Agricultural analysis system and calibration method thereof

Abstract

Disclosed herein are systems, devices, and methods for calibrating agricultural analysis systems. According to one aspect of the disclosure, a method for using an instrument adapted to analyze an agricultural sample is provided, the method comprising continuously providing, e.g., delivering, a calibration stream to the instrument adapted to analyze the agricultural sample, the calibration stream having a composition that changes over a period of time.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 586726, filed September 29, 2023; U.S. Provisional Patent Application No. 63 / 586955, filed September 29, 2023; and U.S. Provisional Patent Application No. 63 / 586966, filed September 29, 2023, the contents of which are incorporated herein by reference in their entirety. Background Technology

[0003] This invention generally relates to agricultural sampling and analysis, and more particularly to an agricultural sample processing and analysis system for analyzing soil and other types of agricultural-related samples using plasma discharge spectroscopy.

[0004] Regular soil testing is an important aspect of agriculture. The results provide valuable information about the soil's chemical composition, such as available nutrients for plants and other important properties (e.g., levels of calcium, magnesium, phosphorus, and potassium, pH), allowing for the addition of various soil amendments to maximize crop quality and yield.

[0005] In some existing soil sampling processes, the collected samples are dried, ground, watered, and then filtered to obtain a soil slurry suitable for analysis. An extractant is added to the slurry to extract various plant-available nutrients (analytes). The slurry is then analyzed to determine the content levels of various plant-available nutrients, thereby enabling soil amendment of certain areas of agricultural fields, if necessary, to replenish depleted nutrients.

[0006] Improvements are needed in the processing and analysis of agricultural samples (such as soil, vegetation, and manure). Summary of the Invention

[0007] This summary is intended only to provide a simplified overview of some aspects of one or more embodiments of the present disclosure. Further applications of the present disclosure will become apparent from the detailed description provided below. This summary is not an extensive overview, nor is it intended to identify key or essential elements of the teachings, nor to describe the scope of the disclosure. Rather, its purpose is merely to present one or more concepts in a simplified form as a prelude to a brief description of the detailed description and accompanying drawings provided below.

[0008] This disclosure generally relates to systems, apparatus, and methods for calibrating agricultural analysis systems. According to one aspect of this disclosure, a method is provided for using an instrument suitable for analyzing agricultural samples, the method comprising: continuously providing (e.g., delivering) a calibration stream to the instrument suitable for analyzing agricultural samples, the calibration stream having components that change over a period of time.

[0009] According to another aspect, a method for calibrating an instrument suitable for analyzing agricultural samples is provided. The method may include: continuously providing (e.g., delivering) a calibration stream to an instrument suitable for analyzing agricultural samples, the calibration stream having a component that changes over a period of time; evaluating the component of the calibration stream during at least a portion of the period of time, wherein at the beginning of the evaluated period, the component of the calibration stream does not contain a standard sample and includes an agricultural sample and a diluent, and wherein at the end of the evaluated period, the component of the calibration stream includes the agricultural sample, the standard sample, and optionally the diluent; determining a detected rate of change of the component of the calibration stream; determining when the detected rate of change of the component is substantially constant; optionally, determining a value of the detected rate of change of the component when the rate of change of the component is substantially constant or constant; determining a detected background value based on the evaluation of the calibration stream when the calibration stream does not contain the standard sample; and calibrating the instrument using the detected background value and the value of the detected rate of change of the component when the rate of change of the component is substantially constant or constant.

[0010] According to another aspect, a system for calibrating an instrument suitable for analyzing agricultural samples is provided. The system typically includes: a plurality of pumps configured to provide a calibration flow to a detector, the calibration flow having a composition that varies over a period of time; and a plasma torch apparatus comprising a plasma chamber and a plasma torch at least partially disposed within the plasma chamber, the plasma torch being fluidly coupled to the plurality of pumps. Attached Figure Description

[0011] The invention will be more fully understood through detailed description and accompanying drawings, wherein like elements are labeled in a similar manner, and wherein:

[0012] Figure 1 A high-level schematic diagram illustrating the steps for generating plasma from an agricultural sample and measuring agricultural-related analytes according to an embodiment of the agricultural sample processing and analysis system of the present disclosure;

[0013] Figure 2 A schematic system diagram of a programmable processor-based central processing unit (CPU) or system controller used to control the systems and devices disclosed herein;

[0014] Figure 3 A schematic flowchart illustrating the flow network formed by internal flow channels in a sample analysis device for processing agricultural samples;

[0015] Figure 4 This is a schematic diagram illustrating an exemplary arrangement of diaphragm valves in a plurality of flow control manifold blocks and the flow network therein;

[0016] Figure 5 This is a first perspective view of the agricultural sample analysis equipment of the system, which is operable to process and analyze flowable sample fluids;

[0017] Figure 6 Its second stereoscopic view;

[0018] Figure 7 Its third stereoscopic view;

[0019] Figure 8 Its fourth stereoscopic view;

[0020] Figure 9 Its fifth stereoscopic image;

[0021] Figure 10 Its sixth stereoscopic image;

[0022] Figure 11 Its seventh stereoscopic diagram;

[0023] Figure 12 Its eighth solid figure;

[0024] Figure 13 This is its first side elevation view;

[0025] Figure 14 This is its second side elevation view;

[0026] Figure 15 Its rear elevation view;

[0027] Figure 16 Its front elevation view;

[0028] Figure 17 Its top view;

[0029] Figure 18 Its bottom view;

[0030] Figure 19 Its first vertical sectional view;

[0031] Figure 20 for Figure 19 Enlarged detail image;

[0032] Figure 21 Its second vertical sectional view;

[0033] Figure 22 for Figure 21 Enlarged detail image;

[0034] Figure 23 This is a perspective view of an agricultural sample analysis device, showing the internal details of the device.

[0035] Figure 24 for Figure 23 The enlarged detail view shows the assembly and connection of the flow control manifold block;

[0036] Figure 25 An exploded perspective view of one of the plurality of diaphragm-operated mixing pumps of the device is shown, the mixing pump having an integrated pilot fluid drive system that operates the diaphragm to pump process fluid.

[0037] Figure 26 for Figure 25 A three-dimensional sectional view of the pump body of the mixing pump;

[0038] Figure 27 The first perspective view of the sample fluid manifold block shows the internal flow channels and diaphragm pumping chamber;

[0039] Figure 28 The second perspective view shows the opposite sides of the sample fluid manifold block;

[0040] Figure 29 This is a perspective view of a mixing manifold block that receives process fluid from a mixing pump;

[0041] Figure 30 This is a top-view perspective view of a plasma torch device for agricultural sample analysis equipment, which generates plasma from a sample fluid for use in measuring agricultural-related analytes by a spectrometer.

[0042] Figure 31 Its first bottom-view stereoscopic view;

[0043] Figure 32 Its second bottom-view stereoscopic view;

[0044] Figure 33 Its front elevation view;

[0045] Figure 34 Its rear elevation view;

[0046] Figure 35 This is its first side elevation view;

[0047] Figure 36 Its second elevation view;

[0048] Figure 37 Its first vertical sectional view;

[0049] Figure 38 Its second vertical sectional view;

[0050] Figure 39 This is a first vertical sectional view of a second embodiment of a diaphragm-operated mixing pump, which includes a pressure-balanced sealing system for a pilot fluid drive system.

[0051] Figure 40 Its second vertical sectional view;

[0052] Figure 41 In order to be able to Figure 5 A cross-sectional view of an air removal device used in agricultural sample analysis equipment;

[0053] Figure 42 Its first stereoscopic view;

[0054] Figure 43 Its second stereoscopic view;

[0055] Figure 44 Its first exploded three-dimensional diagram;

[0056] Figure 45 Its second exploded view;

[0057] Figure 46 Its first side view;

[0058] Figure 47 Its top view;

[0059] Figure 48 Its second side view;

[0060] Figure 49 Its side sectional view;

[0061] Figure 50 A flowchart illustrating a non-limiting exemplary method according to one aspect of the present invention;

[0062] Figure 51 A flowchart of another non-limiting exemplary method according to one aspect of the present invention; and

[0063] Figure 52 A flowchart illustrating a non-limiting example of a process for calibrating a non-limiting example system described herein according to one aspect of the present invention.

[0064] All figures are not necessarily drawn to scale. Unless otherwise expressly stated, a part that appears and is numbered in one figure but appears in another figure but is not numbered is the same part. Unless otherwise expressly stated, references to integer figure numbers appearing in multiple figures with the same integer number but different letter suffixes should be understood as references to all those figures collectively. Detailed Implementation

[0065] The features and advantages of the invention are illustrated and described herein by reference to exemplary (“Example”) embodiments. The description of exemplary embodiments is intended to be read in conjunction with the accompanying drawings, which are considered an integral part of the entire written description. Therefore, this disclosure should not be limited to such exemplary embodiments, which illustrate some possible non-limiting combinations of features that may exist alone or in other combinations of features.

[0066] In the description of the embodiments disclosed herein, any references to direction or orientation are merely for ease of description and not intended to limit the scope of the invention in any way. Relative terms such as “lower,” “upper,” “horizontal,” “vertical,” “above,” “below,” “up,” “top,” and “bottom,” and their derivatives (e.g., “horizontally,” “downward,” “upward,” etc.) should be interpreted as referring to the orientation as described below or shown in the figures discussed. These relative terms are merely for ease of description and do not require the device to be constructed or operated in a particular orientation. Terms such as “attach,” “connect,” “join,” “interconnect,” etc., refer to relationships in which structures are directly or indirectly fixed or attached to each other through intermediate structures, and to movable or rigid attachments or relationships, unless otherwise explicitly stated.

[0067] As used throughout, any range disclosed herein is used to briefly describe each value within that range. Any value within a range may be chosen as an endpoint of that range. Furthermore, all references cited herein are incorporated herein by reference in their entirety. In the event of any conflict between definitions in this disclosure and definitions in the cited references, this disclosure shall prevail.

[0068] This disclosure generally relates to systems, apparatus, and methods for calibrating agricultural analytical systems. The inventors have found that certain systems and methods disclosed herein advantageously enable automated calibration of agricultural analytical systems, significantly faster than conventional standard sample addition methods. Furthermore, calibration methods provided in certain embodiments overcome calibration drift problems.

[0069] According to one aspect of this disclosure, a method 1000 is provided for using an instrument suitable for analyzing agricultural samples. (Reference) Figure 1 Method 1000 typically includes the step of continuously supplying a calibration stream to an instrument suitable for analyzing agricultural samples (see step 1100). Reference Figure 2 Method 2000 typically includes continuously providing (e.g., delivering) a calibration stream to an instrument suitable for analyzing agricultural samples, the calibration stream having components that change over a period of time (see step 2100); evaluating the components of the calibration stream over at least a portion of the time period, wherein at the beginning of the evaluated time period, the components of the calibration stream do not contain a standard sample and include the agricultural sample and a diluent, and wherein at the end of the evaluated time period, the components of the calibration stream include the agricultural sample, the standard sample, and optionally a diluent (see step 2200); and determining the detected changes in the components of the calibration stream. The rate of change of the component is determined (see step 2300); it is determined when the detected rate of change of the component is substantially constant (see step 2400); optionally, when the rate of change of the component is substantially constant or constant, the value of the detected rate of change of the component is determined (see step 2500); when the calibration stream does not contain the standard sample, the detected background value is determined based on the evaluation of the calibration stream (see step 2600); and the instrument is calibrated using the detected background value and the value of the detected rate of change of the component when the rate of change of the component is substantially constant or constant (see step 2700).

[0070] In steps 1100 and / or 2100, a calibration stream is continuously provided (e.g., delivered) to an instrument suitable for analyzing agricultural samples. The calibration stream has components that change over a period of time. For example, one or more components of the calibration stream may increase and / or one or more components of the calibration stream may decrease during said time period, thus causing the composition of the calibration stream to change over said time period.

[0071] The time period can be the time during which the calibration stream is provided to an instrument suitable for analyzing agricultural samples. In any and / or all embodiments described herein, the time period can be the time period being evaluated (e.g., the time period during which the calibration stream is analyzed to calibrate an instrument suitable for analyzing agricultural samples). Figure 2 As seen in the previous section, in some embodiments, the method may include evaluating the components of the calibration stream within at least a portion of the time period (see step 2100).

[0072] The time period and / or the time period being evaluated can be approximately 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 4 minutes, 6 minutes, 8 minutes, 10 minutes, or any range thereof. For example, the time period and / or the time period being evaluated can be from approximately 10 seconds to approximately 10 minutes, approximately 10 seconds to approximately 8 minutes, approximately 10 seconds to approximately 6 minutes, approximately 10 seconds to approximately 4 minutes, approximately 10 seconds to approximately 2 minutes, approximately 10 seconds to approximately 1 minute, approximately 10 seconds to approximately 40 seconds, approximately 10 seconds to approximately 30 seconds, approximately 10 seconds to approximately 20 seconds; from approximately 20 seconds to approximately 10 minutes, approximately 20 seconds to approximately 8 minutes, approximately 20 seconds to approximately 6 minutes, approximately 20 seconds to approximately 4 minutes, approximately 20 seconds to approximately 2 minutes, approximately 20 seconds to approximately 1 minute, approximately 20 seconds to approximately 40 seconds, approximately 20 seconds to approximately 30 seconds; from approximately 30 seconds to approximately 10 minutes, approximately 30 seconds to approximately 8 minutes, approximately 30 seconds to approximately 6 minutes, approximately 30 seconds to approximately 4 minutes, approximately 30 seconds to approximately 4 minutes, approximately 30 seconds to approximately 4 minutes, approximately 30 seconds to approximately 4 minutes, approximately 30 seconds to approximately 30 seconds ... Minutes, from about 30 seconds to about 2 minutes, from about 30 seconds to about 1 minute, from about 30 seconds to about 45 seconds; from about 45 seconds to about 10 minutes, from about 45 seconds to about 8 minutes, from about 45 seconds to about 6 minutes, from about 45 seconds to about 4 minutes, from about 45 seconds to about 2 minutes, from about 45 seconds to about 75 seconds; from about 1 to about 10 minutes, from about 1 to about 8 minutes, from about 1 to about 6 minutes, from about 1 to about 4 minutes, from about 1 to about 2 minutes; from about 2 to about 10 minutes, from about 2 to about 8 minutes, from about 2 to about 6 minutes, from about 2 to about 4 minutes; from about 4 to about 10 minutes, from about 4 to about 8 minutes, from about 4 to about 6 minutes; from about 6 to about 10 minutes, from about 6 to about 8 minutes, from about 8 to about 10 minutes, or any range or subrange thereof.

[0073] At the start of the time period, the calibration stream may include an agricultural sample and a diluent. In some embodiments, the calibration stream may include a standard sample at the start of the time period, for example, in conjunction with the agricultural sample and the diluent. For example, the calibration stream may comprise about 10 to about 60% by volume of agricultural sample relative to the volume of the provided calibration stream. In some embodiments, at the beginning of the time period, the amount of agricultural sample in the calibration stream relative to the volume of the provided calibration stream is approximately 10 to 60 volume%, approximately 10 to 55 volume%, approximately 10 to 50 volume%, approximately 10 to 45 volume%, approximately 10 to 40 volume%, approximately 10 to 35 volume%, approximately 10 to 30 volume%, approximately 10 to 25 volume%, approximately 10 to 20 volume%, approximately 10 to 15 volume%; approximately 10 to 60 volume%, approximately 10 to 55 volume%, approximately 10 to 50 volume%, approximately 10 to 45 volume%, approximately 10 to 40 volume%, approximately 10 to 35 volume%, approximately 10 to 30 volume%, approximately 10 to 25 volume%, approximately 10 to 20 volume%, approximately 10 to 15 volume%; from approximately 15 to 60 volume%, approximately 15 to 55 volume%, approximately 15 to 50 volume%, approximately 15 to 45 volume%, approximately 15 to 40 volume%, approximately 15 to 35 volume%, approximately... 15 to about 30% by volume, about 15 to about 25% by volume, about 15 to about 20% by volume; from about 20 to about 60% by volume, about 20 to about 55% by volume, about 20 to about 50% by volume, about 20 to about 45% by volume, about 20 to about 40% by volume, about 20 to about 35% by volume, about 20 to about 30% by volume, about 20 to about 25% by volume; from about 25 to about 60% by volume, about 25 to about 55% by volume, about 25 to about 50% by volume, about 25 to about 45% by volume, about 25 to about 40% by volume, about 25 to about 35% by volume, about 25 to about 30% by volume; from about 30 to about 60% by volume, about 30 to about 55% by volume, about 30 to about 50% by volume, about 30 to about 45% by volume, about 30 to about 40% by volume, about 30 to about 35% by volume; from about 40 to about 60% by volume, about 40 to about 55% by volume, about 40 to about 50% by volume; about 50 to about 60% by volume, about 50 to about 55% by volume, or any range or subrange thereof.

[0074] The composition of the calibration stream may include a diluent of about 10 to about 90% by volume, relative to the volume of the provided calibration stream. In some embodiments, at the beginning of the time period, the amount of diluent in the calibration stream relative to the volume of the provided calibration stream is from about 10 to about 90% by volume, about 10 to about 85% by volume, about 10 to about 80% by volume, about 10 to about 75% by volume, about 10 to about 70% by volume, about 10 to about 65% by volume, about 10 to about 55% by volume, about 10 to about 45% by volume, about 10 to about 35% by volume, about 10 to about 25% by volume; from about 25 to about 90% by volume, about 25 to about 85% by volume, about 25 to about 80% by volume, about 25 to about 75% by volume, about 25 to about 70% by volume, about 25 to about 65% by volume, about 25 to about 55% by volume, about 25 to about 45% by volume, about 25 to about 35% by volume; from about 40 to about 90% by volume, about 40 to about 85% by volume, about 40 to 80% by volume, about 40 to 75% by volume, about 40 to 70% by volume, about 40 to 65% by volume, about 40 to 55% by volume; from about 55 to 90% by volume, about 55 to 85% by volume, about 55 to 80% by volume, about 55 to 75% by volume, about 55 to 70% by volume, about 55 to 65% by volume; from about 65 to 90% by volume, about 65 to 85% by volume, about 65 to 80% by volume, about 65 to 75% by volume; from about 70 to 90% by volume, about 70 to 85% by volume, about 70 to 75% by volume; from about 75 to 90% by volume, about 75 to 85% by volume, about 75 to 80% by volume; from about 80 to 90% by volume, about 80 to 85% by volume, about 85 to 90% by volume.

[0075] Although the calibration stream may or may not contain a standard sample at the start of the time period, it may include from about 1% to about 90% by volume of the standard sample relative to the volume of the provided calibration stream. For example, at the start of the time period, the amount of standard sample present in the calibration stream relative to the volume of the provided calibration stream may be from about 0% to about 90% by volume, about 0% to about 70% by volume, about 0% to about 50% by volume, about 0% to about 30% by volume, about 0% to about 20% by volume, about 0% to about 10% by volume, about 0% to about 5% by volume, about 0% to about 1% by volume; from about 1% to about 70% by volume, about 1% to about 50% by volume, about 1% to about 30% by volume, about 1% to about 20% by volume, about 1% to about 10% by volume, about 1% to about 5% by volume, about 0.1% to about 1% by volume; from about 5% to about 90% by volume, about 5% to about 1% by volume. About 50% by volume, about 5% to about 30% by volume, about 5% to about 20% by volume, about 5% to about 10% by volume; from about 10% to about 90% by volume, about 10% to about 70% by volume, about 10% to about 50% by volume, about 10% to about 40% by volume, about 10% to about 30% by volume; from about 30% to about 90% by volume, about 30% to about 70% by volume, about 30% to about 50% by volume, about 30% to about 40% by volume; from about 50% to about 90% by volume, about 50% to about 80% by volume, about 50% to about 70% by volume; from about 70% to about 90% by volume, about 70% to about 80% by volume, or about 80% to about 90% by volume.

[0076] In some embodiments, at the start of the time period (e.g., the time period being evaluated), the calibration stream comprises: approximately 0 to approximately 90% by volume of a standard sample relative to the volume of the provided calibration stream; approximately 10 to approximately 90% by volume of a diluent relative to the volume of the provided calibration stream; and approximately 10 to approximately 60% by volume of an agricultural sample relative to the volume of the provided calibration stream.

[0077] The method may include determining the average measurement of constant values ​​of agricultural samples (or their analytes) in the calibration stream at the beginning of the time period and / or before changes in the composition of the calibration stream.

[0078] The method typically involves varying the calibration stream as it is supplied to an instrument suitable for analyzing agricultural samples. The composition of the calibration stream can be varied by increasing or decreasing the amount of agricultural sample, diluent, and / or standard sample in the calibration stream. In at least one embodiment, the amount of diluent in the calibration stream is reduced during the time period as the calibration stream is supplied to the instrument suitable for analyzing agricultural samples. Additionally or alternatively, the amount of standard sample in the calibration stream may be increased during the time period as the calibration stream is supplied to the instrument suitable for analyzing agricultural samples.

[0079] Preferably, the composition of the calibration stream varies continuously over the period of evaluation. However, in some embodiments, the composition of the calibration stream varies in a stepwise manner over the period of evaluation. The composition of the calibration stream may vary continuously at a constant rate of change over the period of evaluation. For example, an increase or decrease in the amount of agricultural sample, diluent, and / or standard sample in the calibration stream may vary continuously at a constant rate of change over the period of evaluation. In some embodiments, the amount of standard sample in the calibration stream increases continuously at a constant rate of change over the period of evaluation. Additionally or alternatively, in some embodiments, the amount of diluent in the calibration stream decreases continuously at a constant rate of change over the period of evaluation.

[0080] In some embodiments, the amount of agricultural sample in the calibration stream remains substantially constant or constant during the time period. For example, the variation in the amount of agricultural sample in the calibration stream during the time period can be about 10% or less, about 8% or less, about 6% or less, about 5% or less, about 4% or less, about 3% or less, about 2% or less, about 1% or less, or about 0.5% or less. In at least one preferred embodiment, the time period is the time period being evaluated. As mentioned above, the time period can be about 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 4 minutes, 6 minutes, 8 minutes, 10 minutes, or any range thereof.

[0081] At the end of the time period (e.g., the time period being evaluated), the composition of the calibration stream may include agricultural samples, standard samples, and optional diluents. For example, at the end of the time period, the composition of the calibration stream may include approximately 50 to approximately 90% by volume of standard samples relative to the volume of the provided calibration stream. In some cases, at the end of the time period, the amount of standard samples present in the calibration stream relative to the volume of the provided calibration stream is from approximately 50 to approximately 90% by volume, approximately 50 to approximately 85% by volume, approximately 50 to approximately 80% by volume, approximately 50 to approximately 75% by volume, approximately 50 to approximately 70% by volume, and approximately 50 to approximately 65% ​​by volume; from approximately 55 to approximately 90% by volume, approximately 55 to approximately 85% by volume, approximately 55 to approximately 80% by volume, approximately 55 to approximately 75% by volume, approximately 55 to approximately 70% by volume, and approximately 55 to approximately 65% ​​by volume; from approximately 60 to approximately 90% by volume, and approximately 60 to approximately 85% by volume, about 60 to about 80% by volume, about 60 to about 75% by volume; from about 65 to about 90% by volume, about 65 to about 85% by volume, about 65 to about 80% by volume, about 65 to about 75% by volume; from about 70 to about 90% by volume, about 70 to about 85% by volume, about 70 to about 80% by volume, about 70 to about 75% by volume; from about 75 to about 90% by volume, about 75 to about 85% by volume, about 75 to about 80% by volume; from about 80 to about 90% by volume, about 80 to about 85% by volume, about 85 to about 90% by volume, or any range or subrange thereof.

[0082] Additionally or alternatively, at the end of the time period, the calibration stream may include 0 to 50% by volume of diluent relative to the volume of the provided calibration stream. At the end of the time period, the calibration stream may be substantially free of or contain no diluent. In some cases, at the end of the time period, the amount of diluent present in the calibration stream relative to the volume of the provided calibration stream may be from 0 to 50% by volume, 0 to 40% by volume, 0 to 30% by volume, 0 to 20% by volume, 0 to 10% by volume, 0 to 8% by volume, 0 to 6% by volume, 0 to 4% by volume, 0 to 2% by volume, 0 to 1% by volume, 0 to 0.5% by volume, and 0 to 0.1% by volume; from about 1 to 50% by volume, about 1 to 40% by volume, about 1 to 30% by volume, about 1 to 20% by volume, about 1 to 10% by volume, about 1 to 8% by volume, about 1 to 6% by volume, about 1 to 4% by volume, and about 1 to 2% by volume; from about 3% by volume to 50% by volume. About 3 to about 40% by volume, about 3 to about 30% by volume, about 3 to about 20% by volume, about 3 to about 10% by volume, about 3 to about 8% by volume, about 3 to about 6% by volume, about 3 to about 4% by volume; from about 6 to about 50% by volume, about 6 to about 40% by volume, about 6 to about 30% by volume, about 6 to about 20% by volume, about 6 to about 10% by volume, about 6 to about 8% by volume; from about 10 to about 50% by volume, about 10 to about 40% by volume, about 10 to about 30% by volume, about 10 to about 20% by volume; from about 20 to about 50% by volume, about 20 to about 40% by volume, about 20 to about 30% by volume; from about 30 to about 50% by volume, about 30 to about 40% by volume, about 40 to about 50% by volume, or any range or subrange thereof.

[0083] At the end of the time period, relative to the volume of the provided calibration stream, the amount of agricultural sample in the calibration stream may be approximately 10 to 60 volume%, approximately 10 to 55 volume%, approximately 10 to 50 volume%, approximately 10 to 45 volume%, approximately 10 to 40 volume%, approximately 10 to 35 volume%, approximately 10 to 30 volume%, approximately 10 to 25 volume%, approximately 10 to 20 volume%, approximately 10 to 15 volume%, approximately 10 to 60 volume%, approximately 10 to 55 volume%, approximately 10 to 50 volume%, approximately 10 to 45 volume%, approximately 10 to 40 volume%, approximately 10 to 35 volume%, approximately 10 to 30 volume%, approximately 10 to 25 volume%, approximately 10 to 20 volume%, approximately 10 to 15 volume; approximately 15 to 60 volume%, approximately 15 to 55 volume%, approximately 15 to 50 volume%, approximately 15 to 45 volume%, approximately 15 to 40 volume%, approximately 15 to 35 volume%, approximately 15 to 35 volume%, approximately 15 From about 30% by volume, about 15% to about 25% by volume, about 15% to about 20% by volume; about 20% to about 60% by volume, about 20% to about 55% by volume, about 20% to about 50% by volume, about 20% to about 45% by volume, about 20% to about 40% by volume, about 20% to about 35% by volume, about 20% to about 30% by volume, about 20% to about 25% by volume; about 25% to about 60% by volume, about 25% to about 55% by volume, about 25% to about 50% by volume, about 25% to about 45% by volume, about 25% to about 40% by volume, about 25% to about 35% by volume, about 25% to about 30% by volume; about 30% to about 60% by volume, about 40% to about 55% by volume, about 40% to about 50% by volume; about 50% to about 60% by volume, about 50% to about 55% by volume, or any range or subrange thereof.

[0084] In some embodiments, at the end of the time period (e.g., the time period being evaluated), the calibration stream comprises: approximately 50 to 90 vol% of a standard sample relative to the volume of the provided calibration stream; 0 to 50 vol% of a diluent relative to the volume of the provided calibration stream; and approximately 10 to 60 vol% of an agricultural sample relative to the volume of the provided calibration stream. In at least one embodiment, at the end of the time period (e.g., the time period being evaluated), the calibration stream comprises or substantially comprises: approximately 50 to 90 vol% of a standard sample relative to the volume of the provided calibration stream; and approximately 10 to 60 vol% of an agricultural sample relative to the volume of the provided calibration stream.

[0085] During the time period, the flow rate of the calibration stream can be substantially constant or constant. In at least one preferred embodiment, the flow rate of the calibration stream provided to an instrument suitable for analyzing agricultural samples is substantially constant or constant during the time period being evaluated. The flow rate can be substantially constant if the variation in the flow rate of a component within a time period (e.g., at least 1 second) does not exceed ±10%. For example, if the flow rate of a component varies by about 10% or less, about 8% or less, about 6% or less, about 4% or less, about 20% or more, about 30% or more, about 40% or more, about 50% or more, about 60% or more, about 75% or more, about 90% or more, about 105% or more, or about 120 seconds or more over a period of at least 1 second (e.g., about 2 seconds or more, about 5 seconds or more, about 10 seconds or more, about 75 seconds or more, about 90 seconds or more, about 105 seconds or more, or about 120 seconds or more), then the flow rate can be determined to be substantially constant. In some embodiments, the time period used to assess whether the flow rate is substantially constant or constant is about 1 to about 60 seconds, about 1 to about 30 seconds, about 1 to about 20 seconds, about 1 to about 10 seconds, about 1 to about 8 seconds, about 1 to about 6 seconds, about 1 to about 5 seconds, about 1 to about 4 seconds, about 1 to about 3 seconds, about 1 to about 2 seconds; about 2 to about 60 seconds, about 2 to about 30 seconds, about 2 to about 20 seconds, about 2 to about 10 seconds, about 2 to about 8 seconds, about 2 to about 6 seconds, about 2 to about 5 seconds, about 2 to about 4 seconds, about 2 to about 3 seconds; about 3 to about 60 seconds, about 3 to about 30 seconds, about 3 to about 20 seconds, about 3 to about 10 seconds, about 3 to about 8 seconds, about 3 to about 6 seconds, about 3 to about 5 seconds, about 3 to about 4 seconds; about 5 to about 60 seconds, about 5 to about 30 seconds, about 5 to about 20 seconds, about 5 to about 10 seconds, about 5 to about 8 seconds, about 5 to about 6 seconds, or any range or subrange thereof.

[0086] Agricultural samples may contain or be composed of substances with agricultural properties, including, but not limited to, soil, vegetation, crop residues, manure, milk, or any other agricultural-related sample material. In some embodiments, before the agricultural sample is provided to an instrument suitable for analyzing agricultural samples, its size may be reduced by grinding or other means, and then optionally mixed with a carrier (e.g., water) to produce a sample slurry.

[0087] Agricultural samples may be soil samples. Soil samples may be soil slurries and / or filtrates of soil slurries. Soil slurries can be obtained by mixing and / or combining soil and water. For example, soil samples may be sieved and mixed with water at a weight-to-volume ratio of 1:3 to produce soil slurries. Soil slurries may be filtered to obtain filtrates of the soil slurries. In some cases, soil samples, soil slurries, and / or filtrates may contain at least one soil particle, extractant, flocculant, and / or carrier. Agricultural samples may include one or more analytes. In some cases, the one or more analytes may be analytes obtained from soil samples or their soil particles, such as nutrients contained in the soil sample. The one or more analytes may be selected from potassium, magnesium, calcium, sodium, cation exchange capacity, zinc, manganese, iron, copper, boron, soluble salts, aluminum, molybdenum, and combinations of two or more of the above. Agricultural samples may be soil samples and include at least one soil particle and one or more analytes selected from potassium, magnesium, calcium, phosphorus, boron, nitrogen, sulfur, their salts, their ions, or combinations of two or more of them.

[0088] In some cases, agricultural samples may include a carrier and at least one soil particle. The at least one soil particle and the carrier may be present in a weight ratio of about 5:1 to about 2:1 (e.g., about 4:1 to about 2:1, about 3:1 to about 2:1, about 5:1 to about 3:1, about 4:1 to about 3:1, or any range thereof). In at least one embodiment, the weight ratio of at least one soil particle to carrier in the agricultural sample is about 3:1.

[0089] Agricultural samples can be plant and / or vegetation samples. The method can identify, determine, and / or evaluate one or more analytes in plant and / or vegetation samples, wherein the one or more analytes are selected from phosphorus, potassium, magnesium, calcium, sodium, cation base saturation, sulfur, zinc, manganese, iron, copper, boron, cobalt, molybdenum, selenium, and combinations of two or more of these.

[0090] In some cases, agricultural samples may be manure samples comprising one or more analytes. The method can identify, determine, and / or evaluate one or more analytes in plant and / or vegetation samples, wherein the one or more analytes are selected from calcium, magnesium, sodium, iron, manganese, copper, zinc, soluble salts, potassium bases, calcium, cobalt, copper, iron, manganese, arsenic, lead, selenium, cadmium, chromium, mercury, nickel, sodium, molybdenum, zinc, and combinations of two or more of these.

[0091] In some embodiments, agricultural samples may be selected from animal feed. The method can identify, determine, and / or evaluate one or more analytes in animal feed, said analytes being selected from arsenic, lead, cadmium, antimony, mercury, calcium, magnesium, sodium, manganese, zinc, potassium, iron, copper (not applicable to premixes), their ions, their salts, and combinations of two or more of them. Analytes in agricultural soil samples may be salts, such as sodium, calcium, magnesium, potassium, their salts, their compounds, their ions, or combinations thereof. In some embodiments, the analytes used for analysis may be, for example, NaCl, NaNO3, CaCl2, Ca(NO3)2, MgCl2, Mg(NO3)2, KCl, KNO3, or combinations thereof.

[0092] Agricultural samples may be selected from forage samples. The method can identify, determine, and / or evaluate one or more analytes in the forage samples, said analytes being selected from copper, sodium, magnesium, potassium, zinc, iron, calcium, manganese, sodium, molybdenum, selenium, and combinations of two or more of these.

[0093] Diluents may include water and acids and / or their salts, such as nitric acid and / or its salts, or hydrochloric acid and / or its salts. For example, the diluent may comprise nitric acid, hydrochloric acid, salts thereof, or combinations thereof, with molar concentrations of about 0.05 to about 0.8 M, about 0.05 to about 0.6 M, about 0.05 to about 0.5 M, about 0.05 to about 0.4 M, about 0.05 to about 0.3 M, about 0.05 to about 0.2 M; about 0.1 to about 0.8 M, about 0.1 to about 0.6 M, about 0.1 to about 0.5 M, about 0.1 to about 0.4 M, about 0.1 to about 0.3 M, about 0.1 to about 0.2 M; about 0.2 to about 0.8 M, about 0.2 to about 0.6 M, about 0.2 to about 0.5 M, about 0.2 to about 0.4 M, about 0.2 to about 0.3 M; about 0.3 to about 0.8 M, about 0.3 to about 0.6 M, about 0.3 to about 0.5 M, about 0.3 to about 0.4 M; about 0.4 to about 0.8 M. M, about 0.4 to about 0.6 M, about 0.4 to about 0.5 M; about 0.5 to about 0.8 M, about 0.5 to about 0.7 M, about 0.5 to about 0.7 M, or any range or subrange thereof. In some embodiments, the diluent includes about 0.1 M nitric acid, about 0.2 M nitric acid, about 0.27 M nitric acid, about 0.1 M hydrochloric acid, about 0.2 M hydrochloric acid, about 0.27 M hydrochloric acid, about 0.5 M nitric acid, and / or about 0.5 M hydrochloric acid. The diluent may be a solvent used for standard samples.

[0094] Standard samples may include metals to serve as standards for evaluating analytes in agricultural samples. Metals used as standards may be selected from potassium, sodium, magnesium, calcium, copper, iron, manganese, lithium, rhodium, thallium, indium, their ions, their salts, and combinations of two or more thereof. In some cases, metals used as standards may be selected from potassium, sodium, magnesium, calcium, copper, iron, manganese, their ions, their salts, and combinations of two or more thereof. Additionally or alternatively, metals used as standards may be selected from lithium, rhodium, thallium, indium, their ions, their salts, and combinations of two or more thereof. In at least one embodiment, the metal used as a standard is lithium, its ions, and / or its salts.

[0095] The method may include evaluating the components of the calibration stream within at least a portion of the time period (see [link]). Figure 2 Step 2200). Evaluation of the calibration flow may include determining the detected rate of change of the components of the calibration flow (see step 2200). Figure 2 (Step 2300). The detected rate of change of a component can be determined based on the rate of change of one or more analytes in a standard sample. For example, an instrument suitable for analyzing agricultural samples can determine the rate of change of analytes (multiple analytes) in a standard sample over a period of time (e.g., as the standard sample increases over such a period of time). In some embodiments, an instrument suitable for analyzing agricultural samples can determine the amount of analytes in a calibration stream by converting a portion of the calibration stream into plasma and using an imaging device to identify the amount of certain analytes in the plasma formed by the calibration stream. For example, the analytes in the standard sample can be selected from potassium, sodium, magnesium, calcium, copper, iron, manganese, lithium, rhodium, thallium, indium, their ions, their salts, and combinations of two or more of them. In some embodiments, the analytes in the standard sample can be selected from potassium, sodium, magnesium, calcium, copper, iron, manganese, their ions, their salts, and combinations of two or more of them. In further embodiments, the analytes in the standard sample can be selected from lithium, rhodium, thallium, indium, their ions, their salts, and combinations of two or more of them.

[0096] In some embodiments, evaluating the calibration flow includes determining when the detected rate of change of a component is substantially constant (see [reference]). Figure 2(Step 2400). In some embodiments, the rate of change of a component can be determined to be substantially constant when the detected rate of change of the standard sample, the detected rate of change of the diluent, the detected rate of change of one or more of its analytes, or the detected rate of change of a combination of two or more of them is substantially constant. In some embodiments, the method includes determining when the detected rate of change of the standard sample or its analytes is substantially constant or constant. Additionally or alternatively, the method may include determining when the detected rate of change of the agricultural sample or its analytes is substantially constant or constant.

[0097] If the detected rate of change of the component does not exceed ±10% over a time period of at least 1 second, then the detected rate of change of the component, diluent, and / or standard sample can be considered substantially constant. For example, if the detected rate of change of the component is about 10% or less, about 8% or less, about 6% or less, about 4% or less, about 25% or more, about 20% or more, about 30% or more, about 40% or more, about 50% or more, about 60% or more, about 75% or more, about 90% or more, about 105% or more, or about 120% or more over a time period of at least 1 second (e.g., about 2 seconds or more, about 5 seconds or more, about 10 seconds or more, about 105 seconds or more, or about 120 seconds or more), then the detected rate of change can be determined to be substantially constant. In some embodiments, evaluating the calibration flow includes determining when the detected rate of change of a component is constant for at least 1 second (e.g., about 2 or more seconds, about 5 or more seconds, about 10 or more seconds, about 15 or more seconds, about 20 or more seconds, about 30 or more seconds, about 40 or more seconds, about 50 or more seconds, about 60 or more seconds, about 75 or more seconds, about 90 or more seconds, about 105 or more seconds, or about 120 or more seconds).

[0098] When the rate of change of a component is substantially constant or constant, the value of the detected rate of change of the component can be determined. For example, a method for calibrating an instrument suitable for analyzing agricultural samples may include evaluating a calibration flow, which involves determining the value of the detected rate of change of a component when the rate of change of the component is substantially constant or constant (e.g., assessment based on the rate of change of one or more analytes in the agricultural sample in the calibration flow) (see See [link to calibration flow]). Figure 2 (Step 2500). As discussed above, the rate of change of the components can be determined.

[0099] When the detected rate of change of the components of the calibration stream is determined to be constant or substantially constant, the method can determine the rate of change of concentration and / or detector of one or more analytes (such as those disclosed herein) in an agricultural sample at one or more time points. The method may also include determining the detected background value based on an evaluation of the calibration stream when the calibration stream does not contain a standard sample (see [link to relevant documentation]). Figure 2 Step 2600). Background values ​​can be detected by determining and / or assessing the amount of one or more analytes in the calibration stream. For example, an instrument suitable for analyzing agricultural samples can ionize a portion of the calibration stream (which preferably does not contain a standard sample) to form a plasma from that portion, use an imaging device to determine the amount of certain analytes (multiple analytes) in the plasma, and detect the background value of the calibration stream based on the determined analytes.

[0100] The instrument suitable for analyzing agricultural samples can be calibrated using the detected background value and the detected rate of change of the component (see step 2700). For example, the method may further include calibrating the instrument using the detected background value and the detected rate of change of the component when the rate of change of the component is substantially constant or constant. Advantageously, the method can calibrate the instrument suitable for analyzing agricultural samples and analyze the agricultural samples in a single run (e.g., without stopping the continuous supply of calibration stream to the instrument suitable for analyzing agricultural samples).

[0101] According to another aspect of this disclosure, a system is provided that can calibrate instruments suitable for analyzing agricultural samples. Figures 1-49 This document illustrates various aspects and features of one embodiment of an agricultural sample analysis apparatus 100 of the sample processing and analysis system disclosed herein. The apparatus receives a sample fluid for analysis, which may be, but is not limited to, a prepared sample slurry. In one non-limiting embodiment, the sample slurry comprises a mixture of agricultural solids and water. In one embodiment, the apparatus may be configured and operated to add an extractant to the sample fluid to precipitate agriculturally relevant analytes (e.g., plant-available nutrients, etc.), mix the extractant and sample fluid, and then analyze the sample fluid-extractant mixture in a single self-supporting unit via inductively coupled plasma glow discharge spectroscopy.

[0102] The sample fluid can be any fluid originating from an agricultural-related source (examples of which are described elsewhere in this document) and containing agricultural-related analytes and the quantifier to be measured. Examples of sample fluids discussed herein can refer to sample slurries formed from a mixture of water and agricultural solid samples, such as soil. However, the systems and apparatus described herein are not limited to use with slurries, which represent only one type of sample fluid that can be processed and analyzed.

[0103] In one embodiment, the sample analysis apparatus 100 typically includes a spectrometer 300, a plasma torch 200, and a fluid handling system comprising a fluidly interconnected flow network 101 formed by a plurality of flow channels 102 that fluidly connect pumps and valves for controlling and guiding the flow of sample fluids (e.g., slurries or others), calibration standard samples (liquid solutions for calibrating the spectrometer), water for cleaning the pump chamber between sample fluid analysis cycles, and diluents.

[0104] In one embodiment, a set of diaphragm-operated mixing pumps may be provided, including a diluent pump M1, a standard sample pump M2, a mixing pump M3, and a sample pump M4. These pumps and associated valves are fluidly connected to... Figure 3 The flow network 101 shown herein is further described.

[0105] Diluent pump M1 is operable to pump a diluent (e.g., nitric acid or others) to plasma torch 200 for use in measuring analytes in sample fluids (e.g., slurries). Standard sample pump M2 is operable to pump a standard sample solution containing a known concentration of the relevant analyte to plasma torch 200 for calibrating the spectrometer. Mixing pump M3 is operable to perform reciprocating fluid exchange with sample pump M4 for mixing sample slurries with extractant and additional water (if desired), as further described herein. Sample pump M4 is operable to pump an agricultural sample slurry mixture (containing extractant and any additional diluent water) to plasma torch 200. Sample slurries may pass through a filter upstream of sample pump M4 (which in turn is upstream of the plasma torch) according to any filter disclosed in the commonly owned patent applications cited herein for slurry size sorting.

[0106] In one embodiment, each of the included diaphragm pumps M1-M4 can be a pilot fluid-actuated diaphragm pump operable to pump a desired fluid, such as agricultural sample slurry, water, standard sample (standard solution), diluent, or another fluid. Each pump includes a pump body 110. In one embodiment, as shown, the pump body can have an integral structure and be formed of a suitable material, which in some embodiments can be metal or plastic. These pumps can be structurally similar or identical, differing only in the purpose and location of the fluid inlet and outlet of each pump. The pump body includes a top 105, a bottom 106, and a plurality of intersecting side surfaces 107 extending between the top and bottom along the pump axis PA. In one embodiment, the pump body 110 can be formed from a solid block of material, such as a suitable metal or preferably plastic. Various internal structures of the pump body described herein can be integrally formed in the pump body as negative features (i.e., openings) by suitable manufacturing and processing methods (e.g., but not limited to casting, molding, 3D printing, drilling, etc., depending on the type of material chosen).

[0107] Pumps M1-M4 each include a recessed pumping chamber 112 formed on an outer surface 107 of the pump body, which is designated herein as the action outer surface 107a, and is associated with the actual diaphragm-acting pumping mechanism of the pump (see, for example, [link to relevant documentation]). Figure 25(Exploded view of the pump). The pumping chamber 112 includes an outwardly open concave surface formed in the working outer surface 107a. An elastically deformable diaphragm 111, formed of a suitable elastomeric or rubber material, is disposed at and covers the pumping chamber 112, and fluidly seals the chamber on its inward-facing side, which is the pilot side. The opposite outward-facing side of the diaphragm 111 constitutes the working side, which comes into direct wet contact with the process fluid (e.g., slurry, standard solution, diluent, water, etc., depending on the pump involved). In one embodiment, the diaphragm 111 may be generally disc-shaped, with a circular or elliptical configuration. A plurality of anti-jamming grooves 113 may be recessed into the arcuately curved bottom wall 114 of the pumping chamber to prevent the diaphragm from adhering to and getting stuck on the surface when the diaphragm is actuated and deformed during the pumping chamber filling stroke. Any suitable configuration of the anti-jamming grooves 113 may be provided, comprising an array of cross grooves as shown in one embodiment. During testing, it was found that if a smooth surface is provided within the pumping chamber 112, the flexible diaphragm can sometimes easily get stuck on the concave curved surface. Unfortunately, this can impede fluid flow and pumping before the diaphragm is fully displaced / deformed, resulting in the incomplete discharge of the appropriate volume of liquid from the lower chamber. This leads to inconsistent fluid volumes pumped with each actuation, which can adversely affect proper sample fluid handling and analysis, as the volume of each pump chamber is carefully pre-set, and the timing of sample fluid discharge into the plasma torch is critical.

[0108] It is worth noting that the concave pumping chamber 112 defines the volumetric capacity allocated to each diaphragm pump during each pump stroke. When pumps M1-M4 are actuated, the flow rate of the pumped process fluid is allocated based on the volumetric capacity of the pumping chamber. In the case of mixed pumps, the allocated volume can infinitely vary up to the maximum volume in the chamber based on the amount of pilot fluid displaced during the pump stroke.

[0109] Each of the diaphragm-operated mixing pumps M1-M4 includes a pilot fluid operating mechanism operable to flow and displace the pilot fluid, which actuates the diaphragm 111 to draw process fluid into the pump and pump it out. In one embodiment, a positive displacement pump operable to pump the pilot fluid and actuate the diaphragm can be directly integrated into the pump body to provide the operating mechanism. This differs from the use of external pumps or external compressed air sources, which can increase the size of the equipment and system. Integrating the positive displacement pump directly into the pump body is both efficient and space-saving.

[0110] In one embodiment, the positive displacement pump can be an injection pump 115, and the pilot fluid can be a liquid fluid, such as oil or water; both of which are generally incompressible relative to air or other gases. In a preferred, but not limiting, embodiment, hydraulic oil can be used as the pilot fluid because the elastomeric or rubber material used to manufacture the pump diaphragm is not completely impermeable to gases (including air). Therefore, if air is used as the pilot fluid for actuating the diaphragm valve, some air may pass through the diaphragm from the pilot fluid side and form bubbles in the process fluid (e.g., slurry, standard solution, diluent, etc.) on the opposite process fluid side of the diaphragm. Due to the viscous properties of oil, it is unlikely to permeate the diaphragm, or at least the permeation is very small and will not interfere with the analysis of the slurry via spectrometer 300. Furthermore, unlike air, liquid fluids such as oil are relatively incompressible, which is preferred for the pilot fluid. However, it is worth noting that in some embodiments, although not preferred, air can still be used as the pilot fluid.

[0111] Each syringe pump 115 may include an elongated pump orifice 116 integrally formed in the pump body 110. The pump orifice contains a certain amount or volume of pilot fluid and is fluidly coupled to the pumping chamber 112 on the inward-facing pilot side of the diaphragm 111 via a transverse flow channel 122a. The syringe pump 115 further includes a pump piston 117 slidably disposed in the pump orifice 116 and coupled to an operating rod 118 of a linear actuator 119. In some embodiments shown, the actuator 119 may be electrically powered; however, in other embodiments, a pneumatic actuator may be used. Any suitable commercially available linear actuator may be used. In one embodiment, an electrically powered linear actuator 127 with a stepper motor may be used. The stepper motor may be externally disposed on the top or bottom of the pump body 110 and closed via a cover 120, which in one embodiment is coupled to the pump body by a threaded fastener 121 or by other coupling method.

[0112] Actuator 119 can be operated alternately to extend or retract the operating lever 118 and piston 117 in the pump orifice 116. Specifically, in one embodiment, the actuator can be operated to: move piston 117 in a first direction to allow pilot fluid to flow into the pumping chamber 112 of pumps M1-M4, causing diaphragm 111 to deform and move toward the process fluid side of the diaphragm to pump process fluid; and move piston in the opposite second direction to withdraw pilot fluid from the pumping chamber, causing diaphragm to move away from the process fluid side, thereby allowing process fluid to be drawn into the pumping chamber.

[0113] In one embodiment, the pilot fluid actuation system for diaphragm pumps M1-M4 may include a pressure relief device 128 comprising a spring-biased piston mechanism that is also directly integrated into the pump body 110 to save space. The pressure relief device 128 includes an elongated pressure relief orifice 122 formed directly into the pump body. In some embodiments, the pressure relief orifice 122 may be parallel to the pump orifice 116, and each pressure relief orifice may be cylindrical. The pressure relief orifice is connected via a transverse flow channel 122a (e.g., see...). Figure 22 A pilot fluid is fluidly connected to the pump orifice so that overpressured pilot fluid can enter the pressure relief orifice from the system to prevent damage to the diaphragm pump's diaphragm. To provide this protection, a pressure relief piston 123 is slidably disposed in the pressure relief orifice and is acted upon by a pressure relief spring 124 within the orifice. The pilot fluid acts directly on the operating surface of the pressure relief piston 123, and the spring acts on the opposite side of the piston. A threaded cap 125 can be connected to the pump body 110 at the pressure relief orifice 122 to retain the spring within the pressure relief orifice. The pressure relief piston and spring assembly work together to act as a fluid damper to suppress pressure fluctuations in the pilot fluid system. During operation, overpressure in the pilot fluid causes the pressure relief piston 123 to move toward the pressure relief spring 124 and compress the spring 124 to absorb excess pressure. When the overpressure condition is relieved, the spring relaxes, allowing the pressure relief piston to move back to its normal operating position in the pressure relief orifice 122.

[0114] In each of the pumps M1-M4, the diaphragm and pumping chamber 112 are preferably vertically oriented, particularly for sample pump M4. Some air may enter the pumping system, which can adversely affect pumping performance and flow. By vertically oriented the pumping chamber and diaphragm, air bubbles will accumulate at the top of the pumping chamber, where they can be removed during commissioning or maintenance. Any air anywhere on the pilot fluid side will reduce the pump's overall displacement and cause compressibility issues in the system, which is highly undesirable. Specifically, to ensure the accuracy of spectral analysis of the sample fluid (e.g., a slurry in one embodiment) in the plasma torch apparatus 200, the sample fluid outlet port 151 of sample pump M4 (which is formed by the pump manifold block 134 described elsewhere herein) is preferably oriented as follows: Figures 27-28 The location shown is in the middle of the pumping chamber. This minimizes the possibility that any air bubbles that accumulate at the top of the pumping chamber will be pumped into the slurry discharge with each pumping stroke instead of remaining at the top of the pumping chamber.

[0115] like Figure 26As shown, pump orifice 116 and pressure relief orifice 122 may be vertically oriented and elongated, integrally formed with pump body 110. In other embodiments, lateral flow channel 122a may be horizontally oriented or oriented at an angle relative to a horizontal reference plane. Orifices 116 and 122 may be parallel to each other, or in some embodiments at an angle to each other or perpendicular to each other, as shown. Pump orifice and pressure relief orifice may include cylindrical walls that slidably engage pump piston 117 and pressure relief piston 123, respectively. Pump orifice 116 terminates at the end opposite actuator 119 with a reduced-diameter flow exchange orifice 116a, smaller in diameter than pump orifice. Similarly, pressure relief orifice 122 terminates at the end opposite spring 124 with a reduced-diameter flow exchange orifice 122b, smaller in diameter than pressure relief orifice. Orifice 122b may extend entirely through pump body 110 to define an externally accessible pilot fluid filling port for adding or removing pilot fluid. In this configuration, orifice 122b is sealed by a removable plug 126 attached to the pump body, which provides optional access to a reservoir of pilot fluid within the pump body (defined primarily by pump orifice 116, pressure relief orifice 122, and lateral flow channel 122a) for filling or extracting the pilot fluid. As shown, the orifices defined by orifices 116a and 122b are fluidly connected to the lateral flow channel 122a, which in turn is fluidly connected to the pumping chamber 112 associated with diaphragm 111.

[0116] In one embodiment, the pressure of the pilot fluid can be monitored by the controller 2820 via a pressure sensor 520, which is operable to measure the pressure of the pilot fluid (e.g., see...). Figure 20 This information can be used for a variety of purposes, including determining whether a blockage has occurred in the flow channels downstream of pumps M1-M4 and for flow diagnostics. Sensor 520 can be operatively coupled to any convenient and accessible portion of pilot fluid reservoir 521 (which is primarily defined by a lateral flow channel 122a holding the majority of the pilot fluid volume, a pump port 116, and a pressure relief port 122), providing a pressure measurement indicating the actual pilot fluid pressure. In one example shown, pressure sensor 520 can be operatively coupled to the pilot fluid via plug 126 that seals the pilot fluid fill port, which is defined by a reduced-diameter flow exchange port 122b associated with pressure relief port 122, as described elsewhere herein. Other connection points (including independent discrete paths to the pilot fluid) can be used to monitor pilot fluid pressure. Any commercially available pressure sensor configured to be operatively and communicatively linked to controller 2820 can be used.

[0117] As shown in one embodiment, pumps M1-M4 can be vertically oriented, wherein pump orifice 116 and pressure relief orifice 122 are vertically elongated orifices. In other embodiments, pumps can be oriented in other ways, including horizontally, wherein orifices 116 and 122 are horizontally elongated orifices. In some embodiments, pumps can also be in an inclined orientation that is neither horizontal nor vertical. Not all pumps need to be in the same orientation, but in some embodiments shown in the figures, they can be in the same orientation.

[0118] Each diaphragm-operated mixing pump M1-M4 has an associated pump manifold block containing flow channels 102 that form part of a multi-branch flow network 101 configured to form Figure 3 The fluid interconnection of the flow path is shown. The manifold blocks control the flow of process fluid into and out of the mixing pump. In one embodiment, four pump manifold blocks may be provided, forming components of the pump assembly, including manifold block 131 corresponding to diluent pump M1, manifold block 132 corresponding to standard sample pump M2, manifold block 133 corresponding to mixing pump M3, and manifold block 134 corresponding to sample pump M4. Other embodiments may have more or fewer diaphragm pumps depending on the different types of process fluids to be used in the sample analysis system. In one embodiment shown, manifold blocks 131-134 and mixing manifold block 130 (further described herein) may have a cuboid shape, allowing them to form a planar-to-planar mating interface with the diaphragm pump for sealing the pumping chamber, as further described herein.

[0119] A portion of the flow passage 102 in each manifold block 131-134 forms at least one fluid inlet port 150 and at least one fluid outlet port 151, the fluid outlet port being in fluid communication with the pumping chamber 112 of pumps M1-M4 for fluid exchange. Some manifold blocks may have additional fluid ports. For illustrative purposes, as an example, Figure 27 and Figure 28A pump manifold block 134 for sample pump M4 is shown. The manifold block 134 may include three fluid ports defined by a flow channel 102 of the manifold block, including a sample fluid inlet port 150a, a bottom fluid port 152a, and a central sample fluid outlet port 151a located anywhere between ports 150a and 152a. Each port 150a, 151a, and 152a is in fluid communication with the pumping chamber 112 of pump M4. In one embodiment, with respect to the vertically oriented pumping chamber 112 as previously described herein, the sample fluid inlet port 150a may be a top port located in a first upper end region of the pumping chamber, the fluid port 152a may be a bottom port located in a second lower end region of the pumping chamber, and the sample fluid outlet port 151a may be located in a central region of the pumping chamber, defined as any location between ports 150a and 152a. In one embodiment, the sample fluid outlet port 151a may be located near the center of the pumping chamber 112, such as... Figure 28 As shown in the image.

[0120] The fluid ports of each manifold block (including) Figures 27-28 Ports 150a-152a of the sample pump manifold block 134 shown can extend completely through the manifold block 134 from one side to the other, and each port is fluidly coupled to a continuation of these ports, the continuation including a corresponding flow channel 102 formed in the mixing manifold block 130 (see, for example, see...). Figure 29 The flow channel mates with the port, which will be described further below. The continuation of ports 150a-152a is... Figure 29 The flow channels are numbered 150b-152b respectively. For the remaining pump manifold blocks 131-133, the structure of the fluid inlet port and fluid outlet port defined by the flow channel 102 in each of the corresponding pumps M1-M3 is similar to that described above.

[0121] Return to reference Figures 27-28 The sample fluid inlet port 150a is used to add agricultural sample slurry into the pumping chamber 112 of the sample pump M4. For example... Figure 3 As shown in the system flow diagram, the bottom fluid port 152a of the sample pump M4 can be used for various purposes. One use of port 152a after processing agricultural slurry for analysis is as follows: Figure 3The process flow diagram shows that rinsing water is introduced from the water source into the pumping chamber 112 of the sample pump (via opening valve V12) to remove residual slurry from the pumping chamber between sample cycles, thus avoiding contamination of the next batch of slurry to be treated. Since different batches of agricultural sample slurry may originate from different areas of the farmland and exhibit varying concentrations / content levels of nutrients available to plants, it is important to avoid cross-contamination to accurately determine the nutrient content levels in each area in order to develop soil remediation programs. By changing... Figure 3 The valve shown is located at the bottom fluid port of sample pump M4, which can be used to discharge flushing water to the waste end by opening valve V8.

[0122] In a second application, the bottom fluid port 152a can also be used to add the extractant from the extractant source to the slurry in the pumping chamber 112 of the sample pump M4 for mixing with the sample slurry to precipitate specific relevant analytes (i.e., plant-available nutrients). The sample fluid outlet port 151a is used to discharge the combined sample slurry and extractant mixture to the plasma torch device 200 for analysis via the spectrometer 300 after the plasma is ignited.

[0123] Actuation of the diaphragm 111 of each pump M1-M4 via the pilot fluid injection pump 115 deforms the diaphragm, allowing process fluid to be pumped out of the pumping chamber 112 by moving the diaphragm toward the process fluid side of the pumping chamber, or to fill the chamber with process fluid by moving the diaphragm back toward the pilot fluid side of the pumping chamber. Typically, during pump operation, the diaphragm can be deformed by actuating the injection pump 115, which moves the pump piston 117 in the opposite direction to push pilot fluid toward the diaphragm to pump process fluid, or to draw pilot fluid back into the pump orifice 116 to fill the pumping chamber of the mixing pump. For example, for the sample pump M4, the diaphragm is deformable to allow agricultural sample fluid to flow into the pumping chamber 112 through the sample fluid inlet port 150a, or to pump sample fluid out of the pumping chamber through the sample fluid outlet port 151a.

[0124] At least some of these manifold blocks 130-133 may also include one or more pneumatic diaphragm valves directly integrated into the manifold block and designated V1 to V10. The term "integrated" here refers to the manifold block body forming the valve seat, as further described herein. The diaphragm valves control the flow of different fluids through the manifold block to and from pumps M1-M4, and to the plasma torch 201, in various ways (see, for example, [link to relevant documentation]). Figure 3 ).

[0125] In some embodiments shown in the figure, the sample pump manifold block 134 may not include any directly integrated diaphragm valve. However, the manifold block 134 may include a pair of two-port electrically operated solenoid valves, which include... Figure 3 and Figure 27 The top water valve V11 and bottom water valve V12 are shown. These valves are physically connected externally to the manifold block and control the flow of water through the flow network shown to the sample pump M4 and mixing pump M3. Water valves V11 and V12 are fluidly connected to a pressurized water source (preferably a pressurized filtered water source) and are normally closed to ensure complete shut-off of water entering the flow network 101 system when not needed. This complete shut-off may not be possible with diaphragm valves, which are opened / closed by pressure applied to the diaphragm by the fluid flow generated from pumps M1-M4. Any suitable commercially available electric solenoid valve can be used, such as those available from SMC Corporation or other suppliers.

[0126] Figure 4 The diagram illustrates the relationship and layout between the plate-mounted diaphragm valve and its respective manifold blocks 131, 132, and 133. Figure 3 and Figure 4 The functions of valves V1-V10 are shown in the diagram. Specifically, the diaphragm valves include: V1 (diluent inlet valve) and V2 (diluent mixing valve) associated with manifold block 131; V3 (standard sample inlet valve) and V4 (standard sample mixing valve) associated with manifold block 132; V5 (sample inlet valve), V6 (sample outlet valve), V7 (extractant inlet valve), and V8 (waste outlet valve) associated with mixing manifold block 130; and V9 (mixing water valve) and V10 (transfer valve) associated with manifold block 133.

[0127] Each valve's elastically deformable diaphragm 144 can be housed in a recessed valve seat 135, which is formed on one or more outer surfaces of pump manifold blocks 131, 132, and 133. In one embodiment, the valve diaphragm 144 and the corresponding valve seat 135 can be circular. One or more operating air manifold blocks 138 may be provided, including an air duct connector 138a, which is fluidly connected to a pressurized operating air source 139 (e.g., see...). Figure 21 In one embodiment, air manifold 138 may be detachably coupled to mixing manifold 130-134 in various ways. Air manifold 138 includes an internal air passage 138b configured to fluidly connect valves V1-V10 to operating air for actuating the valves and moving them between open and closed positions. Operating air acts on one side of valve diaphragm 144, while process fluids (e.g., sample slurry, standard solution, diluent, water, etc.) act on the opposite side, the flow of which through flow network 101 is controlled by valves. These valves are capable of changing between a closed position that prevents flow through the valve and associated flow passages and an open position that allows fluid flow.

[0128] Figure 4 Valves V5-V8 are also shown, which are associated with and incorporated into the mixing manifold 130, the mixing manifold comprising forming Figure 3 Multiple fluid channels 102, which constitute a portion of the flow network 101 shown. Figure 29 As further shown herein, the mixing manifold block 130 includes a main flow channel 130a, which is in direct fluid communication with the plasma torch 201 extending into the plasma chamber 202 of the plasma torch apparatus 200, as further described herein. Figure 3 As shown, the main flow channel 130a is fluidly connected to pumps M1-M4 and flow channel 102. Specifically, the main flow channel 130a collects and receives fluids from diluent pump M1, standard sample pump M2, and sample pump M4, and transmits these fluids to the plasma torch. Since fluids from some of these pumps can be pumped simultaneously to the main flow channel 130a, in some embodiments, the main flow channel may have a larger diameter than the other flow channels in the mixing manifold block 130 to improve flow capacity. Due to this increased flow capacity, the manifold block 130 can be located directly below the plasma torch apparatus at the center of the device 100, allowing the main flow channel 130a to be easily connected to the cathode tube 203 of the plasma torch apparatus 200, as further described herein. The mixing manifold block with diaphragm valves V1-V10, described elsewhere herein, serves as the system's flow control device to receive, discharge, and direct various fluid flows into, through, and out of the flow network 101. Different fluid paths are constructed for different purposes of the system by opening or closing various combinations of valves.

[0129] refer to Figure 29 The upper portion of the main flow channel 130a defines a common mixing zone Z. Flow channels 102 in the mixing manifold block 130 that receive fluid flows from the diluent pump M1 and the standard sample pump M2 are fluidly connected to the main flow channel in this common mixing zone to mix these fluid flows with a sample slurry and extractant mixture from the sample pump M4. Preferably, the mixing zone Z is located at the plasma electrode gap 209 between the anode pin 205 and the cathode tube 203 (e.g., see...). Figure 38 The flow channel should be positioned no more than 3 inches from the sample slurry. This is an important consideration because a larger channel than usual must be used to accommodate solid particles in the sample slurry, thus increasing the volume of the flow channel and ultimately leading to an increase in the volume of sample that must be collected and transported to the system. The shorter length of the central channel 130a in the mixing zone Z allows for a reduction in the fluid volume in the flow channel to complete the spectral detection of the sample slurry.

[0130] In one embodiment, the mixing manifold block 130 can be directly butt-joined and adjacently engaged with pump manifold blocks 131, 132, and 134 to form a sealed flow channel between them at the mating interface. Therefore, the flow channels 102 in these pump manifold blocks are fluidly connected to corresponding flow channels in the mixing manifold block 130 (which serve as continuations of the flow channels in the pump manifold block) to produce… Figure 3 The flow network 101 is shown. The mating interface between the flow channels in the mixing manifold 130 and the pump manifolds 131, 132 and 134 may include an annular seal 137a, such as an O-ring, disposed in a corresponding circular seal groove 137b to form a fluid-impermeable connection therebetween (e.g., see...). Figure 22 and Figure 29 When the manifold blocks are joined and connected adjacent to each other, the seal 137a is compressed and expanded to form a fluid-impermeable liquid interconnect between the blocks.

[0131] Pump manifold blocks 131-134, together with pump body 110, form a complete and fluid-sealed pump assembly for pumps M1-M4. Therefore, each pump manifold block has a flat working outer surface 134a that abuts and engages with the associated working outer surface 107a of the pump body to close and seal the corresponding concave pumping cavity 112, wherein a diaphragm 111 is sandwiched between the two outer surfaces. To illustrate this, as a representative example, Figures 27-28 The pump manifold block 134 associated with the pump assembly of the sample pump M4 is shown. The functional outer surface 134a of the manifold block 134 is adjacent to the functional outer surface 107a of the sample pump body 110 (see, for example, see...). Figure 22 and Figures 25-26 The working outer surface of the manifold block 134 includes a pumping recess 136, the peripheral shape of which is complementary (e.g., shape and size) to the pump cavity 112 of the pump body for the sample pump. In the illustrated embodiment, the pumping recess has a circular peripheral shape. This is in contrast to the concave pump cavity 112 of the pump body 110 (whose bottom wall has an arcuate bend, see, for example, [reference needed]). Figure 22 and Figure 26 Unlike pumps M1, M2, and M3, the bottom wall of the pumping recess 136 can have a flat profile. The pumping recess 136 and the pumping chamber 112 are arranged facing each other to form a complete operating pumping chamber, which is formed by a portion of the pump body and a portion of the associated pump manifold block. Therefore, the manifold block encloses the pumping chamber. The same arrangement and pumping recess are used for the manifold blocks associated with the remaining pumps M1, M2, and M3; for simplicity, it is not necessary to explain each pump individually.

[0132] In some embodiments, similar to the pumping chamber 112 of the mixing pumps M1-M4, the pumping recess 136 of the pump manifold blocks 131-134 may also include anti-jamming grooves 113. These anti-jamming grooves in the manifold block are recessed into the flat bottom wall of the pumping recess 136 to prevent the diaphragm from adhering to and getting stuck on the surface when the diaphragm 111 is actuated and deforms toward the manifold block during the outward fluid pumping stroke. Anti-jamming grooves can be provided in any suitable arrangement as needed to prevent diaphragm jamming.

[0133] The blocky pump body 110, mixing manifold block 130, and pump manifold blocks 131-134 of pumps M1-M4 are polygonal in shape. They can be closely adjacent and detachably connected together to form a compact device housing 100a with the configuration shown. In one embodiment, threaded fasteners 140 (e.g., see...) can be used. Figure 22 These components are connected together in the arrangement shown in the attached figures. Threaded fasteners can also be used in a similar manner to detachably connect each pump manifold block to its corresponding pump. The pump body and manifold block may contain, for example, […]. Figure 29 The fastener mounting opening shown is threadedly engaged with fastener 140. In other embodiments, other mechanical coupling methods may be used instead of threaded fasteners or in addition to threaded fasteners. The housing 110a has sufficient structural rigidity to support the plasma torch 200 and spectrometer 300, which are attached to the bulk component by a suitable means (e.g., threaded fasteners). The housing is structurally self-supporting when the bulk flow-related components are assembled, and is portable and easily transportable. Notably, the fluid-side components, plasma generation components, and spectrometer components are cooperatively packaged together to form a complete agricultural sample fluid analysis system.

[0134] According to one aspect of the invention, the mixing pump M3 and the sample pump M4 are based on... Figure 3The components are fluidly connected together and operable as a mixer for combining an extractant and additional water (if desired) with an agricultural sample fluid (which may be a slurry in some embodiments). Physically, the mixing pump M3 with manifold block 133 can be vertically stacked on top of the sample pump M4 with manifold block 134 to facilitate mixing of fluids / chemicals. As mentioned elsewhere herein, the sample pump manifold block 134 includes three ports: a sample fluid inlet port 150a, a sample fluid outlet port 151a, and a bottom fluid port 152a. The mixing pump M3 is fluidly connected to the sample pump M4 via transfer valve V10. In operation, the sample slurry is added to the sample pump M4 via the sample fluid inlet valve V5. A suitable extractant, formulated to precipitate the relevant analyte from the slurry, is added to the slurry in the sample pump. Additional water (if needed) can be added to the mixture in sample pump M4 via electric water valve V12 to dilute the slurry to a desired water / sample solids ratio (e.g., soil / water ratio in one embodiment). Preferably, each component of the slurry mixture (i.e., slurry, extractant, and water) is added one at a time to the pumping chamber 112 of sample pump M4 to allow for precise metering of the amount of each fluid added, thereby enabling control of the mixture composition. After mixing is complete, mixing pump M3 and sample pump M4 can be operated alternately to exchange the slurry mixture between the pumps to ensure thorough mixing. For example, as... Figure 3 As shown, with transfer valve V10 open, sample pump M4 discharges the slurry mixture into mixing pump M3. Mixing pump M3 then returns the slurry mixture to sample pump M4. This operation can be performed one or more cycles as needed until the slurry mixture is completely mixed. Physical stirring of the slurry mixture is not required. After mixing is complete, sample pump M4 can discharge the slurry mixture via sample fluid outlet port 151a into mixing manifold block 130 and its main flow channel 130a for discharge into plasma torch 201.

[0135] The plasma torch device 200 and spectrometer 300 of the agricultural sample fluid analysis system will now be further described. The plasma torch device 200 is an electrically powered device that prepares agricultural samples for spectroscopic examination by generating plasma through vaporization of an agricultural sample fluid stream (such as slurry or other liquid). Therefore, the plasma torch device 200 includes: a fluid section in fluid communication with a pump M4 for receiving the sample fluid; and an electrical section operable to ignite and vaporize the sample fluid to generate plasma for analysis by the spectrometer 300.

[0136] Figures 30-38The plasma torch apparatus is shown in more detail separately. Referring first to these figures, the plasma torch apparatus 200 generally includes a body 210, which in one embodiment may have a cuboid shape, comprising a top 211, a bottom 212, and four adjacent sides 213. Other configurations of the housing may be used and are not intended to limit the invention. The configuration of the body 210 defines an open plasma chamber 202. The body 210 may be detachably coupled to and supported by one or more diaphragm pumps M1-M4 and / or manifold blocks 130-134. Threaded fasteners, such as those described herein, may be used. The body 210 may have a generally cuboid shape and may comprise an integral body formed of a suitable material, such as metal or plastic, or a combination of these or other materials.

[0137] The plasma torch device body 210 supports the plasma torch 201, which has a portion exposed in the plasma chamber for generating plasma from agricultural sample fluids for analysis. The housing also supports a pair of electrodes; one electrode 208 is electrically connected to a suitable power supply PS, which in one embodiment may be a DC power supply; the other electrode 207 is electrically connected to ground G (in...). Figure 36 (Illustrated schematically).

[0138] The plasma torch 201 includes an anode pin 205 electrically connected to a positive electrode 208 and a cathode tube 203 electrically connected to a ground electrode 207. The anode pin 205 may have a solid structure and is supported by a pin holder 206 connected to the plasma torch assembly body 210 (see, for example, [link to relevant documentation]). Figures 37-38 A pin holder 206 defines a channel 206a in which an anode pin 205 is received at least partially. The pin holder is electrically connected to a power electrode 208, which in turn energizes the anode pin. The cathode tube 203 is supported by a tube holder 204 defining a channel 204a in which the cathode tube is received at least partially. The polarities of the anode and cathode can be reversed and can be varied, for example, but not limited to: (1) a +5 kV positive electrode (anode) at the top and a ground (0 kV) solution (cathode) at the bottom; (2) a +5 kV positive electrode solution at the bottom and a ground electrode at the top; (3) a -5 kV negative electrode at the top and a ground (0 kV) solution at the bottom; or (4) an AC power supply connected to the anode (±5 kV) and the solution grounded (0 kV). The tube holder is electrically connected to a ground electrode 207, which in turn grounds the cathode tube. In one embodiment, the anode pin and the cathode tube may each have a generally cylindrical shape and be formed of a conductive metal. Other shapes and external profiles may also be used.

[0139] One end of each of the anode pin 205 and the cathode tube 203 extends a distance into the plasma chamber 202. In some embodiments, the ends of the anode pin and the cathode tube in the chamber are spaced apart by a gap 209 at which plasma is generated by igniting a flow of agricultural sample fluid (e.g., sample slurry). To deliver the slurry into the plasma chamber, the cathode tube 203 includes a longitudinal fluid channel 203a that extends completely through the tube from a fluid discharge end in the plasma chamber to an opposing fluid inlet end, which may be located within a channel 204a of the cathode tube holder 204 (e.g., see...). Figures 37-38 ).like Figure 3 As shown, cathode tube 203 is fluidly connected (fluidly communicated) to all process fluids, including a main flow channel 130a via mixing manifold block 130 (see, for example, see...). Figure 29 The cathode is fluidly connected (fluidly in communication) to the sample pump M4 for receiving sample slurry. In one embodiment, the cathode may be configured to inject a conductive fluid into its longitudinal fluid channel and mix the conductive fluid with the sample fluid upstream of the gap. Examples of conductive fluids include nitric acid and hydrochloric acid.

[0140] The plasma torch body 210 further includes a waste reservoir 215 positioned within the plasma chamber 202 and integrally formed with the body in one embodiment. The housing may be generally cuboid in shape and may comprise an integral body formed of a suitable material such as metal or plastic. Other body shapes may be used, as a non-limiting example, such as a circular (cylindrical) body. The reservoir includes recesses formed in the bottom wall of the plasma chamber that collect excess process fluids discharged from the cathode tube 203, such as agricultural sample fluids (e.g., sample slurries), standard solutions, diluents, or rinsing water. The reservoir 215 extends partially in a front-rear direction from the front 216 to the rear 217 of the body 210 and partially in a left-right direction in the region below the cathode tube. The waste reservoir may be concave and arc-shaped in the left-right direction so that waste fluids accumulate in the central portion of the reservoir. A waste trough 214 is formed in the bottom wall of a storage tank to collect waste fluid and guide the fluid outward to the waste end through an outlet opening 214a. In one embodiment, the outlet opening 214a extends through one side of the plasma torch housing. A waste fluid connector 214b may be provided, configured to fluidly connect to a waste conduit (e.g., pipe or fitting, not shown) for conveying excess waste process fluid to the waste end.

[0141] The plasma torch device 210 is operatively docked and coupled to a spectrometer 300, which has a direct or indirect line-of-sight path into the plasma chamber 202 to capture light emitted by the plasma for analysis, thereby measuring agriculturally relevant analytes in a sample slurry. A non-limiting example of an indirect line-of-sight path is the use of fiber optic cables or optical lens configurations to capture and guide the light emitted by the plasma to the spectrometer. A non-limiting example of a direct line-of-sight path from the plasma chamber to the spectrometer, illustrated in the figure, is the use of a linear light-collecting tube. For this example, the body 210 of the plasma torch device includes a rear through-channel 220 formed through the rear wall of the body and configured to receive a light-collecting tube 301 of the spectrometer, which provides a direct line-of-sight path for the spectrometer into the plasma chamber 202. In one embodiment, the light-collecting tube 301 may include an objective lens 302 that forms a physical barrier to prevent vapors or mist generated by igniting the plasma in the plasma chamber 202 from reaching and wetting the operating components of the spectrometer, such as photodetectors and electronics. In some embodiments, lens 302 may be made of a suitable material, such as sapphire or quartz. Preferably, lens 302 may be located at a distance CL from the centerline of plasma torch 201 (which is defined by the anode and cathode, see, for example...). Figure 37 At a position of 1-4 inches, in one embodiment as shown, both the anode and cathode can be vertically oriented. Because the intensity of light captured by the spectrometer decreases with increasing distance, it is preferable to position the spectrometer as close as possible to the plasma within this preferred distance range to obtain a stronger light signal, but not too close to reduce lens contamination / fogging issues as described below. In one embodiment, the through-channel 220 can be as follows: Figure 38 It extends horizontally through the rear wall 217a of the main body 210, as best shown in the middle.

[0142] When a moist agricultural sample slurry mixture is ignited and vaporized in plasma chamber 202, lens 302 may fog up. This fogging can adversely affect the measurement accuracy of the spectrometer. To help address this issue, lens 302 is recessed within the through channel 220 and separated from plasma chamber 202 by a distance chosen to minimize vaporized slurry deposition on the lens surface and fogging. In other embodiments where this may not be sufficient to solve the problem, an automated lens cleaning system can be provided to clean and defog the lens.

[0143] In one embodiment, the lens cleaning system may include blowing an airflow across the outer surface of the lens 302 facing the plasma chamber 202. The rear wall 217a of the plasma torch body 210 includes an air inlet channel 221 fluidly connected to a pressurized air source 223 (in...). Figure 38 (Illustrated schematically). In some embodiments, the air may be heated above ambient temperature to increase the dew point of the airflow, prevent condensation, and dry any moisture that may have condensed on the lens. Channel 221 is fluidly coupled to through channel 220 and configured to guide the airflow across the spectrometer lens 302. The air is captured by an air outlet channel 222 in the rear wall 217a of the housing, which is in fluid communication with the low-pressure environment. In one embodiment, the air may travel tangentially across the exposed lens surface to minimize the possibility that some air may escape into the plasma chamber 202 through through channel 220 (which could interfere with the plasma).

[0144] To further prevent the defogging airflow from interfering with and destabilizing the plasma generated in the plasma chamber 202, a light-transmitting barrier 220' is provided (in... Figure 38 (Schematally represented by dashed lines in the middle) can physically seal and isolate the plasma chamber from the spectrometer lens 302 and the airflow.

[0145] Other methods for defogging the spectrometer lens 302 may be used, including but not limited to electrically heating the lens with a heater, continuously applying a cleaning solution fluid to the surface of the lens, physically wiping the lens with a mechanical wiping device (which includes a wiping element that contacts and moves on the surface of the lens), or other methods.

[0146] The spectrometer 300 can be any commercially available spectrometer suitable for use with atmospheric pressure glow discharge flowing liquid cathode atomic emission spectrometry performed by the agricultural sample analysis apparatus 100. Such examination techniques are well known in the art.

[0147] The method or process for operating an agricultural sample analysis apparatus 100 for processing and analyzing agricultural sample fluids will now be briefly described. The process described below, as well as other aspects of processing and analyzing sample fluids, can be automatically controlled and implemented by a programmable controller 2820, which is further described herein.

[0148] In operation, it can initially be turned on / off. Figure 3The appropriate valves shown fill the diaphragm-operated mixing pumps M1, M2, and M4 with the corresponding process fluids, including diluents, standard solutions, and agricultural sample fluids. The sample fluids can be slurries containing solids or filtrates produced by filtering agricultural solid slurries (e.g., soil, crop residues, manure, etc.) outside the device 100, which are then added to sample pump M4. Extractant and additional water (if needed) can be added to sample pump M4 via extractant inlet valve V7 and water valves V11 or V12 to further prepare the sample fluid for processing and analysis. As previously described herein, the mixture can be mixed by one or more cycles of mixture exchange with mixing pump M3 to ensure thorough mixing and produce a homogeneous sample fluid for plasma generation.

[0149] After the diluent pump M1, standard sample pump M2, and sample pump M4 are filled with their respective process fluids, the system is ready to begin pumping the agricultural sample fluid (i.e., a mixture of sample fluid, extractant, and additional water (if added)) to the plasma torch device 200 to generate plasma. Reference Figure 1 This illustrates the basic process flow. Before plasma ignition, diluent, standard solution, and agricultural sample fluid can first be pumped and delivered to plasma torch 201 of plasma torch device 200 via mixing manifold block 130 and its main flow channel 130a (as previously described herein). This provides a "rinse" period to remove any air bubbles that may be entrained in the process fluids before plasma ignition. These three process fluids can be pumped and discharged to the plasma torch at preselected proportional flow rates, which can be programmed into controller 2820, which controls the process sequence and analysis performed by sample analysis device 100. Thus, the process involves varying the independent flow rates of each of the mixing pumps M1, M2, and M4 to achieve a specific ratio of each process fluid in the combined flow to the plasma torch.

[0150] As a non-limiting example of the above proportional flow scheme, in some embodiments, a ratio of 20% sample fluid, 20% standard solution, and 60% diluent can be used. Other proportional flow combinations may be appropriately used for different analytes. These three process fluids are mixed in the mixing zone Z of the mixing manifold block and then flow to the cathode tube 203, from which fluid is distributed into the gap G between the cathode and anode (see also...). Figures 36-38 The flow to the plasma torch can be initiated before the plasma is ignited to allow time for the fluid flow to reach equilibrium. The combined process fluid flow can be delivered to the plasma torch 201 at an appropriately preselected fixed flow rate (e.g., ml / min), which can be at least partially selected to establish a stable plasma.

[0151] Regarding one aspect of igniting a plasma generated from a sample fluid, standard solution, and / or diluent, the inventors have discovered that the steady-state flow rate of these process fluids required for measuring the analyte in the sample fluid is not necessarily the ideal flow rate for igniting and initially sustaining the plasma. Specifically, it has been found that higher flow rates of these process fluids are beneficial for igniting the plasma.

[0152] Therefore, the process or method for operating a plasma torch may include, but is not limited to, the following steps: increasing the flow rate of a process fluid through the hollow electrodes of the plasma torch to a first flow rate; igniting the plasma generated by the process fluid by energizing the hollow electrodes; reducing the flow rate of the process fluid to a second flow rate below the first flow rate; and measuring the process fluid for relevant analytes at this second flow rate. The first flow rate increases the amount of process fluid dispensed, which in turn reduces the effective air gap measured between the fluid and the anode or cathode (one of the two electrodes being a hollow electrode configured to receive and dispense the process fluid, while the other may be a solid electrode). After the plasma has been ignited and stabilized, the flow rate and effective air gap can be reduced to steady-state flow conditions at the second flow rate to collect analyte measurements. The process fluid may include a sample fluid containing agriculturally relevant analytes and agricultural value analytes. This stepwise and staged flow control is effective for igniting and stabilizing the plasma generated by the energized plasma torch.

[0153] After the flow is established, the plasma torch 201 is energized by turning on the power supply to the plasma torch apparatus, which ignites the plasma between the process fluid flow and the opposing electrodes. After the plasma is ignited, the controller 2820 can start a timer for a pre-programmed "wait time." This ensures the plasma has stabilized to avoid inaccurate measurements of agriculturally relevant analytes in the sample fluid. After the timer expires, the spectrometer 300 captures the light (spectrum) emitted by the plasma to measure the analyte. The spectrometer can perform one or more spectral capture events (exposures) to provide multiple data points, which can be averaged to determine the level or concentration of the analyte (e.g., plant-available nutrients) present in the sample. The measurement results are transmitted and sent to the controller 2820.

[0154] After the measurement is completed, the plasma torch 201 is powered off, and pumps M1, M2, and M4 can be stopped. This concludes the first round of sample processing.

[0155] Although in the above non-limiting example process, the plasma is generated by three process fluids and the associated spectral measurements are captured by spectrometer 300, in other embodiments, plasma can be generated and spectral measurements performed by allowing an agricultural sample fluid to flow alone through plasma torch 201. In other variations of the process, a specific ratio of diluent and sample fluid (excluding standard solution) can be used to generate plasma and capture spectral data, followed by replacement of a portion of the diluent with standard solution. For example, in the initial stage, the initial fluid flow to the plasma torch may include 80% diluent and 20% sample fluid to generate plasma and capture spectral data. Then, standard solution can be used to replace a portion of the diluent until a ratio of 20% sample fluid, 20% standard solution, and 60% diluent is established, while maintaining plasma ignition and spectral data capture by spectrometer 300. Other ratios of diluent, standard solution, and sample fluid may be used.

[0156] It is noteworthy that the combined flow of the aforementioned process fluids (diluent, standard solutions containing known amounts of the analyte in the sample, and agricultural sample fluid) enables real-time dynamic calibration of the spectrometer during analysis. In other embodiments, typical batch calibration can be used to calibrate the spectrometer, in which multiple rounds of a single standard solution (each with a different concentration of the analyte) are processed sequentially to generate plasma and capture spectral data. Therefore, any suitable method for calibrating the spectrometer and analyzing agricultural sample fluids can be employed using this agricultural sample processing and analysis system.

[0157] With the aid of controller 2820 and internal flow network 101 implemented in sample analysis apparatus 100 as previously described herein, this agricultural sample processing and analysis system advantageously provides considerable operational flexibility. In addition to achieving proportional flow rates and mixing of different process fluids (e.g., diluents, standard solutions, and agricultural sample fluids) from mixing pumps M1, M2, and M4 as previously described herein, the system can ramp down the flow rate of the first process fluid from the first mixing pump to the plasma torch 201 while ramping up the flow rate of the second process fluid discharged from the second mixing pump to the plasma torch, so as to maintain the flow rate to the plasma torch at the minimum required to maintain plasma stability. Furthermore, the first process fluid can be filled into the first mixing pump while the second process fluid is being discharged from the second mixing pump to the plasma torch. The first and second mixing pumps can be switched back and forth to maintain a continuous supply of either the first or second process fluid to the plasma torch to maintain plasma stability. The foregoing provides some non-limiting examples of the system's operational flexibility. Because the system's flow network 101 includes... Figure 3The mixing pump and valve shown can be adapted to other variations.

[0158] like Figure 3 As shown, the agricultural sample processing and analysis system further includes: rinsing and cleaning the mixing pump M3, the mixing sample pump M4, and the plasma torch 200 with water by opening and closing appropriate valves associated with the water source and pumps. Wastewater is discharged via waste outlet valve V8. A water cleaning system can be used between each sample fluid cycle in the system to prevent sample cross-contamination.

[0159] When made of plastic, in one embodiment a transparent polymeric material can be used to form the monolithic manifold blocks 130-134 and the mixing pump body 110 to allow visual observation of the fluid being processed therein and the operation of the pump and diaphragm valves. Some non-limiting examples of thermoplastics (polymers) that can be used include, but are not limited to, PMMA (polymethyl methacrylate, commonly known as acrylic), PC (polycarbonate), PS (polystyrene), PVC (polyvinyl chloride), CPVC (chlorinated polyvinyl chloride), etc. Examples of suitable elastomeric materials that can be used to form the diaphragms of the mixing pump and valves V1-V10 include, but are not limited to, silicone rubber, PDMS (polydimethylsiloxane), fluorosilicone rubber, neoprene rubber, etc. The pressurized air used to keep the diaphragm valve closed can permeate through the elastomeric diaphragm over time, resulting in the formation of bubbles on the process fluid side of the valve. These bubbles can adversely affect the ability to accurately measure the fluid volume because they occupy the fluid volume that would otherwise be precisely controlled. Fluorosilicone rubber is a preferred, non-limiting material because its low permeability helps reduce the diffusion of gas through the diaphragm over time, thus solving the aforementioned problem.

[0160] Pressure balancing sealing system for positive displacement pumps

[0161] Figure 39 and Figure 40 An alternative embodiment of the mixing pumps M1-M4 is shown, wherein the injection pump 115, which controls the pilot fluid to operate the pumps M1-M4, further includes a pressure-balanced sealing system.

[0162] When a vacuum is present in the pilot fluid (e.g., oil in one embodiment), dynamic seals (such as those formed by the slidable back-and-forth movement of the pump piston 117 within the pump orifice 116 of the injection pump 115 when the mixing pump is actuated) are difficult to maintain their sealing effect. During the return or reverse stroke, as the injection pump retracts in the pump orifice 116 to draw back the pilot fluid from the pumping chamber 112, the diaphragm 111 of the mixing pump is pulled inward against the curved surface of the concave pumping chamber (see also...). Figures 19-22 and Figures 25-26This vacuum condition occurs when the pump piston 117 is in a state of flux. This can cause air to be drawn through and through the seals on the pump piston 117 (via permeation). After the air seeps into the pilot fluid system, it will displace the oil and change the total volume of the pilot fluid system, thereby adversely affecting the normal operation of the system. To solve this problem, according to this disclosure, a method such as... Figures 39-40 The pressure balancing piston device 400 shown is illustrated.

[0163] The pressure balancing piston 400 replaces the single pump piston 117 with a dual-piston assembly 400s, which includes a main operating piston 401 and a secondary sealing piston 402 connected together by a smaller-diameter intermediate connecting member 403. The sealing piston 402 is coupled to an operating lever 118 of a linear actuator 127 for reciprocating movement of the piston assembly within the pump orifice 116 as previously described herein. The piston assembly may have an integral body, wherein the pair of pistons and the connecting member are all formed as an integral part of the body. Thus, the connecting member may be a reduced-diameter intermediate portion of the body. In other embodiments, the connecting member 403 may be a separate component coupled to and located between pistons 401, 402. Each piston 401, 402 includes one or more annular seals 403, such as elastomeric O-rings, to seal the sliding mating interface between the cylindrical piston sidewall and the cylindrical inner surface or wall of the pump orifice 116.

[0164] As shown in the figure, because the diameter of the connecting member 403 is smaller than the diameter of the piston and the pump orifice 116, a pressure-balancing intermediate chamber 404 is formed between pistons 401 and 402 in the pump assembly. Therefore, the annular intermediate chamber 404 contains a certain amount or volume of pilot fluid (e.g., oil), which fills the pilot side of the operating piston 401 opposite to the working side of the piston. When the injection pump 115 is actuated, the working side of the piston operably displaces the pilot fluid in the transverse flow channel 122a to actuate the mixing pump diaphragm 111. As previously described herein, a certain amount or volume of pilot fluid is also contained in the transverse flow channel 122a and the pump orifice 116 on the working side of the operating piston 401. In one embodiment, oil can be used as the pilot fluid.

[0165] A pressure balancing intermediate chamber 404 is fluidly connected to a pressure control device 410 via a flow conduit 406. The device 410 is configured and operated to regulate the pressure in the intermediate chamber during operation of the mixing pump such that the pressure of the pilot fluid in the chamber is less than the pressure of the pilot fluid on the working side of the piston 401. In one embodiment, as previously described herein, the pilot fluid may be used in chamber 404 and in the transverse flow passage 122a between the piston and diaphragm 111 of the mixing pumps M1-M4 on the working side of the operating piston 401. This approach is advantageous if any leakage occurs between the intermediate chamber 404 and the working side of the operating piston across the seals on the operating piston 401. A pilot fluid reservoir 413 may be incorporated into the flow conduit 406 and fluidly inserted between the pressure control device 410 and the intermediate chamber 404 of the operating piston assembly 400a. The reservoir holds a volume of pilot fluid subjected to a negative pressure (vacuum) applied by the device 410.

[0166] Specifically, the pressure control device 410 is configured to control and set the pressure of the pilot fluid in the intermediate chamber 404 during the return stroke of the injection pump 115, when the diaphragm 111 of the mixing pumps M1-M4 is pulled back into the concave groove of the pumping chamber 112. At this time, a vacuum is generated in a first pressure zone on the working side of the main operating piston 401, which, as previously described herein, is in fluid communication with the pumping chamber 112 via a lateral flow channel 122a. In one embodiment, the pressure control device 410 may be a commercially available vacuum pump, which may include a user-adjustable vacuum regulator 411, thereby providing a means for setting the pressure in the intermediate chamber 404. The vacuum pump is fluidly connected to the intermediate chamber 404 of the piston assembly 400a via a fluid permeation in the pump port 116.

[0167] During operation, the pressure control device 410 evacuates the intermediate chamber 404 of the operating piston assembly 400a in the pump orifice 116, such that the pilot fluid pressure in this pressure zone is lower than the pilot fluid pressure in the pressure zone formed on the working side of the operating piston 401. During the return stroke of the operating piston 401a, the pilot fluid pressure in the working side pressure zone preferably remains higher than the pilot fluid pressure in the pilot side pressure zone formed by the intermediate chamber 404 throughout the pump return stroke. This ensures that any air leaking into the pumping system will flow into the lower pressure zone in the intermediate chamber.

[0168] In summary, since positive pressure oil is easier to seal, the back side of the main oil seal (e.g., the main operating piston 401) can be drawn in the intermediate pressure balance chamber 404 via the pressure control device 410 to reduce the pilot fluid pressure therein. This results in the pilot fluid pressure on the operating side of the operating piston 401 acting on the mixing pump diaphragm 111 being higher than the pilot fluid pressure contained in the intermediate pressure balance chamber 404 between pistons 401 and 402. In this case, the operating side pilot fluid cannot draw air into the fluid. Since pistons 401 and 402 have the same area and are connected together via the connecting member 405, the resultant force on the pistons is zero.

[0169] Furthermore, when a fluid such as oil is used as a pilot fluid on both sides of the main operating piston 401, the fluid can be kept in the intermediate pressure balance chamber 404 to maintain the main sealing interface formed by the inner surfaces of the main operating piston 401 and the pump port 116 in an oil-to-oil sealing state, rather than in a more difficult oil-to-air sealing state.

[0170] To further reduce any possibility of air leakage into the pumping system, the same type of piston assembly can be included in the pressure relief system of the mixing pumps M1-M4. Specifically, the pressure relief piston assembly 420 can be slidably disposed in the pressure relief port 122 of the pump body 110. The piston assembly 420 includes a pressure relief piston 421, which is connected to a spaced-apart second sealing piston 422 via a connecting member 423. The piston assembly 420 can be the same as the operating piston assembly 400a previously described herein and contains the same features, such as the seal 403. A second intermediate chamber 425 is formed between pistons 421 and 422. The pressure relief spring 124 remains stationary and acts on the piston assembly.

[0171] In one embodiment, the second intermediate chamber 425 of the pressure relief piston assembly 420 may be fluidly connected to the first intermediate chamber 404 of the operating piston assembly 400a via a pressure balancing channel 424 formed laterally through the pump body 110 between the pump port 116 and the pressure relief port 122. Thus, the pump port 116 and the pressure relief port 122 are in fluid communication, which in turn allows the intermediate chambers 404 and 425 to be in fluid communication with each other. The pressure balancing channel 424 extends laterally through the pump body 110 and is fluidly connected to the pump port 116 and the pressure relief port 122 in the middle portion between the two ends of each, as shown. The channel 424 is positioned such that the intermediate chambers 404 and 425 remain in fluid communication throughout the entire axial range of motion of the pump piston 117 during the pumping and return strokes (e.g., see...). Figure 39 and Figure 40 ).

[0172] The intermediate chamber 425 of the pressure relief piston assembly 420 defines a third pressure zone. In operation, when the pressure control device 410 (e.g., a vacuum pump) evacuates the pressure zone formed by the intermediate chamber 404 of the operating piston assembly 400a, the same vacuum or negative pressure is applied to the intermediate chamber 425 in the pressure relief port 122 via the pressure balancing channel 424. Therefore, the pressures (negative pressure or vacuum) in the two intermediate chambers 404, 425 are equal. Thus, the advantage of providing the pressure balancing channel 424 is that it allows a single vacuum pump to be used as a common pressure control device, simultaneously controlling the pressure in both intermediate chambers, thereby avoiding the cost of providing a second vacuum pump for the pressure relief system.

[0173] Figure 39 The operating piston assembly 400a is shown at the end of the pumping stroke and the beginning of the return stroke of the injection pump 115. Figure 40 The operating piston assembly, via the operation of the linear actuator 119, retracts completely deeper into the pump orifice 116 after the full return stroke. Notably, at the beginning and end of the return pump stroke, intermediate chambers 404 and 425 are kept in fluid communication via proper positioning in the pump body 110 through the pressure balancing passage 424.

[0174] Pilot fluid air removal system

[0175] According to another aspect of the invention, an air removal system 500 is provided, which is configured to actively remove air that may infiltrate and be entrained in the pilot fluid (which can cause potential process fluid pumping problems and inaccuracies previously described herein). In one embodiment, the air removal system 500 is a vacuum-operated system, as further described herein. Figures 41 to 49 A possible, but not limiting, embodiment of the air removal system is shown. The mixing pump M1 is shown as a non-limiting example of the application of the air removal device.

[0176] The air removal system includes an air removal device 502 fluidly connected to an internal reservoir (volume) of pilot fluid in a mixing pump body 110, the internal reservoir being primarily defined by a pump port 116, a pressure relief port 122, and a lateral flow channel 122a. The air removal device 502 includes a housing 501 mechanically connected to a fluid component body, such as the mixing pump body 110. As shown, in one embodiment, the housing 501 may be generally cylindrical; however, other housing configurations are possible, including but not limited to cuboid, hexagonal, octagonal, etc. The invention is not limited to the chosen housing shape.

[0177] The housing 501 includes an internal membrane receiver 503 in which a permeable membrane 504 is disposed. The receiver 503 is fluidly connected to a pilot fluid reservoir inside the pump body 110 via an air inlet 508 on one side of the membrane. The receiver 503 is fluidly connected to a vacuum source 510 on the opposite side of the membrane via an air outlet 509. The vacuum source applies a negative pressure to the membrane to extract entrained air from the pilot fluid through the air inlet 508 and the membrane if entrained air is present in the fluid. In one embodiment, the air inlet 508 is an internal fluid passage defined by the housing, as shown, which may include a rod 508a projecting outward from the housing 501 for connecting an air removal device to the pump body 101. The rod can be partially inserted into an opening in the pump body 110 into a flow passage containing the pilot fluid, such as a pilot fluid filling port defined by a reduced-diameter flow exchange orifice 122b associated with the pressure relief orifice 122 previously described herein. Therefore, the air inlet 508 has a portion extending through the housing 501 and a continuous portion in the rod (see, for example, see...). Figure 49 A pilot fluid fills the air inlet up to membrane 504 and forms a wet contact with the membrane. The pilot fluid side of the membrane is the wet side, while the opposite side of the membrane exposed to vacuum is the dry side.

[0178] In addition to the pilot fluid filling port, the housing 501 of the air removal device 502 can also be fluidly connected to the pump body 110 at any other suitable available port in fluid communication with the pilot fluid, or via a dedicated, separate port in fluid communication with the pilot fluid formed through the pump body 110. Due to the clustered arrangement of the mixing pumps, it may not be possible to directly connect the air removal device 502 to the pilot fluid filling port for each of the mixing pumps M1-M4.

[0179] In other embodiments, the housing 501 of the air removal device 502 may be coupled to other parts of the pump body 110, or, if space and clearance are insufficient for direct coupling, may not be physically attached to the pump body at all. In the latter case, the air removal device may be fluidly coupled to the pilot fluid only through a suitable port on the pump body, such as the aforementioned pilot fluid filling port (i.e., fluid exchange port 122b) or a separate, independent port formed through the pump body 110 that is in fluid communication with the pilot fluid.

[0180] An air outlet 509 extends internally through the housing 501. A fluid fitting 512 may be detachably connected to the housing at the air outlet for connection to an external flow conduit 510a connected to a vacuum source 510, which in one embodiment may be a vacuum pump. In some embodiments, the flow conduit 510a may be a pipe or fitting. Any shape or type of fluid fitting 512 may be used.

[0181] In one embodiment, the membrane receiver 503 includes a wall 509a on the vacuum side of the membrane 504 and a second wall 509b facing each other on the pilot fluid side of the membrane. As shown, these walls may be formed at the bottom of matching recesses in the housing 501. Each of the walls 509a, 509b includes a plurality of matching airflow through openings 511a, 511b that are in fluid communication with the pilot fluid on one side of the membrane 504 and with the negative pressure (i.e., vacuum) generated by the vacuum source 510 on the other side. In one embodiment, the through openings may include curved slots to maximize the amount of air that can be extracted from the pilot fluid. However, any suitable shape or combination of shapes of openings may be used. However, in one embodiment, each through opening 511a preferably has a corresponding matching through opening 511b on the other side of the membrane 504, such that the openings on each side of the membrane are axially aligned with each other. This creates a continuous airflow path through the membrane with minimal pressure drop, optimizing the amount of air extracted from the pilot fluid.

[0182] In one embodiment, housing 501 may be formed of and include a first half 501a, the first half being detachably coupled to a mating second half 501b. For example... Figures 44-45 and Figure 49 As shown in the optimal configuration, the membrane receiver 503 is jointly defined by receiver half 503a in half 501a and receiver half 503b in half 501b. Therefore, when the halves of the housing are joined together, the membrane 504 is confined within the receiver 503 between the halves of the housing.

[0183] The housing halves 501a and 501b can be detachably connected by any suitable mechanical coupling. In one embodiment, a plurality of threaded fasteners 505 (e.g., bolts or screws) can be used. The fasteners are inserted through a fastener opening 506 in half 501a and threadedly engage with a matching threaded socket 507 formed in the mating half 501b. In other embodiments, the socket 507 may alternatively be a through-hole, and a nut may be threaded onto an exposed bottom threaded shank of the fastener extending beyond the through-hole to secure the halves together. Other types of fastener arrangements and other types of fastening techniques may be employed.

[0184] The breathable membrane is formed of a certain material and is configured to form a gas-permeable interface (air being a gas) between the pilot fluid side and the vacuum side of the membrane, said interface not allowing the liquid, acting as the pilot fluid, to pass through. Therefore, air entrained in the liquid can be extracted through the membrane via vacuum / negative pressure, while retaining the liquid pilot fluid on the pilot fluid side of the membrane. In one embodiment, the membrane may be formed of silicone rubber; however, other materials may also be used.

[0185] As already mentioned herein, the agricultural sample processing and analysis system and related processes / methods disclosed herein can be used to process and detect various agricultural materials and substances, such as, but not limited to, soil, vegetation / plants, manure, feed, milk, or other agricultural materials, to obtain relevant parameters and agricultural analytes. In particular, embodiments of the systems disclosed herein, in addition to their use for soil and plant / vegetation sampling, can also be used for the detection of various chemically relevant parameters and analytes (e.g., available plant nutrients / chemicals) in other fields, such as those described above with respect to the calibration methods disclosed herein.

[0186] control system

[0187] The processes described herein and performed by the equipment of the agricultural sample processing and analysis system shown in the accompanying drawings can be automatically controlled and executed by a programmable system controller 2820. The controller can be, for example, as further described herein and... Figure 2 This is part of the main control system shown herein. Controller 2820 is operatively coupled to components (e.g., pumps, valves, plasma torch devices, spectrometers, etc.) of the chemical analysis subsystem 3003 disclosed herein for controlling the process sequence and flow of fluids (e.g., water, air, slurry, extractant, standard solution, etc.) through the system for complete processing and analysis of soil or other types of agricultural samples.

[0188] Figure 2 To illustrate a schematic system diagram of the control or processing system 2800, the control or processing system includes a central processing unit (CPU) or system controller 2820 based on a programmable processor as mentioned herein. The controller 2820 may be operatively and communicatively coupled to... Figure 3 All flow control-related functional components shown (e.g., pumps, valves, etc.), plasma torch device 200, and spectrometer 300. The controller can control the operation, sequence, and timing of the various processes described herein, including the handling and analysis of agricultural sample fluids.

[0189] System controller 2820 may include one or more processors, non-transitory tangible computer-readable media, programmable input / output peripherals, and all other necessary electronic accessories typically associated with a fully functional processor-based controller. Control system 2800, including controller 2820, is operatively and communicatively linked via suitable communication links to the various soil sample processing and analysis systems and apparatuses described elsewhere herein, in order to control the operation of these systems and apparatuses in a fully integrated and orderly manner.

[0190] refer to Figure 2 According to one embodiment, the control system 2800, including the programmable controller 2820, can be mounted on a fixed support in any location, or conversely, mounted on a translationally movable self-propelled or traction machine (e.g., a vehicle, tractor, combine harvester, etc.), which may include agricultural implements (e.g., seeders, cultivators, plows, sprayers, spreaders, irrigation implements, etc.). In one example, the machine performs the operation of a tractor or vehicle coupled to implements for agricultural operations. In other embodiments, the controller may be part of a fixed station or facility.

[0191] The control system 2800 (whether on or off a portable machine) typically includes a controller 2820, a non-transitory tangible computer or machine-accessible and readable medium (such as memory 2805), and a network interface 2815. The computer or machine-accessible and readable medium may include any suitable volatile or non-volatile memory, or a device operatively and communicatively coupled to one or more processors. Any suitable combination and type of volatile or non-volatile memory may be employed, including, but not limited to: random access memory (RAM) and its various types, read-only memory (ROM) and its various types, hard disks, solid-state drives, flash memory, or other memory and devices operatively coupled to and / or readable by a processor operatively coupled to the medium. Both volatile and non-volatile memory can be used to store program instructions or software. In one embodiment, a computer- or machine-accessible, readable, non-transitory medium (e.g., memory 2805) contains executable computer program instructions that, when executed by system controller 2820, cause the system to perform operations or methods of this disclosure, including measuring properties of soil and vegetation samples and performing tests on the soil and vegetation samples. While a machine-accessible, readable, non-transitory medium (e.g., memory 2805) is shown as a single medium in an exemplary embodiment, the term should be understood to include a single medium or multiple media (e.g., a centralized or distributed database, and / or associated cache memory and servers) storing one or more sets of control logic or instructions. The term "machine-accessible, readable, non-transitory medium" should also be understood to include any medium capable of storing, encoding, or carrying a set of machine-executable instructions and causing the machine to perform any one or more methods of this disclosure. Therefore, the term "machine-accessible, readable, non-transitory medium" should also be understood to include, but is not limited to, solid-state memory, optical and magnetic media, and carrier signals.

[0192] Network interface 2815 connects to the agricultural (e.g., soil or other) sample processing and analysis system (and its associated devices) described elsewhere in this document. Figure 2 The system communicates with other systems or devices, including but not limited to machines 2840 that have their own controllers and devices.

[0193] The programmable controller 2820 may include one or more microprocessors, processors, system-on-a-chip (integrated circuits), one or more microcontrollers, or combinations thereof. The processing system includes processing logic 2826 for executing software instructions for one or more programs, and a communication module or unit 2828 (e.g., transmitter, transceiver) for transmitting and receiving communications from a network interface 2815 and / or an agricultural sample processing and analysis system 2803, which includes a sample preparation subsystem 3002 and components further described herein (including components of a closed slurry recirculation flow loop 8002). The communication unit 2828 may be integrated with the control system 2800 (e.g., controller 2820) or separate from the programmable processing system.

[0194] The programmable processing logic 2826 of the control system 2800 (which directs the operation of the system controller 2820, which includes one or more processors) can process communication information received from the communication unit 2828 or the network interface 2815, including agricultural data (e.g., detection data, detection results, GPS data, liquid application data, flow rate, etc.) and data generated by the soil sample processing and analysis system 2803. The memory 2805 of the control system 2800 is configured for pre-programmed variables or setpoints / reference values, storing acquired data, and executable computer instructions or programs (e.g., software 2806) for controlling the operation of the controller 2820. The memory 2805 may store, for example, software components such as detection software for analyzing soil and vegetation samples to perform the operations of this disclosure, or any other software application or module, images 2808 (e.g., captured crop images), alarms, maps, etc. System 2800 may also include an audio input / output subsystem (not shown), which may include a microphone and a speaker for, for example, receiving and sending voice commands or for user authentication or authorization (e.g., biometrics).

[0195] The system controller 2820 communicates bidirectionally with the memory 2805 via communication link 2830, bidirectionally with the network interface 2815 via communication link 2832, bidirectionally with the display device 2830 and an optional second display device 2825 via communication links 2834 and 2835, and bidirectionally with the input / output (I / O) port 2829 via communication link 2836. As shown in the figure, the system controller 2820 can further communicate with the soil sample processing and analysis system 2803 via wired / wireless communication link 5752, through the network interface 2815, and / or directly.

[0196] Display devices 2825 and 2830 can provide a visual user interface for users or operators. The display device may include a display controller. In one embodiment, display device 2825 is a portable tablet or computing device with a touchscreen that displays data (e.g., soil testing results, vegetation testing results, sap application data, captured images, localized view map layers, high-resolution field maps of actual sap application data, actual planting or harvesting data or other agricultural variables or parameters, yield maps, alarms, etc.) and data generated by agricultural data analysis software applications, and receives input from users or operators to obtain an expanded view of the field area, thereby monitoring and controlling field operations. These operations may include configuring machines or implements, reporting data, controlling machines or implements including sensors and controllers, and storing the generated data. Display device 2830 may be a display (e.g., a display provided by an original equipment manufacturer (OEM)) that displays images and data for localized view map layers, actual liquid application data, actual planting data or actual harvesting data, yield data, controls machinery (e.g., seeders, tractors, combine harvesters, sprayers, etc.), operates machinery, and monitors machinery or implements connected to machinery (e.g., seeders, combine harvesters, sprayers, etc.), said machinery or implements having sensors and controllers located on the machinery or implements.

[0197] The system for analyzing agricultural samples disclosed herein can be used in conjunction with and can form part of a whole agricultural sampling and analysis system, which includes, but is not limited to, those disclosed in the following commonly owned documents: U.S. Patent Application Publication Nos. 2018 / 0124992A1, US20210123836A1, US20210123936A1, US20210131917A1, and US20210131929A1. , US20210208035A1, US20210208036A1, US20210208037A1, US20210208123A1, US20210268456A1, US20 210285869A1, US20210341442A1, US20210341452A1, US20220196628A1, US20230133335A1, US20230144 670A1, US20230151810A1, US20230173415A1, US20230243792A1, US20230243801A1, US20230243802A1 , US20230243804A1, US20230266289A1, US20230266290A1, US20230273130A1, US20230273171A1, US202 30273172A1, US20230273173A1, US20230304987A1, US20230417363A1, US20230417635A1, US20240189 743A1, US20240189744A1, US20240192112A1, US20240192708A1, US20240198331A1, US20240200547A1;PCT official numbers WO2021 / 171120, WO2021 / 171121, WO2022 / 243792, WO2022 / 243797, WO2022 / 243806, WO2022 / 243807, WO2022 / 243809, WO2022 / 259071, WO2022 / 259073 , WO2022 / 259074, WO2023 / 031725, WO2023 / 031726, WO2023 / 031727, WO2023 / 04 2032, WO2023 / 042033, WO2023 / 042035, WO2023 / 042036, WO2023 / 042037, WO202 3 / 042038, WO2023 / 042039, WO2023 / 161727, WO2023 / 161728, WO2023 / 170480, WO2023 / 170482, WO2023 / 227959, WO2023 / 227960, WO2023 / 248015, WO2023 / 248 016, WO2024 / 023728, WO2024 / 023729, WO2024 / 023730, hereafter WO2024 / 023731; PCT application No. PCT / IB2024 / 051283 (delivered on February 12, 2024) Japanese PCT / IB2024 / 051820 (delivered on February 26, 2024);U.S. Application Nos. 63 / 551120 (filed February 8, 2024), 63 / 552730 (filed February 13, 2024), 63 / 552739 (filed February 13, 2024), 63 / 559305 (filed February 29, 2024), 63 / 559308 (filed February 29, 2024), 63 / 559312 (filed February 29, 2024), 63 / 559316 (filed February 29, 2024), 63 / 586486 (filed September 29, 2023), and 63 / 586489 (Submitted on September 29, 2023), 63 / 586497 (submitted on September 29, 2023), 63 / 586500 (submitted on September 29, 2023), 63 / 586504 (submitted on September 29, 2023), 63 / 586510 (submitted on September 29, 2023), 63 / 586514 (submitted on September 29, 2023), 63 / 586524 (submitted on October 11, 2023), 63 / 586529 (submitted on September 29, 2023), 63 / 586545 (submitted on September 29, 2023) ), 63 / 586551 (submitted on September 29, 2023), 63 / 586555 (submitted on September 29, 2023), 63 / 586562 (submitted on September 29, 2023), 63 / 586608 (submitted on September 29, 2023), 63 / 586619 (submitted on September 29, 2023), 63 / 586630 (submitted on September 29, 2023), 63 / 586638 (submitted on September 29, 2023), 63 / 586656 (submitted on September 29, 2023), 63 / 586672 (20 Filed on September 29, 2023; 63 / 586702 (filed on September 29, 2023); 63 / 586726 (filed on September 29, 2023); 63 / 586955 (filed on September 29, 2023); 63 / 586966 (filed on September 29, 2023); 63 / 586978 (filed on September 29, 2023); 63 / 586984 (filed on September 29, 2023); 63 / 586990 (filed on September 29, 2023); and 63 / 646070 (filed on May 13, 2024).

[0198] refer to Figure 52 Provides the process for the calibration system described in this document (see Figures 1-51 Non-restrictive examples. For example... Figure 52As seen in the diagram, the system includes multiple pumps (such as slurry pumps, diluent pumps, and standard sample pumps) and multiple corresponding containers filled with the respective solutions. For example, the slurry pump is fluidly connected to a container filled with an agricultural sample solution, the diluent pump is fluidly connected to a container filled with a diluent solution, and the standard sample pump is fluidly connected to a container filled with a standard sample solution, such that each of the multiple pumps can pump the corresponding solution. The multiple pumps can be actuated to generate a calibration flow including agricultural sample solution, diluent, and / or standard sample solution. For example, as... Figure 52 As seen in the diagram, the plurality of pumps can be actuated to generate a calibration stream comprising 50 vol% diluent and 50 vol% agricultural sample, the calibration stream being delivered to a plasma torch apparatus comprising a plasma chamber and a plasma torch at least partially disposed within the plasma chamber.

[0199] The plasma torch can be ignited, for example, to ionize the calibration stream. For example, the calibration stream can be evaluated for about 10 seconds before its composition is changed (e.g., analytes in the calibration stream, such as those in an agricultural stream, can be measured).

[0200] The composition of the calibration stream can be changed over a period of time; for example, by replacing a certain amount (e.g., by volume%) of diluent with an equal amount (e.g., by volume%) of standard sample, while keeping the amount of agricultural sample in the calibration stream constant (e.g., by volume%). The plasma formed by the calibration stream can be measured continuously.

[0201] Example

[0202] The following are non-restrictive examples.

[0203] Example 1 - A method for using an instrument suitable for analyzing agricultural samples, the method comprising: continuously providing a calibration stream to the instrument suitable for analyzing agricultural samples, the calibration stream having components that change over a period of time.

[0204] Example 2 - The method according to Example 1 further includes: evaluating the composition of the calibration stream within at least a portion of the time period.

[0205] Example 3 - The method according to Example 1 or Example 2, wherein the flow rate of the calibration stream provided to the instrument suitable for analyzing agricultural samples is substantially constant over the time period being evaluated.

[0206] Example 4 - A method according to one of Examples 1 to 3, wherein the composition of the calibration stream changes continuously over the time period being evaluated.

[0207] Example 5 - A method according to one of Examples 1 to 3, wherein the composition of the calibration stream varies in a stepwise manner over the time period being evaluated.

[0208] Example 6 - The method according to any of the preceding examples, wherein at the start of the time period being evaluated, the components of the calibration stream include an agricultural sample and a diluent.

[0209] Example 7 - According to the method of Example 6, wherein at the start of the time period being evaluated, the amount of the agricultural sample present in the calibration stream is about 10 to about 60 volumes relative to the volume of the provided calibration stream.

[0210] Example 8 - The method according to Example 6 or Example 7, wherein at the start of the time period being evaluated, the amount of the diluent present in the calibration stream is about 10 to about 90 volumes relative to the volume of the provided calibration stream.

[0211] Example 9 - The method according to any of the foregoing examples, wherein at the end of the time period being evaluated, the components of the calibration stream include agricultural samples, standard samples, and optional diluents.

[0212] Example 10 - According to the method of Example 9, wherein at the end of the time period being evaluated, the amount of the standard sample present in the calibration stream is about 50 to about 90 volumes relative to the volume of the provided calibration stream.

[0213] Example 11 - The method according to Example 9 or Example 10, wherein at the end of the time period being evaluated, the amount of the diluent present in the calibration stream is 0 to about 50 volumes relative to the volume of the provided calibration stream.

[0214] Example 12 - The method according to any of the preceding examples, wherein the composition of the calibration stream comprises a substantially constant amount of agricultural sample.

[0215] Example 13 - The method according to any of the foregoing examples, wherein the agricultural sample comprises at least one soil particle and a carrier, the weight ratio of the at least one soil particle and the carrier being about 3:1.

[0216] Example 14 - A method according to one of Examples 2 to 4 and Examples 6 to 13, wherein evaluating the calibration stream includes determining the detected rate of change of the components of the calibration stream.

[0217] Example 15 - The method according to Example 14, wherein the detected rate of change of the component is determined based on the rate of change of the analyte in the standard sample.

[0218] Example 16 - The method according to Example 15, wherein the analyte is selected from potassium, sodium, magnesium, calcium, copper, iron, manganese, lithium, rhodium, thallium, indium, their ions, their salts, and combinations of two or more of them.

[0219] Example 17 - A method according to one of Examples 14 to 16, wherein evaluating the calibration flow includes determining when the detected rate of change of the component is substantially constant.

[0220] Example 18 - The method according to Example 17, wherein the detected rate of change of the component is substantially constant if the detected rate of change of the component does not exceed ±10% over a time period of at least 1 second.

[0221] Example 19 - The method described in Example 18, wherein the time period is 1 to 6 seconds.

[0222] Example 20 - A method according to one of Examples 14 to 17, wherein evaluating the calibration flow includes determining when the detected rate of change of the component is constant.

[0223] Example 21 - A method according to one of Examples 14 to 20, wherein evaluating the calibration flow includes determining a value of the detected rate of change of the component when the rate of change of the component is substantially constant or constant.

[0224] Example 22 - A method according to one of Examples 1 to 8, wherein the calibration stream does not contain a standard sample.

[0225] Example 23 - The method according to Example 22, wherein evaluating the calibration stream includes determining the detected background value based on the evaluation of the calibration stream when the calibration stream does not contain the standard sample.

[0226] Example 24 - The method according to Example 23 further includes: calibrating the instrument using a detected background value and a value of the detected rate of change of the component when the rate of change of the component is substantially constant or constant.

[0227] Example 25 - The method according to any of the preceding examples, wherein the diluent comprises nitric acid, hydrochloric acid, salts thereof, or a combination of two or more thereof.

[0228] Example 26 - A method for calibrating an instrument suitable for analyzing agricultural samples, the method comprising: continuously providing a calibration stream to the instrument suitable for analyzing agricultural samples, the calibration stream having a component that changes over a period of time; evaluating the component of the calibration stream over at least a portion of the period of time, wherein at the beginning of the evaluated period of time, the component of the calibration stream does not contain a standard sample and includes an agricultural sample and a diluent, and wherein at the end of the evaluated period of time, the component of the calibration stream includes the agricultural sample, the standard sample, and optionally a diluent; determining a detected rate of change of the component of the calibration stream; determining when the detected rate of change of the component is substantially constant; optionally, determining a value of the detected rate of change of the component when the rate of change of the component is substantially constant or constant; determining a detected background value based on the evaluation of the calibration stream when the calibration stream does not contain the standard sample; and calibrating the instrument using the detected background value and the value of the detected rate of change of the component when the rate of change of the component is substantially constant or constant.

[0229] Example 27 - The method according to Example 26, wherein the flow rate of the calibration stream provided to the instrument suitable for analyzing agricultural samples is substantially constant over the time period being evaluated.

[0230] Example 28 - The method according to Example 27, wherein the flow rate of the calibration stream varies by about ±6% or less during the time period.

[0231] Example 29 - A method according to one of Examples 26 to 28, wherein the flow rate of the calibration stream is constant during the time period.

[0232] Example 30 - The method according to any of the foregoing examples further includes: analyzing the amount of analyte in the agricultural sample.

[0233] Example 31 - The method according to Example 30, wherein the analytes in the agricultural sample are selected from sodium, calcium, magnesium, potassium, their salts, and combinations of two or more of them.

[0234] Example 32 - The method according to any of the preceding examples, wherein the agricultural sample is a soil sample.

[0235] Example 33 - A system for calibrating an instrument suitable for analyzing agricultural samples, the system comprising: a plurality of pumps configured to provide a calibration flow to a detector, the calibration flow having a composition that changes over a period of time; and a plasma torch apparatus comprising a plasma chamber and a plasma torch at least partially disposed within the plasma chamber, the plasma torch being fluidly coupled to the plurality of pumps.

[0236] Example 34 - A system according to Example 33, wherein the plurality of pumps includes a slurry pump configured to pump agricultural samples, a standard sample pump configured to pump standard samples, and a diluent pump configured to pump diluent.

[0237] Example 35 - A system according to Example 33 or Example 34, wherein at least one of the plurality of pumps is a diaphragm pump.

[0238] Example 36 - A system according to one of Examples 33 to 35, wherein each of the plurality of pumps is a diaphragm pump.

[0239] Example 37 - A system according to any one of Examples 33 to 36, wherein the plasma torch apparatus includes a plasma chamber and a plasma torch at least partially disposed in the plasma chamber, the plasma torch being fluidly coupled to receive the calibration flow.

[0240] Example 38 - A system according to Example 37, wherein the plasma torch device is configured to discharge the calibration stream in the form of a pulsed stream.

[0241] Example 39 - A system according to Example 37, wherein the plasma torch device is configured to discharge the calibration stream in a continuous flow.

[0242] Example 40 - A system according to one of Examples 33 to 39 further includes a spectrometer having a line-of-sight path into the plasma chamber.

[0243] Example 41 - A system according to Example 40, wherein the spectrometer is operable to detect relevant analytes in the slurry when the slurry pulse stream emitted by the plasma torch is vaporized to form gaseous plasma by energizing the plasma torch.

[0244] The system can repeatedly evaluate and / or determine whether the detected rate of change of the components of the calibration stream is substantially constant or constant. Following the discussion above regarding the methods and / or systems disclosed herein, the system can determine whether the detected rate of change of the components of the calibration stream is substantially constant or constant. When it is determined that the detected rate of change of the components of the calibration stream is constant or substantially constant, the concentrations of one or more analytes (such as those disclosed herein) in the agricultural sample at one or more time points, as well as the detector rate of change, can be determined. The detector rate of change and / or the concentrations of one or more analytes can be used to calibrate the system disclosed herein. In some embodiments, the plasma torch can be shut off (e.g., the flame extinguished), and the agricultural pump and the corresponding container holding the agricultural sample can be cleaned.

Claims

1. A method for using an instrument suitable for analyzing agricultural samples, the method comprising: A calibration stream is continuously supplied to the instrument suitable for analyzing agricultural samples, the calibration stream having components that change over a period of time.

2. The method according to claim 1, further comprising: The components of the calibration stream are evaluated within at least a portion of the time period.

3. The method according to claim 1 or 2, wherein, The flow rate of the calibration stream provided to the instrument suitable for analyzing agricultural samples was substantially constant over the time period being evaluated.

4. The method according to any one of claims 1 to 3, wherein, The components of the calibration stream change continuously over the time period being evaluated.

5. The method according to any one of claims 1 to 3, wherein, The components of the calibration stream change in a stepwise manner over the time period being evaluated.

6. The method according to any one of the preceding claims, wherein, At the start of the period being evaluated, the components of the calibration stream included agricultural samples and diluent.

7. The method according to claim 6, wherein, At the start of the evaluation period, the amount of the agricultural sample present in the calibration stream was approximately 10 to approximately 60 volumes, relative to the volume of the provided calibration stream.

8. The method according to claim 6 or 7, wherein, At the start of the evaluation period, the amount of diluent present in the calibration stream is approximately 10 to approximately 90 volumes, relative to the volume of the calibration stream provided.

9. The method according to any one of the preceding claims, wherein, At the end of the evaluated period, the components of the calibration stream include agricultural samples, standard samples, and optional diluents.

10. The method according to claim 9, wherein, At the end of the evaluated period, the amount of the standard sample present in the calibration stream was approximately 50 to approximately 90 volumes, relative to the volume of the calibration stream provided.

11. The method according to claim 9 or claim 10, wherein, At the end of the evaluated time period, the amount of diluent present in the calibration stream is from 0 to approximately 50 volumes relative to the volume of the provided calibration stream.

12. The method according to any one of the preceding claims, wherein, The components of the calibration stream comprise substantially a constant amount of agricultural sample.

13. The method according to any one of the preceding claims, wherein, The agricultural sample comprises at least one soil particle and a carrier, wherein the weight ratio of the at least one soil particle to the carrier is approximately 3:

1.

14. The method according to any one of claims 2 to 4 and 6 to 13, wherein, Evaluating the calibration stream includes determining the detected rate of change of the components of the calibration stream.

15. The method according to claim 14, wherein, The detected rate of change of the component was determined based on the rate of change of the analyte in the standard sample.

16. The method according to claim 15, wherein, The analytes are selected from potassium, sodium, magnesium, calcium, copper, iron, manganese, lithium, rhodium, thallium, indium, their ions, their salts, and combinations of two or more of the above.

17. The method according to any one of claims 14 to 16, wherein, Evaluating the calibration flow includes determining when the detected rate of change of the component is substantially constant.

18. The method according to claim 17, wherein, If the detected rate of change of the component does not change by more than ±10% over a period of at least 1 second, then the detected rate of change of the component is substantially constant.

19. The method according to claim 18, wherein, The time period is 1 to 6 seconds.

20. The method according to any one of claims 14 to 17, wherein, Evaluating the calibration flow includes determining when the detected rate of change of the component is constant.

21. The method according to any one of claims 14 to 20, wherein, Evaluating the calibration flow includes determining the value of the detected rate of change of the component when the rate of change of the component is substantially constant or constant.

22. The method according to any one of claims 1 to 8, wherein, The calibration stream does not contain standard samples.

23. The method according to claim 22, wherein, Evaluating the calibration stream includes determining the detected background value based on the assessment of the calibration stream when the calibration stream does not contain the standard sample.

24. The method of claim 23, further comprising: The instrument is calibrated using the detected background value and the detected rate of change of the component when the rate of change of the component is substantially constant or constant.

25. The method according to any one of the preceding claims, wherein, The diluent includes nitric acid, hydrochloric acid, their salts, or a combination of two or more of the above.

26. A method for calibrating an instrument suitable for analyzing agricultural samples, the method comprising: A calibration stream is continuously supplied to the instrument suitable for analyzing agricultural samples, the calibration stream having components that change over a period of time; The components of the calibration stream are evaluated during at least a portion of the time period, wherein at the beginning of the evaluated time period, the components of the calibration stream do not contain a standard sample and include an agricultural sample and a diluent, and wherein at the end of the evaluated time period, the components of the calibration stream include the agricultural sample, the standard sample, and an optional diluent. Determine the detected rate of change of the component of the calibration stream; Determine when the detected rate of change of the component is substantially constant; Optionally, when the rate of change of the component is substantially constant or constant, the value of the detected rate of change of the component is determined; When the calibration stream does not contain the standard sample, the detected background value is determined based on the evaluation of the calibration stream; as well as The instrument is calibrated using the detected background value and the detected rate of change of the component when the rate of change of the component is substantially constant or constant.

27. The method according to claim 26, wherein, The flow rate of the calibration stream provided to the instrument suitable for analyzing agricultural samples is substantially constant over the time period being evaluated.

28. The method according to claim 27, wherein, The flow rate of the calibration stream varies by approximately ±6% or less during the time period.

29. The method according to any one of claims 26 to 28, wherein, The flow rate of the calibration stream is constant during the time period.

30. The method according to any one of the preceding claims further comprises: The amount of analyte in the agricultural sample was analyzed.

31. The method according to claim 30, wherein, The analytes in the agricultural samples are selected from sodium, calcium, magnesium, potassium, their salts, and combinations of two or more of the above.

32. The method according to any one of the preceding claims, wherein, The agricultural sample is a soil sample.

33. A system for calibrating an instrument suitable for analyzing agricultural samples, the system comprising: Multiple pumps are configured to provide a calibration flow to a detector, the calibration flow having a component that changes over a period of time; as well as A plasma torch apparatus comprising a plasma chamber and a plasma torch at least partially disposed within the plasma chamber, the plasma torch being fluidly connected to the plurality of pumps.

34. The system according to claim 33, wherein, The plurality of pumps includes a slurry pump configured to pump agricultural samples, a standard sample pump configured to pump standard samples, and a diluent pump configured to pump diluent.

35. The system according to claim 33 or 34, wherein, At least one of the plurality of pumps is a diaphragm pump.

36. The system according to any one of claims 33 to 35, wherein, Each of the plurality of pumps is a diaphragm pump.

37. The system according to any one of claims 33 to 36, wherein, The plasma torch device includes a plasma chamber and a plasma torch at least partially disposed within the plasma chamber, the plasma torch being fluidly coupled to receive the calibration flow.

38. The system according to claim 37, wherein, The plasma torch device is configured to emit a pulsed stream of the calibration stream.

39. The system according to claim 37, wherein, The plasma torch device is configured to emit a continuous stream of the calibration stream.

40. The system according to any one of claims 33 to 39 further includes a spectrometer having a line-of-sight path into the plasma chamber.

41. The system according to claim 40, wherein, The spectrometer is operable to detect relevant analytes in the slurry when the slurry emitted by the plasma torch is vaporized to form a gaseous plasma by energizing the plasma torch.

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