Id 100 User Manual

ID-100 Autodilutor Operator Manual, X Series ICP-MS

Revision 1.6 27th February 2003 P/N 3601099

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ID100 AUTODILUTOR Customer Information Document. Copyright Thermo Electron 2003. Use or Publication of Data This manual contains proprietary documents intended for the exclusive use of Thermo Electron customers and Thermo Electron personnel and may not be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying and recording, for any purpose without the express written permission of Thermo Electron. Trademarks The Thermo Electron and Thermo Elemental logos is a registered trademark of Thermo Electron. The ID100 AUTODILUTOR is a registered trademark of Thermo Electron. Patents The ID100 and its use are part of patent applications GB 0218946 and 0218949.

Thermo Elemental Ion Path Road Three Winsford Cheshire CW7 3BX UK Tel: Fax:

44 (0) 1606 548 100 44 (0) 1606 552 558

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Warranty Policy Thermo Electron warrants instrumentation of its manufacture to be free from defects in material or workmanship and will, as its option, repair or replace, free of charge, or allow credit for any such goods found on examination by Thermo Electron to be defective under normal use and service within 13 months from date of shipment to the customer, provided Thermo Electron is promptly notified in writing upon discovery of such defects and provided any necessary return charges are prepaid. Parts of Thermo Electron’s manufacture supplied to customer during the above warranty period carry the balance of the warranty of the instrument. Parts supplied after the expiration of such period are warranted for 30 days from the date of shipment. Replacement parts are on an exchange basis and will be new standard parts or parts of equal quality. Exchanged parts removed from the instrument shall become property of Thermo Electron. Electronic, electrical and other purchased components carry the guarantees of their respective manufacturers. Expendable items are excluded from this warranty. Note: Thermo Electron makes no warranty of merchantability or fitness for a particular purpose or any other warranty, expressed or implied, except as stated above. The ID100 will be repaired under a “back to base” policy. Should any repair be necessary the unit will be returned to a designated Thermo Electron repair centre under suitable authorisation. Every reasonable effort will be made to repair the device as quickly as possible and once repaired the unit will be returned to the customer.

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Safety Warning Due to design changes and product improvements, the information in this document is subject to change without notice. Thermo Electron reserves the right to change hardware and software designs which may subsequently affect the contents of this customer information document. Thermo Electron assumes no liability for any errors that may appear in this guide. The methods and analytical procedures described in this and other manuals supplied with the ID100 AUTODILUTOR are designed to be carried out by properly trained personnel in a suitably equipped laboratory. In common with many laboratory procedures, the methods described may involve hazardous materials or substances of unknown toxicity. For the correct and safe execution of the methods, it is essential that laboratory personnel follow standard safety procedures for the handling of hazardous materials. Whilst the greatest care has been exercised in the preparation of this document, Thermo Electron expressly disclaims any liability to users of these procedures for consequential damages of any kind arising out of or in connection with use of these procedures. There are many sources of safety information available. Consult your chemical and laboratory supply catalogues. You may also refer to the CRC Handbook of Laboratory Safety, published by CRC Press Inc., Boca Raton, Florida.

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ID100 AUTODILUTOR Customer Information Document. .................................................. 2 Use or Publication of Data.................................................................................... 2 Trademarks ..................................................................................................... 2 Warranty Policy ................................................................................................... 3 Safety Warning .................................................................................................... 4 Preface ............................................................................................................. 7 Health and Safety ........................................................................................... 7 Conformity Statements ..................................................................................... 7 Preparing for Installation ................................................................................... 7 Installation ................................................................................................... 7 Analytical Use ................................................................................................ 7 Maintenance.................................................................................................. 7 Troubleshooting.............................................................................................. 7 Health and Safety Issues ........................................................................................ 8 Declaration of Conformity, EMC Validation, Quality Audit and ISO Safety Validation. .............. 9 Declaration of Conformity.................................................................................... 9 EMC Validation ................................................................................................. 9 Quality Audit ................................................................................................... 9 Safety Validation............................................................................................... 9 Introduction ..................................................................................................... 10 Preparing for Installation...................................................................................... 11 Operating Environment ......................................................................................11 Space Requirements..........................................................................................11 Power Requirements .........................................................................................11 Unpacking the ID100 AUTODILUTOR........................................................................11 Installing the PCI Card in your host computer............................................................. 12 Installing the PCI card........................................................................................12 Installing the PCI card software ............................................................................12 Installing the ID100 AUTODILUTOR.......................................................................... 13 Overview of Connections ....................................................................................13 Connecting to the ICP-MS..................................................................................13 Connecting externals.......................................................................................14 Verifying Communication ....................................................................................14 Configuring the Cetac ASX510 for use with the ID100 Autodilutor...................................16 Installation of ID100 AUTODILUTOR ........................................................................17

6 Initial Set-up ..................................................................................................18 Setting the default flow rates ..............................................................................18 Setting the default Undiluted rate .......................................................................18 Setting the default Uptake rate ..........................................................................19 Setting the default Wash rate ............................................................................20 Verifying Installation........................................................................................... 21 Analytical use of the ID100 Autodilutor .................................................................... 22 Principles of autodilution....................................................................................22 Setting up the sampling sequence for an experiment. ..................................................25 Setting up the uptake and wash in an experiment.......................................................25 Setting up the dilution modes in an experiment. ........................................................26 Prescriptive dilution..........................................................................................27 Pre-emptive dilution. ........................................................................................28 Failed internal standards autodilution.....................................................................32 Over-range autodilution. ....................................................................................34 Maintaining the ID100 AUTODILUTOR....................................................................... 37 Cleaning the ID100 AUTODILUTOR body: ..................................................................37 Optimising Pump Performance:.............................................................................37 Troubleshooting the ID100 AUTODILUTOR................................................................. 38 Power Supply Problems ......................................................................................38 Communication Problems....................................................................................38 Contamination Problems.....................................................................................38 Stability Problems ............................................................................................38 Glossary of Terms............................................................................................... 39

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Preface Thermo Elemental is part of the Thermo Electron Corporation and is a designated centre of excellence for AA, ICP and ICP-MS within the Thermo Electron Group. We would like to thank you for purchasing an ID100 AUTODILUTOR. We are confident that you will be delighted with your purchase and we look forward to fulfilling all your immediate and future elemental instrumental requirements. To ensure that you receive the best possible service throughout the lifetime of your instrument, we have created this Operator Manual. This document is intended to advise you on all aspects of installation, use and maintenance associated with your ID100 AUTODILUTOR. This information Document is divided into several sections. The overview below outlines the contents of each section. Health and Safety Health and Safety warnings are documented on page 8. They must be read, understood and observed by all users at all times. Conformity Statements Statements confirming the ID100 AUTODILUTOR Conformity for Electromagnetic Compatibility, Safety and Quality Systems are displayed on page 9. Preparing for Installation Information on the laboratory requirements for your ID100 AUTODILUTOR and given on page 11. Installation Instructions for installing the ID100 AUTODILUTOR on your ICP-MS are detailed starting on page 13. Page 21 gives information on how you can verify that this installation has been successfully completed. Analytical Use Instructions on how to use the ID100 Autodilutor in its various modes of operation an be found starting at page 22. Maintenance Information on page 37 explains how the ID100 AUTODILUTOR should be maintained to ensure you benefit from optimum performance throughout its lifetime. Troubleshooting The troubleshooting guide on page 38 gives a useful list of potential errors and how they can be resolved.

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Health and Safety Issues Heat Heat is generated by internal components within the ID100 AUTODILUTOR. Ensure that the cooling outlets on the back panel of the ID100 AUTODILUTOR remain unobstructed at all times. Electric Shock Voltages above 50 V AC are present on the instrument.

Flammable Liquid Some applications may use flammable solvents. Ensure safety precautions are taken when using flammable liquids. Dangerous Chemicals Chemicals are used in the normal operation of the instrument that may present a hazard. Ensure safety precautions are taken when dealing with hazardous liquids.

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Declaration of Conformity, EMC Validation, Quality Audit and ISO Safety Validation. Declaration of Conformity Thermo Electron declare under our sole responsibility that the ID100 AUTODILUTOR, to which this declaration relates, is in conformity with the following EMC standards and/or other normative documents:

EMC Validation •

RFI Radiated Emission to EN55011:1998 Group 2 Class A 30-1000 MHz and 0.15-30 MHz

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Terminal Interference Voltage to EN55011:1998 Group 2, Class A.

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BSEN61326;1998.

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Electrostatic Discharge EN61000-4-2:1995: Contact discharge up to ±4 kV.

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RFI Radiated Susceptibility EN61000-4-3: Test Level 3 V/m with 1 kHz, 80% amplitude modulation over the frequency range 80 to 1000 MHz.

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Electrical Fast Transients EN61000-4-4:1995: Test Level (1.0 kV mains).

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Surge Test EN61000-4-5:1995. Test Levels (0.5 kV line to line and 1 kV line to ground).

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RFI Conducted Susceptibility EN61000-4-6:1996.

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Voltage Dips and Interrupts to BS EN61000-4-11:1994.

Quality Audit •

ISO 9001:1994 Quality System-Model for Quality Assurance in Design and Development, Production, Installation and Servicing.

Safety Validation •

EN61010-1: (IEC1010-1): Safety requirements for electrical equipment for measurement control and laboratory use.

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Introduction The ID100 AUTODILUTOR is designed to be sturdy, reliable and easy to use in conjunction with Thermo Electron AA and ICP-MS products. The ID100 AUTODILUTOR provides accurate and precise on-line sample dilution to enable much reduced sample throughput times. The ID100 AUTODILUTOR case is made from corrosion resistant stainless steel and all components within the ID100 AUTODILUTOR are manufactured from inert, non-metallic materials or stainless steel. The ID100 AUTODILUTOR is controlled via the AA or ICP-MS host computer using a serial RS232 communications port. This may entail the fitting of an additional RS232 card to the host computer (for ICP-MS use) where the normal Serial ports on the host computer are already in use. This manual covers the use of the ID100 Autodilutor with the X Series ICP-MS only. For details on it’s use with Thermo Electron’s range of Atomic Absorption products, please consult your local Thermo Electron sales office.

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Preparing for Installation Operating Environment The ID100 AUTODILUTOR is designed for indoor use at an altitude of up to 2,000 metres above sea level and should be installed in a clean working environment meeting Pollution Degree 2 (Office Environment). For altitudes above 2,000 metres please contact Thermo Electron. The operating temperature range of the ID100 AUTODILUTOR is 0 to +50°C, the storage temperature range is -20 to +70°C. The humidity should be <80% non-condensing. Space Requirements For the ID100 AUTODILUTOR to function optimally, it should be located as close to the instrument as possible. In the case of the X Series ICP-MS the ID100 AUTODILUTOR can be ideally located at the right hand side of the instrument between the sample introduction and the Autosampler (where applicable). The minimum footprint of the ID100 AUTODILUTOR is 205x290.5x185.6mm.

The ID100 AUTODILUTOR uses a high precision pump to accurately mix sample with diluent in order to achieve its wide range of dilution. Space should be available close to the ID100 AUTODILUTOR for a receptacle to contain this diluent, the receptacle should be on the same bench level as the ID100 Autodilutor for an analytically stable operation. Power Requirements The ID100 AUTODILUTOR should be placed within 1.2 metres of a power outlet. The electrical supply should satisfy Installation Category II and be in the range 100-240VAC+/-10%, 50/60Hz. The ID100 AUTODILUTOR is rated at 0.5A. Voltage selection is automatic. The ID100 AUTODILUTOR is supplied with a power cord which meets the requirements of the country in which you purchased the instrument. The ID100 AUTODILUTOR is designed for connection to a grounded (earthed) outlet. This is an important safety feature and should not be disabled. Unpacking the ID100 AUTODILUTOR On receipt of your ID100 AUTODILUTOR check the packaging for any signs of external damage, for example holes, tears etc. If there is any sign of damage to the packaging inform the delivery personnel and summarise the fault on the delivery paperwork. Contact your local distribution office as soon as possible. The time at which you sign the delivery document represents the end of our couriers responsibility. DO NOT accept the delivery unless you are satisfied. If the ID100 AUTODILUTOR is to be upacked after storage in a cold environment, allow the packaged equipment time to reach room temperature before opening. This will avoid condensation forming on the equipment which could potentially cause damage.

12 Remove the ID100 AUTODILUTOR from the packing and check of the contents against the Shipping List.

Installing the PCI Card in your host computer The ID100 AUTODILUTOR communicates with your X Series host computer via an RS232 serial connection. If you are using an Autosampler with your X Series both Serial Ports are already in use. In order to communicate to the ID100 AUTODILUTOR you will need to install the additional PCI Serial Card P/N 4600403. This gives an extra 2 Serial Communication Ports on the host computer. Installing the PCI card Observe Static Precautions!!!!! 1. 2. 3. 4. 5. 6. 7. 8.

Switch off the host computer and remove the power cable. Remove the side cover from the computer. Rotate the green slide anticlockwise to remove the card tray. Using a suitable screwdriver remove one of the blanking plates. Unpack the PCI card and carefully insert in one of the available slots. Slide the card tray back into the computer and rotate the green slide clockwise to lock. Replace the side cover. Re-connect the power cable and switch on.

Installing the PCI card software When the computer reboots the ‘New Hardware Detected’ window will be displayed. Select browse and choose the file ‘io’ in the folder IO, PCI IO, Win2k on the supplied CD The driver will now install and you will be asked to reboot the computer. Once the computer has rebooted the card is installed.

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Installing the ID100 AUTODILUTOR Overview of Connections

C. RS232 Serial connector

A. Mains Power inlet (fused)

B. On/Off switch

D. Drip tray overflow spout

E. Power Indication LED

Figure 1 – View of ID100 AUTODILUTOR showing connections Connecting to the ICP-MS For optimum performance on the X Series ICP-MS the ID100 AUTODILUTOR should be placed immediately at the right hand side of the instrument, between the sample introduction and Autosampler (where fitted). The ID100 AUTODILUTOR will not interfere with the opening of the Sample Introduction System on the X series ICP-MS for routine maintenance of the cones. All the connectors and tubing required for connecting the ID100 Autodilutor to the X Series ICPMS is included with the kit and further consumable kits can be purchased using P/N 4600417. The ID100 AUTODILUTOR should be connected as shown in Figure 2, as follows: 1. Take the uptake tube from the Autosampler and connect to the port labelled ‘A’ on the ID100 AUTODILUTOR pump. Ensure that the tube pushes fully through the screw piece and ferrule before screwing into the pump. Also, ensure that the capillary tube is cut flat with no burrs. 2. Take a short length (approx. 20-30mm.) of tube 1.6mm O.D. x 0.5mm I.D. and connect between port ‘B’ on the ID100 AUTODILUTOR pump and one side of the ‘T’ mixing piece provided. 3. Take a length of the 3.2mm O.D. x 1.6mm I.D. and connect this to the central point of the ‘T’ mixing piece. Place the other end of this tube into your diluent receptacle. 4. Fix a short length of tube 1.6mm O.D. x 0.5mm I.D. between the remaining side of the ‘T’ mixing piece and the uptake tube on the Peristaltic pump. To allow for the shortest stabilisation times, the T-piece should be mounted as close as possible to the peristaltic pump and all tubing lengths after the t-piece made as short as possible. This is especially the case when the internal standards are being added on-line via a second T-piece after the peristaltic pump. In this case, it can be faster to use smaller diameter tubes on the peristaltic pump and run the pump at a faster normal uptake rate. With typical setup using a 700ul/min on the ID100 and 900-1000ul/min on the peristaltic pump, with the tubing lengths cut appropriately, a stable signal will be obtained in less than 30 seconds after switching the ID100 to a new pump speed for a dilution. NB: When adding internal standards via a separate T-piece and the tubing sizes and lengths have not been optimised, stabilisation on changing the ID100 pump rate can be longer than 60 seconds.

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Figure 2 - ID100 AUTODILUTOR sample uptake connections Connecting externals Connect the serial cable provided between the 9 way D-type connection on the rear face of the ID100 AUTODILUTOR (C in figure 1) and the Serial Port on the host computer (this will be on the additional RS232 card provided if an Autosampler is fitted). Finger-tighten all screwlocks. Now connect the power cable supplied to the IEC socket on the rear of the ID100 AUTODILUTOR (A in figure 1). Plug the cable into a suitable 100-240VAC +/-10%, 50/60Hz power outlet. Verifying Communication 1. Startup hyperterminal which can be found in the Start menu under Programs/Accessories/Communications.

15 2. The program will prompt you to enter a name for the connection. Type ‘ID100 AUTODILUTOR’ and select OK.

3. Select COM port 3 and click on OK.

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4. Select the properties for the COM port as shown.

You will need to change the following defaults: Bits per second Flow Control You will now have a blank window which should say ‘Connected’ in the status bar in the bottom left hand corner. Now switch the ID100 AUTODILUTOR on using the switch on the rear of the unit (B). The green LED on the front panel of the ID100 AUTODILUTOR should illuminate indicating that the power supply within the ID100 AUTODILUTOR is operational. To confirm that the ID100 is OK you should now type: APRINT ALL This is case sensitive and should be followed by pressing Control-J to action the command. This should produce a list of the ID100 variables and flags. If “?” is returned then there is a communications or controller problem. If you see the variables and flags message installation has been successful and you can continue after closing Hyperterminal. If you do not see the message communications have not been successful. See the troubleshooting guide for more information. Configuring the Cetac ASX510 for use with the ID100 Autodilutor In normal use the ID100 Autodilutor will wash out sample in both directions and as such, the rinse vessel on the ASX510 Autosampler must be adapted to allow this without flooding.

17 On the back of the ASX510 is a two channel peristaltic pump. Determine which channel removes the waste from the rinse vessel by sending the probe to the rinse station and watching the flows. Uncouple from the peristaltic pump the channel that drains the rinse vessel and place the waste bottle it feeds under the autosampler. As long as all tubes and the waste vessel are kept below the level of the rinse station on the ASX510, the rinse station will not flood.

Adding the ID100 AUTODILUTOR to PlasmaLab and Initial set-up Installation of ID100 AUTODILUTOR Insert the CD (P/N 3601111) supplied with the ID100 Autodilutor and it will autostart. If it does not, examine the contents of the CD using Windows Explorer and run the ID100 Setup program. This will install the the validation template for the ID100 and the default ACX script file. The ACX scripts will need to be imported into PlasmaLab. Goto the Instrument/Configuration/ACL script editor page and choose the import script icon as below.

The ID100.ACX script file can be found in the PlasmaLab directory. Import all the default scripts using the wizard.

In the instrument configuration page of Plasmalab open the ‘Accessory’ wizard an ID100 AUTODILUTOR. § § §

and add

Select the required COM Port. Approriate description. Click on FINISH to save.

Click on

to connect to the ID100 AUTODILUTOR, by selecting the autodilutor tab as shown

18 Initial Set-up When unlinked the status buttons should show the current status of the ID100 AUTODILUTOR (stopped) and the current flow rate should read 0.00 ul/min. (all other areas should be greyed out except for Port).

To be activated, the autodilutor software link to the accessory. (All areas activate except for Port). Go to the Autosampler tab and place the tube into the rinse station, go back to the autodilutor tab and link the accesory, select direction to toward instrument set flow rate to 500ul/min by either using the slider or the text box and press Apply. Start the ID100 AUTODILUTOR by clicking on Confirm that, § Flow is in the right direction (If you see bubbles or solution flowing into the rinse station then you have connected the tubing the wrong way to the ID100 AUTODILUTOR). § Correct flow rate as been attained by checking with “Current Flow Rate” allow for a 0.02 discrepancy Setting the default flow rates This part of the setup assumes that a normal 1 ml/min nebuliser is being used and that the sample uptake is between 0.8 and 1.0 ml/min. If lower sample uptake rates are being used, for example if internal standards are being added via a T-piece, and therefore sample flows are lower, reduce the values shown below accordingly. Setting the default Undiluted rate First ensure that the both the ID100 AUTODILUTOR uptake and diluent tubes are placed in separate deionised water.

19 With the ICP-MS operational and the Nebuliser flow rate and Peristaltic Pump running under normal operational parameters click on the button and select the Autodilutor tab. Click on to connect to the Autodilutor. Set the Autodilutor speed to 600ul/min, direction should be pumping towards the instrument and click on to start the pump. If you pull the diluent tube out of the DIW you should see solution being drawn towards the ICP-MS by the Peristaltic Pump. Gradually increase the ID100 AUTODILUTOR flow rate and repeat this process until you see that the solution is no longer drawn towards the Peristaltic Pump, the solution will have a pulsating effect due to the peristaltic pump. At this point all of the sample that is presented to the instrument will come from the ID100 AUTODILUTOR and no diluent is being added. Best stability will be obtained if the “undiluted state” is set to when a little diluent is always being taken by the ICP-MS. Set the ID100 Autodilutor flow so there is a small and relatively pulse free movement of diluent towards the T-piece. This will probably be when the ID100 flow is reduced by 10-20% from when no movement is seen in the diluent line. Click on the button labelled ‘Set default as current’ next to the ‘Undiluted’ to save your settings.

NB If you increase the ID100 AUTODILUTOR pump speed above this rate you will pump sample into the diluent receptacle. This will contaminate your diluent with sample. NB When setting up the ID100 Autodilutor pump flows, remember to take into account expected wear in the peri-staltic pump tubing. This can be done by ensuring there is always a slight dilution, for example, if the measured uptake rate for the ICP-MS nebuliser is 800 ul/min, set the ID100 Autodilutor rate to 700 ul/min. Setting the default Uptake rate If you wish to run the sample uptake with normal peristaltic pump speed then click on ‘Set default as current’ next to the ‘Uptake flow rate’ on the Autodilutor tab. The choice of whether the peristaltic pump and ID100 Autodilutor run faster during the uptake and wash is made through the choice of the ACX script for the instrument configuration in use. These are user editable scripts with some default scripts provided in the standard installation of PlasmaLab and the ID100 Autodilutor. For information on editing the ACX scripts, consult the PlasmaLab on-line help.

This will set the default Uptake rate to be the same as the default Undiluted rate. It is possible to set up the ID100 AUTODILUTOR Uptake rate to improve throughput times by taking advantage of the ability of the X Series ICP-MS to run the Peristaltic Pump at Rabbit speed during sample uptake. With the Peristaltic Pump at Rabbit you can increase the pump rate of the ID100 AUTODILUTOR above the normal Undiluted rate to speed uptake times without contaminating the diluent. This is achieved as follows:

20 First ensure that the both the ID100 AUTODILUTOR uptake and diluent tubes are placed in DIW. With the ICP-MS operational and the Nebuliser flow rate and the Peristaltic Pump running at Rabbit speed. Click on the button and select the Autodilutor tab. Click on to connect to the Autodilutor. Set the Autodilutor speed to 1200ul/min, direction pump towards instrument, and click on to start the pump. If you pull the diluent tube out of the DIW you should see solution being drawn towards the ICP-MS by the Peristaltic Pump. Gradually increase the ID100 AUTODILUTOR flow rate and repeat this process until you see that the solution is no longer drawn towards the Peristaltic Pump, the solution will have a pulsation effect due to the Peristaltic pump. At this point all of the sample that is presented to the instrument will come from the ID100 AUTODILUTOR and no diluent is being added, i.e. the sample is in its undiluted state. Reduce the ID100 Autodilutor flow slightly to avoid contamination of the diluent. Click on the button labelled ‘Set default as current’ next to the ‘Uptake Flow Rate’ to save your settings.

Setting the default Wash rate First ensure that the both the ID100 AUTODILUTOR uptake and diluent tubes are placed in deionised water. With the ICP-MS operational and the Nebuliser flow rate and Peristaltic Pump running under normal operational parameters click on the button and select the Autodilutor tab. Click on to connect to the Autodilutor. The direction should be set to pump away from the instrument, set the Autodilutor speed to 3000ul/min and click on to start the pump. If you wish to run the sample wash uptake with normal peristaltic pump speed then click on ‘Set default as current’ next to the ‘Uptake flow rate’ on the Autodilutor tab.

Default wash rate can be set to the user desired speed, as long as the autosampler probe is in the rinse position or a suitable waste container. When washing the ID100 AUTODILUTOR will take diluent flush out the diluent in a reverse direction hence the negative sign in front of the flow rate. The peristaltic pump will take the diluent towards the instrument hence cleaning the instrument. To determine the default wash rate will depend on the length of tubing and the concentration of the sample being taken up by the ID100 AUTODILUTOR. It is recommended that the Peristaltic pump should be run at rabbit speed during wash periods. NB Some accessory control scripts (ACX scripts) will have been written to flush the ID100 pump in both directions during the wash sequence. This is perfectly normal and depends on the construction of the supplied or user defined ACX script.

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Verifying Installation Supplied with your ID100 AUTODILUTOR is a compact disc containing an experiment template called ‘ID100 AUTODILUTOR Install verification.tet’. When the ID100 Autodilutor CD was installed, this template was copied to the default Templates directory. From Plasmalab, click on the Experiment Icon and select create from template and set up the samples in your Autosampler as shown in the Sample List. NB The validation template assumes that the X Series ICP-MS is functioning normally and a good cross calibration is current. For instructions on how to run the experiment and ACX scripts look in the Analytical Use section of this manual. Queue the experiment. The experiment uses Prescriptive dilution to automatically dilute a 1ppm solution to build a calibration graph. Once the experiment has finished, go to the Results, Calibrations page and view both the calibration curves and the %error. All errors should be <10%, an example is shown below:

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Analytical use of the ID100 Autodilutor Principles of autodilution. The ICP-MS uses a constant sample uptake rate of between 0.8 and 1.0 ml/min normally with the sample being delivered by the peristaltic pump on the X Series ICP-MS. NB In some circumstances the sample uptake rate may be lower due to the use of a different nebuliser type or mixing the internal standard on-line. The autodilution principle is the same under these circumstances but the flow rates used in the illustration below would need to be changed accordingly. The illustration given below assumes the following: • A normal sample nebulisation rate with a glass concentric nebuliser • A Cetac ASX500/510 autosampler is used • Internal standards (if required) are added to the samples and diluent to the same level

When the flow rates are setup as described earlier in this manual, the samples always experience a small amount of dilution. As all the samples have at least this minimum dilution, no correction needs to be made in the software, the effect of the minimum dilution is cancelled out. If the flow rate of the ID100 Autodilutor pump is reduced to half it’s previous amount, the peristaltic pump will continue to uptake at the same level and the extra volume will be drawn from the diluent reservoir. If the ID100 Autodilutor pump flow is reduced again, more diluent will be taken from the reservoir and so on. The relationship between the flow rate on the ID100 Autotdilutor and the dilution factor achieved is linear so long as the peristaltic pump flow rate remains constant (within the normal wear parameters of the pump tubing). In effect the diluent is used merely as a “make up” solution to maintain the nebuliser properties. The size of the aerosol droplets and the droplet size distribution of a nebuliser depends on the total amount of liquid being nebulised, the viscosity of the solution and the gas flow rates. This means that if the diluent and sample both contain internal standards at the same concentration, the measured signal from the internal standards will be independent of the dilution factor used assuming there are no physical effects from the composition of the sample itself. Indeed, such a change in the internal standards when aspirating a sample is a good diagnostic for the performance of the sample when analysed. One of the operation modes of the ID100 Autodilutor is to correct for physical effects of sample composition by monitoring the internal standards and diluting the sample to achieve good internal standard recoveries

23 (the Failed Internal Standard test). This internal standard effect will also be the same if the internal standards are added separately via the third channel on the X Series ICP-MS peristaltic pump as shown in the figure above. If each sample contained an internal standard that was not present in the diluent this would indicate the amount of dilution any sample had in the system by relating the measured internal standard value back to an original undiluted sample at the beginning of the sequence of samples. For this to work effectively the Internal Dilution Standard, as it is known, is first corrected by the main internal standards and then it is compared to the reference value at the start of the sample set. The Internal Dilution Standard is used within the PlasmaLab software as an internal correction mechanism that allows much higher dilution factors to be used than the guaranteed maximum. The errors that might be seen in very high dilutions are due to mixing effects at very low flow rates and the effects of trapped bubbles at very low flow rates. Up to 50:1 dilution with a nebuliser sample pumping rate of 0.8 ml/min are achievable to accuracies and precisions of 5% or less without use of the Internal Dilution Standard. The physical process of autodilution is, as described above, merely the reduction in the delivered flow from the ID100 Autodilutor pump linearly with required dilution factor which can be performed from within the PlasmaLab software. The other issues that need to be considered in the use of the ID100 Autodilutor are: • The setting up of timings in the software to co-ordinate the control and stabilisation of the peristaltic pump and ID100 Autodilutor pump to obtain a stable analytical signal. • The logic process in the software that triggers when a dilution is made and what the dilution should be. • The timings and sequences of how the system should be washed out after each sample and at the end of the set of samples. The timing and control of the pumps is done through the Accessory Control Language (ACX) scripts provided, the setup screens for the pumps and the experiment timings screens in the PlasmaLab software. The use of these is explained in the next section. There are four basic ways in which a sample autodilution is triggered: Prescriptive; here the user can define a dilution for each sample in the sample list which the ID100 Autodilutor will then prepare as each sample is introduced to the ICP-MS. This is only the initial minimum dilution and further dilutions can be made automatically. Prescriptive dilution can not be used in conjunction with pre-emptive dilution mode. Pre-emptive; this mode of operation replaces the Prescriptive mode with a more intelligent automated method of determining what the initial dilution for analysis should be. ICP-MS as a technique has a limitation on the total dissolved solids levels that any solution can contain, traditionally this has meant that some prior knowledge of the sample has been needed in order to dilute the sample to an appropriate level. With pre-emptive mode the user defines the total dissolved solids content by setting a test that the sum of the concentrations of any defined set of analytes must be lower than a given value. For example, that the sum of the Na, Ca, Mg and Fe concentrations should not exceed 500 ppm. The sample is initially introduced to the ICP-MS in it’s most diluted state and a semi-quantitative determination of the analyte concentrations is made. If the dilution corrected value for the sum of the analytes is less than the set value then the ID100 Autodilutor pump will set the flow at its undiluted rate, stabilise for the prescribed time and begin the analysis. If the sum of the dilutions corrected concentrations of the analytes is greater than the set value then the appropriate dilution is calculated, the ID100 Autodilutor flow set to the correct value and the analysis will begin after stabilisation. As with the Prescriptive mode this is only the initial minimum dilution and further dilutions can be made automatically. The sampling sequence would be: 1. Uptake, the user taking care to use uptake timings so as not to expose the interface to undiluted sample 2. Stabilise at the highest dilution factor 3. Acquire defined analytes and associated peaks and calculate total analyte concentration based on user selection

24 4. 5. 6. 7. 8.

If sample can be presented undiluted goto 5, if dilution required goto 10 Set Autodilution pump to normal analytical speed Stabilise Acquire Surveys and Main runs If further dilution is required due to over-range analytes follow as for over-range analytes section (it will still be possible for an analyte to be above the calibration range but the total analyte concentration for the sample to be well within the set limit) 9. Washout 10. Calculate the most appropriate dilution to get the total analyte concentration level to less than the set point an set the ID100 Autodilution pump to that level 11. Stabilise 12. Acquire Surveys and Main runs 13. If further dilution is required due to over-range analytes follow as for over-range analytes section (it will still be possible for an analyte to be above the calibration range but the total analyte concentration for the sample to be well within the set limit) 14. Washout

Failed Internal Standard; as described above this test will indicate when the matrix of the sample is causing poor recoveries on the internal standards. Even after the Pre-emptive dilution has intelligently reduced the total dissolved solids level of a sample, it is possible that the matrix may cause problems with the internal standard. This test measures the internal standard recovery in the sample and if it fails the set criteria, it will dilute the sample by a fixed amount and re-analyse the sample after stabilisation. The sampling sequence would be: 1. Uptake 2. Stabilise 3. Acquire runs 4. If any internal standard analytes fail the criteria and require dilution 5. Dilute by the preset amount by altering the ID100 Autodilutor pump speed 6. Stabilise 7. Acquire Surveys and Main runs 8. If the internal standards all pass the criteria then 9. Acquire the remaining main runs and any survey runs NB This test is reliant upon correct use of the internal standards so if any sample has not been spiked with internal standards or the sample contains natural levels of an internal standard analyte, the failure will be triggered. Over-range; if any analyte in a sample is determined to be above the top calibration standard by a defined amount, the software will calculate the dilution factor required to bring the analytes within the calibration range, apply the ID100 Autodilutor flow and reanalyse the sample after stabilisation. The sampling sequence would be: 1. Uptake 2. Stabilise 3. Acquire all runs 4. If any analytes fail the criteria and require dilution (only for main runs of Fully Quant/Additions analytes, not Surveys and Semi-Quant analytes). 5. Dilute by either a calculated amount by altering the autodilutor pump speed 6. Stabilise 7. Acquire main. The software will estimate the dilution factor to analyse the diluted sample at <90% of the top standard but as the estimation will be based on an extrapolated calibration graph there may be errors and a further dilution become needed. A further refinement to this mode of operation is to use the Bracketed Standards option, here the software will calculate a dilution factor to ensure that analytes are >10% and <90% of the highest standard. Under these circumstances, if multiple analytes are over-range it may be necessary to make multiple dilutions.

25 Setting up the sampling sequence for an experiment. The control of the ID100 during the sample uptake, data acquisition and sample washout is done through the use of Accessory Control Language scripts for X Series (ACX). Default scripts are provided with the PlasmaLab software and description of how these may be edited or created for specialised use can be found in the on-line help. It is recommended that the default scripts are used until the laboratory is fully familiar with the use of the ID100 and ACX. The ACX is designed to: • Control the sample uptake with or without fast uptake • Control of the settling time for the pumps at the analytical speeds • Data acquisition • Sample washout with or without fast wash pump speeds • Flush the ID100 with de-ionised water at the end of the experiment When a sample has been acquired and an autodilution is called for, the software will automatically skip the sample wash and sample uptake, going straight to the stabilisation phase for the new pump speeds. NB: Remember that the stabilisation times will depend on the volume of the tubing and connections after the first T-piece where the ID100 stream merges with the diluent stream so these should be kept to a minimum. During the sample wash the ACX script is designed to co-ordinate the movement of the autosampler and the pumps such that the ID100 is flushed in both directions and air bubbles are introduced into the line to aid the washout. The settling times for the peristaltic pump and ID100 are set in the devices control panels in the instrument section, it is recommended that each pump is set to a minimum of 30 seconds settling time. In order to flush out the pump with de-ionised water at the end of the experiment, the last tube in the last sample rack is used by default. This is assumed to be a Type 60 rack for a Cetac ASX500/510 autosampler and the user should ensure that this tube is filled with de-ionised water before the start of each experiment. If a different tube position is to be used or the rack is not a Type 60 rack then the appropriate command in the ACX as seen below should be changed as described in the on-line help.

Setting up the uptake and wash in an experiment. The sample uptake and wash conditions are setup as previously described for the instrument section and ID100 setup. The default ACX script is designed to work with fast uptake and wash

26 but it is possible to setup the system without these functions used by editing the ACX script and the ID100 and peristaltic pump conditions as previously described. It is possible to use the monitored uptake and wash functions with the ID100 but it is advised that a minimum wash time is set for the monitored wash. This is because the wash solution remaining in the pump and uptake line from the wash sequence could lead to the wash terminating early before any contaminated solution has been monitored. The timings page of the experiment setup should look something like the screen image below.

Setting up the dilution modes in an experiment. The main autodilution setup page is part of the setup section of a PlasmaLab experiment. The page looks like the screen image below and each section will be explained in more detail following the image.

It is possible to combine any of the autodilution modes with the following exception, that prescriptive and pre-emptive autodilution cannot be used together. If all the modes are chosen, the order in which they are applied is: Prescriptive or pre-emptive, then Failed Internal Standards, then Over-range.

27 Prescriptive dilution. When the prescriptive dilution option is ticked as below, the pre-emptive option is automatically disabled.

When enabled, a separate column is available on the sample list for users to prescribe the dilution factor to be used for each sample. As can be seen from the example below, it is possible to construct a calibration from one stock standard tube by making multiple dilutions using the prescriptive mode. The concentrations entered in the sample list for the standards should be the analyte concentrations in the final diluted sample. I.e. if the stock used below is 100 ppb then the standards would be: Standard Cal Lo Cal Mid Cal High Cal Extended

Concentration (ppb) 2 10 50 100

The prescriptive dilution factor can be used for any sample type (except the Instrument Setup Sample) and it must be no higher than the maximum dilution factor defined for the ID100 as part of the instrument setup, as below.

28 In the numerical results section the prescriptive dilution factor used for a sample is shown in the data tooltip.

The XML reports for exporting or printing contain the dilutions used as part of the sample header as seen below:

Pre-emptive dilution. When using pre-emptive autodilution, the prescriptive dilution mode is disabled, including the ability to generate a calibration from one stock solution. The pre-emptive dilution mode uses the semi-quantitative ability of PlasmaLab to determine the approximate concentrations of elements in an unknown sample. Pre-emptive autodilution is not applicable to Blanks, Fully Quant standards, QC Samples or Addition sample types, only unknowns. In order for the pre-emptive mode to work effectively there must be a good semi-quantitative calibration for the experiment. This means that there must be at least a Blank and one Fully Quant standard in the sample list before the Unknown samples and that conditions have been set for a reasonable semi-quantitative calibration. A three point calibration is the most reliable method to build a semi-quant curve from the fully quant calibrations when working in an unattended manner. In the example below the calibration methods page shows all the analytes in the experiment but only the Be, Cd and Pb are used and the curve is characteristic of the use of the Xi interface. NB: Changing experiment parameters such as the points included in calibrations while the experiment is being acquired will not change the calibration data being used by the real time calculations, only the on-screen data display. To change the calibrations in memory being used for the real time calculations, after editing the calibrations on screen, the experiment should be stopped and restarted. The edited changes will then be stored in memory for the current real time calculations.

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The accurate use of semi-quantitative analysis relies on the choice of analytes to build the response curve and the relative sensitivity factors (RSF) used for other analytes. In the above example, the analytes not used to build the curve (the green dots) have fully quantitative calibrations in this experiment so the RSF can be recalculated to improve the accuracy for future experiments under similar conditions that may not be calibrated for these analytes. The RSF can be exported from the experiment using the Analyte Database Wizard described in the on-line help. To use the pre-emptive mode the box must be ticked in the Autodilution setup page and one or more analytes chosen for the test as shown below.

The default is for the sum of the chosen analytes to be below 500 ppm (mg/L) but this value can be changed to whatever is suitable for the work being undertaken. It is worth considering that for each analyte measured there is often an unmeasured counter ion in solution (i.e. sodium is present in solution as the dissolved salt NaNO 3) so to be below the recommended

30 Total Dissolved Solids limit (TDS) of 0.2% for ICP-MS, the total positive ion concentration should be <0.1% (1000 ppm). It is possible to select all the analyte in the database for the test but to speed up the calculations it is worth only entering the expected major elements for the unknown solutions. For each unknown sample a separate Survey run is made and from this the total concentration of the selected analytes is determined. The survey run used takes hard coded non editable default conditions for a survey run allowing the user to define different conditions for the survey run to report data for the sample. The default survey run conditions are shown below.

NB: It is not advisable to use pre-emptive autodilution when also using multiple settings sets in an experiment. For each pre-emptive sample the results will show the sample label for the original sample with the details for the dilution tests in the tooltip. After the pre-emptive survey run, unless the Abort Sample failure action is triggered, a copy of the sample will be inserted into the sample list and the data reported against this new copied sample. The actual pre-emptive survey data can be viewed in the Survey numerical results pages.

Once data has been acquired for the pre-emptive survey run, the calculations will determine the next action. • If the total concentration exceeds the defined value even at the maximum dilution factor there are two possibilities: o Abort sample: here no data is acquired for the sample and the experiment will proceed to the next sample in the sample list. o Acquire the sample but flag the error: here the sample is acquired at the maximum dilution factor and the numerical results will flag that the Preemptive dilution has failed in the sample header for the initial pre-emptive survey.

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o

•

The subsequent sample is automatically added to the sample list (with the prefix $ indicating that it has been inserted by the ID100) and acquired at the maximum dilution factor. A flag in this data will also indicate that the maximum dilution has been reached.

If the total concentration does not exceed the defined value at the maximum dilution factor there are two possibilities: o The sample can be run undiluted. Here the ID100 flow rate is set to the undiluted rate and the sample is acquired after stabilisation. The data is reported after the pre-emptive survey with the sample label prefixed with a $. o The sample can be diluted to get the total analyte concentration below the set level. The ID100 flow rate is adjusted to effect the necessary dilution and the sample is acquired after stabilisation. The data is reported after the preemptive survey with the sample label prefixed with a $. The actual dilution factor used is reported with the sample details in the tooltip for the diluted sample.

32 Failed internal standards autodilution. The failed internal standard test is only applied to unknown sample types and it assumes that the internal standards are within acceptable levels for the previous clean QC or calibration sample as per US EPA guidelines. The internal standards can be checked in every incidence of a Blank verification or External Calibration verification QC sample. The limits for the internal standards in QC samples are set in the QC Setup section and a failure will trigger the action for the individual QC sample. The US EPA require that the instrument be recalibrated if the internal standards in a QC sample fail, this will reset the internal standards back to 100% (an ISF of 1.00 in the calculations).

The failure limits for unknown samples are set in the Autodilution setup page along with the fixed dilution factor that should be applied if the internal standards fail the limits in the unknown sample.

The internal standard test will trigger a failure if any of the internal standards in the unknown sample are outside of the set limits. If after the first autodilution the internal standards still fail the recovery tests, further autodilutions will be made until the internal standards pass the test, the maximum number of autodilutions set by the user has been reached or the maximum dilution factor for the ID100 has been reached. NB This test is reliant upon correct use of the internal standards so if any sample has not been spiked with internal standards or the sample contains natural levels of an internal standard analyte, the failure will be triggered. If a sample fails the internal standard test, the sample is flagged and the data excluded from the numerical results and report.

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The subsequent autodiluted sample will show the dilution factor applied in the final results details and report.

If the maximum number of dilutions possible has been reached, the data is flagged as such to indicate that the internal standards have failed but no further autodilutions will be made.

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By default the excluded data is still shown in the results but with the cell background in grey. It is possible to not display excluded data at all by using the data filters as below.

By unticking the Excluded Data box in the Flags Visible section, the report will show dashes for any excluded data.

Over-range autodilution. Over-range autodilution is triggered whenever an analyte in an unknown sample is found to be above the limit set on the calibration methods page. The over-range failure is set individually for each analyte and it based on the top calibration standard defined for that analyte. The over range fail limit should be set to a minimum of 100% of the top standard.

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If multiple analytes are over-range the software will determine the dilution factor required to allow all analytes to be <90% of the top standard. If this is not possible at the maximum dilution factor for the ID100, the data is flagged appropriately.

If an analyte is found to be over-range it is automatically excluded, if in the next autodiluted sample the analyte is within the calibration range it is reported. If the sample has to be further autodiluted, the analyte will also be excluded from these samples. This means that in the results/report the analyte will only be reported once with the appropriate dilution factor. A further option available is to “bracket standards” for analytes, this option can be used to ensure that analytes are not autodiluted so far that the measured concentration is very close to the detection limit. When this option is ticked, the software will autodilute an analyte so that the estimated value would be >10% of the top standard. With this option, the software may need to make multiple autodilutions of the sample to get all the analytes in range. If it is not possible to fit all the analytes into range with one autodilution, a bracket standards warning will be flagged.

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Maintaining the ID100 AUTODILUTOR The ID100 AUTODILUTOR has been designed as a robust part of your sample introduction system, and is provided with a drip tray which will safely remove large volumes of solution spilt onto the unit. However, observing the guidelines below will help ensure that your ID100 AUTODILUTOR gives optimum performance throughout its life. Cleaning the ID100 AUTODILUTOR body: Cleaning the outer body of the ID100 AUTODILUTOR regularly will help maintain its appearance and should be carried out as follows: 1. 2. 3. 4. 5.

Switch off the ID100 AUTODILUTOR and disconnect from the AC power outlet. Wipe the drip tray and cabinet with a towel dampened with lab-grade cleaning agent. Repeat this process using clean water Dry all components. Ensure all components are dry before re-connecting to power outlet and switching back on.

Optimising Pump Performance: To obtain maximum performance from your ID100 AUTODILUTOR it is recommended that you adhere to the following guidelines: • • • •

Flush the pump with de-ionised water after each use. Do not run the pump dry for extended periods. Wipe up all spills on and around the pump immediately. The fluid path through the pump can be cleaned by pumping a weak lab grade detergent through the pump.

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Troubleshooting the ID100 AUTODILUTOR

The ID100 AUTODILUTOR has been designed to be simple to operate and extremely reliable. In the event of problems occurring, step through the following guide to find the cause: Power Supply Problems If the green Power Indicator LED on the front of the ID100 AUTODILUTOR is not illuminated, then the ID100 AUTODILUTOR pump is not getting any power. 1. Check at the wall socket for power. 2. If the wall socket is powered then check the fuses on the IEC connector at the rear of the ID100 AUTODILUTOR. Communication Problems The ID100 AUTODILUTOR is controlled via the host compute using a serial connection. If the RS232 communications between the ID100 AUTODILUTOR and host computer are not correctly set up then the ID100 AUTODILUTOR will not work. Check the following: 1. Ensure the power supply is plugged in and switched on 2. Check that the RS232 cable is securely fitted between the rear of the ID100 AUTODILUTOR and the host computer. 3. If you have installed the additional PCI card, check the installation guide to ensure that it has been installed correctly. Contamination Problems If you believe you are getting high background counts which may be coming from the ID100 AUTODILUTOR and its associated tubing: 1. Replace all tubing to and from the ID100 AUTODILUTOR. 2. Run a weak lab grade detergent solution through the ID100 AUTODILUTOR at a rate of 3ml/min for 10 minutes. Next aspirate a clean DIW solution. Stability Problems If you are getting poor RSD’s from your instrument: 1. first eliminate any possible instrument problems by aspirating solutions directly without the ID100 AUTODILUTOR. 2. Once you have confirmed that the RSDs are good without the ID100 AUTODILUTOR, retry with the ID100 AUTODILUTOR in line. If the RSD’s are still poor, try changing the peristaltic pump uptake tubing. 3. If the RSD’s are still poor, an air bubble may have become trapped in the ID100 Autodilutor pump. Flush the pump with a weak laboratory grade detergent solution at 3 ml/min for 10 minutes. Then flush the pump with DI water and test the system again.

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Glossary of Terms Diluent – The solution used to dilute the sample from the ID100 AUTODILUTOR before it enters the ICP-MS. Peristaltic Pump – The pump on the ICP-MS used to control flow of solution into the instrument. RSD – The % Relative Standard Deviation. This figure is widely used to quote the stability of repeat readings taken using an ICP-MS. Host Computer – The computer used to control the X Series ICP-MS Plasmalab – The Thermo Electron software package used to control and acquire data from the X Series ICP-MS