共查询到20条相似文献，搜索用时 62 毫秒
1.
An improved algorithm for the generalized rank annihilation method(GRAM)is presented.GRAM isa method for multicomponent calibration using two-dimensional instruments,such as GC-MS.In thispaper an orthonormal base is first computed and used to project the calibration and unknown sampleresponse matrices into a lower-dimensional subspace.The resulting generalized eigenproblem is thensolved using the QZ algorithm.The result of these improvements is that GRAM is computationally morestable,particularly in the case where the calibration sample contains chemical constituents not present inthe unknown sample and the unknown contains constituents not present in the calibration(the mostgeneral case). 相似文献
2.
Traditionally,one form of preprocessing in multivariate calibration methods such as principal componentregression and partial least squares is mean centering the independent variables(responses)and thedependent variables(concentrations).However,upon examination of the statistical issue of errorpropagation in multivariate calibration,it was found that mean centering is not advised for some datastructures.In this paper it is shown that for response data which(i)vary linearly with concentration,(ii)have no baseline(when there is a component with a non-zero response that does not change inconcentration)and(iii)have no closure in the concentrations(for each sample the concentrations of allcomponents add to a constant,e.g.100%)it is better not to mean center the calibration data.That is,the prediction errors as evaluated by a root mean square error statistic will be smaller for a model madewith the raw data than a model made with mean-centered data.With simulated data relativeimprovements ranging from 1% to 13% were observed depending on the amount of error in thecalibration concentrations and responses. 相似文献
3.
Stefan Engels Angela E. Self Tomi P. Luoto Stephen J. Brooks Karin F. Helmens 《Journal of Paleolimnology》2014,51(4):529-547
Multiple regional chironomid–climate calibration datasets are available to reconstruct quantitatively July air temperatures from fossil chironomid assemblages. We examined the relationship between July air temperature and the 40 most common chironomid taxa in three independent Eurasian calibration (training) sets. The estimated temperature optimum of each chironomid taxon is systematically lower (by ~1–2 °C) in a Norwegian calibration set compared to Finnish and Russian calibration sets. This result might partly be explained by the fact that the Norwegian calibration set extends further at the cold end of the temperature gradient. A difference in continentality between the Russian sites and the European sites might also contribute to this pattern. The number of taxa that show a statistically significant unimodal response to temperature is higher in the Norwegian calibration set (34 out of 40 taxa) compared to the modern Finnish (11 of 37 taxa; 3 common taxa absent) and the Russian calibration set (20 of 40 taxa), probably due to the longer temperature gradient incorporated in the Norwegian calibration set. We applied all three calibration sets to fossil chironomid assemblages from the high-latitude study site of Sokli (northeast Finland), a site with a unique series of lacustrine deposits covering (amongst others) the Holocene, part of early MIS 3 (at ~53 ka) and MIS 5d–c (at ~110–95 ka) and with independent proxy-records for comparison. In the early Holocene and during MIS 5c, the chironomid-based temperature inferences from all three inference models had similar values. Temperature reconstructions based on the Norwegian calibration set are 2–4 °C lower for the late Holocene, early MIS 3 and MIS 5d than the inferred temperatures based on the other calibration sets. Although the lakes included in the Finnish calibration set are located closest to the site of Sokli, evaluation tests and a comparison with independent proxy data suggests that the Norwegian calibration set provides the most suitable analogues for reconstruction purposes for most of the fossil assemblages. Our results imply that when choosing a calibration set for quantitative climate reconstructions on glacial timescales, regional proximity of the fossil site may not be a sufficient basis, and the length of the temperature gradient of the calibration dataset and factors such as the continentality gradient covered by the calibration set must also be considered. 相似文献
4.
SIJMEN DE JONG 《地理学报(英文版)》1993,(6)
PLS1 regression is generally viewed as lying in between PCR and OLS regression.Proof is given thatthe coefficient of determination,R~2,for a PLS multivariate calibration model is at least as high as thatfor a PCR model with the same number of components.It appears that PLS can be linked to acorrelation-weighted polynomial regression of a constant response on the eigenvalues of the covariancematrix of the predictor variables. 相似文献
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7.
Diatom-based water chemistry reconstructions from northern Sweden: a comparison of reconstruction techniques 总被引：6，自引：0，他引：6
The diatom composition in surface sediments from 119 northern Swedish lakes was studied to examine the relationship with lake-water pH, alkalinity, and colour. Diatom-based predictive models, using weighted-averaging (WA) regression and calibration, partial least squares (PLS) regression and calibration, and weighted-averaging partial least squares (WA-PLS) regression and calibration, were developed for inferences of water chemistry conditions. The non-linear response between the diatom assemblages and pH and alkalinity was best modelled by weighted-averaging methods. The lowest prediction error for pH was obtained using weighted averaging, with or without tolerance downweighting. For alkalinity there was still some information in the residual structure after extracting the first weighted-averaging component, which resulted in a slight improvement of predictions when using a two component WA-PLS model. The best colour predictions were obtained using a two component PLS model. Principal component analysis (PCA) of the prediction errors, with some characteristics of the training set included as passive variables, was performed to compare the results for the different alkalinity predictive models. The results indicate that calibration techniques utilizing more than one component (PLS and WA-PLS) can improve the predictions for lakes with diatom taxa that have broad tolerances. Furthermore, we show that WA-PLS performs best compared with the other techniques for those lakes that have a high relative abundance of the most dominant taxa and a corresponding low sample heterogeneity. 相似文献
8.
Several multivariate methods are now available for the calibration of second-order or hyphenatedinstruments(e.g.GC/MS).When applied to bilinear data,it has been shown that calibration can beperformed in the presence of unknown interferences-a significant advantage over first-order calibration.In this paper,non-bilinear rank annihilation(NBRA),a method which has the potential of handling,second-order non-bi-linear data,is studied through theoretical analysis and computer simulation.It isfound that the second-order advantage can be carried over to non-bilinear data if a property defined asnet analyte rank(NAR)holds for the analyte of interest.The net analyte signal(NAS)is definedaccordingly for second-order calibration and the analogy to and difference from lower-order calibrationare discussed.With NAS,some analytical figures of merit such as signal-to noise ratio,selectivity,sensitivity and limit of determination can be calculated for second order calibration.An application toMS/MS data is also given. 相似文献
9.
RECENT DEVELOPMENTS IN MULTIVARIATE CALIBRATION 总被引：1，自引：0，他引：1
B.R.KOWALSKI M.B.SEASHOLTZ Laboratory for Chemometrics BG- University of Washington Seattle WA U.S.A. 《地理学报(英文版)》1991,(3)
With the goal of understanding global chemical processes,environmental chemists have some of the mostcomplex sample analysis problems.Multivariate calibration is a tool that can be applied successfully inmany situations where traditional univariate analyses cannot.The purpose of this paper is to reviewmultivariate calibration,with an emphasis being placed on the developments in recent years.The inverseand classical models are discussed briefly,with the main emphasis on the biased calibration methods.Principal component regression(PCR)and partial least squares(PLS)are discussed,along with methodsfor quantitative and qualitative validation of the calibration models.Non-linear PCR,non-linear PLSand locally weighted regression are presented as calibration methods for non-linear data.Finally,calibration techniques using a matrix of data per sample(second-order calibration)are discussed briefly. 相似文献
10.
Gaute Velle Richard J. Telford Oliver Heiri Joshua Kurek H. John B. Birks 《Journal of Paleolimnology》2012,48(3):545-558
Most calibration data sets used to infer past environmental conditions from biological proxies are derived from many sites. An alternative strategy is to derive the calibration data set from within a single site. Transfer functions derived from such intra-site calibration data sets are usually applied to fossil assemblages from the focal lake, but a recent development has been to apply these transfer functions to other sites. Transfer functions derived from intra-site calibration data sets can have impressive cross-validation performance, but that gives little indication of their performance when applied to other sites. Here, we develop transfer functions for lake depth from intra-lake chironomid calibration data sets in Norway and Alaska and test the resulting models by cross-validation and against known depth in external lakes. Lake depth is a statistically significant predictor of chironomid assemblages at all these lakes, and most intra-lake transfer functions perform reasonably well under cross-validation, but their performance against external data is erratic. Downcore reconstructions from transfer functions developed on different lakes are dissimilar. Ignoring the poorly performing transfer functions, only 3 of 14 downcore reconstructions are statistically significant. Few assemblages downcore had good modern analogues in the calibration data set, even when the core was from the same lake as the calibration data set. We conclude that intra-site calibration data sets can find site-specific rather than general relationships between species and the environment and thus should be applied with care and to external sites only after careful and critical validation. 相似文献
11.
JOHN H.KALIVAS 《地理学报(英文版)》1991,(1)
ealibrared.The diseussion in this PaPer foeuses on near一infrared(NIR)sPeetroseoPy as the examPle instrument.However,the Proeedures Presented are aPPlieable tomost methods of instrumental analysis.Essentially,ealibration eonsists of assembling a seriesof samPles eontaining the analyte or analytes at 相似文献
12.
A. M. García I. Santé M. Boullón R. Crecente 《International journal of geographical information science》2013,27(8):1593-1611
Cellular automata (CA) stand out among the most commonly used urban models for the simulation and analysis of urban growth because of their ability to reproduce complex dynamics, similar to those found in real cities, from simple rules. However, CA models still have to overcome some shortcomings related to their flexibility and difficult calibration. This study combines various techniques to calibrate an urban CA that is based on one of the most widely used urban CA models. First, the number of calibration parameters is reduced by using various statistical techniques, and, second, the calibration procedure is automated through a genetic algorithm. The resulting model has been assessed by simulating the urban growth of Ribadeo, a small village of NW Spain, characterized by low, slow urban growth, which makes the identification of urban dynamics and consequently the calibration of the model more difficult. Simulation results have shown that, by automating the calibration procedure, the model can be more easily applied and adapted to urban areas with different characteristics and dynamics. In addition, the simulations obtained with the proposed model show better values of cell-to-cell correspondence between simulated and real maps, and the values for most spatial metrics are closer to real ones. 相似文献
13.
机载成像光谱数据预处理方法研究--以江苏宜兴市为例 总被引：4，自引：2，他引：2
该文基于土地利用／土地覆盖分类目的,对国产128波段的宜兴市机载成像光谱数据进行了数据导入、镜像变换、辐射畸变纠正、相对反射率转换和几何精纠正以及多航带间的镶嵌试验研究。通过分析发现：经验线性法定标效果明显好于其他两种定标方法;图像精纠正后多条带镶嵌图能够与土地利用现状数据库较好吻合。 相似文献
14.
L. V. PEREZ-ARRIBAS F. NAVARRO-VILLOSLADA M. E. LEON-GONZALEA L. M. POLO-DIEZ Departamento de Quimica Analiti Facultad de Ciencias Quimicas Universidad Complutense E- Madri Spain 《地理学报(英文版)》1993,(4)
The usefulness of the Kalman filter as an algorithm for calibration in a real system is shown. Results arecompared with classical least squares and pure component calibration. The prediction of four prioritypollutant chlorophenols in binary, ternary and quaternary mixtures was also carried out by Kalmanfiltering. The condition number, standard deviation and prediction error have been employed to choosethe most suitable wavelength range. Comparison of the standard error of prediction in the validation setshows significant differences between the evaluated chlorophenols, the best results being obtained withKalman multivariate calibration. 相似文献
15.
A modification of a technique proposed by Lorber and Kowalski for the estimation of prediction errorsis presented.The method is applied to five data sets.The results show that for some data sets theestimated prediction errors are close to the actual prediction errors for samples within the calibrationrange,while samples outside the calibration range must be background corrected before quantificationof the prediction error. 相似文献
16.
Atmosphere-borne acidic pollutants constitute an important, potentially critical, risk to aquatic ecosystems. Long-time series
datasets are a requirement in the assessment of the biological impacts of both increased and decreased loadings of acidic
pollutants and allow for the anticipation of future pollution loadings and their effects that can be acted upon with some
confidence. Little is known concerning levels of deposition of atmospheric pollutants and their effects on acid-sensitive
aquatic ecosystems in Ireland. Moreover, unequivocal evidence of acidification by atmospheric deposition is limited. The objective
of this study was to provide a preliminary assessment of pH response in three lake sites that are situated in acid-sensitive
areas of Ireland, and to determine whether pH response tends to be uniform or differs due to variations in atmospheric loading
and catchment properties. Levels of spheroidal carbonaceous particle (SCP) deposition have been used as a general indicator
of the timing and extent of atmospheric pollutant loading and ecosystem response has been assessed by estimating diatom-inferred
pH with a weighted-averaging calibration model (72 lakes) developed specifically for the Irish ecoregion. Levels of diatom-inferred
pH (DI-pH) appear to respond to increased and decreased levels of atmospheric pollution loads—as represented by SCPs—at two
of the three sites examined in the east and west of Ireland. In contrast, the site situated in the southwest of Ireland showed
a varying and less directional DI-pH response, possibly due to lower deposition pressures, large lake size, and more buffered
edaphic geology. 相似文献
17.
Wibjörn Karlén & Jessica L. Black 《Geografiska Annaler: Series A, Physical Geography》2002,84(3-4):225-232
Two lichenometric techniques were compared in a study of lichen growth–rate in northern Sweden. The first technique, based on the maximum lichen diameter on glacier moraines, was identical to the technique used in the 1970s, whereas the other utilized the lichen diameter measured on 100 randomly selected boulders. The results indicate that it does not matter which technique is chosen, as long as the technique is used consistently on both the calibration surfaces and the surfaces to be dated. The use of data from both the 1970s and the 2000s increased the number of calibration surfaces available. The new calibration curve indicates that the age of Little Ice Age moraines was underestimated by up to about 30 years in the study conducted in the 1970s. 相似文献
18.
Wibjörn Karlén & Jessica L. Black 《Geografiska Annaler: Series A, Physical Geography》2002,84(3&4):225-232
Two lichenometric techniques were compared in a study of lichen growth–rate in northern Sweden. The first technique, based on the maximum lichen diameter on glacier moraines, was identical to the technique used in the 1970s, whereas the other utilized the lichen diameter measured on 100 randomly selected boulders. The results indicate that it does not matter which technique is chosen, as long as the technique is used consistently on both the calibration surfaces and the surfaces to be dated. The use of data from both the 1970s and the 2000s increased the number of calibration surfaces available. The new calibration curve indicates that the age of Little Ice Age moraines was underestimated by up to about 30 years in the study conducted in the 1970s. 相似文献
19.
The reliability of quantitative paleoenvironmental reconstructions from lake sediment cores depends in part on the accuracy of the environmental data used in calibration. For paleoclimate reconstructions, gridded datasets provide convenient and consistent modern climate data for calibration. We show, however, that commonly used gridded climate data may have regional biases, which can affect calibration models and the paleoclimate reconstructions derived from them. Although there may be few alternatives to their use, researchers should be aware of potential problems, especially if unusual or counter-intuitive calibration models or reconstructions are obtained. 相似文献
20.
Michelle Goman 《Journal of Paleolimnology》2001,26(4):393-409
The feasibility of developing a seed calibration data set to infer environmental constraints was examined by studying modern seed and vegetation assemblages from 53 stations at three distinct tidal marshes within the San Francisco Bay (salt, brackish and freshwater). Pearson's correlation indicates autochthonous derivation of seeds at the marsh sites. Multivariate statistical analysis of the vegetation and seed data indicates discrete assemblages, which can be used as a proxy for modern salinity and tidal inundation within the estuary. Canonical discriminant analysis indicates that the vegetation and seed assemblages of the three marsh types are statistically distinct. Cluster analysis suggests that marsh vegetation is zoned at the mean higher high water mark at all the sites. The calibration set was then applied to stratigraphic seed data from the estuary to infer changes in paleo-salinity and -tidal inundation during the Holocene. The results of the calibration are compared to earlier reconstructions within the estuary. While the calibrated reconstruction broadly compares to previous reconstructions, a period of inferred lower salinity within the estuary between 3800–2000 cal yr B.P. is calibrated as brackish and not fresh by the calibration model. 相似文献