NL2012174C2 - Method for the determination of elements in manure by nmr spectroscopy and manure transport vehicle. - Google Patents

Method for the determination of elements in manure by nmr spectroscopy and manure transport vehicle. Download PDF

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Publication number
NL2012174C2
NL2012174C2 NL2012174A NL2012174A NL2012174C2 NL 2012174 C2 NL2012174 C2 NL 2012174C2 NL 2012174 A NL2012174 A NL 2012174A NL 2012174 A NL2012174 A NL 2012174A NL 2012174 C2 NL2012174 C2 NL 2012174C2
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Netherlands
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manure
nmr
channel
determined
transport
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NL2012174A
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Dutch (nl)
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Walter Theodorus Maria Veenhuis
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Veenhuis Machines
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Priority to NL2012174A priority Critical patent/NL2012174C2/en
Priority to DE202015100443.5U priority patent/DE202015100443U1/en
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Publication of NL2012174C2 publication Critical patent/NL2012174C2/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
    • G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01C—PLANTING; SOWING; FERTILISING
    • A01C23/00—Distributing devices specially adapted for liquid manure or other fertilising liquid, including ammonia, e.g. transport tanks or sprinkling wagons
    • A01C23/007—Metering or regulating systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01C—PLANTING; SOWING; FERTILISING
    • A01C23/00—Distributing devices specially adapted for liquid manure or other fertilising liquid, including ammonia, e.g. transport tanks or sprinkling wagons
    • A01C23/008—Tanks, chassis or related parts
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/483—Physical analysis of biological material
    • G01N33/487—Physical analysis of biological material of liquid biological material
    • G01N33/48707—Physical analysis of biological material of liquid biological material by electrical means
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/10—Devices for withdrawing samples in the liquid or fluent state
    • G01N1/20—Devices for withdrawing samples in the liquid or fluent state for flowing or falling materials
    • G01N1/2035—Devices for withdrawing samples in the liquid or fluent state for flowing or falling materials by deviating part of a fluid stream, e.g. by drawing-off or tapping
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/28—Details of apparatus provided for in groups G01R33/44 - G01R33/64
    • G01R33/30—Sample handling arrangements, e.g. sample cells, spinning mechanisms
    • G01R33/307—Sample handling arrangements, e.g. sample cells, spinning mechanisms specially adapted for moving the sample relative to the MR system, e.g. spinning mechanisms, flow cells or means for positioning the sample inside a spectrometer

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Biomedical Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Immunology (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Pathology (AREA)
  • Environmental Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Soil Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Medicinal Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Urology & Nephrology (AREA)
  • Molecular Biology (AREA)
  • Hematology (AREA)
  • Biophysics (AREA)
  • Investigating Or Analyzing Materials By The Use Of Magnetic Means (AREA)

Abstract

Manure transport vehicle, particularly a truck or ship that is designed for the transport of manure, especially manure and slurry to a storage tank, the manure stores, wherein the storage tank with at least one channel to the inlet and / or outlet of manure, said the channel is provided with NMR-measurement devices for the quantitative determination of at least one element in the manure flowing in the current flowing state through the channel, said NMR measurement means comprise: Magnet means for producing a magnetic field in at least part of the channel, an RF pulse device to excite the element to be determined and a receiver for measuring the electromagnetic signals from the excited element.

Description

METHOD FOR THE DETERMINATION OF ELEMENTS IN MANURE BY NMR SPECTROSCOPY AND MANURE TRANSPORT VEHICLE
The invention relates to a method for the quantitative determination of at least one element in liquid or semi-liquid manure by Nuclear Magnetic Resonance (NMR) spectroscopy. The invention further relates to a manure transport vehicle provided with equipment for performing the method.
BACKGROUND
Manure is rich in components such as nitrogen, phosphates and potassium. Although such components may be used advantageously, for instance in fertilizers, there is a need to control the spreading of manure, as the components may cause environmental harm when certain components exceed certain concentrations.
Many authorities use registration methods regarding the transporting and use of manure. Such a method is used in the Netherlands for the registration under the authority of the government of manure transport and the harmful substances present therein. The registration is carried out by a central official authority in order to prevent undesirably large amounts of harmful substances, such as Nitrogen species, phosphates and potassium finding their way into the environment as fertilizer. A number of analytical methods are available to quantitatively determine the amounts of harmful substances in manure. An example is found in EP2674734, which describes a method and device for the registration of manure transport, wherein a Near InfraRed Spectroscopy (NIR or NIRS) sensor is used in a transport vehicle.
Nuclear Magnetic Resonance (NMR) spectroscopy is another analytical method that may be used to determine harmful species in manure. For instance, the publication by B.L.Turner and A.B. Leytem, Environ. Sci. Technol. 2004, 38, p. 6101-6108, describes the analysis of dissolved phosphate species by 31P NMR. The analytical method involves a number of sample preparation steps and the extraction of dissolved phosphates. The prepared sample was measured in a 500 MHz spectrometer, involving a superconducting magnet cooled with liquid nitrogen. S. Jayasundera, W. F. Schmidtl, J. B. Reeves III and T. Η. Dao, Journal of Food, Agriculture & Environment Vol.3 (2) 2005: p. 328 - 333 describes a solid state 31P MAS NMR method applied to determine the phosphorus content of dairy manure. In this method, the intact manure is measured in a 400 MHz spectrometer using the so-called ‘Magic Angle Spinning’ (MAS) technique. This spectrometer also involves the use of a liquid nitrogen-cooled superconducting magnet.
In practice, the known NMR methods are unsuitable for routine phosphate quantification for registration purposes. The sample taking and preparation used in the known methods are too time consuming to process the vast amounts of manure that are produced and transported on a daily basis.
As a complicating factor, the authorities in some countries, including the Netherlands, may not accept analysis based on samples, and require the quantitative analysis of the entire batch of manure, which is impossible in terms of manure volume to be processed when using the NMR methods to analyze manure known in the art.
It is an object of the invention to provide an improved method of analyzing manure, in particular for the determination of phosphates, nitrogen and/or potassium. In particular, it is an object to provide a less time consuming analysis method.
The invention relates to a method for the quantitative determination of at least one element in liquid or semi-liquid manure by Nuclear Magnetic Resonance (NMR) spectroscopy, wherein an NMR measurement is done in-line or semi-in-line during transportation of the manure through a transport channel. Such a method allows for the determination of elements of interest by NMR spectroscopy during the manure transport process, in particular during loading/unloading of a manure transport vehicle.
Preferably, the determination is done during the transfer of the manure in a transport channel to or from a transport vehicle. By measuring during the transfer of the manure, the time required for transferring manure is efficiently used.
It is advantageous if the NMR measurement is done on manure in flowing condition. By measuring in a flowing condition, the accumulated data collected during the transfer represents an averaged signal even when some inhomogeneity is present in the sample, which is of particular relevance for semi-liquid manure which may contain inhomogeneity caused by solid particles.
It is preferred if the NMR measurement is used quantitatively to determine the concentration of the element per volume or per weight. Although NMR is often capable of discerning specific species in a certain sample, this would set higher requirements for the homogeneity of the magnetic field, whereas the requirements are lower for quantitative measurements, allowing for a more simple measurement procedure.
In a preferred embodiment, the NMR measurements involves the simultaneous subjecting of manure to a magnetic field, irradiating the manure with a radiofrequency pulse of a predetermined frequency, adapted to the element to be determined, and receiving electromagnetic signals from the element to be determined. The frequencies for the radio pulse, as well as the receiving frequency range, can be optimized for a particular isotope to be measured.
It is preferred if the strength from the signal received from the element in the manure is compared to an internal standard or a calibration sample in order to quantitatively determine the amount of element. This measurement may be done previous to the actual measurement, when calibrating the method for a certain element.
In a preferred embodiment, the element to be determined is 31P. 31P has a 100% natural isotopic abundance, and shows a relatively strong signal. In manure, the 31P signal is correlated with the phosphate content. Phosphorus may be present in manure in various chemical forms. It is preferred if the NMR measurement on 31P is used to determine the concentration of phosphates in the manure.
In another preferred embodiment, the method according to any of the preceding claims wherein the element to be determined is 14N or 15N, preferably 14N. The 14N isotope has a better natural abundance, and is therefore more suitable 15N. 14N represents a molar fraction of more than 99 % of the natural nitrogen composition, whereas less than 1% is 15N. Preferably, the NMR measurement on 14N or 15N is used to determine the concentration of nitrogen in the manure. The nitrogen may be present in various chemical forms in the manure.
In yet another preferred embodiment, the element to be determined is either 39K, 40K or 41K, preferably 39K. The natural molar fractions of 39K, 40K or 41K are 93%, approximately 0.1% and approximately 1%, respectively. Preferably, the NMR measurement on 39K, 40K or41K is used to determine the concentration of potassium in the manure.
The invention also provides a manure transport vehicle, in particular a truck or a boat, designed for transporting manure, in particular liquid or semi-liquid manure, comprising a storage tank for storing manure during transport, which storage tank is provided with at least one channel for inlet and/or outlet of manure, wherein the channel is provided with NMR measurement means for quantitative determination of the at least one element in manure flowing through the channel, the NMR measurements means comprising: magnetic means for providing a magnetic field in at least part of the channel; a radiofrequency pulse means for exciting the element to be determined, and a receiver for measuring the electromagnetic signals from the excited element. The magnetic means may for example be an electromagnet or a permanent magnet. The radiofrequency pulse transmitter and receiver may be integrated in one device. Such devices are known from existing NMR spectroscopy devices. The incorporation in a transport vehicle allows for analysis of the manure by NMR during the transport process, in particular during loading or unloading of the manure transport vehicle.
Preferably, the transport vehicle further comprises communication means designed for electronically transmitting information regarding the weight of the cargo of the vehicle to a registering authority, wherein the communication means are coupled to the NMR measurement means to further transmit information on the quantity of the element to be measured, in particular potassium, nitrogen and/or phosphor.
It is advantageous if the vehicle comprises dosing means for depositing manure on an area, wherein the dosing means are coupled with the NMR measuring means in order to control a manure deposition rate as a function of the concentration of the element as determined by the NMR measurement means.
In a preferred embodiment, the NMR measurement means are adapted for changing the radio pulse frequency and receiving frequency in order to measure different elements in the same batch of cargo.
The invention will now be further elucidated by the following non-limiting examples.
Figure 1 shows an NMR measurement unit for determining
Figure 2 shows a manure transport vehicle according to the invention.
Figure 1 schematically shows an NMR measurement cell 1 for measuring flowing manure. The cell has a central channel 2 though which the manure can flow. The magnetic field needed for NMR measurements is provided by a permanent magnet 3, for instance a neodymium magnet, arranged around the central channel 2. The wall 4 of the channel can be made of any NMR-compatible material, in particular glass or polymer materials such as polyethylene and polypropylene are suitable. Care should be taken that the material does not comprise the element to be measured, which could interfere with the actual measurement.
The diameter 5 of the wall 4 can be chosen according to the needed manure flow debit through the channel 2. It is noted that for a larger channel diameter 5, a larger permanent magnet 3 would be needed in order to provide a sufficiently homogenous magnetic field in the channel. However, for quantitative measurements for a certain element a certain inhomogeneity can be tolerated, as for quantification of the total signal for the element of interest it is not necessary to obtain separated signals after Fourier transformation.
In the measuring area 6, a transmitter/receiver RF coil is provided. The RF coil is embedded in the wall 4 in order to avoid direct contact with the manure. Various types of RF coils suitable for NMR spectroscopy are known in the art. The RF coil 7 is connected through wiring 8 with an external RF receiver/transmitter 9. The radiofrequencies for the exciting pulse and receiver can be adjusted according to the isotope that is to be measured, such as 31P, 14N and potassium 39K.
The measurement cell 1 can be coupled to an inlet or outlet of a manure storage container or a manure transport vehicle through flanges 10. The flanges could be replaced by other suitable coupling means. The coupling means 10 allows the NMR unit to be placed in-line in a manure transport channel, ensuring that all of the transported manure is analyzed. It is also possible to place the NMR measurement unit in a channel parallel to a main channel, but in such a case only a predetermined fraction of the manure is actually analyzed.
Figure 2 schematically shows a manure transport vehicle 11 according to the present invention. The manure transport vehicle 11 is a trailer on wheels 12, a chassis 13 and a storage tank 14. Weighing cells 15 are provided between the storage tank 14 and the chassis 13 for determining the weight of the cargo in the storage tank 14. The storage tank 14 is provided with a fill and discharge line 16 and a sensor unit 17, which comprises an NMR measurement unit. The NMR measurement unit may be used when filling and emptying the storage tank to provide an instantaneous analysis of the concentrations of nitrogen and/or phosphate and/or potassium in the manure flowing through the fill and discharge line 16. The data collected by the NMR unit 17 is connected to a computer unit 18, by means of which data analyzed by the NMR unit 17 and determined by the weighing cells 15 are converted into a total weight of nitrogen and/or phosphate. The computer unit subsequently transmits the computed data to a modem 19. The weighing cells are likewise connected to the modem 19 and transmit data regarding the weight of the cargo to the modem 19 before and after the loading and before and after the discharging of the manure. A GPS receiver 20 installed in the manure transport vehicle 11 receives position data from a satellite 21 which, incidentally, does not form part of the manure transport vehicle 11 according to the present invention, and subsequently transmits the data to the modem 19. The collected data are transmitted to an authority (not shown in figure 3) by the modem 19 in accordance with a method shown in figures 1 and 2. The NMR measurement may be combined with other analytical equipment present in the same manure transport vehicle. NMR measurements in flowing manure
Test measurements were done in flowing liquid manure in an NMR flow probe cell in a static magnetic field, wherein the pulse frequencies of the transmitter and the receiver frequency, as well as the sampling window for the free induction decay (FID) signal, a were optimized for phosphorus 31P, nitrogen 14N and potassium 39K, respectively. The liquid manure was pumped without any sample preparation from a reservoir through the flow probe cell.
The measurements were carried out using a 60 MHz permanent neodymium magnet with a simple flow cell having a system volume of 5 ml. The flow rate was 10 ml/minute. It is noted that for use in practice a flow cell of larger diameter would be needed. For each of the elements of interest, the free induction decay (FID) signals were measured as a function of time. The measured FIDs are accumulated. As the manure flows while measuring, the accumulated FID signals give an signal correlated for the total amount of the element measured present in the batch of manure transported through the flow cell.
The measurements were calibrated using manure compositions comprising a known composition of phosphorus, nitrogen and potassium. Linear calibration lines could be obtained by measuring the amount of signal in relation to the concentration of the respective element for a series of diluted samples. The concentrations were diluted with water. As the amounts of 31P, nitrogen 14N and potassium 39K are present in their natural abundances, the signal for each specific isotope directly correlates with the total amount of these elements in the samples. For phosphorus, an excellent signal-to-noise ratio was obtained; nitrogen and potassium showed a significantly lower sensitivity, due to the intrinsic line broadening and lower isotope abundance, but still a useful signal for quantitative measurements could be obtained.

Claims (16)

1. Werkwijze voor de kwantitatieve bepaling van ten minste een element in vloeibare of semi-vloeibare mest door kernspinresonantie (NMR) spectroscopie, waarbij de NMR-meting wordt gedaan in-line of semi-in-line gedurende transport van de mest door een transportkanaal.A method for quantitative determination of at least one element in liquid or semi-liquid manure by nuclear magnetic resonance (NMR) spectroscopy, wherein the NMR measurement is done in-line or semi-in-line during transport of the manure through a transport channel . 2. Werkwijze volgens conclusie 1, waarbij de bepaling is gedaan gedurende de overbrenging van de mest in een transportkanaal van of naar een transportvoertuig.Method according to claim 1, wherein the determination is made during the transfer of the manure in a transport channel from or to a transport vehicle. 3. Werkwijze volgens conclusie 1 of 2, waarbij de NMR-meting is gedaan aan mest in een vloeiende toestand.The method according to claim 1 or 2, wherein the NMR measurement is made on manure in a flowing state. 4. Werkwijze volgens conclusie 3, waarbij de NMR-meting kwantitatief wordt gebruikt voor het bepalen van de concentratie van een element per volume of per gewicht.The method of claim 3, wherein the NMR measurement is used quantitatively to determine the concentration of an element by volume or by weight. 5. Werkwijze volgens een van de voorgaande conclusies, waarbij de NMR-meting omvat het simultaan onderwerpen van de mest aan een magnetisch veld, het bestralen van de mest met een radiofrequentiepuls van een vooraf bepaalde frequentie, aangepast aan het te bepalen element, en het ontvangen van elektromagnetische signalen van het te bepalen element.A method according to any one of the preceding claims, wherein the NMR measurement comprises simultaneously applying the manure to a magnetic field, irradiating the manure with a radio frequency pulse of a predetermined frequency, adapted to the element to be determined, and the receiving electromagnetic signals from the element to be determined. 6. Werkwijze volgens conclusie 5, waarbij de sterkte van het ontvangen signaal van het element in de mest wordt vergeleken met een interne standaard of een kalibratiemonster voor het kwantitatief bepalen van de hoeveelheid van het element.The method of claim 5, wherein the strength of the received signal from the element in the manure is compared to an internal standard or a calibration sample for quantitatively determining the amount of the element. 7. Werkwijze volgens een der voorgaande conclusies, waarbij het te bepalen element 31P is.A method according to any one of the preceding claims, wherein the element to be determined is 31P. 8. Werkwijze volgens conclusie 5, waarbij de NMR-meting op 31P gebruikt wordt om de concentratie fosfaten in de mest te bepalen.The method of claim 5, wherein the NMR measurement at 31 P is used to determine the phosphate concentration in the manure. 9. Werkwijze volgens een der voorgaande conclusies, waarbij het te bepalen element 14N of 15N is, bij voorkeur 14N.A method according to any one of the preceding claims, wherein the element to be determined is 14 N or 15 N, preferably 14 N. 10. Werkwijze volgens conclusie 7, waarbij de NMR-meting op 14N of 15N wordt gebruikt voor het bepalen van de concentratie van stikstof in de mest.The method of claim 7, wherein the NMR measurement at 14 N or 15 N is used to determine the concentration of nitrogen in the manure. 11. Werkwijze volgens een der voorgaande conclusies, waarbij het te bepalen element 39K, 40K of41K is, bij voorkeur 39K.A method according to any one of the preceding claims, wherein the element to be determined is 39K, 40K or 41K, preferably 39K. 12. Werkwijze volgens conclusie 7, waarbij de NMR-meting op 39K, 40K of 41K wordt gebruikt voor het bepalen van de concentratie van kalium in de mest.The method of claim 7, wherein the NMR measurement at 39K, 40K or 41K is used to determine the concentration of potassium in the manure. 13. Mesttransportvoertuig, bij voorkeur een vrachtwagen of een boot, ontworpen voor het transporteren van mest, in het bijzonder vloeibare of semi-vloeibare mest, omvattende een opslagtank voor het opslaan van mest gedurende transport, waarbij de opslagtank is voorzien van ten minste één kanaal voor het inlaten en/of uitlaten van mest, waarbij het kanaal is voorzien van NMR-meetmiddelen voor kwantitatieve bepaling van ten minste één element in mest vloeiend door het kanaal, waarbij de NMR-meetmiddelen omvatten: - magnetische middelen voor het verschaffen van een magnetisch veld in ten minste een deel van het kanaal; - een radiofrequentiepulsmiddel voor het exciteren van het te bepalen element, en - een ontvanger voor het meten van elektromagnetische signalen van het geëxciteerde element.13. Manure transport vehicle, preferably a truck or a boat, designed for transporting manure, in particular liquid or semi-liquid manure, comprising a storage tank for storing manure during transport, wherein the storage tank is provided with at least one channel for inlet and / or outlet of manure, wherein the channel is provided with NMR measuring means for quantitative determination of at least one element in manure flowing through the channel, the NMR measuring means comprising: - magnetic means for providing a magnetic field in at least a part of the channel; - a radio frequency pulse means for exciting the element to be determined, and - a receiver for measuring electromagnetic signals from the excited element. 14. Mesttransportvoertuig volgens conclusie 13, waarbij het transportvoertuig verder omvat communicatiemiddelen ontworpen voor het elektronisch overbrengen van informatie betreffende het gewicht van de lading van het voertuig aan een registratie-autoriteit, waarbij de communicatiemiddelen gekoppeld zijn met NMR-meetmiddelen verdere informatie over te brengen betreffende de kwantiteit van het te bepalen element, in het bijzonder kalium, stikstof en/of fosfor.A manure transport vehicle according to claim 13, wherein the transport vehicle further comprises communication means designed for electronically transmitting information regarding the weight of the load of the vehicle to a registration authority, the communication means being coupled to NMR measuring means for transmitting further information concerning the quantity of the element to be determined, in particular potassium, nitrogen and / or phosphorus. 15. Mesttransportvoertuig volgens conclusie 13 of 14, waarbij het voertuig doseermiddelen omvat voor het deponeren van mest op een oppervlak, waarbij de doseermiddelen gekoppeld zijn met NMR-meetmiddelen om een mestdeponeersnelheid te controleren als functie van de concentratie van het element zoals bepaald door de NMR-meetmiddelen.The manure transport vehicle according to claim 13 or 14, wherein the vehicle comprises dosing means for depositing manure on a surface, the dosing means being coupled to NMR measuring means to control a manure depositing speed as a function of the concentration of the element as determined by the NMR measuring instruments. 16. Mesttransportvoertuit volgens conclusie 13 of 14, waarbij de NMR-meetmiddelen zijn aangepast voor het veranderen van de radiopulsfrequentie en ontvangfrequentie om verschillende elementen te kunnen meten in dezelfde lading.The manure transport feed spout according to claim 13 or 14, wherein the NMR measuring means is adapted to change the radio pulse frequency and receive frequency to be able to measure different elements in the same load.
NL2012174A 2014-01-30 2014-01-30 Method for the determination of elements in manure by nmr spectroscopy and manure transport vehicle. NL2012174C2 (en)

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DE202015100443.5U DE202015100443U1 (en) 2014-01-30 2015-01-30 Dung transport vehicle

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EP0451962A2 (en) * 1990-04-09 1991-10-16 THE GENERAL ELECTRIC COMPANY, p.l.c. Methods and apparatus for investigating the composition of material
WO1992016040A1 (en) * 1991-03-08 1992-09-17 Elbit-Ati, Ltd. Apparatus for in-line analysis of flowing liquid and solid materials by nuclear magnetic resonance
DE102008005650A1 (en) * 2008-01-23 2009-07-30 Zunhammer, Sebastian, Dipl.-Ing. (FH) Method for optimizing application amount of liquid manure e.g. pig slurry, substance to soil, involves controlling distributor device based on control data such that manure amount to be applied is regulated according to control data
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Title
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, vol. 56, no. 6, March 2008 (2008-03-01), pages 2131 - 2138, ISSN: 0021-8561, DOI: 10.1021/JF071588X *

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