Air Monitoring Semi-continuous determination of ambient air quality The Particle Into Liquid Sampler – a simple solution for the determination of ions in aerosol particles Combustion of fossil fuels for energy production pollutes The Particle Into Liquid Sampler, or PILS1 for short, samples 02 the environment with large quantities of harmful sub ­ aerosol particles from an air flow and brings them into the stances in the form of gases or aerosols. These emissions aqueous phase. Subsequently, they can be analyzed using cause damage, not only at their source, but also far ion chromatography or voltammetry. In order to analyze away from it. The chemical and physical properties of the the gas phase, we recommend the 920 Absorber Module emissions from anthropogenic as well as natural sources or a MARGA2 system, available from Metrohm Applikon. are highly relevant to the climate and the environment. Impactor Aqueous Water-soluble aerosol Aerosol solution components Continuous flow through sample loop of an ion chromatograph Analysis osol component Aer Time Flow diagram for Particle Into Liquid Sampler combined with ion chromatography (PILS­IC) PILS mode of operation The PILS puts aerosols into a supersaturated water vapor The size of the aerosol particles to be determined is phase, where they quickly grow into droplets. These limited by a cyclone or an impactor at the inlet. This droplets are separated on the basis of their inertia and makes it possible, for example, to analyze particles pumped on with a carrier fluid, which contains an internal smaller than 1 µm, 2.5 µm or 10 µm (PM , PM , PM ). 1 2.5 10 standard to allow simple quantification. Air bubbles that To prevent interferences, the gases are absorbed by are present are removed in a so­called debubbler, and the denuder systems. A vacuum pump produces an air flow aqueous phase is transferred to an ion chromatograph, in the system with a flow rate of 1 m3/h. for example, for analysis. The time resolution for the determination of aerosols that can be achieved with this simple technique is far superior to that possible with filter samples. 1 PILS is a coproduction of Metrohm Applikon and Metrohm. 2 Monitor for Aerosols & Gases in ambient Air. Advantages of the PILS • Determination of ions in aerosols with high temporal resolution 03 • Simple interfacing to an ion chromatography and voltammetry system • High sampling rate • Diurnal variation analysis with high time resolution • Direct on­site sample analysis • Contamination-free aerosol collection technique (particles PM , PM , PM ) 1 2.5 10 • No sample storage required • Direct analysis without any further sample preparation Application areas The PILS can be directly coupled with various analytical Application areas for PILS – IC: techniques. With ion chromatography, water­soluble • Monitoring of pollutants inside buildings anions and cations can be determined simultaneously. • Emission control at the workplace for worker protection Heavy metals can be determined using a voltammetric • Monitoring of outside air measuring stand. The PILS can also be used for offline • Measurements of tunnel air sampling with an autosampler. Other examples are the • Determination of stack emissions determination of total organic carbon (together with a • Mobile use, for example on aircraft TOC Analyzer) or interfacing with ICP techniques. 2.8 765.5 2.6 2.4 766.0 Lithium; 80.0 µg/L ] 2.2 Bromide; 920.0 µg/L 766.5 2.0 767.0 1.8 1.6 767.5 Nitrate; 295.2 µg/L Conductivity [µS/cm] Ammonium; 91.1 µg/L Conductivity [µS/cm 1.4 768.0 1.2 Chloride; 11.0 µg/L Nitrite; 2.5 µg/L Sulfate; 31.5 µg/L Sodium; 6.2 µg/L Potassium; 11.4 µg/L Calcium; 7.0 µg/L 1.0 768.5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Time [min] Time [min] Anion and cation chromatogram for outside air determination and aerosol particles smaller than 2.5 µm (PM ). Lithium bromide 2.5 was used as an internal standard. Heavy metal determination using PILS-VA Combining a PILS with a 884 Professional VA enables analysis below, the copper and cadmium concentrations semi­continuous determination of a range of heavy metals in the air rise constantly over several days, up to the point (Cd, Pb, Zn, Cu, Ni, Co, etc.) in particulate matter. The where the rain that sets in washes the majority of the high time resolution records even the smallest changes copper and cadmium out of the air (wet deposition). 04 in the chemical composition of aerosols. In the example Semi­continuous voltammetric determination of heavy metal content (Cd, Pb, and Cu) in outside air samples from Herisau (Switzerland), using a PILS sampling system. Standard ion and heavy metal determination using PILS-IC-VA Coupling with multiple analyzers simultaneously is also ion chromatograph for anion and cation analysis, and to possible. In the case of PILS-IC-VA, particles brought into a voltammetric measuring stand for heavy metal cation solution are transferred in three streams to a dual channel determination. Semi­continuous ion chromatographic determination of anion and cation content, and voltammetric determination of heavy metal content in outside air samples from Herisau (Switzerland). To simulate contamination events, sparklers that had previously been immersed in heavy metal salt solutions were burned. The 920 Absorber Module – an automatic gas sampler The 920 Absorber Module can also be used as a semi-Additionally, the analytical system can be calibrated auto-05 online sampler. In this case, the gaseous compounds matically from a single multi-ion standard using Metrohm (NH , HNO , HNO , HCl, SO ) are absorbed directly in a intelligent Partial Loop Technique (MiPT). Since MiPT allows 3 2 3 2 solution over a defined period of time. An external gas for flexible injection volumes (4–200 µL), it covers a wide flow meter keeps the gas flow constant throughout this range of concentrations. period. The absorbent selected should have a high level of solubility for the gas flow and also be affordable. A 10-port valve, a 6-port valve, and two 800 Dosinos are Typically, ultrapure water is used. available for the entire Liquid Handling. The Liquid Handling controlled by the MagIC Net soft-As a result, the 920 Absorber Module can be used to ware includes sample preparation, as well as all rinsing monitor volatile organic acids in process exhaust gases, procedures. The collected sample can then be transferred for example, or in the ambient air at workplaces. directly to an ion chromatograph for analysis. The 920 Absorber Module (right) is able to collect samples fully automatically and transfer them to the 930 Compact IC Flex (left), for example, for ion chromatographic determination. Features and benefits of PILS-IC-VA 06 Fully automated analysis Once the sample table has been created in the MagIC Net software, the PILS-IC-VA system operates fully au - to matically. The voltammetric determination is syn chronized and the measuring results are transferred directly to the MagIC Net database. No time-consuming sample preparation The samples are directly brought into solution by the Particle Into Liquid Sampler. The next step is straight forward analysis by ion chromatography or voltammetry without any subsequent time­consuming sample preparation or storage, something that would be required with filter samples, for instance. Analyses at hourly intervals The samples are collected and analyzed fully automatically at hourly intervals. Semi­continuous analysis enables con siderably higher time resolution than conventional techniques, particularly those involving filters. 07 Multi-parameter monitoring With this combination, both standard anions and cations as well as heavy metals can be determined in a single analysis. The software automatically calculates the corresponding concentrations in the air. High flexibility The PILS is highly flexible. It can also be used for de - ter minations in combination with mass spectrometry or water soluble organic carbon analyzers, for example. Alternatively, the samples can be collected in sample vessels for offline determination, using an autosampler. Unattended measuring Thanks to the use of supply bottles and rinsing can isters, automated measurements are possible even over extended period of time. Standardized, automated sampling and analysis ensure superior reproducibility. Ordering information Metrohm instruments Further application-specific equipment PILS For sample delivery it is possible to use a vacuum pump 2.136.0400 Particle Into Liquid Sampler ADI 2081 with a drying system made by KNF (vacuum pump 2.136.0500 Peristaltic pump, 8 channels with N860.3FT.40.18). The gas phase is separated with 6 rollers denuder systems (e.g., Multi Channel Annular Denuders 6.5335.000 Liquid Handling Set for PILS made by URG, model no. URG-2000-30x242-4CSS). Inlet systems such as the cyclones made by URG (e.g., PM IC 2.5 URG, model no. URG-2000-30EH) allow aerosols to 2.940.2500 940 Professional Vario TWO/Ses/PP be diffe ren tiated by particle size. 6.2832.000 MSM Rotor A 6.2842.000 Adapter sleeve for Suppressor Vario 2.920.0010 920 Absorber Module 6.6059.322 MagIC Net 3.2 Professional For this system setup, we also recommend a 941 Eluent Production Module. Voltammetry 2.884.1110 884 Professional VA semiautomated for MME 2.843.0240 843 Membrane Pump Station for Professional VA/CVS systems 6.5339.030 VA Electrode equipment with MME pro 6.6065.202 viva 2.0 Columns 6.1006.510 Metrosep A Supp 5 - 100/4.0 6.1006.500 Metrosep A SUPP 4/5 Guard/4.0 6.1050.410 Metrosep C 4 - 100/4.0 6.1050.500 Metrosep C 4 Guard/4.0 www.metrohm.com EN – 2016-11 000.5215 Subject to change Layout by Ecknauer+Schoch ASW, printed in Switzerland by Metrohm AG, CH-9100 Herisau 8.