Real-time Raman spectroscopic monitoring of wine properties and constituents during wine production
A method of characterizing and monitoring a pressing process includes acquiring online Raman spectra of a juice pressing process within a vessel at different times during the pressing process to generate a training data set; acquiring physical samples from pressing process near in time to the acquired Raman spectra; performing offline measurements of the target analyte properties and/or compositions using an assay measurement technique; generating a correlative model of the target analyte such that spectral changes in the training data set correlate with the offline measurements of the target analyte properties and/or compositions; acquiring online Raman spectra of a subsequent run of the pressing process within the vessel at different times during the run to generate a process data set; and applying the correlative model to the process data set to qualitatively and/or quantitatively predict a value of a property and/or composition of the target analyte.
1. A method of characterizing and monitoring a juice pressing process, the method comprising:
acquiring Raman spectra of a juice pressing process within a vessel at different times during the pressing process to generate a training data set;
applying spectral preprocessing to the training data set such that non-correlative and covariant changes due to non-relevant species and/or properties are minimized and correlative changes due to a target analyte is amplified;
acquiring physical samples from the pressing process near in time to the acquired Raman spectra;
performing offline measurements of the target analyte properties and/or compositions using an assay measurement technique;
generating a correlative model of the target analyte such that spectral changes in the training data set correlate with the offline measurements of the target analyte properties and/or compositions;
acquiring online Raman spectra of a subsequent run of the pressing process within the vessel at different times during the run to generate a process data set; and
applying the correlative model to the process data set to qualitatively and/or quantitatively predict a value of a property and/or composition of the target analyte.
2. The method of claim 1 , wherein the target analyte includes more than one species or property of the pressing process.
3. The method of claim 1 , wherein the acquiring of Raman spectra of the juice pressing process is performed online in real time during operation of the juice pressing process.
4. The method of claim 3 , the method further comprising acquiring offline Raman spectra from a predetermined set of the physical samples before and/or after online Raman spectra are acquired.
5. The method of claim 4 , wherein data from the acquired offline Raman spectra are included in the training data set.
6. The method of claim 1 , wherein the physical samples are acquired concurrently with the Raman spectra.
7. The method of claim 1 , the method further comprising preparing experimental samples and acquiring offline Raman spectra and offline assay measurements of the experimental samples, wherein data of the experimental samples are included in the training data set.
8. The method of claim 7 , wherein the experimental samples are prepared according to a predetermined design of experiment in which selected analyte variables are prepared to predetermined values such that variance of the experimental samples is statistically controlled.
9. The method of claim 1 , wherein the spectral preprocessing includes a series of optimizations adapted to discern an optimal preprocessing algorithm for the pressing process.
10. The method of claim 1 , wherein the corelative model is generated using a univariate modeling methodology.
11. The method of claim 1 , wherein the corelative model is generated using a multivariate modeling methodology.
12. The method of claim 1 , the method further comprising iteratively refining the correlative model using modeling statistics such that correlation of the training data set to the offline measurements is increased.
13. The method of claim 1 , the method further comprising generating a signal, alarm or report when the value of the target analyte deviates from a desired range based on threshold limits.
14. The method of claim 1 , wherein the target analyte includes at least one of fructose concentration, glucose concentration, degrees Brix value, pH value, tartaric acid concentration, malic acid concentration, total acidity value, citric acid concentration, acetic acid concentration, gluconic acid concentration, lactic acid concentration, glycerol concentration, sulfur dioxide concentration, total phenolic content value, catechin concentration, procyanidin concentration, anthocyanin concentration, flavonol concentration, hydroxycinnamate concentration, hydroxybenzoates concentration, and total amount of suspended colloidal proteins, anthocyanins and tannins that contribute to brown, red and/or pink colors.
15. A computer program product comprising a non-transitory machine-readable storage medium encoding instructions that, when executed by one or more programmable processors, cause the one or more programmable processors to perform operations comprising:
acquiring online Raman spectra of a juice pressing process within a vessel at different times during the fermentation process to generate a training data set;
applying spectral preprocessing to the training data set such that non-correlative and covariant changes due to non-relevant species and/or properties are minimized and correlative changes due to a target analyte is amplified;
generating a corelative model of the target analyte such that spectral changes of the target analyte properties and/or compositions in the training data set corelate with offline assay measurements of physical samples taken from the pressing process near in time to the acquired Raman spectra;
acquiring a subsequent online Raman spectrum during a subsequent run of the pressing process within the vessel; and
applying the correlative model to the subsequent online Raman spectrum to qualitatively and/or quantitatively predict a value of a property and/or composition of the target analyte.
16. The computer program product of claim 15 , wherein the operations further comprise generating a signal, alarm or report when the value of the target analyte deviates from a desired range based on threshold limits.
17. The computer program product of claim 15 , wherein the target analyte includes at least one of fructose concentration, glucose concentration, degrees Brix value, pH value, tartaric acid concentration, malic acid concentration, total acidity value, citric acid concentration, acetic acid concentration, gluconic acid concentration, lactic acid concentration, glycerol concentration, sulfur dioxide concentration, total phenolic content value, catechin concentration, procyanidin concentration, anthocyanin concentration, flavonol concentration, hydroxycinnamate concentration, hydroxybenzoates concentration, and total amount of suspended colloidal proteins, anthocyanins and tannins that contribute to brown, red and/or pink colors.
18. A Raman analysis system, the system comprising:
a light source configured to emit excitation light;
an optical probe coupled to the light source via an optical cable such that the excitation light is emitted from a probehead of the probe into a sample volume, wherein the probe is configured to receive and transmit a Raman signal from the sample volume via the optical cable or another optical cable;
a spectrograph configured to spectrally separate the transmitted Raman signal;
a detector configured to receive the separated Raman signal and convert the separated Raman signal into a Raman spectrum; and
a controller configured to:
acquire online Raman spectra of a juice pressing process within a vessel at different times during the pressing process by actuating the light source to emit the excitation light and receiving the Raman spectrum from the detector;
apply a correlative model to the Raman spectrum to qualitatively and/or quantitatively predict a value of a property and/or composition of a target analyte, wherein the correlative model is adapted such that spectral changes of the target analyte properties and/or compositions in previously acquired Raman spectra correlate with offline assay measurements of physical samples taken from a previous pressing process; and
monitor the pressing process by periodically acquiring subsequent online Raman spectra.
19. The system of claim 18 , wherein the controller is further configured to generate a signal, alarm or report when the value of the target analyte deviates from a desired range based on threshold limits.
20. The method of claim 18 , wherein the target analyte includes at least one of fructose concentration, glucose concentration, degrees Brix value, pH value, tartaric acid concentration, malic acid concentration, total acidity value, citric acid concentration, acetic acid concentration, gluconic acid concentration, lactic acid concentration, glycerol concentration, sulfur dioxide concentration, total phenolic content value, catechin concentration, procyanidin concentration, anthocyanin concentration, flavonol concentration, hydroxycinnamate concentration, hydroxybenzoates concentration, and total amount of suspended colloidal proteins, anthocyanins and tannins that contribute to brown, red and/or pink colors.