Determination of Nutrients in Liquid Manures and Biogas Digestates by Portable Energy-Dispersive X-ray Fluorescence Spectrometry.

Knowing 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.

Soil Nutrient Detection for Precision Agriculture Using Handheld Laser-Induced Breakdown Spectroscopy (LIBS) and Multivariate Regression Methods (PLSR, Lasso and GPR).

Precision 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.

Hyperspectral Imaging Tera Hertz System for Soil Analysis: Initial Results.

Analyzing 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.

Evaluating Soil-Borne Causes of Biomass Variability in Grassland by Remote and Proximal Sensing.

On 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.

Comparison of Calibration Approaches in Laser-Induced Breakdown Spectroscopy for Proximal Soil Sensing in Precision Agriculture.

The 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.

Terahertz Spectroscopy for Proximal Soil Sensing: An Approach to Particle Size Analysis.

Spatially resolved soil parameters are some of the most important pieces of information for precision agriculture. These parameters, especially the particle size distribution (texture), are costly to measure by conventional laboratory methods, and thus, in situ assessment has become the focus of a new discipline called proximal soil sensing. Terahertz (THz) radiation is a promising method for nondestructive in situ measurements. The THz frequency range from 258 gigahertz (GHz) to 350 GHz provides a good compromise between soil penetration and the interaction of the electromagnetic waves with soil compounds. In particular, soil physical parameters influence THz measurements. This paper presents investigations of the spectral transmission signals from samples of different particle size fractions relevant for soil characterization. The sample thickness ranged from 5 to 17 mm. The transmission of THz waves was affected by the main mineral particle fractions, sand, silt and clay. The resulting signal changes systematically according to particle sizes larger than half the wavelength. It can be concluded that THz spectroscopic measurements provide information about soil texture and penetrate samples with thicknesses in the cm range.

Vertical soil profiling using a galvanic contact resistivity scanning approach.

Proximal sensing of soil electromagnetic properties is widely used to map spatial land heterogeneity. The mapping instruments use galvanic contact, capacitive coupling or electromagnetic induction. Regardless of the type of instrument, the geometrical configuration between signal transmitting and receiving elements typically defines the shape of the depth response function. To assess vertical soil profiles, many modern instruments use multiple transmitter-receiver pairs. Alternatively, vertical electrical sounding can be used to measure changes in apparent soil electrical conductivity with depth at a specific location. This paper examines the possibility for the assessment of soil profiles using a dynamic surface galvanic contact resistivity scanning approach, with transmitting and receiving electrodes configured in an equatorial dipole-dipole array. An automated scanner system was developed and tested in agricultural fields with different soil profiles. While operating in the field, the distance between current injecting and measuring pairs of rolling electrodes was varied continuously from 40 to 190 cm. The preliminary evaluation included a comparison of scan results from 20 locations to shallow (less than 1.2 m deep) soil profiles and to a two-layer soil profile model defined using an electromagnetic induction instrument.

Effects of sample pre-treatments on the analysis of liquid organic manures by visible and near-infrared spectrometry.

Proper application of a fertilizer requires precise knowledge of its nutrient composition. In the case of liquid organic manures (LOM), this information is often lacking due to heterogeneous nature of these fertilizers. Published "book values" of nutrient contents present the average from a wide range of possible nutrient characteristics, but usually differ considerably from the concentration in a particular manure. Thus, chemical analyses are recommended before applying the specific LOM. Unfortunately, this is usually too costly and time-intensive in practical farming. On-farm analysis by optical spectrometry in the visible and near-infrared (Vis-NIR) range is considered as an efficient alternative. However, calibration of Vis-NIR spectrometry for LOM is challenging as shown in many studies. One reason is LOMs' tendency to rapidly segregate into a fuzzy continuum with liquid and solid properties. By separating LOM into well-defined liquid and solid phases and measuring them separately, calibration of Vis-NIR spectrometry might be improved. In this study, the effects of four sample pre-treatment techniques on the prediction accuracy of macronutrients (N, P, K, Mg, Ca, S), micronutrients (B, Mn, Fe, Cu, Zn), dry matter and pH of LOM using visible and near infrared spectrometry were comprehensively investigated. The concentrations were referred either to wet basis or to dry matter basis. For the study, a total of 163 samples, separated in two similar LOM sets (pig, cattle, digestates), were either dried, filtered, or centrifuged and always compared to non-treated samples. The experiments demonstrate that in comparison to raw samples (Ø r2 = 0.85) neither filtering (Ø r2 = 0.76 for filtrates and Ø r2 = 0.71 for filter residues), centrifugation (Ø r2 = 0.59 for supernatants and Ø r2 = 0.79 for pellets), nor drying (Ø r2 = 0.74) revealed to be a helpful preparation step significantly improving prediction results, independent from referring to wet or dry basis concentrations.

Application of terahertz radiation to soil measurements: initial results.

Developing soil sensors with the possibility of continuous online measurement is a major challenge in soil science. Terahertz (THz) electromagnetic radiation may provide the opportunity for the measurement of organic material density, water content and other soil parameters at different soil depths. Penetration depth and information content is important for a functional soil sensor. Therefore, we present initial research on the analysis of absorption coefficients of four different soil samples by means of THz transmission measurements. An optimized soil sample holder to determine absorption coefficients was used. This setup improves data acquisition because interface reflections can be neglected. Frequencies of 340 GHz to 360 GHz and 1.627 THz to 2.523 THz provided information about an existing frequency dependency. The results demonstrate the potential of this THz approach for both soil analysis and imaging of buried objects. Therefore, the THz approach allows different soil samples to be distinguished according to their different absorption properties so that relations among soil parameters may be established in future.

Soil pH mapping with an on-the-go sensor.

Soil pH is a key parameter for crop productivity, therefore, its spatial variation should be adequately addressed to improve precision management decisions. Recently, the Veris pH Manager™, a sensor for high-resolution mapping of soil pH at the field scale, has been made commercially available in the US. While driving over the field, soil pH is measured on-the-go directly within the soil by ion selective antimony electrodes. The aim of this study was to evaluate the Veris pH Manager™ under farming conditions in Germany. Sensor readings were compared with data obtained by standard protocols of soil pH assessment. Experiments took place under different scenarios: (a) controlled tests in the lab, (b) semicontrolled test on transects in a stop-and-go mode, and (c) tests under practical conditions in the field with the sensor working in its typical on-the-go mode. Accuracy issues, problems, options, and potential benefits of the Veris pH Manager™ were addressed. The tests demonstrated a high degree of linearity between standard laboratory values and sensor readings. Under practical conditions in the field (scenario c), the measure of fit (r(2)) for the regression between the on-the-go measurements and the reference data was 0.71, 0.63, and 0.84, respectively. Field-specific calibration was necessary to reduce systematic errors. Accuracy of the on-the-go maps was considerably higher compared with the pH maps obtained by following the standard protocols, and the error in calculating lime requirements was reduced by about one half. However, the system showed some weaknesses due to blockage by residual straw and weed roots. If these problems were solved, the on-the-go sensor investigated here could be an efficient alternative to standard sampling protocols as a basis for liming in Germany.

Evaluating Spatially Resolved Influence of Soil and Tree Water Status on Quality of European Plum Grown in Semi-humid Climate.

In orchards, the variations of fruit quality and its determinants are crucial for resource effective measures. In the present study, a drip-irrigated plum production (Prunus domestica L. "Tophit plus"/Wavit) located in a semi-humid climate was studied. Analysis of the apparent electrical conductivity (ECa) of soil showed spatial patterns of sand lenses in the orchard. Water status of sample trees was measured instantaneously by means of leaf water potential, Ψleaf [MPa], and for all trees by thermal imaging of canopies and calculation of the crop water stress index (CWSI). Methods for determining CWSI were evaluated. A CWSI approach calculating canopy and reference temperatures from the histogram of pixels from each image itself was found to suit the experimental conditions. Soil ECa showed no correlation with specific leaf area ratio and cumulative water use efficiency (WUEc) derived from the crop load. The fruit quality, however, was influenced by physiological drought stress in trees with high crop load and, resulting (too) high WUEc, when fruit driven water demand was not met. As indicated by analysis of variance, neither ECa nor the instantaneous CWSI could be used as predictors of fruit quality, while the interaction of CWSI and WUEc did succeed in indicating significant differences. Consequently, both WUEc and CWSI should be integrated in irrigation scheduling for positive impact on fruit quality.

Proximal Soil Sensing - A Contribution for Species Habitat Distribution Modelling of Earthworms in Agricultural Soils?

BACKGROUND: Earthworms are important for maintaining soil ecosystem functioning and serve as indicators of soil fertility. However, detection of earthworms is time-consuming, which hinders the assessment of earthworm abundances with high sampling density over entire fields. Recent developments of mobile terrestrial sensor platforms for proximal soil sensing (PSS) provided new tools for collecting dense spatial information of soils using various sensing principles. Yet, the potential of PSS for assessing earthworm habitats is largely unexplored. This study investigates whether PSS data contribute to the spatial prediction of earthworm abundances in species distribution models of agricultural soils. METHODOLOGY/PRINCIPAL FINDINGS: Proximal soil sensing data, e.g., soil electrical conductivity (EC), pH, and near infrared absorbance (NIR), were collected in real-time in a field with two management strategies (reduced tillage / conventional tillage) and sandy to loam soils. PSS was related to observations from a long-term (11 years) earthworm observation study conducted at 42 plots. Earthworms were sampled from 0.5 x 0.5 x 0.2 m³ soil blocks and identified to species level. Sensor data were highly correlated with earthworm abundances observed in reduced tillage but less correlated with earthworm abundances observed in conventional tillage. This may indicate that management influences the sensor-earthworm relationship. Generalized additive models and state-space models showed that modelling based on data fusion from EC, pH, and NIR sensors produced better results than modelling without sensor data or data from just a single sensor. Regarding the individual earthworm species, particular sensor combinations were more appropriate than others due to the different habitat requirements of the earthworms. Earthworm species with soil-specific habitat preferences were spatially predicted with higher accuracy by PSS than more ubiquitous species. CONCLUSIONS/SIGNIFICANCE: Our findings suggest that PSS contributes to the spatial modelling of earthworm abundances at field scale and that it will support species distribution modelling in the attempt to understand the soil-earthworm relationships in agroecosystems.

Precision agriculture and food security.

Precision agriculture comprises a set of technologies that combines sensors, information systems, enhanced machinery, and informed management to optimize production by accounting for variability and uncertainties within agricultural systems. Adapting production inputs site-specifically within a field and individually for each animal allows better use of resources to maintain the quality of the environment while improving the sustainability of the food supply. Precision agriculture provides a means to monitor the food production chain and manage both the quantity and quality of agricultural produce.