Spark-induced breakdown spectroscopy (“SIBS”) is an atomic emission spectroscopic technique that can be used to detect and quantify the elemental content of an analyte. In operation, a powerful electric spark discharge between two electrodes creates a small volume of a high-temperature plasma. An analyte, which may be aerosolized, is quickly vaporized and/or atomized by the plasma. High-energy electrons from the electric spark excite the analyte atoms to one or more excited electronic states. As an element relaxes back toward the ground state, it emits a characteristic atomic emission spectrum which is detected by a spectrometer and recorded. Based on the signature emission spectrum, the elemental content of the analyte can be determined. A representative SIBS apparatus is disclosed in U.S. Pat. No. 6,034,768, the entire teachings of which are incorporated herein by reference.
Such systems can be used for real-time detection of elements in an analyte, which may be used to detect the presence of hazardous airborne heavy metals, such as lead or chromium, or other chemicals, such as chemical or biological weapons. Other applications of the technology include process control, emission compliance, and industrial hygiene.
While SIBS is a sensitive technique for elemental detection, it is not without its drawbacks. Generating a spark requires the use of two electrodes positioned at an appropriate distance. Over time, the electrodes wear down and become smaller in length, which causes two problems. As the electrodes degrade, debris from the electrodes accumulates within the housing where the spark is generated. This debris can coat the optical equipment and reduce sensitivity of the apparatus, thereby requiring periodic cleaning. In addition, as the electrodes erode, the location of the spark may shift. In precision analytical equipment, even modest adjustments in the location of the spark can impact the sensitivity of the measurement.
Accordingly, there is a need for an improved SIBS apparatus that can be used to determine the elemental content of an analyte, particularly an aerosolized analyte, that substantially prevents debris from fouling the optical equipment and at least partially stabilizes the spark location.
A spark-induced breakdown spectroscopy (SIBS) apparatus of the invention includes a housing having an inlet and an outlet that define an analyte flow path from the inlet to the outlet of the housing. A laser defines a laser pathway generally transverse to and intersecting the analyte flow path. A pair of electrode mounts are arranged within the housing such that tips of electrodes mounted in the housing define a line that is generally transverse to the analyte flow path. An insulating shield is at each electrode mount. The edges of the insulating shields at least partially define a spark path that is transverse to and intersecting at a point in the analyte flow path and downstream along the analyte flow path from the point of intersection of the laser pathway and the analyte flow path. An optical detection element defines an optical path generally transverse to the analyte flow path at a point proximate to the intersection of the spark path and the analyte flow path. The tips of the electrodes and insulating shields can be generally parallel to the laser pathway. The optical pathway can be generally transverse to the spark path. Electrodes can be mounted on the electrode mounts, and the shields can be sleeves that at least partially surround the electrode and extend beyond the tip of the electrode. The SIBS apparatus can also include an advancement component at each of the electrodes, whereby each electrode can advance along its respective major longitudinal axis as each electrode erodes at its respective tip to thereby keep each tip essentially in the same position within the chamber, whereby the path of the spark defined by the tips and insulating shields is maintained at an essentially constant length. The distal end of the sleeves can have an opening that is located beyond the tip of its respective electrode. The opening can have a diameter that is essentially that of the diameter of the electrode, or the opening can be smaller than that of the electrode. The openings can be coplanar with a plane extending transversely to the major axis of the electrode, at portions of the sleeves that are most proximal to each other, at portions of the sleeves most distal from each other, at portions of the sleeves intermediate between the most proximal and most distal positions, or coplanar with a plane having an axis parallel to a major longitudinal axis of the respective electrode. The major longitudinal axes of the electrodes can be collinear, can intersect at a positive angle in the plane of the path of the analyte through the chamber, can intersect at an angle of about 90 degrees, or can be essentially parallel. The electrodes have a diameter in a range of between about 0.25 mm and about 5 mm. The electrodes can include at least one member of the group consisting of rhenium, silver, molybdenum, tungsten, or iridium. The insulating shields can be made of alumina, polytetrafluoroethylene, glass, and various plastics. The SIBS apparatus can further include a focusing mirror within the housing positioned to reflect light towards the optical detection element. The SIBS apparatus can further include a lens within the housing positioned to focus light toward the optical detection element. The optical detection element can be an optically dispersive spectrometer with a focal plane that records an optical spectrum, or can be one or more detectors, such as photomultiplier tubes or photodiodes, with narrow bandpass optical filters. The tips of the electrodes and insulating shields can be generally parallel to the laser pathway. The optical path can be generally transverse to the spark pathway.
A method for conducting spark-induced breakdown spectroscopy includes directing an analyte through a housing as an aerosol. The housing has an inlet and an outlet defining an analyte flow path from the inlet to the outlet of the housing. A laser is directed generally transverse to and intersecting the analyte flow path. A spark is generated across the analyte flow path between a pair of electrodes mounted within the housing. Each electrode has a tip, wherein a straight line extending between the tips of the electrodes is traversed by shields, a shield being mounted at each electrode, and wherein the shields each have an edge, the edges at least partially defining a spark path that is generally transverse to and intersecting at a point in the analyte flow path and downstream along the analyte flow path from the point of intersection of the laser pathway and the analyte flow path such that a spark ionizes the analyte to form a plasma. An emission is received from the ionized analyte by an optical detection element in order to optically identify the analyte following ionization as it continues along its path through the housing. The shields can each be a sleeve that at least partially surrounds the electrode and extends beyond the tip of each electrode. The method can further include an advancement component at each of the electrodes, whereby each electrode is advanced along its respective major longitudinal axis as each electrode erodes at its respective tip to thereby keep each tip essentially in the same position within the chamber, whereby the path of the spark defined by the tips and insulating shield is maintained at an essentially constant length. The sleeves can each define an opening at an end of the sleeve that is located beyond the tip of its respective electrode, and wherein the edge is defined by the opening. The opening can have a diameter that is essentially that of the diameter of the electrode, or the opening can be smaller than that of the electrode. The openings can be coplanar with a plane extending transversely to the major axis of its respective electrode, at portions of the sleeves that are most proximal to each other, at portions of the sleeves most distal from each other, or coplanar with a plane having an axis parallel to a major longitudinal axis of the respective electrode. The major longitudinal axes of the electrodes can be collinear, intersect at a positive angle in the plane of the path of the analyte through the chamber, intersect at an angle of about 90 degrees, or be essentially parallel. The electrodes can have a diameter in a range of between about 0.25 mm and about 5 mm. The electrodes can include at least one member of the group consisting of rhenium, silver, molybdenum, tungsten, or iridium. The insulating shields can be made of alumina, polytetrafluoroethylene, glass, and various plastics. At least a part of the emission from the ionized analyte can be reflected towards the optical detection element by a focusing mirror within the housing. At least a part of the emission from the ionized analyte can be focused towards the optical detection element by a lens within the housing. The optical detection element can be an optically dispersive spectrometer with a focal plane that records an optical spectrum, or can be one or more detectors, such as photomultiplier tubes or photodiodes, with narrow bandpass optical filters. The tips of the electrodes and insulating shields can be generally parallel to the laser pathway. The optical path can be generally transverse to the spark pathway.
A spark-generating device can have a pair of electrodes, each having a tip. The two tips define a spark path. An insulating shield is proximal to each tip and in an interfering relation with the spark path such that each shield defines a opening through which the spark passes.
The improved SIBS apparatus disclosed herein has several advantages. The insulating sleeves can control the debris emitted from the electrode. In operation, the debris can coat the optics of the SIBS apparatus. When the optics are coated, the SIBS apparatus must be cleaned, which not only requires additional labor, but results in downtime of the SIBS apparatus. Thus, controlling the debris from the electrode reduces maintenance costs and increases operational time. Additionally, the insulating sleeves can control the spark localization, even as the electrodes erode during use. Since the spark generates the plasma, controlling the spark location is important to improve sensitivity of the SIBS apparatus, particularly when the analyte has been aerosolized.
The foregoing will be apparent from the following more particular description of example embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating embodiments of the present invention.
A laser 280 defines a laser pathway 289 by providing light through windows 283 on either side of the housing. The laser pathway 289 is generally transverse to and intersects the analyte flow path 120.
A pair of electrode mounts 200 are contained within housing 105 such that tips of electrodes 220 are positioned at the ends of a line that is generally transverse to the analyte flow path 120 and generally parallel to the laser pathway 289. The electrodes can have any suitable diameter for generating a spark, typically ranging from about 0.25 mm to about 5 mm. The electrodes can be made from any suitable material, such as rhenium, silver, molybdenum, tungsten, or iridium. One of skill in the art will understand that the electrode can be made of many other materials, as may be suitable to optimize detection of an analyte or components of an analyte.
Insulating shield 270 at least partially surrounds electrode 220. At a minimum, the shield 270 has a higher dielectric constant than air. Preferably, the shield 270 has minimal spectral lines or a complete absence of spectral lines. Suitable materials of construction of shield 270 include, for example, alumina, polytetrafluoroethylene, glass, and various plastics. One of skill in the art will recognize that the shield can be made of many other types of material, so long as it is sufficiently insulating to cause a spark typically used in SIBS to be diverted about insulating shield 270. Each shield 270 has an edge 275, and the combination of edges 275 and tips of the electrodes 220 defines a spark path 250 for a spark generated between electrodes 220. Spark path 250 is transverse to and in the analyte flow path 120, generally parallel to the laser pathway 289, and downstream along the analyte flow path 120 relative to the laser pathway 289. Thus, spark 250 generated between the tips of electrodes 220 will extend across edges 275 of shields 270 and across analyte flow path 120 and intersect the optical detection path 130.
Optical detection element 125 defines optical path 130 generally transverse to the analyte flow path. Examples of optical detection elements 125 suitable for use in the spark-induced breakdown spectroscopy analysis apparatus of the invention are known in the art and include, for example, an optically dispersive spectrometer with a focal plane that records an optical spectrum, or can be one or more detectors, such as photomultiplier tubes or photodiodes, with narrow bandpass optical filters. An optional focusing mirror 293 within the housing 105 can be positioned to reflect light towards the optical detection element 125. An optional lens 298 can be positioned within the housing 105 to focus light toward the optical detection element 125.
In operation, an analyte, which can be aerosolized, flows from inlet 110 to outlet 115 along analyte flow path 120. The analyte crosses the laser pathway 289. The laser can be used to measure the size and fluorescence of the analyte to thereby detect whether a particle of interest has crossed the laser pathway. If the particle is a particle of interest, a spark can be generated along spark path 250, thereby creating a cloud of ionized plasma for approximately one half of a microsecond. The ionized cloud of plasma then emits a spectrum characteristic of the analyte, which is detected by the optical detection element 125.
While this invention has been particularly shown and described with reference to example embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.
This invention was made with government support under USAF FA8721-05-C-0002 from the United States Department of Defense. The government has certain rights in the invention.
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