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1.
Glob Chang Biol ; 30(1): e17089, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38273490

RESUMO

Given the importance of soil for the global carbon cycle, it is essential to understand not only how much carbon soil stores but also how long this carbon persists. Previous studies have shown that the amount and age of soil carbon are strongly affected by the interaction of climate, vegetation, and mineralogy. However, these findings are primarily based on studies from temperate regions and from fine-scale studies, leaving large knowledge gaps for soils from understudied regions such as sub-Saharan Africa. In addition, there is a lack of data to validate modeled soil C dynamics at broad scales. Here, we present insights into organic carbon cycling, based on a new broad-scale radiocarbon and mineral dataset for sub-Saharan Africa. We found that in moderately weathered soils in seasonal climate zones with poorly crystalline and reactive clay minerals, organic carbon persists longer on average (topsoil: 201 ± 130 years; subsoil: 645 ± 385 years) than in highly weathered soils in humid regions (topsoil: 140 ± 46 years; subsoil: 454 ± 247 years) with less reactive minerals. Soils in arid climate zones (topsoil: 396 ± 339 years; subsoil: 963 ± 669 years) store organic carbon for periods more similar to those in seasonal climate zones, likely reflecting climatic constraints on weathering, carbon inputs and microbial decomposition. These insights into the timescales of organic carbon persistence in soils of sub-Saharan Africa suggest that a process-oriented grouping of soils based on pedo-climatic conditions may be useful to improve predictions of soil responses to climate change at broader scales.


Assuntos
Carbono , Solo , Solo/química , Minerais , Sequestro de Carbono , África Subsaariana
2.
PLoS Biol ; 19(11): e3001441, 2021 11.
Artigo em Inglês | MEDLINE | ID: mdl-34723965

RESUMO

Open access, high-resolution soil property maps have been created for Africa at 30 m resolution, using machine learning trained on over 100,000 analysed soil samples. Combined with other field-level information, iSDAsoil enables the possibility of site-specific agronomy advisory for smallholder farmers.


Assuntos
Solo , África , Geografia , Concentração de Íons de Hidrogênio
3.
Geoderma ; 375: 114474, 2020 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-33012837

RESUMO

Soil mineral compositions are often complex and spatially diverse, with each mineral exhibiting characteristic chemical properties that determine the intrinsic total concentration of soil nutrients and their phyto-availability. Defining soil mineral-nutrient relationships is therefore important for understanding the inherent fertility of soils for sustainable nutrient management, and data-driven approaches such as cluster analysis allow for these relations to be assessed in new detail. Here the fuzzy-c-means clustering algorithm was applied to an X-ray powder diffraction (XRPD) dataset of 935 soils from sub-Saharan Africa, with each diffractogram representing a digital signature of a soil's mineralogy. Nine mineralogically distinct clusters were objectively selected from the soil mineralogy continuum by retaining samples exceeding the 75 % quantile of the membership coefficients in each cluster, yielding a dataset of 239 soils. As such, samples within each cluster represented mineralogically similar soils from different agro-ecological environments of sub-Saharan Africa. Mineral quantification based on the mean diffractogram of each cluster illustrated substantial mineralogical diversity between the nine groups with respect to quartz, K-feldspar, plagioclase, Fe/Al/Ti-(hydr)oxides, phyllosilicates (1:1 and 2:1), ferromagnesians, and calcite. Mineral-nutrient relationships were defined using the clustered XRPD patterns and corresponding measurements of total and/or extractable (Mehlich-3) nutrient concentrations (B, Mg, K, Ca, Mn, Fe, Ni, Cu and Zn) in combination with log-ratio compositional data analysis. Fe/Al/Ti/Mn-(hydr)oxides and feldspars were found to be the primary control of total nutrient concentrations, whereas 2:1 phyllosilicates were the main source of all extractable nutrients except for Fe and Zn. Kaolin minerals were the most abundant phyllosilicate group within the dataset but did not represent a nutrient source, which reflects the lack of nutrients within their chemical composition and their low cation exchange capacity. Results highlight how the mineral composition controls the total nutrient reserves and their phyto-availability in soils of sub-Saharan Africa. The typical characterisation of soils and their parent material based on the clay particle size fraction (i.e. texture) and/or the overall silica component (i.e. acid and basic rock types) alone may therefore mask the intricacies of mineral contributions to soil nutrient concentrations.

4.
Geoderma ; 337: 413-424, 2019 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-30828102

RESUMO

X-ray powder diffraction (XRPD) is widely applied for the qualitative and quantitative analysis of soil mineralogy. In recent years, high-throughput XRPD has resulted in soil XRPD datasets containing thousands of samples. The efforts required for conventional approaches of soil XRPD data analysis are currently restrictive for such large data sets, resulting in a need for computational methods that can aid in defining soil property - soil mineralogy relationships. Cluster analysis of soil XRPD data represents a rapid method for grouping data into discrete classes based on mineralogical similarities, and thus allows for sets of mineralogically distinct soils to be defined and investigated in greater detail. Effective cluster analysis requires minimisation of sample-independent variation and maximisation of sample-dependent variation, which entails pre-treatment of XRPD data in order to correct for common aberrations associated with data collection. A 24 factorial design was used to investigate the most effective data pre-treatment protocol for the cluster analysis of XRPD data from 12 African soils, each analysed once by five different personnel. Sample-independent effects of displacement error, noise and signal intensity variation were pre-treated using peak alignment, binning and scaling, respectively. The sample-dependent effect of strongly diffracting minerals overwhelming the signal of weakly diffracting minerals was pre-treated using a square-root transformation. Without pre-treatment, the 60 XRPD measurements failed to provide informative clusters. Pre-treatment via peak alignment, square-root transformation, and scaling each resulted in significantly improved partitioning of the groups (p < 0.05). Data pre-treatment via binning reduced the computational demands of cluster analysis, but did not significantly affect the partitioning (p > 0.1). Applying all four pre-treatments proved to be the most suitable protocol for both non-hierarchical and hierarchical cluster analysis. Deducing such a protocol is considered a prerequisite to the wider application of cluster analysis in exploring soil property - soil mineralogy relationships in larger datasets.

5.
Chemometr Intell Lab Syst ; 153: 92-105, 2016 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-27110048

RESUMO

We propose four methods for finding local subspaces in large spectral libraries. The proposed four methods include (a) cosine angle spectral matching; (b) hit quality index spectral matching; (c) self-organizing maps and (d) archetypal analysis methods. Then evaluate prediction accuracies for global and subspaces calibration models. These methods were tested on a mid-infrared spectral library containing 1907 soil samples collected from 19 different countries under the Africa Soil Information Service project. Calibration models for pH, Mehlich-3 Ca, Mehlich-3 Al, total carbon and clay soil properties were developed for the whole library and for the subspace. Root mean square error of prediction was used to evaluate predictive performance of subspace and global models. The root mean square error of prediction was computed using a one-third-holdout validation set. Effect of pretreating spectra with different methods was tested for 1st and 2nd derivative Savitzky-Golay algorithm, multiplicative scatter correction, standard normal variate and standard normal variate followed by detrending methods. In summary, the results show that global models outperformed the subspace models. We, therefore, conclude that global models are more accurate than the local models except in few cases. For instance, sand and clay root mean square error values from local models from archetypal analysis method were 50% poorer than the global models except for subspace models obtained using multiplicative scatter corrected spectra with which were 12% better. However, the subspace approach provides novel methods for discovering data pattern that may exist in large spectral libraries.

6.
PLoS One ; 17(2): e0262754, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35108304

RESUMO

Adept use of fertilizers is critical if sustainable development goal two of zero hunger and agroecosystem resilience are to be achieved for African smallholder agroecosystems. These heterogeneous systems are characterized by poor soil health mainly attributed to soil nutrient depletion. However, conventional methods do not take into account spatial patterns across geographies within agroecosystems, which poses great challenges for targeted interventions of nutrient management. This study aimed to develop a novel population-based farm survey approach for diagnosing soil nutrient deficiencies. The approach embraces principles of land health surveillance of problem definition and rigorous sampling scheme. The advent of rapid soil testing techniques, like infrared spectroscopy, offers opportune avenues for high-density soil and plant characterization. A farm survey was conducted on 64 maize fields, to collect data on soil and plant tissue nutrient concentration and grain yield (GY) for maize crops, using hierarchical and purposive sampling. Correlations between soil test values with GY and biomass were established. The relationship between GY, soil NPK, and the tissue nutrient concentrations was evaluated to guide the setting up of localized critical soil test values. Diagnosis Recommendation Integrated System (DRIS) indices for total nitrogen (N), total phosphorus (P), and total potassium (K) were used to rank and map the prevalence of nutrient limitations. A positive correlation existed between plant tissue nutrient concentration with GY with R2 values of 0.089, 0.033, and 0.001 for NPK, respectively. Soil test cut-off values were 0.01%, 12 mg kg-1, 4.5 cmolc kg-1 for NPK, respectively, which varied slightly from established soil critical values for soil nutrient diagnostics. N and K were the most limiting nutrients for maize production in 67% of sampled fields. The study demonstrates that a population-based farm survey of crop fields can be a useful tool in nutrient diagnostics and setting priorities for site-specific fertilizer recommendations. A larger-scale application of the approach is warranted.


Assuntos
Ecossistema , Nutrientes/análise , Biomassa , Grão Comestível/metabolismo , Fazendas , Nitrogênio/análise , Fósforo/análise , Folhas de Planta/química , Folhas de Planta/metabolismo , Potássio/análise , Solo/química , Espectrofotometria Infravermelho , Zea mays/química , Zea mays/crescimento & desenvolvimento , Zea mays/metabolismo
7.
Sci Rep ; 12(1): 5162, 2022 03 25.
Artigo em Inglês | MEDLINE | ID: mdl-35338205

RESUMO

Realistic targets for soil organic carbon (SOC) concentrations are needed, accounting for differences between soils and land uses. We assess the use of SOC/clay ratio for this purpose by comparing changes over time in (a) the National Soil Inventory of England and Wales, first sampled in 1978-1983 and resampled in 1994-2003, and (b) two long-term experiments under ley-arable rotations on contrasting soils in the East of England. The results showed that normalising for clay concentration provides a more meaningful separation between land uses than changes in SOC alone. Almost half of arable soils in the NSI had degraded SOC/clay ratios (< 1/13), compared with just 5% of permanent grass and woodland soils. Soils with initially large SOC/clay ratios (≥ 1/8) were prone to greater losses of SOC between the two NSI samplings than those with smaller ratios. The results suggest realistic long-term targets for SOC/clay in arable, ley grass, permanent grass and woodland soils are 1/13, 1/10, and > 1/8, respectively. Given the wide range of soils and land uses across England and Wales in the datasets used to test these targets, they should apply across similar temperate regions globally, and at national to sub-regional scales.


Assuntos
Carbono , Solo , Carbono/análise , Sequestro de Carbono , Argila , Poaceae , País de Gales
8.
PLoS One ; 17(1): e0262460, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35015770

RESUMO

With the increasing popularity of local blending of fertilisers, the fertiliser industry faces issues regarding quality control and fertiliser adulteration. Another problem is the contamination of fertilisers with trace elements that have been shown to subsequently accumulate in the soil and be taken up by plants, posing a danger to the environment and human health. Conventional characterisation methods necessary to ensure the quality of fertilisers and to comply with local regulations are costly, time consuming and sometimes not even accessible. Alternatively, using a wide range of unamended and intentionally amended fertilisers this study developed empirical calibrations for a portable handheld X-ray fluorescence (pXRF) spectrometer, determined the reliability for estimating the macro and micro nutrients and evaluated the use of the pXRF for the high-throughput detection of trace element contaminants in fertilisers. The models developed using pXRF for Mg, P, S, K, Ca, Mn, Fe, Zn and Mo had R2 values greater or equal to 0.97. These models also performed well on validation, with R2 values greater or equal to 0.97 (except for Fe, R2val = 0.55) and slope values ranging from 0.81 to 1.44. A second set of models were developed with a focus on trace elements in amended fertilisers. The R2 values of calibration for Co, Ni, As, Se, Cd and Pb were greater than or equal to 0.80. At concentrations up to 1000 mg kg-1, good validation statistics were also obtained; R2 values ranged from 0.97-0.99, except in one instance. The regression coefficients of the validation also had good prediction in the range of 0-100 mg kg-1 (R2 values were from 0.78-0.99), but not as well at lower concentrations up to 20 mg kg-1 (R2 values ranged from 0.10-0.99), especially for Cd. This study has demonstrated that pXRF can measure several major (P, Ca) and micro (Mn, Fe, Cu) nutrients, as well as trace elements and potential contaminants (Cr, Ni, As) in fertilisers with high accuracy and precision. The results obtained in this study is good, especially considering that loose powders were scanned for a maximum of 90 seconds without the use of a vacuum pump.


Assuntos
Monitoramento Ambiental/métodos , Fertilizantes/análise , Nutrientes/análise , Poluentes do Solo/análise , Solo/química , Espectrometria por Raios X/métodos , Oligoelementos/análise
9.
Sci Rep ; 11(1): 6130, 2021 03 17.
Artigo em Inglês | MEDLINE | ID: mdl-33731749

RESUMO

Soil property and class maps for the continent of Africa were so far only available at very generalised scales, with many countries not mapped at all. Thanks to an increasing quantity and availability of soil samples collected at field point locations by various government and/or NGO funded projects, it is now possible to produce detailed pan-African maps of soil nutrients, including micro-nutrients at fine spatial resolutions. In this paper we describe production of a 30 m resolution Soil Information System of the African continent using, to date, the most comprehensive compilation of soil samples ([Formula: see text]) and Earth Observation data. We produced predictions for soil pH, organic carbon (C) and total nitrogen (N), total carbon, effective Cation Exchange Capacity (eCEC), extractable-phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), sulfur (S), sodium (Na), iron (Fe), zinc (Zn)-silt, clay and sand, stone content, bulk density and depth to bedrock, at three depths (0, 20 and 50 cm) and using 2-scale 3D Ensemble Machine Learning framework implemented in the mlr (Machine Learning in R) package. As covariate layers we used 250 m resolution (MODIS, PROBA-V and SM2RAIN products), and 30 m resolution (Sentinel-2, Landsat and DTM derivatives) images. Our fivefold spatial Cross-Validation results showed varying accuracy levels ranging from the best performing soil pH (CCC = 0.900) to more poorly predictable extractable phosphorus (CCC = 0.654) and sulphur (CCC = 0.708) and depth to bedrock. Sentinel-2 bands SWIR (B11, B12), NIR (B09, B8A), Landsat SWIR bands, and vertical depth derived from 30 m resolution DTM, were the overall most important 30 m resolution covariates. Climatic data images-SM2RAIN, bioclimatic variables and MODIS Land Surface Temperature-however, remained as the overall most important variables for predicting soil chemical variables at continental scale. This publicly available 30-m Soil Information System of Africa aims at supporting numerous applications, including soil and fertilizer policies and investments, agronomic advice to close yield gaps, environmental programs, or targeting of nutrition interventions.

11.
PLoS One ; 15(6): e0234213, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32502217

RESUMO

Agricultural development projects have a poor track record of success mainly due to risks and uncertainty involved in implementation. Cost-benefit analysis can help allocate resources more effectively, but scarcity of data and high uncertainty makes it difficult to use standard approaches. Bayesian Networks (BN) offer a suitable modelling technology for this domain as they can combine expert knowledge and data. This paper proposes a systematic methodology for creating a general BN model for evaluating agricultural development projects. Our approach adapts the BN model to specific projects by using systematic review of published evidence and relevant data repositories under the guidance of domain experts. We evaluate a large-scale agricultural investment in Africa to provide a proof of concept for this approach. The BN model provides decision support for project evaluation by predicting the value-measured as net present value and return on investment-of the project under different risk scenarios.


Assuntos
Agricultura/economia , Clima , Investimentos em Saúde/estatística & dados numéricos , Política , Teorema de Bayes , Modelos Estatísticos , Risco , Incerteza
12.
PLoS One ; 15(12): e0242821, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-33301449

RESUMO

Portable X-ray fluorescence (pXRF) and Diffuse Reflectance Fourier Transformed Mid-Infrared (DRIFT-MIR) spectroscopy are rapid and cost-effective analytical tools for material characterization. Here, we provide an assessment of these methods for the analysis of total Carbon, Nitrogen and total elemental composition of multiple elements in organic amendments. We developed machine learning methods to rapidly quantify the concentrations of macro- and micronutrient elements present in the samples and propose a novel system for the quality assessment of organic amendments. Two types of machine learning methods, forest regression and extreme gradient boosting, were used with data from both pXRF and DRIFT-MIR spectroscopy. Cross-validation trials were run to evaluate generalizability of models produced on each instrument. Both methods demonstrated similar broad capabilities in estimating nutrients using machine learning, with pXRF being suitable for nutrients and contaminants. The results make portable spectrometry in combination with machine learning a scalable solution to provide comprehensive nutrient analysis for organic amendments.


Assuntos
Fertilizantes/análise , Aprendizado de Máquina , Nutrientes/análise , Agricultura Orgânica , Solo/química , Espectrometria por Raios X , Espectroscopia de Infravermelho com Transformada de Fourier
13.
Geoderma ; 154(1-2): 93-100, 2009 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-27397933

RESUMO

Human induced soil erosion has severe economic and environmental impacts throughout the world. It is more severe in the tropics than elsewhere and results in diminished food production and security. Kenya has limited arable land and 30 percent of the country experiences severe to very severe human induced soil degradation. The purpose of this research was to test visible near infrared diffuse reflectance spectroscopy (VNIR) as a tool for rapid assessment and benchmarking of soil condition and erosion severity class. The study was conducted in the Saiwa River watershed in the northern Rift Valley Province of western Kenya, a tropical highland area. Soil 137Cs concentration was measured to validate spectrally derived erosion classes and establish the background levels for difference land use types. Results indicate VNIR could be used to accurately evaluate a large and diverse soil data set and predict soil erosion characteristics. Soil condition was spectrally assessed and modeled. Analysis of mean raw spectra indicated significant reflectance differences between soil erosion classes. The largest differences occurred between 1,350 and 1,950 nm with the largest separation occurring at 1,920 nm. Classification and Regression Tree (CART) analysis indicated that the spectral model had practical predictive success (72%) with Receiver Operating Characteristic (ROC) of 0.74. The change in 137Cs concentrations supported the premise that VNIR is an effective tool for rapid screening of soil erosion condition.

14.
Nutr Cycl Agroecosyst ; 113(1): 1-19, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-32684797

RESUMO

Improving fertilizer recommendations for farmers is essential to increase food security in smallholder landscapes. Currently, blanket recommendations are provided across agro-ecological zones, although fertilizer response and nutrient use efficiency by maize crop are spatially variable. We aimed to identify factors that could help to refine fertilizer recommendation by analyzing the variability in fertilizer response (FR) and the agronomic nitrogen use efficiency (N-AE). A literature search for on-farm studies across Kenya and Sub-Sahara Africa (SSA), excluding Kenya, yielded 71 publications. The variability in FR was studied using a meta-analysis whereas key factors that influence FR and N-AE were studied with linear regression models. On average, the FR was 2, but it varied considerably from 1 to 28.5 (excluding outliers). In SSA, 18% of the plots were non-responsive plots with an FR < 1. The main factors affecting N-AE for Kenya were P-Olsen, silt content, soil pH, clay and rainfall, whereas only soil pH, exchangeable K and texture were important for SSA. However, our study indicates that available data on soil, climate and management factors could explain only a small part (< 33%) of the variation in FR and N-AE. Soil pH, P-Olsen, silt content, and rainfall had significant but low levels of power in explaining variation in FR and N-AE. Our findings indicate that strategies to refine fertilizer recommendation should include information on soil types and soil properties.

15.
Nutr Cycl Agroecosyst ; 109(1): 77-102, 2017 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-33456317

RESUMO

Spatial predictions of soil macro and micro-nutrient content across Sub-Saharan Africa at 250 m spatial resolution and for 0-30 cm depth interval are presented. Predictions were produced for 15 target nutrients: organic carbon (C) and total (organic) nitrogen (N), total phosphorus (P), and extractable-phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), sulfur (S), sodium (Na), iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), aluminum (Al) and boron (B). Model training was performed using soil samples from ca. 59,000 locations (a compilation of soil samples from the AfSIS, EthioSIS, One Acre Fund, VitalSigns and legacy soil data) and an extensive stack of remote sensing covariates in addition to landform, lithologic and land cover maps. An ensemble model was then created for each nutrient from two machine learning algorithms- random forest and gradient boosting, as implemented in R packages ranger and xgboost-and then used to generate predictions in a fully-optimized computing system. Cross-validation revealed that apart from S, P and B, significant models can be produced for most targeted nutrients (R-square between 40-85%). Further comparison with OFRA field trial database shows that soil nutrients are indeed critical for agricultural development, with Mn, Zn, Al, B and Na, appearing as the most important nutrients for predicting crop yield. A limiting factor for mapping nutrients using the existing point data in Africa appears to be (1) the high spatial clustering of sampling locations, and (2) missing more detailed parent material/geological maps. Logical steps towards improving prediction accuracies include: further collection of input (training) point samples, further harmonization of measurement methods, addition of more detailed covariates specific to Africa, and implementation of a full spatiotemporal statistical modeling framework.

16.
PLoS One ; 10(6): e0125814, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-26110833

RESUMO

80% of arable land in Africa has low soil fertility and suffers from physical soil problems. Additionally, significant amounts of nutrients are lost every year due to unsustainable soil management practices. This is partially the result of insufficient use of soil management knowledge. To help bridge the soil information gap in Africa, the Africa Soil Information Service (AfSIS) project was established in 2008. Over the period 2008-2014, the AfSIS project compiled two point data sets: the Africa Soil Profiles (legacy) database and the AfSIS Sentinel Site database. These data sets contain over 28 thousand sampling locations and represent the most comprehensive soil sample data sets of the African continent to date. Utilizing these point data sets in combination with a large number of covariates, we have generated a series of spatial predictions of soil properties relevant to the agricultural management--organic carbon, pH, sand, silt and clay fractions, bulk density, cation-exchange capacity, total nitrogen, exchangeable acidity, Al content and exchangeable bases (Ca, K, Mg, Na). We specifically investigate differences between two predictive approaches: random forests and linear regression. Results of 5-fold cross-validation demonstrate that the random forests algorithm consistently outperforms the linear regression algorithm, with average decreases of 15-75% in Root Mean Squared Error (RMSE) across soil properties and depths. Fitting and running random forests models takes an order of magnitude more time and the modelling success is sensitive to artifacts in the input data, but as long as quality-controlled point data are provided, an increase in soil mapping accuracy can be expected. Results also indicate that globally predicted soil classes (USDA Soil Taxonomy, especially Alfisols and Mollisols) help improve continental scale soil property mapping, and are among the most important predictors. This indicates a promising potential for transferring pedological knowledge from data rich countries to countries with limited soil data.


Assuntos
Monitoramento Ambiental/métodos , Solo/química , África , Modelos Teóricos
17.
Sci Total Environ ; 463-464: 374-88, 2013 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-23831788

RESUMO

Total X-ray fluorescence spectroscopy (TXRF) determines concentrations of major and trace elements in multiple media. We developed and tested a method for the use of TXRF for direct quantification of total element concentrations in soils using an S2 PICOFOX™ spectrometer (Bruker AXS Microanalysis GmbH, Germany). We selected 15 contrasting soil samples from across sub-Saharan Africa for element analysis to calibrate the instrument against concentrations determined using the inductively coupled plasma-mass spectroscopy (ICP-MS) standard method. A consistent underestimation of element concentrations using TXRF compared to ICP-MS reference analysis occurred, indicating that spectrometer recalibration was required. Single-element recalibration improved the TXRF spectrometer's sensitivity curve. Subsequent analysis revealed that TXRF determined total element concentrations of Al, K, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, and Ga accurately (model efficacy/slope close to 1:1 line, and R(2)>0.80) over a wide range of soil samples. Other elements that could be estimated with an acceptable precision (R(2)>0.60) compared with ICP-MS although generally somewhat under- or overestimated were P, Ca, As, Rb, Sr, Y, Pr, Ta and Pb. Even after recalibration, compared to ICP-MS the TXRF spectrometer produced underestimations for elements Na, Mg, Ba, Ce, Hf, La, Nd, W and Sm and overestimations for elements Bi, Tl and Zr. We validated the degree of accuracy of the TXRF analytical method after recalibration using an independent set of 20 soil samples. We also tested the accuracy of the analysis using 2 multi-element standards as well as the method repeatability on replicate samples. The resulting total element concentration repeatability for all elements analyzed were within 10% coefficient of variability after the instrument recalibration except for Cd and Tl. Our findings demonstrate that TXRF could be used as a rapid screening tool for total element concentrations in soils assuming that sufficient calibration measures are followed.

18.
Food Sci Nutr ; 1(1): 45-53, 2013 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-24804013

RESUMO

There is uncertainty on how generally applicable near-infrared reflectance spectroscopy (NIRS) calibrations are across genotypes and environments, and this study tests how well a single calibration performs across a wide range of conditions. We also address the optimization of NIRS to perform the analysis of crude protein (CP) content in a variety of cowpea accessions (n = 561) representing genotypic variation as well as grown in a wide range of environmental conditions in Tanzania and Uganda. The samples were submitted to NIRS analysis and a predictive calibration model developed. A modified partial least-squares regression with cross-validation was used to evaluate the models and identify possible spectral outliers. Calibration statistics for CP suggests that NIRS can predict this parameter in a wide range of cowpea leaves from different agro-ecological zones of eastern Africa with high accuracy (R (2)cal = 0.93; standard error of cross-validation = 0.74). NIRS analysis improved when a calibration set was developed from samples selected to represent the range of spectral variability. We conclude from the present results that this technique is a good alternative to chemical analysis for the determination of CP contents in leaf samples from cowpea in the African context, as one of the main advantages of NIRS is the large number of compounds that can be measured at once in the same sample, thus substantially reducing the cost per analysis. The current model is applicable in predicting the CP content of young cowpea leaves for human nutrition from different agro-ecological zones and genetic materials, as cowpea leaves are one of the popular vegetables in the region.

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