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Optical Spectrometry to Determine Nutrient Concentrations and other Physicochemical Parameters in Liquid Organic Manures: A Review
Nutrient 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.
Combined In Vitro Toxicity and Immunogenicity of Cold Plasma and Pulsed Electric Fields
In modern oncology, therapies are based on combining monotherapies to overcome treatment resistance and increase therapy precision. The application of microsecond-pulsed electric fields (PEF) is approved to enhance local chemotherapeutic drug uptake within combination electrochemotherapy regimens. Reactive oxygen species (ROS) have been implicated in anticancer effects, and cold physical plasma produces vast amounts of ROS, which have recently been shown to benefit head and neck cancer patients. PEF and cold plasma technology have been linked to immunogenic cell death (ICD) induction, a regulated cell death accompanied by sterile inflammation that promotes antitumor immunity. To this end, we investigated the combined effect of both treatments regarding their intracellular ROS accumulation, toxicity, ICD-related marker expression, and optimal exposure sequence in a leukemia model cell line. The combination treatment substantially increased ROS and intracellular glutathione levels, leading to additive cytotoxic effects accompanied by a significantly increased expression of ICD markers, such as the eat-me signal calreticulin (CRT). Preconditioned treatment with cold plasma followed by PEF exposure was the most potent treatment sequence. The results indicate additive effects of cold plasma and PEF, motivating further studies in skin and breast tumor models for the future improvement of ECT in such patients.
Simulating Cotton Growth and Productivity Using AquaCrop Model under Deficit Irrigation in a Semi-Arid Climate
AquaCrop is a water-driven model that simulates the effect of environment and management on crop production under deficit irrigation. The model was calibrated and validated using three databases and four irrigation treatments (i.e., 100%ET, 80%ET, 70%ET, and 50%ET). Model performance was evaluated by simulating canopy cover (CC), biomass accumulation, and water productivity (WP). Statistics of root mean square error (RMSE) and Willmott’s index of agreement (d) showed that model predictions are suitable for non-stressed and moderate stressed conditions. The results showed that the simulated biomass and yield were consistent with the measured values with a coefficient of determination (R2) of 0.976 and 0.950, respectively. RMSE and d-index values for canopy cover (CC) were 2.67% to 4.47% and 0.991% to 0.998% and for biomass were 0.088 to 0.666 ton/ha and 0.991 to 0.999 ton/ha, respectively. Prediction of simulated and measured biomass and final yield was acceptable with deviation ˂10%. The overall value of R2 for WP in terms of yield was 0.943. Treatment with 80% ET consumed 20% less water than the treatment with 100%ET and resulted in high WP in terms of yield (0.6 kg/m3) and biomass (1.74 kg/m3), respectively. The deviations were in the range of −2% to 11% in yield and −2% to 4% in biomass. It was concluded that AquaCrop is a useful tool in predicting the productivity of cotton under different irrigation scenarios.
Scientific Irrigation Scheduling for Sustainable Production in Olive Groves
The present study aimed at investigating scientific irrigation scheduling (SIS) for the sustainable production of olive groves. The SIS allows farmers to schedule water rotation in their fields to abate crop water stress and maximize yields, which could be achieved through the precise monitoring of soil moisture. For this purpose, the study used three kinds of soil moisture sensors, including tensiometer sensors, irrometer sensors, and gypsum blocks for precise measurement of the soil moisture. These soil moisture sensors were calibrated by performing experiments in the field and laboratory at Barani Agricultural Research Institute, Chakwal in 2018 and 2019. The calibration curves were obtained by performing gravimetric analysis at 0.3 and 0.6 m depths, thereby equations were developed using regression analysis. The coefficient of determination (R2 ) at 0.3 and 0.6 m depth for tensiometer, irrometer, and gypsum blocks was found to be equal to 0.98, 0.98; 0.75, 0.89; and 0.82, and 0.95, respectively. After that, a drip irrigation system was installed with the calibrated soil moisture sensors at 0.3 and 0.6 m depth to schedule irrigation for production of olive groves as compared to conventional farmer practice, thereby soil moisture profiles of these sensors were obtained to investigate the SIS. The results showed that the irrometer sensor performed as expected and contributed to the irrigation water savings between 17% and 25% in 2018 and 2019, respectively, by reducing the number of irrigations as compared toother soil moisture sensors and farmer practices. Additionally, olive yield efficiencies of 8% and 9%were observed by the tensiometer in 2018 and 2019, respectively. The outcome of the study suggests that an effective method in providing sustainable production of olive groves and enhancing yield efficiency.
Management-induced changes in soil organic carbon on global croplands
Soil organic carbon (SOC), one of the largest terrestrial carbon (C) stocks on Earth, has been depleted by anthropogenic land cover change and agricultural management. However, the latter has so far not been well represented in global C stock assessments. While SOC models often simulate detailed biochemical processes that lead to the accumulation and decay of SOC, the management decisions driving these biophysical processes are still little investigated at the global scale. Here we develop a spatially explicit data set for agricultural management on cropland, considering crop production levels, residue returning rates, manure application, and the adoption of irrigation and tillage practices. We combine it with a reduced-complexity model based on the Intergovernmental Panel on Climate Change (IPCC) tier 2 method to create a half-degree resolution data set of SOC stocks and SOC stock changes for the first 30 cm of mineral soils. We estimate that, due to arable farming, soils have lost around 34.6 GtC relative to a counterfactual hypothetical natural state in 1975. Within the period 1975-2010, this SOC debt continued to expand by 5 GtC (0.14 GtCyr-1) to around 39.6 GtC. However, accounting for historical management led to 2.1 GtC fewer (0.06 GtCyr-1) emissions than under the assumption of constant management. We also find that management decisions have influenced the historical SOC trajectory most strongly by residue returning, indicating that SOC enhancement by biomass retention may be a promising negative emissions technique. The reduced-complexity SOC model may allow us to simulate management-induced SOC enhancement - also within computationally demanding integrated (land use) assessment modeling.
Surface Plasmon Resonance Sensitivity Enhancement Based on Protonated Polyaniline Films Doped by Aluminum Nitrate
Complex composite films based on polyaniline (PANI) doped hydrochloric acid (HCl) incorporated with aluminum nitrate (Al(NO3)3) on Au-layer were designed and synthesized as a surface plasmon resonance (SPR) sensing device. The physicochemical properties of (PANI-HCl)/Al(NO3)3 complex composite films were studied for various Al(NO3)3 concentrations (0, 2, 4, 8, 16, and 32 wt.%). The refractive index of the (PANI-HCl)/Al(NO3)3 complex composite films increased continuously as Al(NO3)3 concentrations increased. The electrical conductivity values increased from 5.10 µS/cm to 10.00 µS/cm as Al(NO3)3 concentration increased to 32 wt.%. The sensitivity of the SPR sensing device was investigated using a theoretical approach and experimental measurements. The theoretical system of SPR measurement confirmed that increasing Al(NO3)3 in (PANI-HCl)/Al(NO3)3 complex composite films enhanced the sensitivity from about 114.5 [Deg/RIU] for Au-layer to 159.0 [Deg/RIU] for Au-((PANI-HCl)/Al(NO3)3 (32 wt.%)). In addition, the signal-to-noise ratio for Au-layer was 3.95, which increased after coating by (PANI-HCl)/Al(NO3)3 (32 wt.%) complex composite layer to 8.82. Finally, we conclude that coating Au-layer by (PANI-HCl)/Al(NO3)3 complex composite films enhances the sensitivity of the SPR sensing device.
Analysis of complex drugs by comprehensive two-dimensional gas chromatography and high-resolution mass spectrometry: detailed chemical description of the active pharmaceutical ingredient sodium bituminosulfonate and its process intermediates
The European pharmacopeia provides analytical methods for the chemical characterization of active pharmaceutical ingredients (APIs). However, the complexity of some APIs exceeds the limitations of the currently prevailing physicochemical methods. Sodium bituminosulfonate (SBS) is described by the collection of key parameters of generalizing criteria such as dry matter, sulfur and sodium content, and neutrality, but techniques to unravel the complexity on a molecular level are lacking. We present a study based on online derivatization with tetramethylammonium hydroxide in combination with comprehensive two-dimensional gas chromatography coupled to an electron ionization high-resolution time-of-flight mass spectrometer (GC × GC-HR-ToF–MS) for the chemical description of SBS as well as its process intermediates. The application of GC × GC allowed the comprehensive description of the chemical components in the API and the process intermediates for the first time. Furthermore, it was possible to classify peaks regarding their elemental and structural composition based on accurate mass information, elution behavior, and mass fragmentation pattern. This work demonstrates not only the general applicability, advantages but also limitations of GC × GC for the characterization of APIs for complex drugs. Graphical Abstract: [Figure not available: see fulltext.]
Dielectrophoresis: An Approach to Increase Sensitivity, Reduce Response Time and to Suppress Nonspecific Binding in Biosensors?
The performance of receptor-based biosensors is often limited by either diffusion of the analyte causing unreasonable long assay times or a lack of specificity limiting the sensitivity due to the noise of nonspecific binding. Alternating current (AC) electrokinetics and its effect on biosensing is an increasing field of research dedicated to address this issue and can improve mass transfer of the analyte by electrothermal effects, electroosmosis, or dielectrophoresis (DEP). Accordingly, several works have shown improved sensitivity and lowered assay times by order of magnitude thanks to the improved mass transfer with these techniques. To realize high sensitivity in real samples with realistic sample matrix avoiding nonspecific binding is critical and the improved mass transfer should ideally be specific to the target analyte. In this paper we cover recent approaches to combine biosensors with DEP, which is the AC kinetic approach with the highest selectivity. We conclude that while associated with many challenges, for several applications the approach could be beneficial, especially if more work is dedicated to minimizing nonspecific bindings, for which DEP offers interesting perspectives.
Melt Electrowriting of Scaffolds with a Porosity Gradient to Mimic the Matrix Structure of the Human Trabecular Meshwork
The permeability of the Human Trabecular Meshwork (HTM) regulates eye pressure via a porosity gradient across its thickness modulated by stacked layers of matrix fibrils and cells. Changes in HTM porosity are associated with increases in intraocular pressure and the progress of diseases like glaucoma. Engineered HTMs could help to understand the structure-function relation in natural tissues, and lead to new regenerative solutions. Here, melt electrowriting (MEW) is explored as a biofabrication technique to produce fibrillar, porous scaffolds that mimic the multilayer, gradient structure of native HTM. Poly(caprolactone) constructs with a height of 125-500 μm and fiber diameters of 10-12 μm are printed. Scaffolds with a tensile modulus between 5.6 and 13 MPa, and a static compression modulus in the range of 6-360 kPa are obtained by varying the scaffolds design, i.e., density and orientation of the fibers and number of stacked layers. Primary HTM cells attach to the scaffolds, proliferate, and form a confluent layer within 8-14 days, depending on the scaffold design. High cell viability and cell morphology close to that in the native tissue are observed. The present work demonstrates the utility of MEW to reconstruct complex morphological features of natural tissues.
Comparison of Methane Emission Patterns from Dairy Housings with Solid and Slatted Floors at Two Locations
Methane (CH4) emissions from dairy husbandry are a hot topic in the context of active climate protection, where housing systems with slatted floors and slurry storage inside are in general expected to emit more than systems with solid floors. There are multiple factors, including climate conditions, that modulate the emission pattern. In this study, we investigated interrelations between CH4 emission patterns and climate conditions as well as differences between farm locations versus floor effects. We considered three data sets with 265, 264 and 275 hourly emission values from two housing systems (one slatted, one solid floor) in Switzerland and one system with solid floors in Germany. Each data set incorporated measurements in summer, winter and a transition season. The average CH4 emission was highest for the slatted floor system. For the solid floor systems, CH4 emissions at the Swiss location were around 30% higher compared to the German location. The shape of the distributions for the two solid floor systems was rather similar but very different from the distribution for the slatted floor system, which showed higher prevalence for extreme emissions. Rank correlations, which measure the degree of similarity between two rankings in terms of linear relation, were not able to detect dependencies at the selected significance level. In contrast, mutual information, which measures more general statistical dependencies in terms of shared information, revealed highly significant dependencies for almost all variable pairs. The weakest statistical relation was found between winds speed and CH4 emission, but the convection regime was found to play a key role. Clustering was consistent among the three data sets with five typical clusters related to high/low temperature and wind speed, respectively, as well as in some cases to morning and evening hours. Our analysis showed that despite the disparate and often insignificant correlation between environmental variables and CH4 emission, there is a strong relation between both, which shapes the emission pattern in many aspects much more in addition to differences in the floor type. Although a clear distinction of high and low emission condition clusters based on the selected environmental variables was not possible, trends were clearly visible. Further research with larger data sets is advisable to verify the detected trends and enable prognoses for husbandry systems under different climate conditions.