Spray Chambers and Desolvation Systems

4 Spray Chambers and Desolvation Systems. A nebulizer must produce droplets less than 10 /im in diameter in order to achieve a high aerosol transport efficiency (the percentage of the mass of nebulized solution that reaches the plasma), and rapid desolvation, volatilization, and atomization of the aerosol droplets. Pneumatic nebulizers, especially, produce highly poly dispersive aerosols with droplets up to 100 jwm in diameter and these large droplets must be removed by a spray chamber. 

A barrel-type spray chamber removes the large droplets by turbulent deposition on the inner walls of the chamber or by gravitational action. 

The nebulization rates achieved with the spray and nebulizer systems used in ICP spectrometry are much slower than those used in flame atomic absorption. The transport efficiency of the sample introduction systems is less than 3% in ICP spectrometry, whereas that in flame atomic absorption is about 15% or less. 

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Chilled spray chambers and desolvation systems Direct injection nebnlizers (DIN)... 

NEBULISERS, SPRAY CHAMBERS AND DESOLVATION SYSTEMS - OVERVIEW... 

To assist in the deposition of these larger droplets, nebulizer inlet systems frequently incorporate a spray chamber sited immediately after the nebulizer and before the desolvation chamber. Any liquid deposited in the spray chamber is wasted analyte solution, which can be run off to waste or recycled. A nebulizer inlet may consist of (a) only a nebulizer, (b) a nebulizer and a spray chamber, or (c) a nebulizer, a spray chamber, and a desolvation chamber. Whichever arrangement is used, the object is to transfer analyte to the plasma flame in as fine a particulate consistency as possible, with as high an efficiency as possible. 

The combination of the ultrasonic nebulizer, heated spray chamber and condenser/desolvator leads to improvements in detection limits by a factor of about 10 compared to that of a pneumatic nebulizer without a desolvation system. This is the main reason ultrasonic nebulizers are used despite their higher cost (approximately U.S. 15,000 in 1998). 

There are several drawbacks to ultrasonic nebulizer/desolvation systems. Precision is typically somewhat poorer (1% to 3% relative standard deviation) than for pneumatic nebulizers (0.5% to 1.0% relative standard deviation) and washout times are often longer (60 to 90 sec compared to 20 to 30 sec for a pneumatic nebulizer/spray chamber without desolvation). Furthermore, chemical matrix effects are dependent on the amount of concomitant species that enter the ICP per second. Therefore, use of any sample introduction device that increases the amount of sample entering the plasma per second also naturally leads to more severe matrix effects when the sample contains high concentrations of concomitant species. 

Such is the added capability and widespread use of these nebulizers across all application areas that manufacturers are developing application-specific integrated systems that include the spray chamber and a choice of different desolvation techniques to reduce the amount of solvent aerosol entering the plasma. Depending on the types of samples being analyzed, some of these systems include a low-flow nebulizer, Peltier-cooled spray chambers, heated spray chambers, Peltier-cooled condensers, and membrane desolvation technology. Some of the commercially available equipment include the following ... 

Microflow nebulizer with heated spray chamber and Peltier-cooled condenser An example of this design is the Apex inlet system from ESI. This unit includes a microflow nebulizer, heated cyclonic spray chamber (up to 140°C), and a Peltier multipass condenser/cooler (down to -5°C). A number of different spray chamber and nebulizer options and materials are available, depending on the application requirements. Also, the system is available with Teflon or Nafion microporous membrane desolvation, depending on the types of samples being analyzed. Figure 17.12 shows a schematic of the Apex sample inlet system with the ctoss-Aow nebulizer. 

On line additions of aqueous standard solutions for the calibration of LA-ICP-MS including a comparison of wet and dry plasma conditions are discussed by O Connor et al.ls For solution calibration of standard solutions the authors used a 100 (xl PFA nebulizer together with a cyclonic spray chamber or a MCN-6000 sample introduction system with desolvator, to study the wet and dry plasma, respectively. A polypropylene Y piece was applied to mix the laser ablated material and the nebulized standard solutions. The authors found that the on line addition of water is the preferred mode of operation for quantification by LA-ICP-MS, i.e., wet plasma is more stable (improved standard deviation of sensitivity ratios). 

Desolvation systems can provide three potential advantages for ICP-MS higher analyte transport efficiencies, reduced molecular oxide ion signals, and reduced solvent loading of the plasma. Two different approaches have been used for desolvation in ICP-MS. The heated spray chamber/condenser combination has been discussed it is the most commonly used system. The extent of evaporation of the solvent from the aerosol and cooling to reduce vapor loading varies from system to system. The second approach is the use of a membrane separator to remove solvent vapor before it enters the ICP. 

The vast majority of ICP-based analyzes are performed on liquid samples that are introduced to the plasma in the form of an aerosol. In this case, sample introduction system consists of four parts (i) a nebulizer, which generates an aerosol (ii) a spray chamber, which filters the aerosol and transports it to the plasma (hi) a desolvation system to reduce the mass of solvent reaching the plasma (iv) an injector tube to introduce the aerosol into the plasma base. 

To assist in the deposition of these larger droplets, nebulizer inlet systems frequently incorporate a spray chamber sited immediately after the nebulizer and before the desolvation chamber. Any liquid deposited in the spray chamber is wasted analyte solution, which can be run off to waste or recycled. 

The Thermospray jet is introduced into a spray chamber which is heated sufficiently to complete the vaporization process. Helium is added through a gas inlet in sufficient quantity to maintain the desired pressure and flow rate. The fraction of the solvent vaporized in the thermospray vaporizer and the temperature of the desolvation chamber is adjusted so that essentially all of the solvent is vaporized within the desolvation region. The Thermospray system allows very precise control of the vaporization so that all of the solvent can be vaporized while most of even slightly less volatile materials will be retained in the unvaporized particles. 

In this device the liquid sample is sprayed into a heated spray chamber, where the nebulizer gas transfers the aerosol through the membrane desolvator. An argon flow removes the solvent vapour from the exterior of the membrane. If compared to conventional pneumatic nebulizers, this system enhances analyte transport efficiency and limits solvent loading to the plasma. Oxide and hydride polyatomic ion interferences are significantly reduced, improving the detection limits by an order of magnitude. 

Cross contamination encountered with desolvation systems has been greatly reduced by using a concentric sheath to prevent deposits on tube walls. It is important to note that nebulisers and spray chambers operate interactively and must be optimised as a unit rather than individually. There are, however, certain parameters that need to be considered in relation to the spray chamber ... 

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