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Quality attributes of fruit determine its acceptability by the retailer and consumer. The objective of this work was to investigate the potential of absorption (μa) and reduced scattering (μs’) coefficients of European pear to analyze its fruit flesh firmness and soluble solids content (SSC). The absolute reference values, μa* (cm−1) and μs’* (cm−1), of pear were invasively measured, employing multi-spectral photon density wave (PDW) spectroscopy at preselected wavelengths of 515, 690, and 940 nm considering two batches of unripe and overripe fruit. On eight measuring dates during fruit development, μa and μs’ were analyzed non-destructively by means of laser light backscattering imaging (LLBI) at similar wavelengths of 532, 660, and 830 nm by means of fitting according to Farrell’s diffusion theory, using fix reference values of either μa* or μs’*. Both, the μa* and the μa as well as μs’* and μs’ showed similar trends. Considering the non-destructively measured data during fruit development, μa at 660 nm decreased 91 till 141 days after full bloom (dafb) from 1.49 cm−1 to 0.74 cm−1 due to chlorophyll degradation. At 830 nm, μa only slightly decreased from 0.41 cm−1 to 0.35 cm−1. The μs’ at all wavelengths revealed a decreasing trend as the fruit developed. The difference measured at 532 nm was most pronounced decreasing from 24 cm−1 to 10 cm−1, while at 660 nm and 830 nm values decreased from 15 cm−1 to 13 cm−1 and from 10 cm−1 to 8 cm−1, respectively. When building calibration models with partial least-squares regression analysis on the optical properties for non-destructive analysis of the fruit SSC, μa at 532 nm and 830 nm resulted in a correlation coefficient of R = 0.66, however, showing high measuring uncertainty. The combination of all three wavelengths gave an enhanced, encouraging R = 0.89 for firmness analysis using μs’ in the freshly picked fruit.
Turbidity measurements are frequently implemented for the monitoring of heterogeneous chemical, physical, or biotechnological processes. However, for quantitative measurements, turbidity probes need calibration, as is requested and regulated by the ISO 7027:1999. Accordingly, a formazine suspension has to be produced. Despite this regulatory demand, no scientific publication on the stability and reproducibility of this polymerization process is available. In addition, no characterization of the optical properties of this calibration material with other optical methods had been achieved so far. Thus, in this contribution, process conditions such as temperature and concentration have been systematically investigated by turbidity probe measurements and Photon Density Wave (PDW) spectroscopy, revealing an influence on the temporal formazine formation onset. In contrast, different reaction temperatures do not lead to different scattering properties for the final formazine suspensions, but give an access to the activation energy for this condensation reaction. Based on PDW spectroscopy data, the synthesis of formazine is reproducible. However, very strong influences of the ambient conditions on the measurements of the turbidity probe have been observed, limiting its applicability. The restrictions of the turbidity probe with respect to scatterer concentration are examined on the basis of formazine and polystyrene suspensions. Compared to PDW spectroscopy data, signal saturation is observed at already low reduced scattering coefficients.
Terrestrial gravimetry is increasingly used to monitor mass transport processes in geophysics boosted by the ongoing technological development of instruments. Resolving a particular phenomenon of interest, however, requires a set of gravity corrections of which the uncertainties have not been addressed up to now. In this study, we quantify the time domain uncertainty of tide, global atmospheric, large-scale hydrological, and nontidal ocean loading corrections. The uncertainty is assessed by comparing the majority of available global models for a suite of sites worldwide. The average uncertainty expressed as root-mean-square error equals 5.1nm/s(2), discounting local hydrology or air pressure. The correction-induced uncertainty of gravity changes over various time periods of interest ranges from 0.6nm/s(2) for hours up to a maximum of 6.7nm/s(2) for 6months. The corrections are shown to be significant and should be applied for most geophysical applications of terrestrial gravimetry. From a statistical point of view, however, resolving subtle gravity effects in the order of few nanometers per square second is challenged by the uncertainty of the corrections. Plain Language Summary Many scientists are exploring ways to benefit from gravity measurements in fields of high societal relevance such as monitoring of volcanoes or measuring the amount of water in underground. Any application of such new methods, however, requires careful preparation of the gravity measurements. The intention of the preparation process is to ensure that the measurements do not contain information about processes that are not of interest. For that reason, the influence of atmosphere, ocean, tides, and hydrology needs to be reduced from the gravity. In this study, we investigate how this reduction process influences the quality of the measurement. We found that the precision degrades especially owing to the hydrology. The ocean plays an important role at sites close to the coast and the atmosphere at sites located in mountains. The overall errors of the reductions may complicate a reliable use of gravity measurements in certain studies focusing on very small signals. Nevertheless, the precision of gravity reductions alone does not obstruct a meaningful use of gravity measurements in most research fields. Details specifying the reduction precision are provided in this study allowing scientist dealing with gravity measurements to decide if their signal of interest can be reliably resolved.
In spite of the fundamental role of the landscape water balance for the Earth's water and energy cycles, monitoring the water balance and its components beyond the point scale is notoriously difficult due to the multitude of flow and storage processes and their spatial heterogeneity. Here, we present the first field deployment of an iGrav superconducting gravimeter (SG) in a minimized enclosure for long-term integrative monitoring of water storage changes. Results of the field SG on a grassland site under wet-temperate climate conditions were compared to data provided by a nearby SG located in the controlled environment of an observatory building. The field system proves to provide gravity time series that are similarly precise as those of the observatory SG. At the same time, the field SG is more sensitive to hydrological variations than the observatory SG. We demonstrate that the gravity variations observed by the field setup are almost independent of the depth below the terrain surface where water storage changes occur (contrary to SGs in buildings), and thus the field SG system directly observes the total water storage change, i.e., the water balance, in its surroundings in an integrative way. We provide a framework to single out the water balance components actual evapotranspiration and lateral subsurface discharge from the gravity time series on annual to daily timescales. With about 99 and 85% of the gravity signal due to local water storage changes originating within a radius of 4000 and 200m around the instrument, respectively, this setup paves the road towards gravimetry as a continuous hydrological field-monitoring technique at the landscape scale.
Field-scale subsurface flow processes are difficult to observe and monitor. We investigated the value of gravity time series to identify subsurface flow processes by carrying out a sprinkling experiment in the direct vicinity of a superconducting gravimeter. We demonstrate how different water mass distributions in the subsoil affect the gravity signal and show the benefit of using the shape of the gravity response curve to identify different subsurface flow processes. For this purpose, a simple hydro-gravimetric model was set up to test different scenarios in an optimization approach, including the processes macropore flow, preferential flow, wetting front advancement (WFA), bypass flow and perched water table rise. Besides the gravity observations, electrical resistivity and soil moisture data were used for evaluation. For the study site, the process combination of preferential flow and WFA led to the best correspondence to the observations in a multi-criteria assessment. We argue that the approach of combining field-scale sprinkling experiments in combination with gravity monitoring can be transferred to other sites for process identification, and discuss related uncertainties including limitations of the simple model used here. The study stresses the value of advancing terrestrial gravimetry as an integrative and non-invasive monitoring technique for assessing hydrological states and dynamics.
Advances in hydrogravimetry
(2023)
The interest of the hydrological community in the gravimetric method has steadily increased within the last decade. This is reflected by numerous studies from many different groups with a broad range of approaches and foci. Many of those are traditionally rather hydrology-oriented groups who recognized gravimetry as a potential added value for their hydrological investigations. While this resulted in a variety of interesting and useful findings, contributing to extend the respective knowledge and confirming the methodological potential, on the other hand, many interesting and unresolved questions emerged.
This thesis manifests efforts, analyses and solutions carried out in this regard. Addressing and evaluating many of those unresolved questions, the research contributes to advancing hydrogravimetry, the combination of gravimetric and hydrological methods, in showing how gravimeters are a highly useful tool for applied hydrological field research.
In the first part of the thesis, traditional setups of stationary terrestrial superconducting gravimeters are addressed. They are commonly installed within a dedicated building, the impermeable structure of which shields the underlying soil from natural exchange of water masses (infiltration, evapotranspiration, groundwater recharge). As gravimeters are most sensitive to mass changes directly beneath the meter, this could impede their suitability for local hydrological process investigations, especially for near-surface water storage changes (WSC). By studying temporal local hydrological dynamics at a dedicated site equipped with traditional hydrological measurement devices, both below and next to the building, the impact of these absent natural dynamics on the gravity observations were quantified. A comprehensive analysis with both a data-based and model-based approach led to the development of an alternative method for dealing with this limitation. Based on determinable parameters, this approach can be transferred to a broad range of measurement sites where gravimeters are deployed in similar structures. Furthermore, the extensive considerations on this topic enabled a more profound understanding of this so called umbrella effect.
The second part of the thesis is a pilot study about the field deployment of a superconducting gravimeter. A newly developed field enclosure for this gravimeter was tested in an outdoor installation adjacent to the building used to investigate the umbrella effect. Analyzing and comparing the gravity observations from both indoor and outdoor gravimeters showed performance with respect to noise and stable environmental conditions was equivalent while the sensitivity to near-surface WSC was highly increased for the field deployed instrument. Furthermore it was demonstrated that the latter setup showed gravity changes independent of the depth where mass changes occurred, given their sufficiently wide horizontal extent. As a consequence, the field setup suits monitoring of WSC for both short and longer time periods much better. Based on a coupled data-modeling approach, its gravity time series was successfully used to infer and quantify local water budget components (evapotranspiration, lateral subsurface discharge) on the daily to annual time scale.
The third part of the thesis applies data from a gravimeter field deployment for applied hydrological process investigations. To this end, again at the same site, a sprinkling experiment was conducted in a 15 x 15 m area around the gravimeter. A simple hydro-gravimetric model was developed for calculating the gravity response resulting from water redistribution in the subsurface. It was found that, from a theoretical point of view, different subsurface water distribution processes (macro pore flow, preferential flow, wetting front advancement, bypass flow and perched water table rise) lead to a characteristic shape of their resulting gravity response curve. Although by using this approach it was possible to identify a dominating subsurface water distribution process for this site, some clear limitations stood out. Despite the advantage for field installations that gravimetry is a non-invasive and integral method, the problem of non-uniqueness could only be overcome by additional measurements (soil moisture, electric resistivity tomography) within a joint evaluation. Furthermore, the simple hydrological model was efficient for theoretical considerations but lacked the capability to resolve some heterogeneous spatial structures of water distribution up to a needed scale. Nevertheless, this unique setup for plot to small scale hydrological process research underlines the high potential of gravimetery and the benefit of a field deployment.
The fourth and last part is dedicated to the evaluation of potential uncertainties arising from the processing of gravity observations. The gravimeter senses all mass variations in an integral way, with the gravitational attraction being directly proportional to the magnitude of the change and inversely proportional to the square of the distance of the change. Consequently, all gravity effects (for example, tides, atmosphere, non-tidal ocean loading, polar motion, global hydrology and local hydrology) are included in an aggregated manner. To isolate the signal components of interest for a particular investigation, all non-desired effects have to be removed from the observations. This process is called reduction. The large-scale effects (tides, atmosphere, non-tidal ocean loading and global hydrology) cannot be measured directly and global model data is used to describe and quantify each effect. Within the reduction process, model errors and uncertainties propagate into the residual, the result of the reduction. The focus of this part of the thesis is quantifying the resulting, propagated uncertainty for each individual correction. Different superconducting gravimeter installations were evaluated with respect to their topography, distance to the ocean and the climate regime. Furthermore, different time periods of aggregated gravity observation data were assessed, ranging from 1 hour up to 12 months. It was found that uncertainties were highest for a frequency of 6 months and smallest for hourly frequencies. Distance to the ocean influences the uncertainty of the non-tidal ocean loading component, while geographical latitude affects uncertainties of the global hydrological component. It is important to highlight that the resulting correction-induced uncertainties in the residual have the potential to mask the signal of interest, depending on the signal magnitude and its frequency. These findings can be used to assess the value of gravity data across a range of applications and geographic settings.
In an overarching synthesis all results and findings are discussed with a general focus on their added value for bringing hydrogravimetric field research to a new level. The conceptual and applied methodological benefits for hydrological studies are highlighted. Within an outlook for future setups and study designs, it was once again shown what enormous potential is offered by gravimeters as hydrological field tools.
The coil-to-globule transition of poly(N-isopropylacrylamide) (PNIPAM) microgel particles suspended in water has been investigated in situ as a function of heating and cooling rate with four optical process analytical technologies (PAT), sensitive to structural changes of the polymer. Photon Density Wave (PDW) spectroscopy, Focused Beam Reflectance Measurements (FBRM), turbidity measurements, and Particle Vision Microscope (PVM) measurements are found to be powerful tools for the monitoring of the temperature-dependent transition of such thermo-responsive polymers. These in-line technologies allow for monitoring of either the reduced scattering coefficient and the absorption coefficient, the chord length distribution, the reflected intensities, or the relative backscatter index via in-process imaging, respectively. Varying heating and cooling rates result in rate-dependent lower critical solution temperatures (LCST), with different impact of cooling and heating. Particularly, the data obtained by PDW spectroscopy can be used to estimate the thermodynamic transition temperature of PNIPAM for infinitesimal heating or cooling rates. In addition, an inverse hysteresis and a reversible building of micrometer-sized agglomerates are observed for the PNIPAM transition process.
Objective Due to multiple light scattering that occurs inside and between cells, quantitative optical spectroscopy in turbid biological suspensions is still a major challenge. This includes also optical inline determination of biomass in bioprocessing. Photon Density Wave (PDW) spectroscopy, a technique based on multiple light scattering, enables the independent and absolute determination of optical key parameters of concentrated cell suspensions, which allow to determine biomass during cultivation. Results A unique reactor type, called "mesh ultra-thin layer photobioreactor" was used to create a highly concentrated algal suspension. PDW spectroscopy measurements were carried out continuously in the reactor without any need of sampling or sample preparation, over 3 weeks, and with 10-min time resolution. Conventional dry matter content and coulter counter measurements have been employed as established offline reference analysis. The PBR allowed peak cell dry weight (CDW) of 33.4 g L-1. It is shown that the reduced scattering coefficient determined by PDW spectroscopy is strongly correlated with the biomass concentration in suspension and is thus suitable for process understanding. The reactor in combination with the fiber-optical measurement approach will lead to a better process management.
Industrial applications of photon density wave spectroscopy for in-line particle sizing [Invited]
(2013)
Optical spectroscopy in highly turbid liquid material is often restricted by simultaneous occurrence of absorption and scattering of light. Photon Density Wave (PDW) spectroscopy is one of the very few, yet widely unknown, technologies for the independent quantification of these two optical processes. Here, a concise overview about modern PDW spectroscopy is given, including all necessary equations concerning the optical description of the investigated material, dependent light scattering, particle sizing, and PDW spectroscopy itself. Additionally, it is shown how the ambiguity in particle sizing, arising from Mie theory, can be correctly solved. Due to its high temporal resolution, its applicability to highest particle concentrations, and its purely fiber-optical probe, PDW spectroscopy possesses all fundamental characteristics for optical in-line process analysis. Several application examples from the chemical industry are presented. (C) 2013 Optical Society of America