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- ItemOptical Spectrometry to Determine Nutrient Concentrations and other Physicochemical Parameters in Liquid Organic Manures: A Review(Basel : MDPI, 2022) Horf, Michael; Vogel, Sebastian; Drücker, Harm; Gebbers, Robin; Olfs, Hans-WernerNutrient concentrations in livestock manures and biogas digestates show a huge variability due to disparities in animal husbandry systems concerning animal species, feed composition, etc. Therefore, a nutrient estimation based on recommendation tables is not reliable when the exact chemical composition is needed. The alternative, to analyse representative fertilizer samples in a standard laboratory, is too time-and cost-intensive to be an accepted routine method for farmers. However, precise knowledge about the actual nutrient concentrations in liquid organic fertilizers is a prerequisite to ensure optimal nutrient supply for growing crops and on the other hand to avoid environmental problems caused by overfertilization. Therefore, spectrometric methods receive increasing attention as fast and low-cost alternatives. This review summarizes the present state of research based on optical spectrometry used at laboratory and field scale for predicting several parameters of liquid organic manures. It emphasizes three categories: (1) physicochemical parameters, e.g., dry matter, pH, and electrical conductivity; (2) main plant nutrients, i.e., total nitrogen, ammonium nitrogen, phosphorus, potassium, magnesium, calcium, and sulfur; and (3) micronutrients, i.e., manganese, iron, copper, and zinc. Furthermore, the commonly used sample preparation techniques, spectrometer types, measuring modes, and chemometric methods are presented. The primarily promising scientific results of the last 30 years contributed to the fact that near-infrared spectrometry (NIRS) was established in commercial laboratories as an alternative method to wet chemical standard methods. Furthermore, companies developed technical setups using NIRS for on-line applications of liquid organic manures. Thus, NIRS seems to have evolved to a competitive measurement procedure, although parts of this technique still need to be improved to ensure sufficient accuracy, especially in quality management.
- ItemBase Neutralizing Capacity of Agricultural Soils in a Quaternary Landscape of North-East Germany and Its Relationship to Best Management Practices in Lime Requirement Determination(Basel : MDPI AG, 2020) Vogel, Sebastian; Bönecke, Eric; Kling, Charlotte; Kramer, Eckart; Lück, Katrin; Nagel, Anne; Philipp, Golo; Rühlmann, Jörg; Schröter, Ingmar; Gebbers, RobinDespite being a natural soil-forming process, soil acidification is a major agronomic challenge under humid climate conditions, as soil acidity influences several yield-relevant soil properties. It can be counterbalanced by the regular application of agricultural lime to maintain or re-establish soil fertility and to optimize plant growth and yield. To avoid underdose as well as overdose, lime rates need to be calculated carefully. The lime rate should be determined by the optimum soil pH (target pH) and the response of the soil to lime, which is described by the base neutralizing capacity (BNC). Several methods exist to determine the lime requirement (LR) to raise the soil pH to its optimum. They range from extremely time-consuming equilibration methods, which mimic the natural processes in the soil, to quick tests, which rely on some approximations and are designed to provide farmers with timely and cost-efficient data. Due to the higher analytical efforts, only limited information is available on the real BNC of particular soils. In the present paper, we report the BNC of 420 topsoil samples from Central Europe (north-east Germany), developed on sediments from the last ice age 10,000 years ago under Holocene conditions. These soils are predominantly sandy and low in humus, but they exhibit a huge spatial variability in soil properties on a small scale. The BNC was determined by adding various concentrations of Ca(OH)2 and fitting an exponential model to derive a titration curve for each sample. The coefficients of the BNC titration curve were well correlated with soil properties affecting soil acidity and pH buffer capacity, i.e., pH, soil texture and soil organic matter (SOM). From the BNC model, the LRs (LRBNC) were derived and compared with LRVDLUFA based on the standard protocol in Germany as established by the Association of German Agricultural Analytic and Research Institutes (VDLUFA). The LRBNC and LRVDLUFA correlated well but the LRVDLUFA were generally by approximately one order of magnitude higher. This is partly due to the VDLUFA concept to recommend a maintenance or conservation liming, even though the pH value is in the optimum range, to keep it there until the next lime application during the following rotation. Furthermore, the VDLUFA method was primarily developed from field experiments where natural soil acidification and management practices depressed the effect of lime treatment. The BNC method, on the other hand, is solely based on laboratory analysis with standardized soil samples. This indicates the demand for further research to develop a sound scientific algorithm that complements LRBNC with realistic values of annual Ca2+ removal and acidification by natural processes and N fertilization.
- ItemRapid determination of lime requirement by mid-infrared spectroscopy: A promising approach for precision agriculture(Weinheim : Wiley-VCH, 2019) Leenen, Matthias; Welp, Gerhard; Gebbers, Robin; Pätzold, StefanMid-infrared spectroscopy (MIRS) has proven to be a cost-effective, high throughput measurement technique for soil analysis. After multivariate calibration mid-infrared spectra can be used to predict various soil properties, some of which are related to lime requirement (LR). The objective of this study was to test the performance of MIRS for recommending variable rate liming on typical Central European soils in view of precision agriculture applications. In Germany, LR of arable topsoils is commonly derived from the parameters organic matter content (SOM), clay content, and soil pH (CaCl2) as recommended by the Association of German Agricultural Analytical and Research Institutes (VDLUFA). We analysed a total of 458 samples from six locations across Germany, which all revealed large within-field soil heterogeneity. Calcareous topsoils were observed at some positions of three locations (79 samples). To exclude such samples from LR determination, peak height at 2513 cm−1 of the MIR spectrum was used for identification. Spectra-based identification was accurate for carbonate contents > 0.5%. Subsequent LR derivation (LRSPP) from MIRS-PLSR predictions of SOM, clay, and pH (CaCl2) for non-calcareous soil samples using the VDLUFA look-up tables was successful for all locations (R2 = 0.54–0.82; RMSE = 857–1414 kg CaO ha−1). Alternatively, we tested direct LR prediction (LRDP) by MIRS-PLSR and also achieved satisfactory performance (R2 = 0.52–0.77; RMSE = 811–1420 kg CaO ha−1; RPD = 1.44–2.08). Further improvement was achieved by refining the VDLUFA tables towards a stepless algorithm. It can be concluded that MIRS provides a promising approach for precise LR estimation on heterogeneous arable fields. Large sample numbers can be processed with low effort which is an essential prerequisite for variable rate liming in precision agriculture. © 2019 The Authors. Journal of Plant Nutrition and Soil Science published by WILEY-VCH Verlag GmbH & Co. KGaA
- ItemDirect prediction of site-specific lime requirement of arable fields using the base neutralizing capacity and a multi-sensor platform for on-the-go soil mapping(Dordrecht [u.a.] : Springer Science + Business Media B.V, 2021-7-26) Vogel, Sebastian; Bönecke, Eric; Kling, Charlotte; Kramer, Eckart; Lück, Katrin; Philipp, Golo; Rühlmann, Jörg; Schröter, Ingmar; Gebbers, RobinLiming agricultural fields is necessary for counteracting soil acidity and is one of the oldest operations in soil fertility management. However, the best management practice for liming in Germany only insufficiently considers within-field soil variability. Thus, a site-specific variable rate liming strategy was developed and tested on nine agricultural fields in a quaternary landscape of north-east Germany. It is based on the use of a proximal soil sensing module using potentiometric, geoelectric and optical sensors that have been found to be proxies for soil pH, texture and soil organic matter (SOM), which are the most relevant lime requirement (LR) affecting soil parameters. These were compared to laboratory LR analysis of reference soil samples using the soil’s base neutralizing capacity (BNC). Sensor data fusion utilizing stepwise multi-variate linear regression (MLR) analysis was used to predict BNC-based LR (LRBNC) for each field. The MLR models achieved high adjusted R2 values between 0.70 and 0.91 and low RMSE values from 65 to 204 kg CaCO3 ha−1. In comparison to univariate modeling, MLR models improved prediction by 3 to 27% with 9% improvement on average. The relative importance of covariates in the field-specific prediction models were quantified by computing standardized regression coefficients (SRC). The importance of covariates varied between fields, which emphasizes the necessity of a field-specific calibration of proximal sensor data. However, soil pH was the most important parameter for LR determination of the soils studied. Geostatistical semivariance analysis revealed differences between fields in the spatial variability of LRBNC. The sill-to-range ratio (SRR) was used to quantify and compare spatial LRBNC variability of the nine test fields. Finally, high resolution LR maps were generated. The BNC-based LR method also produces negative LR values for soil samples with pH values above which lime is required. Hence, the LR maps additionally provide an estimate on the quantity of chemically acidifying fertilizers that can be applied to obtain an optimal soil pH value.
- ItemGuidelines for precise lime management based on high-resolution soil pH, texture and SOM maps generated from proximal soil sensing data(Dordrecht [u.a.] : Springer Science + Business Media B.V, 2020) Bönecke, Eric; Meyer, Sven; Vogel, Sebastian; Schröter, Ingmar; Gebbers, Robin; Kling, Charlotte; Kramer, Eckart; Lück, Katrin; Nagel, Anne; Philipp, Golo; Gerlach, Felix; Palme, Stefan; Scheibe, Dirk; Zieger, Karin; Rühlmann, JörgSoil acidification is caused by natural paedogenetic processes and anthropogenic impacts but can be counteracted by regular lime application. Although sensors and applicators for variable-rate liming (VRL) exist, there are no established strategies for using these tools or helping to implement VRL in practice. Therefore, this study aimed to provide guidelines for site-specific liming based on proximal soil sensing. First, high-resolution soil maps of the liming-relevant indicators (pH, soil texture and soil organic matter content) were generated using on-the-go sensors. The soil acidity was predicted by two ion-selective antimony electrodes (RMSEpH: 0.37); the soil texture was predicted by a combination of apparent electrical resistivity measurements and natural soil-borne gamma emissions (RMSEclay: 0.046 kg kg−1); and the soil organic matter (SOM) status was predicted by a combination of red (660 nm) and near-infrared (NIR, 970 nm) optical reflection measurements (RMSESOM: 6.4 g kg−1). Second, to address the high within-field soil variability (pH varied by 2.9 units, clay content by 0.44 kg kg−1 and SOM by 5.5 g kg−1), a well-established empirical lime recommendation algorithm that represents the best management practices for liming in Germany was adapted, and the lime requirements (LRs) were determined. The generated workflow was applied to a 25.6 ha test field in north-eastern Germany, and the variable LR was compared to the conventional uniform LR. The comparison showed that under the uniform liming approach, 63% of the field would be over-fertilized by approximately 12 t of lime, 6% would receive approximately 6 t too little lime and 31% would still be adequately limed. © 2020, The Author(s).
- ItemDetermination of Nutrients in Liquid Manures and Biogas Digestates by Portable Energy-Dispersive X-ray Fluorescence Spectrometry(Basel : MDPI AG, 2021) Horf, Michael; Gebbers, Robin; Vogel, Sebastian; Ostermann, Markus; Piepel, Max-Frederik; Olfs, Hans-WernerKnowing the exact nutrient composition of organic fertilizers is a prerequisite for their appropriate application to improve yield and to avoid environmental pollution by over-fertilization. Traditional standard chemical analysis is cost and time-consuming and thus it is unsuitable for a rapid analysis before manure application. As a possible alternative, a handheld X-ray fluorescence (XRF) spectrometer was tested to enable a fast, simultaneous, and on-site analysis of several elements. A set of 62 liquid pig and cattle manures as well as biogas digestates were collected, intensively homogenized and analysed for the macro plant nutrients phosphorus, potassium, magnesium, calcium, and sulphur as well as the micro nutrients manganese, iron, copper, and zinc using the standard lab procedure. The effect of four different sample preparation steps (original, dried, filtered, and dried filter residues) on XRF measurement accuracy was examined. Therefore, XRF results were correlated with values of the reference analysis. The best R2s for each element ranged from 0.64 to 0.92. Comparing the four preparation steps, XRF results for dried samples showed good correlations (0.64 and 0.86) for all elements. XRF measurements using dried filter residues showed also good correlations with R2s between 0.65 and 0.91 except for P, Mg, and Ca. In contrast, correlation analysis for liquid samples (original and filtered) resulted in lower R2s from 0.02 to 0.68, except for K (0.83 and 0.87, respectively). Based on these results, it can be concluded that handheld XRF is a promising measuring system for element analysis in manures and digestates.
- ItemHyperspectral Imaging Tera Hertz System for Soil Analysis : Initial Results(Basel : MDPI, 2020) Dworak, Volker; Mahns, Benjamin; Selbeck, Jörn; Gebbers, Robin; Weltzien, CorneliaAnalyzing soils using conventional methods is often time consuming and costly due to their complexity. These methods require soil sampling (e.g., by augering), pretreatment of samples (e.g., sieving, extraction), and wet chemical analysis in the laboratory. Researchers are seeking alternative sensor-based methods that can provide immediate results with little or no excavation and pretreatment of samples. Currently, visible and infrared spectroscopy, electrical resistivity, gamma ray spectroscopy, and X-ray spectroscopy have been investigated extensively for their potential utility in soil sensing. Little research has been conducted on the application of THz (Tera Hertz) spectroscopy in soil science. The Tera Hertz band covers the frequency range between 100 GHz and 10 THz of the electromagnetic spectrum. One important feature of THz radiation is its correspondence with the particle size of the fine fraction of soil minerals (clay < 2 µm to sand < 2 mm). The particle size distribution is a fundamental soil property that governs soil water and nutrient content, among other characteristics. The interaction of THz radiation with soil particles creates detectable Mie scattering, which is the elastic scattering of electromagnetic waves by particles whose diameter corresponds approximately to the wavelength of the radiation. However, single-spot Mie scattering spectra are difficult to analyze and the understanding of interaction between THz radiation and soil material requires basic research. To improve the interpretation of THz spectra, a hyperspectral imaging system was developed. The addition of the spatial dimension to THz spectra helps to detect relevant features. Additionally, multiple samples can be scanned in parallel and measured under identical conditions, and the high number of data points within an image can improve the statistical accuracy. Technical details of the newly designed hyperspectral imaging THz system working from 250 to 370 GHz are provided. Results from measurements of different soil samples and buried objects in soil demonstrated its performance. The system achieved an optical resolution of about 2 mm. The sensitivity of signal damping to the changes in particle size of 100 µm is about 10 dB. Therefore, particle size variations in the µm range should be detectable. In conclusion, automated hyperspectral imaging reduced experimental effort and time consumption, and provided reliable results because of the measurement of hundreds of sample positions in one run. At this stage, the proposed setup cannot replace the current standard laboratory methods, but the present study represents the initial step to develop a new automated method for soil analysis and imaging.
- ItemComparison of Calibration Approaches in Laser-Induced Breakdown Spectroscopy for Proximal Soil Sensing in Precision Agriculture(Basel : MDPI, 2019) Riebe, Daniel; Erler, Alexander; Brinkmann, Pia; Beitz, Toralf; Löhmannsröben, Hans-Gerd; Gebbers, RobinThe lack of soil data, which are relevant, reliable, affordable, immediately available, and sufficiently detailed, is still a significant challenge in precision agriculture. A promising technology for the spatial assessment of the distribution of chemical elements within fields, without sample preparation is laser-induced breakdown spectroscopy (LIBS). Its advantages are contrasted by a strong matrix dependence of the LIBS signal which necessitates careful data evaluation. In this work, different calibration approaches for soil LIBS data are presented. The data were obtained from 139 soil samples collected on two neighboring agricultural fields in a quaternary landscape of northeast Germany with very variable soils. Reference analysis was carried out by inductively coupled plasma optical emission spectroscopy after wet digestion. The major nutrients Ca and Mg and the minor nutrient Fe were investigated. Three calibration strategies were compared. The first method was based on univariate calibration by standard addition using just one soil sample and applying the derived calibration model to the LIBS data of both fields. The second univariate model derived the calibration from the reference analytics of all samples from one field. The prediction is validated by LIBS data of the second field. The third method is a multivariate calibration approach based on partial least squares regression (PLSR). The LIBS spectra of the first field are used for training. Validation was carried out by 20-fold cross-validation using the LIBS data of the first field and independently on the second field data. The second univariate method yielded better calibration and prediction results compared to the first method, since matrix effects were better accounted for. PLSR did not strongly improve the prediction in comparison to the second univariate method.
- ItemEvaluating Soil-Borne Causes of Biomass Variability in Grassland by Remote and Proximal Sensing(Basel : MDPI AG, 2019) Vogel, Sebastian; Gebbers, Robin; Oertel, Marcel; Kramer, EckartOn a grassland field with sandy soils in Northeast Germany (Brandenburg), vegetation indices from multi-spectral UAV-based remote sensing were used to predict grassland biomass productivity. These data were combined with soil pH value and apparent electrical conductivity (ECa) from on-the-go proximal sensing serving as indicators for soil-borne causes of grassland biomass variation. The field internal magnitude of spatial variability and hidden correlations between the variables of investigation were analyzed by means of geostatistics and boundary-line analysis to elucidate the influence of soil pH and ECa on the spatial distribution of biomass. Biomass and pH showed high spatial variability, which necessitates high resolution data acquisition of soil and plant properties. Moreover, boundary-line analysis showed grassland biomass maxima at pH values between 5.3 and 7.2 and ECa values between 3.5 and 17.5 mS m−1. After calibrating ECa to soil moisture, the ECa optimum was translated to a range of optimum soil moisture from 7% to 13%. This matches well with to the plant-available water content of the predominantly sandy soil as derived from its water retention curve. These results can be used in site-specific management decisions to improve grassland biomass productivity in low-yield regions of the field due to soil acidity or texture-related water scarcity.
- ItemSoil Nutrient Detection for Precision Agriculture Using Handheld Laser-Induced Breakdown Spectroscopy (LIBS) and Multivariate Regression Methods (PLSR, Lasso and GPR)(Basel : MDPI, 2020) Erler, Alexander; Riebe, Daniel; Beitz, Toralf; Löhmannsröben, Hans-Gerd; Gebbers, RobinPrecision agriculture (PA) strongly relies on spatially differentiated sensor information. Handheld instruments based on laser-induced breakdown spectroscopy (LIBS) are a promising sensor technique for the in-field determination of various soil parameters. In this work, the potential of handheld LIBS for the determination of the total mass fractions of the major nutrients Ca, K, Mg, N, P and the trace nutrients Mn, Fe was evaluated. Additionally, other soil parameters, such as humus content, soil pH value and plant available P content, were determined. Since the quantification of nutrients by LIBS depends strongly on the soil matrix, various multivariate regression methods were used for calibration and prediction. These include partial least squares regression (PLSR), least absolute shrinkage and selection operator regression (Lasso), and Gaussian process regression (GPR). The best prediction results were obtained for Ca, K, Mg and Fe. The coefficients of determination obtained for other nutrients were smaller. This is due to much lower concentrations in the case of Mn, while the low number of lines and very weak intensities are the reason for the deviation of N and P. Soil parameters that are not directly related to one element, such as pH, could also be predicted. Lasso and GPR yielded slightly better results than PLSR. Additionally, several methods of data pretreatment were investigated.