流量站进行了实测数据的不确定度分析,同时对白河站进行了Monte Carlo试验,比较插值方差估计法得到的不确定度与真实误差的差异。结果表明,插值方差估计法能较好地反映水位变化的影响,插值方差估计法所得到的不确定度与真实测流误差的相关系数达0.64,与断面水位变化的Spearman相关系数达0.79,高、中水位情况下插值方差估计法的不确定度估计结果较为合理,低水位情况下偏高。 相似文献
14.
Temperature and pressure estimates for Earth's upper mantle generally are based on indirect information derived from phase equilibria studies and the measurement of temperature and pressure dependent physical and chemical properties for relevant mantle materials. This paper describes an alternative approach, based on solid-inclusion piezothermometry, which utilizes the thermoelastic properties of direct mantle derived mineral samples. In particular, this study provides the theoretical development, based on the Murnaghan equation of state for solids, for a simple method of calculating isomeke lines for host and inclusion minerals of cubic symmetry which may be extrapolated accurately to upper mantle pressure and temperature conditions. The method is demonstrated for the particular case of garnet inclusions in diamond, for which adequate laboratory thermoelastic data are available. A specific application is made in the evaluation of the depth of formation of the D1 garnet-diamond inclusion system described by Harris et al. (1970). The pressure and temperature conditions of inclusion formation lie along the calculated isomeke line within the range constrained by recent graphite-diamond phase equilibria data. However, because the isomeke line for the garnet-diamond system and the graphite-diamond phase transition are very similar in slope, a further constraint is required. Assuming, therefore, that temperature in the upper mantle is bounded by the “Oceanic” and “Shield” geotherms of Clark and Ringwood (1964), the present results indicate that the D1 garnet-diamond system formed within the depth range 138 to 155 km (about 45 to 53 kbar pressure). This result, which relates to the genesis of kimberlite xenoliths, is generally consistent with the results of other studies which utilize phase equilibria data. 相似文献
15.
Estimation of kinetic Monod parameters for anaerobic degradation of benzene in groundwater 总被引：1，自引：0，他引：1
To date, evidence for the degradation of benzene under anaerobic conditions has been established only in few studies under
field and laboratory conditions. Recently, we demonstrated the mineralization of benzene under sulfate-reducing conditions
in a large-scale column experiment at a field site by balancing electrons (Vogt et al. in Biodegradation, 2007, in press).
Here, from a modelling approach, kinetic Monod parameters are estimated for the degradation of benzene in the columns, Monod
kinetics proved useful to simulate benzene concentrations at the column outflow. The uncertainty of the obtained parameters
is determined in a sensitivity analysis. A total mass of degraded benzene of 23 g or 80% of the total influx over a period
of three months was calculated. The estimated maximum utilization rate was calculated to be around 70 times lower than from
aerobic benzene degradation experiments. 相似文献
16.
位场垂向导数广泛应用于位场数据处理与解释当中,目前求取位场各阶垂向导数方法大致可以分为两类：①在频率域进行;②在空间域进行。针对这两类方法存在着稳定性较差的问题,这里介绍了计算位场各阶垂向导数的ISVD算法,并通过对单一地质体模型和地质体组合模型产生的布格重力异常进行处理分析,证明了ISVD算法在计算位场各阶垂向导数时,特别是在计算位场高阶垂向导数时,比在频率域及空间域计算结果具有较好的稳定性,ISVD算法能够有效地识别出浅层小尺度地质体边界。为了验证该方法对实际资料的处理效果,对某区块实际布格重力异常数据应用ISVD算法试算各阶垂向导数,结合地质背景等资料划分出断裂体系。结果证明,应用ISVD算法计算的位场各阶垂向导数,对于确定浅层小尺度地质体边界有较好的效果。 相似文献
17.
变质流体的溶液化学 总被引：2，自引：0，他引：2
Brucew.D.Yardley 《地学前缘》1994,(Z1)
变质流体中载有重要的溶解物质，这些溶解物不但在交代作用过程中起着重要作用，而且还影响着固相平衡。岩石中的某些组分（如氧化硅），虽溶于水但却不能形成络合物，即便在有附加配位体的情况下也是如此。大多数阳离子的浓度主要取决于络合配位体的有效性。尽管氯化物是配位体中最重要的成员，但对某些金属而言，那些较次要的配位体却更为有效。 相似文献
18.
Gregory B. Baecher 《Georisk: Assessment and Management of Risk for Engineered Systems and Geohazards》2016,10(2):92-108
The character and importance of uncertainty in dam safety risk analysis drives how risk assessments are used in practice. The current interpretation of uncertainty is that, in addition to the aleatory risk which arises from presumed uncertainty in the world, it comprises the epistemic aspects of irresolution in a model or forecast, specifically model and parameter uncertainty. This is true in part but it is not all there is to uncertainty in risk analysis. The physics of hazards and of failure may be poorly understood, which goes beyond uncertainty in its conventional sense. There may be alternative scenarios of future conditions, for example non-stationarity in the environment, which cannot easily be forecast. There may also be deep uncertainties of the type associated with climate change. These are situations in which analysts do not know or do not agree on the system characterisation relating actions to consequences or on the probability distributions for key parameters. All of these facets are part of the uncertainty in risk analysis with which we must deal. 相似文献
19.
Katy A. Boon Paul D. Taylor Michael H. Ramsey 《Geostandards and Geoanalytical Research》2007,31(3):237-249
Measurements taken to characterise environmental contamination contain uncertainty, which is generated by both field sampling and chemical analyses. Recently devised techniques have been applied for the first time to estimate this uncertainty in the commercial monitoring and assessment of contaminated land. The uncertainty reduces the reliability of the classification of the land that is made following a site investigation. The possible misclassification of areas of land, as a result of measurement uncertainty, can lead to substantial financial penalties, resulting from litigation or unnecessary remediation. Previous studies have developed methods for the estimation and financial optimisation of measurement uncertainty. These methods have now been applied to a series of six contrasting site investigations, which were conducted by various commercial organisations. The previous uses of these sites included a gas works, a tin mine and railway sidings. The measurement uncertainty was successfully estimated for each of the six investigations, showing its applicability to a wide range of different sampling methods, such as trial pits, window sampling and augering. The measurement uncertainty ranged widely between sites from 25% to 158%, indicating that investigations can differ widely in their reliability. The field sampling tended to generate the largest component of the measurement uncertainty when compared to the contribution from the chemical analysis. The Optimised Contaminated Land Investigation (OCLI) method was applied to each site, with the initial aim of estimating the financial losses that could be incurred as a result of misclassifying the land, due to the uncertainty. It showed that the expectation of loss value per sampling location ranged from only £58 at one site to over £ 11 000 at another. The optimal level of uncertainty that produced the minimal financial loss was then calculated for each site. It provided a reduction in the expectation of loss for the whole site of over £ 10 000 at two of the sites and over £90 000 at two others. These findings demonstrate that implementing concepts of uncertainty can have practical benefits in environmental monitoring, and can enable improvements to be made in the quality of sampling and hence of measurements in general. 相似文献
20.
In this contribution we report the results of an experimental study that investigated equilibrium and fractional crystallization of hydrous, transitional alkaline basalt at low oxygen fugacity, under lower to middle crustal conditions to constrain the generation of subaluminous and peralkaline differentiation products that typically occur in rift systems. The experiments reveal that liquids produced by equilibrium crystallization in the range 0.7–1 GPa cannot cross the subaluminous/peralkaline compositional divide. In contrast, fractional crystallization experiments under isobaric and polybaric conditions approach closer the naturally observed trend from subaluminous to evolved peralkaline products suggesting that polybaric differentiation starting at elevated pressures can indeed lead to the transition from subaluminous to peralkaline derivative liquids. The presence of water in the parental magmas of silicic derivative products is of prime importance for the fractionation equilibria as well as for the mobility of such magmas toward shallow crustal levels.
We suggest that peralkaline magmas in rift environments are indicative for differentiation under relatively low oxygen fugacity conditions in an extensional environment characterized by a high degree of crustal fracturing that allows rapid upward migration of mafic parental magmas and formation of shallow magma reservoirs. Crystallization–differentiation of parental, hydrous transitional alkaline basalt in such reservoirs is controlled by low pressure phase equilibria that typically evolve through early saturation of anorthite-rich plagioclase and suppressed amphibole crystallization resulting in ‘low-alumina’, peralkaline derivative liquids. 相似文献