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Stanford University Stable Isotope Lab

1. Stanford University Stable Isotope Laboratory On line Manual Prepared by David A Mucciarone Section 3C Preparation of Elemental Analyzer Oxidation Column This procedure is designed to prepare an oxidation column for the Carlo Erba NA1500 Series II elemental analyzer EA The entire procedure should be performed over a secondary container such as a tray to capture any spilled materials Safety glasses rubber gloves face mask and a lab coat apron are required throughout the acid preparation Unlike the reduction column on the EA the oxidation column is changed on a 4 1 ratio i e 4 reduction columns to 1 oxidation column which is approximately every 2000 samples This ratio was set because at 1020 C the quartz tube begins to weaken and beyond 4 1 there is a greater risk to tube failure The reagents in the oxidation column are still good and can be removed and reused The purpose of this section is to serve as a guide you should not attempt this unless you have been trained and have a good understanding on operating the EA and the mass spectrometer Before you begin preparing the new oxidation column you should first clear an area on the bench top obtain and organize all of the materials and equipment listed below Materials Costech Analytical chromium IID oxide silvered cobalt II III oxide quartz wool and one 1 8 cm x 45 cm quartz tube Fig P1 Equipment Funnel template ruler push rod and tray Fig P1 1
2. Put approximately 7mm of quartz wool into the bottom of the insert Fig P3 Carefully slide the quartz insert into reactor column until it stops do not push or force insert Fig 3 The insert should stop approximately 5mm above top of reactor column If the insert falls below the top of the reactor column add an appropriate amount of quartz wool to the reactor column not the insert then slide the insert in again With the insert in the proper position gently push the insert down until it is flush with the top of the reactor column do not force Reposition the carousel onto the reactor column and secure both connections at the reactor column and the helium carrier line Fig P4 Carousel Operation Fig P5 a b Front panel Toggle switch up 32 hole sample drum Toggle switch down 50 hole sample drum Black push button advances drum forward 1 position Round switch up on red light on Round switch down off red light off Rear panel Switch on the rear panel is to align the carousel after swapping out sample drums Toggle switch up advance sample drum by steps Toggle switch down reverse sample drum by steps Load samples into carousel Fig P6 a b C d Loosen the 3 thumbscrews on the top of the carousel loosen back two first then front and fold out of the way Flip back the carousel lid to expose sample drum Using forceps carefully load samples into sample drum If first sample is not in hol
3. Stanford University Stable Isotope Laboratory Standard Operating Procedures Manual Last Updated 1 28 03 David Mucciarone Lab Manager Stanford University Department of Geological amp Environmental Sciences Stanford CA 94305 2115 Stanford University Stable Isotope Lab On line Manual Prepared by David A Mucciarone Table of Contents Section 1A D Finnigan MAT252 Kiel III carbonate device 3 31 Section 1A Finnigan MAT252 with Kiel III carbonate device 3 8 Section 1B Finnigan MAT252 Kiel III Carbonate Device Operation 9 21 Section 1C Finnigan MAT252 24x Multiport Operation 22 30 Section 1D Preparation of 100 Phosphoric Acid H3PO for Kiel Carbonate Device 31 Section 1E Preparation of samples for Kiel Carbonate Device Not complete Section 2A 2D Finnigan MAT Delta pus ConfloII and Carlo Erba NA 1500 32 54 Section 2A Finnigan MAT Delta operation principles for elemental N C 5 5N 3C analyses 32 39 Section 2B Finnigan Delta and Carlo Erba NA 1500 Elemental Analyzer with ConFloll interface 40 43 Section 2C Finnigan Delta Carlo Erba Elemental Analyzer Operation 44 54 Section 2D Finnigan Delta source cleaning and filament change Not completed Section 3A 3F Carlo Erba NA 1500 Series 2 Elemental Analyzer 55 92 Section 3A Carlo Erba NA 1500 Elemental Analyzer Procedure 55 73 Section 3B Preparation of Elemental Analyzer Reduction Cu Column 74 79 Section 3C
4. 0 97002 5 8Oguow 29 98 Eq 4 You may also find this standard referred to as Vienna Standard Mean Ocean Water or V SSMOW which was prepared by H Craig for the AEA in Vienna Austria Hoefs 1980 Two other water standards used are SLAP Standard Light Antarctic Precipitation which was introduced by Gonfiantini in 1976 Gonfiantini 1978 for the IAEA and GISP Greenland Ice Sheet Precipitation which was prepared by W Dansgaard Listed in Table are the isotopic compositions of commonly used standards most of these can be obtained from the National Institute of Standards and Technology NIST in Gaithersburg MD 20899 0001 For more information consult the reference list below Table 1 Isotopic compositions of standard reference materials Standard Description oo 5180 ppp 00 880 gyrowy P 00 5 3Cpppy oo PDB Peedee belemnite 0 00 0 00 SMOW Standard Mean Ocean Water 0 00 NBS 1 Water 7 86 NBS 1A Water 24 21 NBS 18 Carbonatite 23 05 5 04 NBS 19 TS limestone 2 20 28 65 1 95 NBS 20 Solenhofen limestone 4 18 26 64 1 06 NBS 21 Graphite 28 10 NBS 22 Oil 29 63 SLAP Standard Light Antarctic Precipitation 55 50 GISP Greenland Ice Sheet Precipitation 24 85 II References Coplen T B C Kendall J Hopple 1983 Comparison of stable isotope reference samples Nature 302 236 238 Craig H 1957 Isotopic standards for carbon and oxygen and correction factors for mass spectrographic analyses of carbon dio
5. 5 N is expressed relative to Air and 8 C 5 C relative to the international PDB standard Eq 1 as defined by 8 oo RatiOsample RatiOstandara RatiOstandara x 1000 Eq 1 PDB refers to a Cretaceous belemnite called Belemnitella americana from the Peedee formation in South Carolina and is defined as 0 for both 8 3C and has been exhausted however there may be a few labs that still have a small quantity remaining The carbon standard NBS 21 USGS 24 both graphite NBS 22 oil and NIST 1547 peach leaves where NBS is an acronym for the National Bureau of Standards which was replaced by NIST or the National Institute of Standards and Technology and USGS or U S Geologic Survey are standards used to calibrate to PDB The CO reference gas used is research grade and has been calibrated to PDB using these standards Nitrogen isotopes are compared to Air which is defined as zero The N reference gas we use is research grade and has been calibrated to Air using IAEA N1 and IAEA N3 USGS 26 where IAEA is an acronym for the International Atomic Energy Agency To reduce the possibility of exhausting these international standards laboratories establish working standards that have been calibrated against various known standards and with other laboratories to use routinely in the laboratory Listed in Table are the isotopic compositions of commonly used standards most of these can be obtained from the National Institute of Standards an
6. References Bohlke J K and T B Coplen 1993 Interlaboratory comparison of reference material for nitrogen isotope ration measurements in Reference and intercomparison materials for stable isotopes of light elements Procedings of a consultants meeting Vienna 1 3 December 1993 IAEA 51 66 Barrie A J Bricout and J Koziet 1984 Gas chromatography Stable isotope ratio analysis at natural abundance levels Biomed Mass Spectrom 11 583 588 Coplen T B J A Hopple J K B hlke H S Peiser S E Rieder h R Krouse K J R Rosman T Ding R D Vocke Jr K M R v sz A Lamberty P Taylor and P Ed Bi vre 2002 Complications of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents USGS Water Res Inv Rep 01 4222 98p Craig H 1957 Isotopic standards for carbon and oxygen and correction factors for mass spectrographic analyses of carbon dioxide Geochim Cosmochim Acta 12 133 149 Fry B W Brand F J Mersch K Tholke and R Garritt 1992 Automated analysis system for coupled 85 C and 5 N measurements Anal Chem 64 288 291 Hoefs J 1980 Stable Isotope Geochemistry Springer Verlag Berlin 208p Kendall C and E Grim 1990 Combustion tube method for measurement of nitrogen isotope ratios using calcium oxide for total removal of carbon dioxide and water Anal Chem 62 526 529 Mariotti A 1983 Atmospheric nitrogen is a reliable stand
7. To confirm data in memory Figure 8a EAGER 100 Integration parameter sub table CALCULATION PARAMETERS Carbon Retention Time seconds 350 Hydrogen Retention Time seconds 0 Nitrogen Retention Time seconds 190 Oxygen Retention Time seconds 0 Sulfur Retention Time seconds 0 Calc Method 0 K Fact 1 Linear Reg 0 Protein Factor 0 No Protein calc 0 Calorific calc 1 Solid 2 Liquid 0 ESC to Exit ENTER To confirm data in memory Figure 8b EAGER 100 Integration parameter sub table Note The number of analyses depends on how many conditioners blanks standards and samples are to be run and the sample drum used in the Costech zero blank carousel Note The hydrogen should be set to 0 if the anhydrone water trap is installed Otherwise the standards will not calculate K factor values correctly E System Default Parameters This menu is activated by pressing lt F4 gt from the main menu Fig 2 The main purpose of this menu is allow the operator the option of where to store the analytical data Output header information can also be entered Enter the information displayed in Figure 9 For the RAW and REP filenames it is useful to use the same for both There is no need to add the extension to the filename this will be done automatically You will note that in Figure 8a the parameter for plotting on paper is turned off All of the data obtained from each run is saved on disk When the run is completed this file
8. on Jobin OW HHA 1 Combustion eduction reactor 4 Pat nd column inr MCE determination E mieghi fren iD _ Quartz Wo L TT Tanpi Anteyiacig i F Fiii Pira Goppet ire Appendix Figure 4 Sulfur only configuration on Carlo Erba NA1500 Series 2 elemental analyzer Stanford University Stable Isotope Laboratory On line Manual Prepared by David A Mucciarone Section 3B Preparation of Elemental Analyzer Reduction Cu Column This procedure is designed to prepare a reduction copper Cu column for the Carlo Erba NA1500 Series II elemental analyzer EA The entire procedure should be performed over a secondary container such as a tray to capture any spilled materials Safety glasses rubber gloves face mask and a lab coat apron are required throughout the acid preparation Unlike the oxidation column on the EA the reduction column needs to be changed approximately every 500 samples This can best be determined by monitoring the mass 30 28 ratio from the Finnigan Delta mass spectrometer When the 30 28 ratio becomes greater than 1000 on the IAEA N1 standard the column is close to exhaustion and needs to be closely monitored At 5000 it is time to change the reduction column or the precision of 5 N values will degrade If 5 N or N are not desired you can run approximately 100 to 150 more sample as 5 C and C only The purpose of this section is to serve as a guide you should not attempt this unles
9. using a pipette Fill 2ml cryogenic vial or cryovial with supernatant label vial and refrigerate 3 Decant as much of the supernatant as possible without losing any solid material from the container into a squirt bottle This bottle should be labeled Formalin You will use this formalin seawater mix in the squirt bottle through out the handling of its respective sample see following note 4 Gently swirl remaining supernatant and solids in its host container and then pour into the sample splitter and split the sample by rotating the splitter wheel back and forth several times to split the sample evenly Fig 2 When finished pour the sample material into the splitter containers by tilting the wheel back Fig 2 Use the trap supernatant in the squirt bottle conservatively to loosen solids stuck inside the splitter wheel You now have two half splits NOTE Throughout the splitting process you will need to use the supernatant in the squirt bottle to clean out the splitter and other containers decanters used in this procedure Make sure to use supernatant conservatively but it is necessary to clean thoroughly at each step in the process Take 1 2 of this first split and decant into the appropriate sized Nalgene bottle 250ml This is your 1 2 split archive Label the bottle with the trap sample name and 1 2 Split Archive and refrigerate You will now split the remaining 1 2 again Place the half split into the sample splitter again
10. 150 200 250 Retention time s Figure 1 Schematic representation of the nitrogen portion of a nitrogen carbon analysis Notice that the N2 reference gas is injected prior to the unknown N2 sample peak A slow peak jump routine is performed as the instrument prepares to analyze CO This routine require about 75 seconds and involves a change in electromagnet current BDAC injection of CO2 reference gas from the ConFloll interface and centers the high voltage HVDAC on mass 45 or beam 2 When complete a new graphics display window will appear Approximately 18 seconds into the run the CO peak from the sample will elute out of the 4 m GC column Depending on the amount of C in the sample the peak will have a retention time of approximately 75 to 130 seconds At 185 seconds a signal is sent to the ConFlollI interface and CO reference gas is injected into the mass spectrometer for 20 seconds One second before the end of the run the helium dilution is turned off and the carbon portion of the run has ended and the analysis of the sample is completed Fig 2 This method of analysis continues until the run sequence in finished The above discussion has been about obtaining elemental and isotopic values from N and C from the same sample Table 2 is a quick reference on how the EA and ConFlolI are configured to run N and C on the same sample It is also possible to run only N or C where peak jumping is not required It is however necessary to configure
11. Click ALT T Click on CNF B ACON B 2 SEQUENCE ACQ Click on TABLE DIR Shift F10 TABLE NAME reselect the correct table name e g DM041702 START LINE begin where the error took place END LINE 46 if for a full carousel run MODE NIGHT FILENAME should be as follows Path D DATA filename WKS Filename is 8 characters WKS The filename should have the format operators first initial date followed by a next letter in the sequence after the original that began A and followed by WKS e g D041702B WKS Type in the path and filename then press lt Enter gt e g the line should read as follows D DATA D041702B WKS f LIST TYPE FORMAT3 ONLY g FILE TYPE LOT h SAVE DATA TO DATABASE COL Click SAVE to save sequence Make sure there is plenty of paper in printer to complete the run To transfer the run data from hard disk to floppy disk you Press Ctrl and 2 from the number keypad Using DOS i e CD DATA and DIR and COPY commands go to the directory D DATA and copy the file to floppy disk e g at prompt D DATA gt Type COPY D041702A WKS A or COPY D041702 A to copy all associated files Press Ctrl and 1 from keypad to return to ISODAT oaao 10 Click MEASURE to begin run Stanford University MAT252 Kiel III Carbonate Device Operation III Run interrupted by error 1 PART 1 Able to escape out of error A If a gray window with at red bar will be displayed on the screen obstructing the norma
12. Click on ALT T upper left screen This will exit CNF A ACON A 2 Click on CNF A ACON A 2 SEQUENCE ACQ Click on TABLE DIR Shift F10 Table name reselect the correct table name e g DM091701 Start Line begin where the error took place End Line 24 if both banks are being run 12 if only 1 bank Mode DAY Filename should be as follows Path D DATA filename WKS Filename is 8 characters WKS The filename should have the format operators first initial date followed by a next letter in the sequence after the original that began A and followed by WKS e g D091702B WKS Type in the path and filename then press lt Enter gt e g the line should read as follows D DATA D091702B WKS f List Type FORMAT1 ONLY g File TYPE LOT h Save DATA to database COL Click SAVE F9 to save sequence Make sure there is plenty of paper in printer to complete run Click MEASURE to begin run If you were able to escape from the error or the run was able to continue the data was saved to the database called ISOBASE and to the filename you created On the other hand if you were not able to escape and had to refer to Part 2 of this section then the data was only saved to the database and not to the file you created in the SEQUENCE ACQ screen This file will only have 128K You will need to review the recover data section IV for instructions on how to obtain the run data ene oe Mn BW Stanford University MAT252 24x Mu
13. Costech Analytical zero blank carousel from EA reactor column First open the purge valve on top left photo then loosen the connections to the reactor column middle photo and the helium line right photo Then move carousel to the side to allow removal of the quartz insert Figure P3 Removing quartz insert from EA reactor column A marker pen works great at removing the insert left photo Once the insert is removed enough grab the top with your fingers remove completely and place into the waste beaker middle photo Note the location of the carousel In this position there is no obstruction when removing the insert Place approximately 7 mm of quartz wool in the bottom of the insert and slide it into the reactor column right photo Figure P4 Replacing the Costech Analytical zero blank carousel on to the EA reactor column First secure the connections to the reactor column left photo and the helium line middle photo If you are not loading samples allow 2 minutes for the carousel head space to purge before closing the purge valve on top of the carousel right photo Figure P5 Costech Analytical zero blank carousel operation Use the toggle switch to select sample drum 32 hole up 50 hole down left photo Use button to advance carousel one position middle photo Use switch on rear panel to align carousel up advance down reverse right photo Figure P6 Loading Costech Analytical zero blank carousel
14. First open the purge valve on top left photo then loosen the connections to the reactor column middle photo and the helium line right photo Then move carousel to the side to allow removal of the quartz insert Figure 13 Removing quartz insert from EA reactor column A marker pen works great at removing the insert left photo Once the insert is removed enough grab the top with your fingers remove completely and place into the waste beaker middle photo Note the location of the carousel In this position there is no obstruction when removing the insert Place approximately 7 mm of quartz wool in the bottom of the insert and slide it into the reactor column right photo Figure 14 Replacing the Costech Analytical zero blank carousel on to the EA reactor column First secure the connections to the reactor column left photo and the helium line middle photo If you are not loading samples allow 2 minutes for the carousel head space to purge before closing the purge valve on top of the carousel right photo Figure 15 Costech Analytical zero blank carousel operation Use the toggle switch to select sample drum 32 hole up 50 hole down left photo Use button to advance carousel one position middle photo Use switch on rear panel to align carousel up advance down reverse right photo Figure 16 Loading Costech Analytical zero blank carousel First open the purge valve on top of the carousel left photo
15. First open the purge valve on top of the carousel left photo Next loosen the 3 thumbscrews middle photo and then open the lid to the carousel right photo When finished close the lid and secure with thumbscrews Allow the carousel to purge for a minimum of 2 minutes before closing purge valve Figure P7 Checking and changing the magnesium perchlorate water trap on the Carlo Erba NA1500 Observe upper left portion of trap to see if magnesium perchlorate is sticking or degrading To remove the water trap loosen the red caps on both ends of the glass trap left and middle photo Remove Teflon silicon seals from both ends and check for cracking right photo Replace if necessary or reuse seals Make sure silicon portion of seal seats against the glass trap and the Teflon against the stainless steal flange Figure P8 Leak checking the Carlo Erba NA1500 Move stainless steal line from Vent M to Vent R see Fig 1 and place plug left photo on Vent M Turn down counter clockwise rotation the helium pressure by using the knob labeled M on the EA right photo Observe the M helium gauge for leaks When finished restore helium pressure to 90kPa clockwise rotation Figure P9 Select the helium dilution on the Finnigan ConFloI interface box left photo Depending on the samples being analyzed you my need to adjust the helium dilution prior to beginning a run right photo Figure P10 Checking the base level on the Carlo Erba
16. If the computer is ready and displaying the EAGER 100 main menu Fig 2 as below then you are ready to begin setting up the elemental analyzer CARLO ERBA STRUMENTAZIONE ELEMENTAL ANALYSIS E A G E R 100 F1 RUN F2 STBY STOP F3 Calc Inter Param F4 Sysem Default F5 Sample Table F6 Recalculation F10 Exit to Operating Sys Date 08 08 2001 13 36 55 Sample Index 1 Status STBY Level 1109 Figure 2 EAGER 100 Main Menu on Carlo Erba NA1500 Series 2 elemental analyzer F refers to the function keys on the top of the keyboard 1 Temperature and Time Settings for NC analyses See Appendix for column configuration for NC analysis The following parameter are when using a 4 m GC column To perform the following steps refer to Figures 3 and 4 for all buttons and dials 1 Check to see if the filament and oven are off standby if not turn on the filament see 11 Fig 3 and take the furnace off standby both buttons should be up see 10 Fig 3 2 Make sure the furnace temperatures are set correctly If they are not set as listed below use the respective dial s to the proper temperature a Left furnace 1020 C see 1 Fig 3 b Right furnace 650 C see 2 Fig 3 c Oven 60 C see 3 Fig 3 d Filament 190 C see 4 Fig 3 3 Make sure the run times are set properly if they are not use the respective dials to set them as listed below a Cycle time 110 seconds for C amp N analyses see 5 Fig 3 b Sam
17. MAT252 Kiel III Carbonate Device Operation I Run terminated without error NORMAL Click on ALT T upper left screen This will exit CNF B ACON B Click on CNF B SUPP B This will enter Kiel support screen Click on TAKE MAG F7 This will remove vials from ports Fig P1 Lower and remove liquid nitrogen LN dewar and remove ice Fig P2 This is necessary if beginning a new run or if run terminated by error and was sitting many hours Remove carousel Fig P3 Be careful not to hit capillaries or drip counter Install new carousel Fig P3 again be careful not to hit the drip counters or capillaries Clean acid drip counter and capillaries with 2 propanol Fig P4 Clean o rings on both ports with 2 propanol and then lightly grease o rings with Apiezon L Fig P5 Click on KBD INPUT F5 Type P5 lt Enter gt Click on KBD INPUT again Type P1 lt Enter gt this will reset the carousel 10 If ice around cold traps has been removed and LN is ready i e LS160 dewars and small blue dewar replaced and approximately 1 from top click on T1 then click on analog temperature bar at approximately 170 C to 180 C This will fill the blue LN dewar Remember as it begins to fill approximately 1 2 bring the dewar snug to the cold trap plate 11 If LN is not ready click on LOAD MAG F6 This will load the vials on the ports Fig P6 12 Click on CNF B EDIT B 2 SEQUENCE EDITOR Prepare a new table by copying a previous sequ
18. Next loosen the 3 thumbscrews middle photo and then open the lid to the carousel right photo When finished close the lid and secure with thumbscrews Allow the carousel to purge for a minimum of 2 minutes before closing purge valve I Servicing Magnesium Perchlorate Water Trap and Leak Checking 1 Check the magnesium perchlorate water trap Change when the upper 10 to 15mm of magnesium perchlorate granules appear fused together Fig 17 a b C d To change loosen red caps on both ends of trap and remove Teflon silicon seals usually stick to the glass trap remove seals check for cracks and replace if necessary otherwise clean and use Place 5 to 7mm of quartz wool in one end of a clean trap located in oven and fill with magnesium perchlorate granules and gently tap trap on bench top to compact granules Be sure to leave approximately 5 to 7mm of space in order to insert quartz wool into the open end Clean both faces of trap and reassemble Place seals in red caps with Teflon portion of seal against the metal flange and secure finger tight Magnesium perchlorate from used trap needs to be removed and placed into the waste container Glass trap can then be cleaned with water and placed into the oven to dry Perform a leak check EA Fig 18 a b Place a plug over Vent M release pressure on M helium regulator on EA turn black silver knob counterclockwise If there is a leak the pressure on the M helium gaug
19. Preparation of Elemental Analyzer Oxidation Column 80 85 Section 3D Preparation of Elemental Analyzer Water magnesium perchlorate Trap 86 89 Section 3E Changing Elemental Analyzer quartz insert 90 92 Section 3F Preparation of samples for Elemental Analyzer Not completed Section 4A 4B UIC Coulometer Section 4A TDIC concentrations in sea water Not completed Section 4B Percent inorganic carbon in solids CaCOQOs Not completed Section 5A Continous flow C TDIC Section 5A TDIC 8 C TDIC extraction line Not completed Section 6A 6G Laboratory Methods 93 106 Section 6A Biogenic Silica Analysis Procedure 93 105 Section 6B Seawater alkalinity Not completed Section 6C Sediment trap splitting 106 108 Section 6D Phosphate analysis Not completed Section 6E Cellulose extraction from plants Not completed Section 6F Cellulose extraction from sediment Not completed Section 6G Sediment washing for forams Not completed Stanford University Stable Isotope Laboratory On line Manual Prepared by David A Mucciarone Section 1A Finnigan MAT252 with Kiel III carbonate device I Operation Principles for 180 and 8 3C Analyses in carbonates Before you can operate the Finnigan MAT252 mass spectrometer you must have training Once trained the following procedures will serve as an operational guide The Kiel III carbonate device KCI is connected to the MAT252 mass spectrometer changeover va
20. Switch the stainless steel line from Vent M to Vent R Fig P2 Turn down the left oxidation oven from 1020 C to 320 C and the right reduction oven from 650 C to 250 C Fig P3 Allow both ovens to cool before removing the oxidation column While the ovens are cooling you can prepare a new oxidation column 2 We have two types of quartz tubes opaque and clear It is easy to observe the packing and measure the amount of material added to a clear tube but more difficult to do the same on the opaque tubes When using the opaque tubes the push rod and template will assist you in determining the amount of material in the tube 3 Insert 3 5 to 4 0 cm of quartz wool into the bottom of the quartz reduction tube Fig P4 Place bottom of tube against the tray and use the push rod to tamp down the quartz wool Fig P4 4 Using a funnel add approximately 6 0 to 6 5 cm of silvered cobalt II IIT oxide to the quartz tube Fig P4 Gently tap the tube to compact the reagent It is necessary to insure good packing of all reagents added to the quartz tube or separations will occur inside the tube when the column is heated to 1020 C Use the push rod as a measuring device against the template The total accumulation of both quartz wool and silvered cobalt II HI oxide should be 10 cm 5 Add 1 0 cm of quartz wool to separate the silvered cobalt II IIT oxide from the chromium III oxide 6 Again using a funnel add 11 0 cm of chromium IID oxid
21. a Method in ISODAT to perform this task correctly In addition it is also possible to configure the EA differently to run O in the form of CO Section 2D or S in the form of SO Section 2E To do this it is necessary to reconfigure the EA with different reactor and or reactor reduction columns and GC columns New Methods will need to be created in ISODAT to accommodate the modifications in the EA Aside from running an EA on our Delta plus other peripherals can be attached that run via continuous flow For example we have a HP5890 GC configured to do compound specific GC C IRMS Section 2F It is necessary to review and understand the operation of the elemental analyzer before operating the mass spectrometer This section was written a synopsis and as a guide to the safe operation of the Delta plus You will receive all of the necessary information for operating the instrument from your training However you can find more details on the mass spectrometer and elemental analyzer in the sorted Finnigan Delta plus and Carlo Erba user manuals Delta EA Carbon Run CO Std CO SA He dilution off begin peak jump to M 150 200 Retention time s 0 50 100 Figure 2 Schematic representation of the carbon portion of the nitrogen carbon analysis Notice that unlike the nitrogen run the CO reference gas is injected after the unknown CO sample peak this is because of the slow peak jump routine from N to C Table 2 Set up pa
22. against the tray and use the push rod to tamp down the quartz wool Fig P4 4 Using a funnel add approximately 2 5 to 3 0 cm of quartz turnings to the quartz tube Fig P4 Gently tap the tube to compact the quartz turnings It is necessary to insure good packing of all reagents added to the quartz tube or separations will occur inside the tube when the column is heated to 650 C Use the push rod as a measuring device against the template The total accumulation of both quartz wool and turnings should be 5 cm 5 Again using a funnel add 29 to 30 cm of pure Cu wires to the quartz tube Fig P4 As you add the Cu to the tube gently tamp the tube to compact the Cu to avoid separation when the column is heated to 650 C Use the push rod to measure the amount of Cu added 6 Add approximately 9 0 to 9 5 cm of quartz turnings on top of the Cu and plug the rest of the open tube with quartz wool Fig P4 7 Install a black sealing ring at the top with the flat portion down Fig P5 Clean the outside of the reduction tube with a Kimwipe and 2 propanol and set the tube aside Fig P5 9 When the oven has cooled and the new reduction column is ready you can begin removing the used reduction column Co 10 Remove both braces at the bottom of the oxidation and reduction columns Fig P7 12 13 14 15 16 Remove the furnace cover to expose the bottom of the reduction column Fig P6 Completely loosen the fittings on the bottom of
23. and J M Hayes 1985 Exchange of oxygen isotopes in carbon dioxide phosphoric acid systems Isot Geosci v 52 p 365 374 Stanford University Stable Isotope Laboratory On line Manual Prepared by David A Mucciarone Finnigan Deltapus Carlo Erba NA 1500 Elemental Analyzer Section 2A Finnigan Delta Operation Principles for elemental N C 515N and 53C analyses I Operation Principles for 5 5N and 5 3C Analyses in organic and inorganic materials Before you can operate the Finnigan Delta plus mass spectrometer you must have training Once trained the following procedures will serve as an operational guide You should also read Section 2A on the ConFloll interface and Section 2C which you can use as a quick reference guide to daily operation of the Delta plus EA The Delta plus mass spectrometer is connected to the Carlo Erba NA1500 elemental analyzer Section 3 via a Finnigan ConFlolII interface Section 2A The ConFlolI interface allows us to connect two reference gases N and CO3 and dilution gas He which is split off from the main EA carrier gas Operation is as follows Helium carrier gas constantly travels to the EA ConFlolII and mass spectrometer Samples in the zero blank carousel are combusted in an enriched oxygen environment in the combustion oxidation column producing CO N O SO2 and H 0 The combustion oxidation column reduction column and water trap work in series to insure that only N and CO enter the GC colum
24. caps numbered Nalgene 50 ml centrifuge tubes 1000 ml volumetric flask 4 500 ml volumetric flasks 50 ml Nalgene volumetric flasks 1200 ml stainless steel beaker liter Nalgene bottle safety glasses gloves and lab coat ID Reagents 1 Sodium hydroxide solution make a 0 1M sodium hydroxide NaOH solution by dissolving 16 0 g NaOH in 4 liter of Nanopure water in a 4 liter Nalgene bottle Let sit or mix until the NaOH is completely dissolved 2 Molybdate reagent In a fume hood dissolve 8 0 g ammonium paramolybdate NH4 Mo70 4H O in approximately 600 ml of Nanopure water using a 1000 ml volumetric flask Add 24 ml concentrated hydrochloric acid 12N 37 HCI to the ammonium paramolybdate solution mix and then bring the total to 1000 ml using Nanopure Store in a brown polyethylene bottle out of direct sunlight The reagent is stable for many months but should be discarded if any white precipitate forms enough for 2 runs 3 Metol sulfite solution In a fume hood dissolve 12 0 g anhydrous sodium sulfite Na SO3 in approximately 600 ml Nanopure water using a 1000 ml volumetric flask and Add 20 0 g metol P methylaminophenol sulfate to the same volumetric flask mix and fill to 1000 ml When the metol has dissolved filter the solution through a No 1 Whatman filter and then store in a clean dark glass bottle This solution may deteriorate quite rapidly and should be made fresh every month 4 Oxalic acid solution In a fume
25. directory D DATA and copy the file to floppy disk e g at prompt D DATA gt Type COPY D091702A WKS A Press Ctrl and 1 from the number keypad to return to ISODAT Click MEASURE F5 to begin run Make sure there is plenty of paper in printer to complete the run When the run display has refreshed i e updated screen display you can crack all sample tubes Fig 4 Try and do this in an orderly manner so you do not miss any tubes It takes approximately 4 hours to run one bank of samples Two complete runs 4 banks can easily be run in a day To accomplish this you will need to have your samples prepared in advance Stanford University Stable Isotope Laboratory Finnigan MAT252 mass spectrometer with dual inlet and 24 port manifold Stanford University MAT252 24x Multiport Operation II Run terminated with error l 2 3 Click on ALT T upper left screen This will exit CNF A ACON A Determine source of the problem and fix When problem is resolved begin run where it was terminated Click on CNF A ACON A 2 SEQUENCE ACQ Click on TABLE DIR Shift F10 progr mam TABLE NAME reselect the correct table name e g DM091701 START LINE begin where the error took place END LINE 24 if both banks are being run 12 if only 1 bank MODE DAY FILENAME should be as follows Path D DATA filename WKS Filename is 8 characters WKS The filename should have the format operators first initial date fol
26. gt type C EAGER not case specific lt ENTER gt A list of filenames will appear on the screen Type START lt ENTER gt This will load a new sample table and clear out the old previous runs standard values 2 To enter labels run type and weights in the table lt F 1 gt Edit Sample Array see Figure 6 Once in the sample table enter the sample name followed by an lt ENTER gt Fig 7 a The first samples run will be conditioners which are simply standard approx 0 3 to 0 6mg folded in a tin or silver capsule The protocol is three 3 conditioners which are Acetanilide standard A label COND is sufficient b Two 2 blanks are run after the standards folded empty tin or silver capsules and can be labeled BLANK SAMPLE TABLE F1 Edit Sample Array F2 Edit Standard Array F3 Calc Inter Param F4 Save Table on Disk F5 Clear Sample Data ESC Exit Date 08 08 2001 13 36 55 Sample Index 1 Status STBY Level 1109 Figure 6 EAGER 100 Sample Table Menu c Three 3 standards are run next and can be labeled Acetanilide AA is sufficient d Unknowns of course have their own identification and are run next Since it is a tedious process of typing and there is not copy paste function you can use abbreviations but keep track of what you select 2 Sample type is 3 for conditioners and unknowns 2 for standards and 1 for blanks lt ENTER gt Fig 7 3 Standard type only applies to standards e g Acetanilid
27. into a waste container and release the clamp Insert the sipper tube into a beaker containing about 50 ml of Nanopure water Flush about 10 ml to 20 ml of Nanopure water into the cell using the gray WASH button Fig P4 on the front of the sipper until all of the lines are filled and there are no bubbles Figure 2 Installing the Reference cell into the Hitachi U 2001 Spectrophotometer Push back the lid to the auto sip device left photo then locate the reference cell port in the back right corner middle photo and gently insert the reference cell into the port right photo with the clear portion of the cell facing both sides of the instrument Figure 3 Engage disengage tension plate on the Hitachi U 2001 Spectrophotometer auto sip device Pull back the pump tube tensioning plate until you hear a click left photo and the release button pops up Then slide the cover above the sipper closed middle photo When finished press the release button right photo and then close sipper lid middle photo Figure 4 Operating the Hitachi U 2001 Spectrophotometer auto sip device Fill sipper cell using the WASH button left photo with Nanopure water prior to performing an AUTO ZERO Use the stainless steel sip actuator middle photo to sample Nanopure water for AUTO ZERO When ready use the sample sip actuator to run standards unknowns and blanks right photo 7 Run 3 to 5 sample cycles through the cell by pressing the large stainless
28. is at right angles to the ion trajectory b The trap collects all electrons not involved in the collision with the N or COs and is positioned opposite the filament c The extraction plates accelerate ions out of the ionization chamber and direct the ions toward the exit slits and focusing plates The accelerating voltage on the Delta plus is 3kV d There are a number of different focusing plates that are designed to progressively focus the ion beam leaving the source The voltage is variable depending on the isotopic species being analyzed e The final focusing plate defines the maximum beam width prior to passage into the flight tube JOE wah 4 s im mera AAH Mk front erg Figure 2 Schematic of Delta plus ion source within the source housing analyzer head Gases enter through the SGE valve into the ionization chamber Illustration is from Finnigan users manual msi anu a a oa poe a ee ee a Pik agentes JAD a re ee ee ee eee a L a PS al Dy eed a ia EPO ee He Figure 3 Schematic of Delta plus ion source components Values are ion source potential in relation to ground at 3kV ion acceleration voltage Illustration is from Finnigan user manual mass number MEMCO armpiifier multiplexer cup Secondary electron Suppression Shield Figure 4 Schematic representation of faraday cup collectors on the Delta plus A represents an overview of the collector system B is an enlarged view of the collec
29. mass spectrometer Fig 4 These cups are grounded through high ohm resistors As the ion current passes to ground the drop in the resistor acts as a measure of the ion current In addition each collector also has a feedback resistor therefore each amplifier can be matched to the isotope collected in a particular faraday cup There are two types of collectors major and minor The major collector is usually larger and less sensitive than the minor collector These collectors can either be fixed to a correct spacing for a particular set of masses or adjustable In the case of N or CO a triple collector mass spectrometer can detect all three masses 28 major 29 minor or 44 major 45 minor and 46 minor and calculate 5 N and C in one run without changing feedback resistors The ISODAT software cup configuration utility does this automatically The signals received by the collectors are amplified and transferred to voltage to frequency converters VFC on a system control board in a microprocessor This system board basically digitizes the analog signal for processing by an interfaced computer The analog and digital output is then sent to disk and a printer In the course of one analysis for 8 N and amp C on the Delta plus mass spectrometer one reference and one sample injection are measured to determine the concentration and isotopic composition All of the data are expressed in conventional delta 5 notation where the isotopic ratio of 8 N
30. much helium dilution is required there is a regulator and pressure gauge on the front panel of the ConFlolI housing that allows the user to preset a pressure for a run sequence When using helium dilution on any gas es the user must keep in mind that changing helium dilution pressure will affect the isotopic composition of the gas and the amount of gas entering the mass spectrometer The user should ra M Ty oo inn EA PA ee i e M h F ea J if B A He cushian Helium atution candlary meke up Figure 3 Schematic of the Finnigan ConFloll interface injecting helium Often when N and C are analyzed from the same sample helium dilution is required As with the two reference capillaries the helium in the dilution capillary is always flowing When required the helium dilution capillary moves from position A not injecting or off to B injecting or on Depending on the preset pressure of the helium dilution regulator less gas from the EA is allowed to enter the inner portion of the open split reducing the amount of sample gas entering the mass spectrometer MS capillary predetermine the amount of helium dilution required for any given run sequence set the gauge pressure using the regulator and do not change the pressure until the beginning of another run sequence A run sequence consists of three conditioning standards two capsule blanks suite of standards for determining concentrations and isotopic composition a s
31. of standard mg Tstd theoretical percentage of standard Area std peak area or integral of standard Area blk peak area or integral of blank Weight percent K Factor Area unk Area blk Wt unk Where K Factor average K Factor value Area unk peak area or integral of unknown Area blk peak area or integral of blank Wt unk weight of unknown mg G Data Conversion and Transfer When the run is complete you will need to convert the REP file into a DBF file The REP file is an ASCII file that is designed to output to a printer not a file so it is necessary to convert this to a more useful format The Eager 100 software has a program that converts the REP file to a database 3 formatted file or DBF A VBASIC program is then used to convert the DBF file into an Excel XLS file for post processing and data management The following steps will help you through this process 1 Press lt F10 gt Exit to Operating sys Fig 2 At the prompt Press Y to confirm or any other key to renounce Type Y lt ENTER gt This will allow you to exit the Eager 100 software and bring you to the C EAGER gt MS DOS prompt 2 At the C EAGER gt prompt type DB3CONV lt ENTER gt and follow the prompts This will start the database conversion program 3 Press lt F1 gt to Start program 4 At the prompt PLEASE GIVE INPUT FILENAME xxxxxxxx REP gt Type filename REP used lt ENTER gt e g DAM1 do not add the REP 5 At t
32. samples have been analyzed intermittently for large batches of samples run Nanopure water to check for instrument drift Record the readings and continue or go to the next step 11 Place the sipper tube into a beaker containing approximately 50 ml of 0 1M NaOH Flush the sipper cell by pressing the gray WASH button on the front of the sipper Fig 4 Next flush approximately 100 ml of Nanopure water through the system in the same manner 12 Replace the clamp to the waste line 13 Slide the sipper cover open and release the tension on the pump tube by pulling back the tension plate and pressing the release button Fig 3 14 Remove the reference cuvet drain and dry Close the sipper cover 15 Turn power off replace dust cover 16 Remove waste and dispose of properly V Data reduction When you are finished analyzing all of your standards blanks and unknowns you will need to enter the results into the OPAL Program Vbasic Macro to obtain a standards curve and weight percent values for the unknown samples A simple linear regression is used to calculate the slope and intercept on the standard values entered into the program The weight percent biogenic silica results are calculated using the following equation Wt SiO SiO 0 5 ml aliquot volume 60 1 g Si mole 0 0001 Sample wt Where SiO absorbance y intercept slope absorbance reading from spectrophotometer aliquot amount of sample
33. second set Continue until all tubes are sampled for the hour m Figure 6 At sample time remove 8 centrifuge tubes from water bath and place them into the centrifuge Lift the lid until it locks into place To close release the lid lock slide the bar back as illustrated in the right photo Figure 7 To operate the centrifuge flip the toggle switch up as shown in the upper right photo Off is in the middle and the brake is in the down position Dial the rotation speed to 10 using the black knob on the right of the front panel then set the time to 3 minutes using the black knob on the left of the front panel This will start the centrifuge At the end of this time the centrifuge will turn off automatically You can apply the brake by flipping the toggle switch down Allow the rotor inside the centrifuge to spin down to a stop before opening the lid and removing samples Figure 8 To sample remove cap and pipette out 250 ul from each centrifuge tube and place into a labeled 12 ml vial Figure 9 After taking 250 ul of sample from the centrifuge tube add 250 ul of Nanopure water to the 12 ml vial then rinse the pipette tip with Nanopure water before taking the next sample 3 After the last sample has been taken for the hour and all tubes are back in the bath Use the Lab Industries Repipet set and add 4 5 ml of Nanopure water to each of the vials to bring the total volume to 5 0 ml Fig 10 Figure 10 After taking 250 ul o
34. source through an inlet probe not to be confused with the inlet system which simply directs the gas flow directly into the source block more precisely the ionization chamber see Fig 4 The gas flow in the ion source is always molecular Attached to the source block are the filament cathode trap ion extraction plates and focusing plates Fig 5 a The filament cathode often tungsten emits electrons in a helical orbit under the influence of small source magnets in which the CO gas molecules collide with the electron beam making a CO ion The electron beam is at right angles to the ion trajectory b The trap collects all electrons not involved in the collision with the CO and is positioned opposite the filament c The extraction plates accelerate ions out of the ionization chamber and direct the ions toward the exit slits and focusing plates The accelerating voltage on the MAT252 is 10kV Figure 4 Schematic representation of the MAT252 analyzer system and the arrangement of components Illustration is from the Finnigan operations manual d There are a number of different focusing plates that are designed to progressively focus the ion beam leaving the source The voltage is variable depending on the isotopic species being analyzed e The final focusing plate defines the maximum beam width prior to passage into the flight tube The flight tube has a 90 deflection path Fig 4 having a radius of R fitted with a permanent
35. steel actuator on the front of the sipper After each run the instrument will display the result on the screen When the results of these runs are consistent press the AUTO ZERO on the keypad Fig P5 Sample the Nanopure water 3 to 5 time again to make sure the instrument is stable at 0 000 40 001 The instrument is now ready for standards Figure 5 AUTO ZERO the Hitachi U 2001 Spectrophotometer Fill sipper cell using the WASH button with Nanopure water prior to performing an AUTO ZERO Use the stainless steel sip actuator to sample Nanopure water for AUTO ZERO When the results are consistent Press the AUTO ZERO key Then repeat 3 to 5 more times to make sure the value is 0 000 0 001 8 Standards should always be performed first to insure that the instrument and biogenic silica chemistry are sound Once verified the blanks and unknown samples can be done 9 Insert the sipper tube into the standard sample vial and press the stainless steel actuator Fig P4 Keep in mind the first reading may not be valid but will serve mostly to flush out the previous standard sample Subsequent readings up to 3 ina 10 ml volume should be accurate and reproducible to 0 005 Record the readings after each sampling Also insure the sipper tube remains in the liquid so that bubbles are not introduced into the sipper cell Finally depending on the color difference between samples more sips may be required before the results are reproducible 10 When all
36. step b before continuing Do not perform any functions until Step c As the computer is booting up a lot of information will display on the screen You will need to follow the screen throughout this sequence After the screen displays the following lines Adaptec AHA 2940 Ultra Ultra W SCSI BIOS v1 32S4 c 1997 Adaptec Inc All Rights Reserved lt lt lt Press lt Ctrl gt lt A gt for SCSISelect TM Utility gt gt gt SCSI ID 5 PLEXTOR CD ROM PX 32TS gt Plug and Play peripheral SCSI ID auto assigned SCSI BIOS not installed you will need to be prepared to press F8 located on the upper row of the keyboard After this last line SCSI BIOS not installed is displayed the following screen will be displayed AMIBIOS System Configuration C 1985 1996 American Megatrends Inc Main Processor P55C MMX Base Memory Size 640KB Math Processor Built In Ext Memory Size 31744KB Floppy Drive A 1 44 MB 3 1 2 Display Type VGA EGA Floppy Drive B None Serial Ports 3F8 2F8 AMIBIOS Date 07 15 95 Parallel Ports 378 Processor Clock 200MHz External Cache 512KB Enabled Hard Disk s Cyl Heads Sector Size LBA 32Bit Block PIO Mode Mode Mode Mode Primary Master 14848 9 64 4111MB LBA On 16Sec 4 PCI Devices PCI Onboard Bridge Device PCI Onboard USB Controller PCI Onboard IDE PCI Slot 2 SCSI PCI Slot 3 VGA ROM ID AAES045 When the above screen is displayed you will need to pres
37. will be converted into Excel and processed SYSTEM DEFAULT Form Feed N No Y Yes N Save Raw Data on Disk N No Y Yes Y Disk and Directory Name for Ray Data A B C C EAGER Filename for Raw Data xxxxx RAW Disk and Directory name for Report A B C C EAGER Filename for Report xxxxx REP Company Name XXXXXXXXXXXXXXXXXXXX Stanford University Operator Name XXXXXXXXXXXXXXXXXXXX Stable Isotope Lab ESC to Exit ENTER To confirm data in memory Figure 9 EAGER 100 System Default Menu Note An example would be DAM1 which would end up being DAM11 RAW DAM12 RAW DAM13 RAW to DAM1 RAW There would be as many RAW files as there are runs and they would be labeled in sequence The REP file is a report of all the runs therefore there will only be one file called DAM1 REP in this example F Recalculation Parameters This menu is activated by pressing lt F6 gt from the main menu Fig 2 This menu routine allows the operator to change K factor and Blank values Fig 10a For example if one standard was out of line with the others you could manually recalculate the standard average and enter the new value s in the table When satisfied with the new values press lt ESC gt and enter which samples you want the new K factors to effect Fig 10b The following are the equations used to calculate K Factors and Weight percent K Factor Wt std Tstd Area std Area blk Where Wt std weight
38. 1 to 0 5 ml however we usually take 0 25 ml If less than 0 5 ml is taken you want to add enough Nanopure to bring the total volume to 0 5 ml 1 For simplicity lets assume you take a sample every hour for five hours This means you will need five 12 ml vials for each sample you plan to analyze remember to always include the blank All vials should be numbered and records kept to prevent confusion Fig 5 Figure 5 Place numbered 12 ml standard and sample vials on tray The tray is required as secondary containment in the event of a spill It will also facilitate carrying the vials to the spectrophotometer 2 On each hour remove the first eight centrifuge tubes and place into the centrifuge and spin for approximately 3 minutes Fig 6 See Figure 7 for centrifuge operation procedure Remove tubes from centrifuge and place into a centrifuge tube holder Place the second eight sample tube in the centrifuge and spin for 3 minutes While the second set is spinning take 0 25 ml 250 ul of sample from each tube using a 250 ul pipette and place it in the appropriate vial Fig 8 Add 250 ul of Nanopure for a total of 0 5 ml 500 ul then rinse pipette tip with Nanopure water Fig 9 Cap each tube tightly shake and place it back into the bath This sample routine takes approximately 3 to 5 minutes for eight tubes Take the second set of eight tubes from centrifuge and replace with the next set let spin for 3 minutes while spinning sample the
39. 52 mass spectrometer the CO gas After 120 seconds at 196 C Trap 2 is isolated from Trap 1 by a series of valves Trap 2 is then warmed to 30 C and the resulting CO then travels down the capillary to the changeover valve Attached to the other side of the changeover valve is a capillary connected to the mass spectrometer inlet system Fig 2 The inlet system is a symmetrical valve system composed of a reference and sample side where the valve volume and configuration are identical on both sides Also equipped on x I iH 1 1 E e RE as E E 18 n a i 3 H i My jis umri en Figure 2 Schematic diagram of MAT252 inlet system The numbers denote valve identification valve numbers 31 34 represent the changeover valve Volume of inlet bellows are indicated in inlet gas pressures are measured in mbar and roughing vacuum in ubar MS indicates capillary attaching the inlet system to changeover valve on the MAT252 mass spectrometer Anile Le Figure 3 Schematic diagram of MAT252 changeover valve Inlet 1 connects to the left side sample of inlet system Inlet 2 connects to the right side reference of the inlet system Inlet 3 connects to the Kiel II carbonate device and Inlet 4 is a spare MS indicates capillary attaching the inlet system to changeover valve on the MAT252 mass spectrometer the inlet system are variable reservoirs flexible bellows which allow for additional control of inlet gas pressures A referenc
40. A1500 Series 2 elemental analyzer When elemental analyzer is coupled to the Finnigan Delta plus IRMS Vent M 7 connected to the 2 The purge should also be on The purge line on this instrument runs to a storage flask containing magnesium perchlorate for the water trap It is always best to make sure see 2 Fig 5 3 Set the Helium carrier gas and Reference pressures to 95 KPa which is approximately 55 to 65 ml min see 3 amp 4 Fig 5 4 Set the Oxygen pressure to 100 KPa which is about 20 to 30 ml min see 5 Fig 5 5 The Air pressure should already set to 350KPa for the small volume pneumatic carousel AS 200 the Costech Zero Blank carousel does not require air however the pressure should remain at 350KPa see 6 Fig 5 B Pressures at the tank regulators should be set at the following 1 Helium UHP Grade 4 6 at 40psi 2 2 Oxygen UHP Grade 4 3 at 40psi If for some reason the instrument was on stand by it will take approximately 20 to 30 minutes for the left furnace to reach 1020 C from the stand by temperature of 768 C C Entering sample identification labels and weights Most of what you will have to do with the computer is menu driven by function keys These keys are located on the top of the keyboard labeled F1 through F10 1 To prepare a sample table Press lt F5 gt Sample Table from the main menu Fig 1 then lt F3 gt Load Table From Disk Fig 6 At the prompt Drive name and directory lt A xxxx
41. ENCE NAME e g DM041702 Search by sequence name of run Click on DIRECTORY Shift F5 Click on TAG ALL F5 if all of the runs need to be transferred to disk or use TAG F6 to select the runs needed to be transferred Click on FORMAT F8 and then enter the following exactly OUTLIER TEST D2 STANDARD IDENT SIL 2 LIST TYPE NO GRAPHICS NO ALPHA CO3 CORRECTION YES ALPHA H20 CORRECTION NO ATOM APE REPORT NO FILENAME D DATA FILENAME WKS e g D041702A WKS Make sure the filename you select will not overwrite data on the disk The computer will not prompt you LIST TYPE FORMAT3 FILE TYPE LOT j 6 Click on EVALUATE F7 This will begin the data transfer Wait for the transfer to be complete 7 before pressing ALT T To transfer the run data you just transferred from hard disk to floppy disk you Press Ctrl and 2 from the number keypad Using DOS i e CD DATA and DIR and COPY commands go to the directory D DATA and copy the file to floppy disk e g at prompt D DATA gt Type COPY D041702A WKS A or COPY D041702 A to copy all associated files Press Ctrl and 1 from the number keypad to return to ISODAT Stanford University MAT252 Kiel III Carbonate Device Operation V Acid Drip Test Procedure l 2 on Click on CNF B SUPP B 1 CARBONATE UNIT This will enter the Kiel support screen Open acid valve 10 and 20 Both can be open at the same time Allow each to drop 2 to 3 drops of ac
42. II To remove carefully lift the carousel to free the shaft from the pivot base left photo Slide carousel out without touching the capillaries counters or pistons with the carousel or vials To install taking the same precautions as above carefully slide the carousel in and gently place the carousel shaft onto the pivot base middle photo You will need to align the pin on the carousel shaft with the slot on the pivot base as well as the slot on the carousel top shroud with the vertical rod at the back of the unit right photo Figure P4 Clean the acid drip counters and capillaries on both Port 1 left photo and Port 2 right photo using 2 propanol and a cotton swab Extra care should be taken not to alter the alignment between the counter and capillary Figure P5 Servicing the o rings on the Finnigan Kiel III ports Clean both the o rings and stainless steel areas around Ports 1 upper left photo and 2 upper right photo using 2 propanol and a cotton swab Place a small portion of Apiezon L on your index finger and lightly grease Ports 1 lower left photo and 2 lower right photo Figure P6 Reloading the sample vials after cleaning and greasing Ports and 2 top left to bottom right Stanford University Stable Isotope Lab On line Manual Prepared by David A Mucciarone Section 1C Finnigan MAT252 24x Multiport Operation D Run terminated without error NORMAL 1 2 3 Click on ALT T upper left scre
43. NA1500 Series 2 elemental analyzer Principles of Operation The objective of this section is to give you an understanding on how the Finnigan ConFloll interface operates using the Finnigan Delta plus and Carlo Erba NA1500 as an example Most of the information outlined in this section can be found in the Finnigan operations manual however it is synthesized here so that it applies to the instrumentation we have in the Stanford Stable Isotope Laboratory Once trained the following procedures will serve as an operational or reference guide In our laboratory the Delta plus mass spectrometer is connected to the Carlo Erba NA1500 elemental analyzer EA via a Finnigan ConFlolII interface The ConFlolII interface allows us to connect two reference gases N and CO2 and dilution gas He which is split off from the main EA carrier gas Operation is as follows Helium carrier gas travels to both the EA and the ConFlolII into the Delta plus mass spectrometer The helium carrier gas travels through the EA 60 to 65 ml min carousel combustion and reduction columns water trap 4m GC column and exits the instrument through the 1 8 3 175mm stainless steel tubing attached to Vent M CE NA1500 This tubing connects the EA to the ConFloII interface At this point the gas enters an open split Fig 1 The mass spectrometer requires molecular flow lt 10 Torr in order to ionize gas efficiently This is accomplished in the open split Gases produced in the EA are
44. NA1500 prior to beginning a run When the base level is between 660 to 725uV and stable switch the stainless steel line connection EA to the ConFloll interface from Vent R to Vent M Fig 1 The baseline level will drop about 50 70UV and stabilize This is normal because you are pulling a vacuum on the mass spectrometer fused silica capillary Stanford University Stable Isotope Laboratory On line Manual Prepared by David A Mucciarone Section 3A Carlo Erba NA 1500 Elemental Analyzer Procedure I Operation Principles for CHNS Analyses Elemental analyzers Fig 1 operate based on a flash combustion in which a sample contained within a tin or silver capsule is dropped into a combustion reduction reactor for CHNS analyses held at 1020 C This short flash combustion is accomplished when the tin capsule is exposed to a gas flow temporarily enriched with ultra high purity UHP grade 4 3 oxygen The resulting oxidation raise temperatures to gt 1700 C The encapsulated sample depending on its composition will combust generating one or more of these gases NOx CO2 H2O and SO Depending on the type of gas es you want to analyze a combustion reduction column or separate combustion and reduction columns usually at 650 C must be installed in the elemental analyzer furnace Example 1 If you want to analyze CNS you must install a single combustion reduction column is used and would contain tungstic anhydride which is required for sample
45. PY commands go to the directory D DATA and copy the file to floppy disk e g at prompt D DATA gt Type COPY D091701A WKS A Press Ctrl and 1 from keypad to return to ISODAT Stanford University Delta Carlo Erba Elemental Analyzer Operation III Run interrupted by error 1 PART 1 Able to escape out or error A If a gray window with at red bar will be displayed on the screen obstructing the normal display Locate the source of the error e g high voltage out Fix error then attempt to press ESC If the error display disappears and the instrument appears to be working watch it carefully because it may actually be hung up and just going through the motions It is best to just press ALT T the run If the error appeared a short time ago it is just a simple matter of restarting the sequence as follows 1 2 Nn BW Click on ALT T upper left screen This will exit CNF B ACON B Click on CNF A ACON A 2 SEQUENCE ACQ Click on TABLE DIR Shift F10 a TABLE NAME reselect the correct table name e g DM041700 b START LINE begin where the error took place c END LINE 31 d MODE NIGHT e FILENAME should be as follows Operators first initial date followed by a next letter in the sequence after the original that began A and followed by WKS e g D091701B WKS The entire line needs to be typed in without mistakes You cannot edit the line it needs to be entered in one shot or press lt Enter gt and begin again e
46. Place a plug over Vent M release pressure on M helium regulator on EA turn black silver knob counterclockwise 2 If there is a leak the pressure on the M helium gauge will decrease If this occurs check for leaks The most common source of leaks will be at the carousel connection to the reactor oxidation column or the carousel lid seal Make sure to restore helium pressure to 90kPa before checking for leaks Repeat 1 and 2 if necessary until leak is repaired 3 If there is no leak remove plug on Vent M and restore helium pressure to 90kPa Figure P1 Switch stainless steel line exiting the elemental analyzer EA from Vent M on the left to Vent R in the middle The oxygen vent is on the right Figure P2 Removing the Costech Analytical zero blank carousel from EA reactor column First open the purge valve on top left photo then loosen the connections to the reactor column middle photo and the helium line right photo Then move carousel to the side to allow removal of the quartz insert Figure P3 Removing quartz insert from EA reactor column A marker pen works great at removing the insert left photo Once the insert is removed enough grab the top with your fingers remove completely and place into the waste beaker middle photo Note the location of the carousel In this position there is no obstruction when removing the insert Place approximately 7 mm of quartz wool in the bottom of the insert and slide it into the reactor c
47. ak shape on N3 a Click on CNF A SUPP A and 1 CONFLO II CTRL This will allow control of ConFlolII valves b Click on REF1 OFF Shift F6 or click REF 1 hourglass icon then click on REF2 ON F8 or click on the REF 2 hourglass icon Fig 1 This will stop CO from entering the mass spectrometer and introduce N into the mass spectrometer via the ConFloll interface Click on ALT T Click on CNF D ACON D and 1 INSTR CONTROL This will allow control of Deltapius source d Click on CUP CFG Shift F10 left click on N2 COMNF then right click or lt ENTER gt to select This will select the correct magnet and source voltage setting for N gt e Click on CENTER F6 this will center the source voltage when finished click on SHAPE F8 followed by MEASURE F5 to perform a peak shape on mass 28 29 30 When complete click on EXIT F10 g Figure 1 ConFloll reference gas and helium dilution control CNF A SUPP A and 1 CONFLO II CTRL screen Black hourglass indicates open valve white represents a closed valve 12 Click on ALT T to exit CNF D ACON D and 1 INSTR CONTROL 13 Click on ALT T to exit CNF A SUPP A and 1 CONFLO II CTRL 14 Click on CNF A EDIT A and 2 SEQUENCE EDITOR Prepare a new table which can be done by copying a previous sequence and modify as needed The filename should be named after the type of 16 17 16 18 samples being loaded e g ODP1098 1 ODP1098 2 etc Enter new run information Mak
48. an use either a 32 or 50 hole drum where the sample yield is 31 and 49 respectively because one of the holes in each drum is oriented over the top of the oxidation column In order to extend the run and add more samples to the carousel the run must be stopped carousel opened loaded and purged It only takes a few extra minutes to add an insert change to this process thereby reducing the risk of bad data due to excess ash accumulation To set up and run a 31 sample sequence takes approximately 5 5 to 6 hours and a 49 sample run takes 7 5 to 8 hours Before you begin preparing the new water trap you should first clear an area on the bench top obtain and organize all of the materials and equipment listed below Table 1 Number of conditioners blanks standards and samples that can be run on one quartz insert using the Costech Analytical zero blank carousel Material Weight mg Total number of runs Soils 20 35 mg 31 Sediments 20 35 mg 31 GF C filter N A 31 Plants leaves 2 5 mg 49 Animal parts 1 5 mg 49 High organic material 0 1 1 mg 49 Materials Costech Analytical quartz insert and quartz wool Fig P3 Equipment Sharpie felt pen or forceps Fig P2 I Removing the quartz insert 1 Switch stainless steel line exiting the elemental analyzer EA from Vent M to Vent R Fig P1 2 Remove quartz insert from EA reactor oxidation column a Loosen purge valve on top of carousel Fig P2 b Next loosen the fittings connec
49. and filtering while centrifuging sample Place the other 1 4 split into the splitter again rotating the wheel back and forth and then pour the contents into the splitter containers You know have two 1 8 splits At this point you have two possible protocols to follow If the sample has very little solid material you will continue with step 11 skipping only step 12 and continue to the end of the procedure However if you have a large amount of solid material you will skip step 11 and go to step 12 and continue to the end of the procedure If your sample has very little solid material decant one of the 1 8 splits into a clean Nalgene bottle or beaker and set aside Place the other 1 8 split portion into the sample splitter and split a Place three weighed Nuclepore Milipore filters on the filter frits of the filter rig Use a little Nanopure water to keep the filters in place then use the clamps to secure the funnels in place Place the labeled empty media dishes in front of the appropriate filter Separately filter both 1 16 splits using the first two filter rig setups b Decant the remaining 1 8 split from holding container bottle or beaker into sample splitter and split Take one 1 16 split and decant this into the remaining filter rig Make sure to label the filter media dishes with the sample name and 1 16 split and turn on the vacuum line to begin filtering c Take the remaining 1 16 split and decant into a small Nalgene bottle and
50. ap tube middle photo Dispose of used magnesium perchlorate into labeled waste container right photo Remove remaining quartz wool from trap tube then was the trap tube in deionized water Stanford University Stable Isotope Laboratory On line Manual Prepared by David A Mucciarone Section 3E Changing Elemental Analyzer quartz insert This procedure is designed to illustrate how to change the quartz insert in the oxidation column on the Carlo Erba NA1500 Series II elemental analyzer EA Unlike the oxidation and reduction columns and water trap on the EA the quartz insert needs to be changed after each run sequence i e every 31 to 49 samples depending on what type of samples are being analyzed and the drum used When a sample is dropped into the reactor or oxidation column on the EA the sample contained in either a tin or silver capsule is combusted and subsequently turned into an ash deposit Obviously samples combusted in tin and having a high organic content will ash better than samples with high clay content in silver capsules or glass fiber filters in tin capsules The total number of samples that can be analyzed in a run sequence depends on how well the sample combusts in the oxidation column Table 1 shows examples of sample runs where the total number of runs includes conditioners blanks standards and samples Since our lab uses the Costech Analytical zero blank carousel we have adopted the following protocol This carousel c
51. ard for natural ISN abundance measurements Nature 303 685 687 Mariotti A 1984 Natural ISN abundance measurements and atmospheric nitrogen standard calibration Nature 311 251 252 Minagawa M D A Winter and I R Kaplan 1984 Comparison of Kjeldahl and combustion methods for measurement of nitrogen isotope ratios in organic matter Anal Chem 56 1859 1861 M ller P J 1977 C N ratios in Pacific deep sea sediments Effect of inorganic ammonium and organic nitrogen compounds sorbed by clays Geochim Cosmochim Acta 41 765 776 Mook W G and Jongsma J 1987 Measurement of the NO correction for 8 C ratios of atmospheric CO by removal of NO Tellus 39B 96 99 Nevins J L M A Altabet and J J McCarthy 1985 Nitrogen isotope ration analysis of small samples Sample preparation and calibration Anal Chem 57 2143 2145 Verado D J P N Froelich and A McIntyre 1990 Determination of organic carbon and nitrogen in marine sediments using the Carlo Erba NA 1500 analyzer Deep Sea Res 37 157 165 Stanford University Stable Isotope Lab On line Manual Prepared by David A Mucciarone Section 2B Finnigan Delta pus and Carlo Erba NA 1500 Elemental Analyzer with ConFlolII interface I Operation Principles for elemental N C 5 5N and 5 3C Analyses Before you can operate the Finnigan Delta plus mass spectrometer you must have training You should also consult Section 3 of this on line manual Carlo Erba
52. ata was saved to the database called ISOBASE and to the filename you created On the other hand if you were not able to escape and had to refer to Part 2 of this section then the data was only saved to the database and not to the file you created in the SEQUENCE AQQ screen This file will only have 128K You will need to review the recover data section IV for instructions on how to obtain the run data Stanford University MAT252 Kiel III Carbonate Device Operation 2 PART 2 Unable to escape out or error A Ifa gray window with at red bar will be displayed on the screen obstructing the normal display If after looking for the fault and do not see one then attempt to press ESC If the error display does not disappear to the point where the screen freezes then you will have to reboot the computer by following the reboot sequence AUNI NWN Press Ctrl Alt Del to reboot computer At the Load Real 32 prompt Type N lt Enter gt this will load Win95 At login prompt Type sil lt OK gt Click on Scan Disk on desktop Let the program delete any fragments DO NOT FIX THEM just delete them Restart the computer using the START button At the Load Real 32 prompt Type Y lt Enter gt this will load ISODAT v7 2 allow the microprocessor to reset before doing anything message is displayed at top of screen B Continue as follows to prepare the run ra Click on CNF B SUPP B 1 CARBONATE UNIT This will enter Kiel su
53. bserve the M helium gauge for leaks When finished restore helium pressure to 90kPa clockwise rotation Stanford University Stable Isotope Laboratory On line Manual Prepared by David A Mucciarone Section 3D Preparation of Elemental Analyzer Water magnesium perchlorate Trap This procedure is designed to prepare a water magnesium perchlorate or anhydrone trap for the Carlo Erba NA1500 Series II elemental analyzer EA The entire procedure should be performed over a secondary container such as a tray to capture any spilled materials Safety glasses rubber gloves particle mask and a lab coat apron are required throughout the acid preparation Unlike the oxidation and the reduction columns on the EA the water trap needs to be changed on a regular basis i e every 1 to 3 days or approximately 80 to 200 runs depending on what type of samples are being analyzed This can best be determined by monitoring consistency of the magnesium perchlorate in the clear glass trap tube As the magnesium perchlorate becomes wet it begins to clump together When the upper 1 cm shows obvious texture change then it is time to change the trap You can also use the ISODAT software on the Finnigan Delta mass spectrometer to monitor mass 18 on beam 2 This reading is normally below 3 V so if it is higher the trap needs to be changed In order to keep the magnesium perchlorate granules dehydrated they are stored in a flask in a helium environment supplied b
54. d Technology NIST in Gaithersburg MD 20899 0001 For more information consult the reference list below Now that you have a general understanding on how the Finnigan Delta plus operates you can continue with Part B of this section to see how the gases generated by the EA move through the system and how they are analyzed Consult Section 2A for a discussion on the ConFlolII interface and Section 2 C for the quick reference guide to the operation of the EA and the Delta plus Table 1 Isotopic compositions of standard reference materials Coplen et al 2002 Pe ete ete cst olen oe Meee eal Standard Description oo SIN Ain 00 5180 cuowy 00 513C pppy oo PDB Peedee belemnite 30 91 0 00 SMOW Standard Mean Ocean Water 0 00 Air Air 0 00 IAEA N1 Ammonium sulfate 0 43 IAEA N3 Potassium nitrate 4 69 USGS 26 Ammonium sulfate 53 62 NBS 19 TS limestone 28 65 1 95 USGS 24 Graphite 15 99 NBS 21 Graphite 28 10 NBS 22 Oil 29 74 ID Chromatography and Isotopic Analysis The Delta plus is connected to an EA via a ConFlolI open split interface Helium carrier gas flowing through the entire system in conjunction with the length of the GC column and the temperature of the GC oven will control the retention times of the N and CO These parameters have been selected so that we can maximize both separation and chromatography shape of the sample peaks These two factors are important for a couple of reasons First separation be
55. d of problem however do not restart the instrument until the counter on the front panel of the instrument reads 000 See 1 Fig 4 When finished do not place elemental analyzer on stand by the instrument should always be in ready mode unless service of maintenance is required Putting the instrument into stand by mode with the Delta plus IRMS and ConFloll interface connected to either Vent M or Vent R could cause the helium carrier flow to the ion source to drop low enough to allow atmospheric gases to enter the open split of the ConFlolI and contaminate the ion source As explained above attached to the elemental analyzer is a mass spectrometer that enables us to analyze N and CO gas generated in the combustion reduction reactor for 5 N and 81 C analysis Configuration of the combustion reduction reactor along with other parameters such as oven temperatures flow rates retention times are presented in Table 1 Do not alter these parameters The METHODS in ISODAT are setup according to these parameters especially peak jumping Please note that shorter columns can be used which will decrease the total run time peak width and separation between peaks Higher flow rates can also be achieved with shorter columns because there is less back pressure Changing the column temperature will also affect peak shape and retention times When this is done the METHODS in ISODAT will need to be altered to work with these changes Table 1 Set up param
56. e 1 record start position on sample log sheet This will be helpful if there is a problem with the run e g sample capsule wedges in hole and does not drop samples need to be removed Once samples are loaded close lid and secure using the 3 thumbscrews Tighten back two first them front Allow carousel to purge for 2 minutes before closing purge valve on the top of carousel lid Check magnesium perchlorate water trap Change when the upper 10 to 15mm of magnesium perchlorate granules appear fused together Fig P7 a b To change loosen red caps on both ends of trap and remove Teflon silicon seals usually stick to the glass trap remove seals check for cracks and replace if necessary otherwise clean and use Place 5 to 7mm of quartz wool in one end of a clean trap located in oven and fill with magnesium perchlorate granules and gently tap trap on bench top to compact granules Be sure to leave approximately 5 to 7mm of space in order to insert quartz wool into the open end c Clean both faces of trap and reassemble Place seals in red caps with Teflon portion of seal against the metal flange and secure finger tight d Magnesium perchlorate from used trap needs to be removed and placed into the waste container Glass trap can then be cleaned with water and placed into the oven to dry 8 Perform a leak check EA Fig P8 a Place a plug over Vent M release pressure on M helium regulator on EA turn black silver knob countercl
57. e CO gas gas of known isotopic composition is placed into the reference side of the inlet system for comparison with a known or unknown sample gas from the carbonate device A series of standards of known isotopic composition are commonly run through the carbonate device to assure proper reference gas calibration and sampling protocol The reference gas is a large quantity of gas that occupies the entire reference side of the inlet including the bellows This gas will remain in the inlet throughout many known and unknown sample runs In order to obtain useful isotopic data it is necessary to balance the pressure and volume of the known reference gas and unknown sample from carbonate device gas This is done using the reference bellows and valves in the inlet system Gas in the inlet system Reference side and carbonate device flow down capillaries and through changeover valves Fig 3 into the ion source These capillaries have an extremely small inside diameter At the end of the capillaries are crimps which are adjusted so that the flow and depletion rates of sample and reference CO gas are identical The crimps are also the transition point between low vacuum viscous lt 10 4 Torr and high vacuum molecular gt 10 4 Torr gas flow The capillaries are connected to a set of changeover valves that control the input of the inlet gases allowing for only one gas to be analyzed at a time Once the gas passes through the changeover valves it enter the
58. e is 3 Sulfanilamide is 4 lt ENTER gt Fig 7 4 Sample weight are typed in followed by lt ENTER gt 5 Samples can be entered while the instrument is in operation however you need to load all of you samples into the Costech zero blank carousel first Note you must exit the sample table after each sample run before the next sample will be analyzed This should not be a problem since there is 10 minutes between runs SAMPLE TABLE Sample Name Sample Type Standard Type Weight 1 2 3 4 5 6 7 8 9 10 Sample Type 0 Bypass 1 Blank 2 Std 3 Unk F3 Calc Inter Param F4 Save Table on Disk F5 Clear Sample Data ESC Exit Date 08 08 2001 13 36 55 Sample Index 1 Status STBY Level 1109 Figure 7 EAGER 100 Sample Table Menu D Calculation and Integration Parameters This menu routine contains all the major run parameters and can be accessed from the main menu by pressing lt F3 gt Fig 2 This menu contains retention times run time plot attenuation etc Fig 8a b There are two pages to this menu All changes to the menu must be followed by lt ENTER gt The following are examples of the Integration Parameters Menu INTEGRATION PARAMETERS Minimum Height millivolts 10 Inhibit Time seconds 10 Run Time seconds 525 Plot Attenuation mV 0 Autorange 2 Number of Analyses variable 1 49 Sample Index 1 Plot on Paper O No 1 Yes 0 Report on 0 Video 1 Printer 2 Disk 2 ESC to Exit ENTER
59. e sure you have selected the correct METHOD when creating a sequence table When finished save and exit F10 Sequence Editor then Click on ALT T Click on CNF A ACON A 2 SEQUENCE ACQ Click on TABLE DIR Shift F10 TABLE NAME e g ODP1098 1 START LINE 1 END LINE 31 make sure start and end line numbers are correct MODE NIGHT FILENAME should be as follows Operators first initial date followed by a letter beginning with A followed by WKS e g D091701A WKS The line should read as follows D DATA D091701A WKS f LIST TYPE should be FORMAT3 g FILE TYPE LOT h SAVE DATA TO DATABASE NO Click SAVE to save sequence When the base level is between 660 to 725uV and stable Fig P10 switch the stainless steel line connection EA to the ConFloll interface from Vent R to Vent M Fig P1 The baseline level will drop about 50 70uV and stabilize This is normal because you are pulling a vacuum on the mass spectrometer fused silica capillary Click MEASURE to begin run Make sure there is plenty of paper in printer to complete the run To transfer the run data from hard disk to floppy disk you Press Ctrl and 2 from the number keypad Using DOS i e CD DATA and DIR and COPY commands go to the directory D DATA and copy the file to floppy disk e g at prompt D DATA gt Type COPY D091701A WKS A Press Ctrl and 1 from the number keypad to return to ISODAT oanp Stanford University Stable Isoto
60. e to the quartz tube Fig P4 As you add the reagent to the tube gently tamp the tube to compact the reagent to avoid separation when the column is heated to 1020 C Use the push rod to measure the amount of chromium III oxide added 7 Add approximately 1 0 to 1 5 cm of quartz wool on top of the chromium IID oxide for a total of 23 5 cm Fig P5 8 Prepare a quartz insert by placing 5 to 7 mm of quartz wool at the bottom of the tube Slide the insert into the top of the oxidation column The insert should extend past the top of the oxidation column by 1 to 2 mm If the insert is flush or below the top of the oxidation column you will need to at an appropriate amount of quartz wool to the column Fig P5 9 Install a black sealing ring at the top with the flat portion down Fig P6 10 Clean the outside of the oxidation tube with a Kimwipe and 2 propanol and set the tube aside Fig P6 11 When the oven has cooled and the new oxidation column is ready you can begin removing the used oxidation column 12 Remove the furnace cover to expose the bottom of the oxidation column Fig P7 13 Remove both braces at the bottom of the oxidation and reduction columns Fig P8 14 Completely loosen the fittings on the bottom of the reduction column right and the bottom of the oxidation column left and remove the coupling Fig P8 15 Loosen the fittings connecting the carousel to the oxidation reactor column and helium input line Move car
61. e will decrease If this occurs check for leaks The most common source of leaks will be at the carousel connection to the reactor column seals in water trap or the carousel lid seal Make sure to restore helium pressure to 90kPa before checking for leaks Repeat 18a and 18b if necessary until leak is repaired c Ifthere is no leak remove plug on Vent M and restore helium pressure to 90kPa Figure 17 Checking and changing the magnesium perchlorate water trap on the Carlo Erba NA1500 Observe upper left portion of trap to see if magnesium perchlorate is sticking or degrading To remove the water trap loosen the red caps on both ends of the glass trap left and middle photo Remove Teflon silicon seals from both ends and check for cracking right photo Replace if necessary or reuse seals Make sure silicon portion of seal seats against the glass trap and the Teflon against the stainless steal flange Figure 18 Leak checking the Carlo Erba NA1500 Move stainless steal line from Vent M to Vent R see Fig 11 and place plug left photo on Vent M Turn down counter clockwise rotation the helium pressure by using the knob labeled M on the EA right photo Observe the M helium gauge for leaks When finished restore helium pressure to 90kPa clockwise rotation J Begin Analyses ConFloll interface is connected to the EA via a stainless steel tube When the elemental analyzer is used as a stand alone instrument this stainless steel tube m
62. el and rotate making a score completely around the sample tube Figure P3 Loading sample tubes into tube crackers of the Finnigan MAT 252 24 port manifold upper left photo Note the orientation of the tube crackers on the 24 port manifold Bank 2 B2 Tube cracker 1 T1 is located at the upper left top row counting to the right to B2 T6 second row B2 T7 to B2 T12 third row Bank 1 B1 T1 to B1 T6 forth bottom row B1 T7 to B1 T12 Select tube cracker upper right photo then loosen and remove end cap from tube cracker lower left photo Remove previous sample tube if present and install new scored sample tube into tube cracker lower right photo then replace and tighten end cap Figure P4 After you press measure F5 you need to crack all sample tubes It is best to do this in an orderly manner so you do not miss any samples Crack sample tubes by bending the bellows tube until you hear the glass sample tube break right photo Stanford University Stable Isotope Laboratory On line Manual Prepared by David A Mucciarone Section 1D Preparation of 100 Phosphoric Acid H3PQ for Kiel Carbonate Device This procedure is designed to prepare approximately 425 ml of 100 phosphoric acid H3PO The entire procedure should be performed under a fume hood Goggles rubber gloves and a lab coat apron are required throughout the acid preparation Materials Ar grade 85 Phosphoric acid H3PO Equipment Graduated cyl
63. en This will exit CNF A ACON A Click on CNF A SUPP A and 2 MULTIPORT CTRL This will enter multiport support screen Note fore vacuum baseline Fig P1 and open the following valves in order Click on valves 39 13 12 and 14 Fig 1 Allow vacuum to regain baseline Prepare and order sample tubes to be loaded into tube cracker manifold Using a file or Dremel Tool to score the glass in the middle of the sample tube Fig P2 Make sure the scoring goes completely around the sample tube Click on CNF A EDIT A 3 SEQUENCE EDITOR Prepare a new table by copying a previous sequence The filename should be in the format operators first and last initial followed by the date e g DM091702 Enter new run information Make sure that the reference refills RR 120 are in the correct locations When finished press exit save F10 Sequence Editor then Click on ALT T Unloading loading sample tubes in crackers Fig P3 a Open the bottom of the crackers by loosening the Swagelok cap fitting on the bottom This can be done by hand or with two 9 16 wrenches Remove spent ampoules from crackers c Place scored ampoules into cracker and secure with Swagelok cap fitting Tighten fitting by hand or use two 9 16 wrenches Be careful not to over tighten the fitting Click on CNF A SUPP A and 2 MULTIPORT CTRL Fig 1 a Click on the Bank or Bank2 on the upper left of the screen until the correct bank is selected b Close valve 14 c C
64. ence The filename should be in the format operators first and last initial followed by the date e g DM041902 Enter new run information Make sure that the reference refills RR 120 are in the correct locations When finished save and exit Sequence Editor then Click on ALT T 13 Return to CNF B SUPP B if acid temperature is at 69 C and LN dewar is filled and cold trap is at the temperature you selected above then Click ALT T 14 Click on CNF B ACON B 2 SEQUENCE ACQ Click on TABLE DIR Shift F10 a TABLE NAME e g DM041702 b START LINE 1 c END LINE 46 make sure start and end line numbers are correct e g 1 and 46 for a full carousel run d MODE DAY e FILENAME should be as follows Path D DATA filename WKS Filename is 8 characters WKS The filename should have the format operators first initial date followed by a letter beginning with A ending with WKS e g D041702A WKS Type in the path and filename then press lt Enter gt e g the line should read as follows D DATA D041702A WKS f LIST TYPE FORMAT3 ONLY g FILE TYPE LOT h SAVE DATA TO DATABASE COL 15 Click SAVE to save sequence 16 To transfer the run data from hard disk to floppy disk you Press Ctrl and 2 from the number keypad Using DOS i e CD DATA and DIR and COPY commands go to the directory D DATA and copy the file to floppy disk e g at prompt D DATA gt Type COPY D041700A WKS A Press Ctrl and 1 from the number key
65. er will not prompt you i LIST TYPE FORMAT j FILE TYPE LOT pe me aoge j Click on EVALUATE F7 This will begin the data transfer Wait for the transfer to be complete before pressing ALT T To transfer the run data you just transferred from hard disk to floppy disk you Press Ctrl and 2 from the number keypad Using DOS i e CD DATA and DIR and COPY commands go to the directory D DATA and copy the file to floppy disk e g at prompt D DATA gt Type COPY D091702A WKS A or COPY D091702 A to copy all associated files Press Ctrl and 1 from the number keypad to return to ISODAT d Figure P1 Perform a fore vacuum check by pressing the black FV Inlet button on the far right and monitor by reading the lower green bar left photo When finished press the black HV source button on the far right and monitor by reading the upper red bar right photo Figure P2 Scoring sample tubes using file left photo or the Dremel Tool With either technique it is necessary to make a score completely around the glass sample tube Also care should be taken not to break the glass sample tube or cutting your hand With the file technique left photo apply enough pressure with your thumb to allow the file to cut into the glass while also allowing you to rotate the sample tube with the opposite hand When using the Dremel Tool right photo set the Variac controller on 20 to 25 out of 100 press the sample tube against grinding whe
66. eters for N and C analysis using the Carlo Erba Na1500 Series 2 elemental analyzer and a 4 m GC column Instrument Temperatures C Combustion oven 1020 Reduction oven 650 Chromatographic column 60 Filament 190 Flow Rates ml min Helium Grade 4 6 Zero 95 105kPa 55 65 Oxygen Grade 5 UHP 100 105kPa 20 25 Element Retention Times seconds Nitrogen as N2 205 220 Carbon as CO2 390 410 Additional Parameters seconds Cycle time 600 Sample time begin end Costech Zero Blank carousel 15 amp 16 Sample time begin end Carlo Erba AS 200 15 amp 60 Oxygen injection 65 Run time for N and C 620s 10 5 min Column Configuration cm Quartz combustion column 1 x w 45 0 x 1 8 From bottom to top Quartz wool 4 0 Silvered cobaltic oxide Co30 Ag 6 0 Quartz wool 0 5 Chromium oxide Cr03 10 5 Quartz wool 0 5 Quartz reduction column 1 x w 45 0 x 1 8 From bottom to top Quartz wool 4 0 Reduced copper wires approx 150g 30 0 Quartz silica chips 9 0 Quartz wool 1 5 K Summary of Operation 1 Move Vent M see 7 Fig 5 to Vent R see 8 Fig 5 This will separate the Carlo Erba NA1500 from the Finnigan Delta plus 2 Check instrument run parameters as in Table 1 above 3 Press lt F5 gt Sample Table 4 Press lt F3 gt Load Table from Disk 5 Type C EAGER lt ENTER gt 6 Type START lt ENTER gt to load new sample table 7 Press lt F1 gt Edit sample array 8 Press lt F4
67. f sample from the centrifuge tube and adding the 250 ul of Nanopure water to the 12 ml vial total volume of 0 5 ml use the repipette to dispense 4 5 ml of Nanopure water to each vial 4 After the first hour or first sampling prepare the standards Using the concentrations prepared earlier in the outline described above in Part II Number 7 of the Reagents section add 0 5 ml 500 ul of each concentration to a vial using a 500 ul pipette Use the Lab Industries Repipet set and add 4 5 ml of Nanopure water to each of the vials to bring the total volume to 5 0 ml C Adding reagents Once all of the samples have been taken you will be adding 2 ml of Molybdate reagent and 3 ml of Reducing solution to each of the sample blank and standard vials Timing is important when adding these reagents You will begin by adding the Molybdate reagent then the Reducing solution However you have to wait a minimum of 10 minutes to a maximum of 30 minutes before you can add the Reducing solution So if it takes 20 minutes to go from vial 1 to vial at about 10 seconds per vial when you finish vial you can begin adding the Reducing solution to vial 1 because it took more than 10 minutes However you must now take the same amount of time to add the Reducing solution to each vial 1 Use the Oxford adjustable pipette and set to 2 ml Noting the time add 2 ml of Molybdate reagent Part II Number 2 in the Reagents section to each of the sample blank a
68. g the line should read as follows D DATA D091701B WKS f LIST TYPE should be FORMAT3 g FILE TYPE LOT h SAVE DATA TO DATABASE NO Click SAVE to save sequence Make sure there is plenty of paper in printer to complete the run Click MEASURE to begin run To transfer the run data from hard disk to floppy disk you Press Ctrl and 2 from the number keypad Using DOS i e CD DATA and DIR and COPY commands go to the directory D DATA and copy the file to floppy disk e g at prompt D DATA gt Type COPY D091701A WKS A Press Ctrl and 1 from keypad to return to ISODAT Stanford University Delta i Carlo Erba Elemental Analyzer Operation 2 PART 2 Unable to escape out or error A If a gray window with at red bar will be displayed on the screen obstructing the normal display If after looking for the fault and do not see one then attempt to press ESC If the error display does not disappear to the point where the screen freezes then you will have to reboot the computer by following the reboot sequence AUNE O U Press Ctrl Alt Del to reboot computer At the Load Real 32 prompt Type N lt Enter gt this will load Win95 At login prompt Type sil lt OK gt Click on Scan Disk on desktop Let the program delete any fragments DO NOT FIX THEM just delete them Restart the computer using the START button At the Load Real 32 prompt Type Y lt Enter gt this will load ISODAT v7 1 allow the micro
69. gt Save table on disk 9 Press lt ESC gt to exit 10 Press lt F3 gt Calc Integ Param Modify list to correspond to instrument parameters 11 Press lt ESC gt to main menu 12 Load samples into carousel Once you have checked the baseline level to be better than 1150 and stable you are ready to begin Press lt F1 gt Run Part L Appendix Various elemental analyzer configurations E Aethicton reecter aa oe wu E i Dapp LN LJ ca pH Le Ee 1 Combustion resctor k Ademeplion tap ter GO fe Cuorir Fii Goda bria PES aw Charie Geis fow Himni Gibai omake Qaia Jw hijian mop for COL 4 Agsoretinn trap tor Ha E Pakad bhurn tor H detercenaiion En mg am I ay anivanee LF a Appendix Figure 1 Nitrogen only configuration on Carlo Erba NA1500 Series 2 elemental analyzer Adele pariar t Com maiian reactor 2 Adisnpika inp lor OD A cl Chaar Wire Bij lim PaT Chroreasi hanhi Bie pra kemi Cohelemocteiic Orija at ow Ararp m irap for LO 4c Aelsorption ita fer Hp pacing a H deermineson i i tom Anhaia Appendix Figure 2 Nitrogen and carbon configuration on Carlo Erba NA1500 Series 2 elemental analyzer 2 Adeonptlon irap for HO rev Aino Cont 3 Packed column for BCS determination Fm agih om O Appendix Figure 3 Nitrogen carbon and sulfur configuration on Carlo Erba NA1500 Series 2 elemental analyzer 2 Ageonplion timp inr Hp
70. gure 2 You will only find the ConFlolIl system in this position when gas es from the EA do not require helium dilution which is often the case when running nitrogen or when running small samples for carbon without analyzing for nitrogen In most natural abundance samples such as soils sediment and plants it is common that the amount of carbon present exceeds nitrogen C N anywhere from 5 1 to 15 1 Therefore most samples when analyzing Laminar pas flow sp iting Gutar Be inner ype y M Figure 2 Schematic of the Finnigan ConFloll interface Gas from the elemental analyzer EA enters the open slit where over 90 of the gas will exit the slit and the remaining gas enters the mass spectrometer MS capillary Reference gas from the N2 and CO2 capillaries is always flowing and vents the open slit by the helium carrier flow traveling through the apparatus Note that when the reference capillaries are not being injected the are above the MS capillary therefore they do not enter the MS capillary The helium dilution capillary is in the injection position it is normally located above the MS capillary unless injection is required for N and C from the same sample run require helium dilution of the CO in order to reduce the amount of gas so that the sample can be analyzed by the Delta plus So depending on the C N ratio of the samples run on the EA helium dilution may be required and the gas would behave as illustrated in Figure 3 Depending on how
71. he prompt PLEASE GIVE DISK NAME FOR INPUT FILENAME gt Type C lt ENTER gt 6 At the prompt PLEASE GIVE OUTPUT FILENAME xxxxxxxx DBF gt Type same as input filename used lt ENTER gt e g DAM1 do not add the DBF 7 Review the screen to make sure the source and destination are correct e g the line should read SOURCE C DAM1 REP DESTINATION C DAM1 DBF PLEASE GIVE CONFIRMATION Y N gt Type Y lt ENTER gt 8 When the program finishes you will return to the C EAGER gt prompt Insert a diskette into the floppy drive and copy the following REP and DBF files from the C drive to the A drive see the following example At the C EAGER gt prompt type COPY DAM1 REP A lt ENTER gt then type COPY DAM1 DBF A lt ENTER gt To continue running the Eager 100 software and the elemental analyzer type RLDEAGER 10 If finished running the elemental analyzer as a stand alone unit simply reboot the computer by pressing Ctrl Alt Del The computer will eventually prompt you with LOAD Real 32 Y or N Type Y this will load the Finnigan ISODAT software K FACTORS K Factor Average Blank Average Peak Name 1 0 0 Carbon 2 0 0 Hydrogen 3 0 0 Nitrogen 4 0 0 Oxygen 5 0 0 Sulfur ESC to Exit ENTER To confirm data in memory F1 Cursor Down Average calculation will restart from first calibration given 0 to factors Figure 10a EAGER 100 Recalculation sub menu RECALCULATION RETURN f
72. he steel seat inside the red cap and the silicon face goes against the glass water trap tube II Perform a leak check EA Fig P5 1 Place a plug over Vent M release pressure on M helium regulator on EA turn black silver knob counterclockwise 2 If there is a leak the pressure on the M helium gauge will decrease If this occurs check for leaks The most common source of leaks will be at the carousel connection to the reactor column seals in water trap or the carousel lid seal Make sure to restore helium pressure to 90kPa before checking for leaks Repeat 8a and 8b if necessary until leak is repaired 3 If there is no leak remove plug on Vent M and restore helium pressure to 90kPa III Cleaning water trap 1 Remove quartz wool from on end of the trap to expose the magnesium perchlorate Fig P6 Use a spatula to loosen the magnesium perchlorate and dispose in the labeled waste container Fig P6 3 When all of the magnesium perchlorate has been emptied remove the remaining quartz wool and wash the trap with deionized water and place in oven at 60 C 4 Secure lid on waste container Figure P1 Helium line feeding magnesium perchlorate storage flask left photo Material required to prepare magnesium perchlorate water trap on the Carlo Erba NA1500 Series II elemental analyzer right photo Figure P2 Switch stainless steel line exiting the elemental analyzer EA from Vent M on the left to Vent R in the middle The
73. hood prepare a saturated oxalic acid solution by adding 60 0 g of oxalic acid dihydrate COOH 2H O with 1000 ml Nanopure water in a 1000 ml volumetric flask Let stand overnight Decant solution from crystals into a glass storage bottle The solution is stable indefinitely 5 Sulfuric acid solution 18N 50 In a fume hood using a 1000 ml volumetric flask poor 300 ml concentrated sulfuric acid 36N 98 H2SO into a 1000 ml volumetric flask Cool to room temperature and bring volume to 1000 ml Store in a 1 liter Nalgene bottle 6 Reducing solution This solution is mixed for each set of samples In a fume hood use a graduated cylinder to measure out equal amounts of Metol sulfite solution Oxalic acid solution and Sulfuric acid The amount of reducing solution required depends on the number of samples blanks standards and number of hours sampled At the end of your sampling you will have to add 3 0 ml of reducing solution to each vial For example You have 17 samples 1 blank and 9 standards and you sample each hour for a total of 5 hours You will generate 5 vials per sample or 18 samples 5 vial sample 3 ml 9 standards 3 ml standard 297 ml of reducing solution or 300 ml total reducing solution As a precaution you should make about 360 ml which is divisible by 3 120ml ea reagent 7 Primary silica standard dissolve 0 5642 g in a Nalgene 1 liter volumetric flask fill to 1 liter with Nanopure water Dissolution is sl
74. ic silica analyses and placing them into centrifuge tubes 2 Turn on Hitachi U 2001 spectrophotometer to allow it to stabilize Zero instrument using Nanopure water See Part IV in this section for Hitachi spectrophotometer instructions 3 Fill Blue M water bath with deionized water DI and turn on water bath Fig 3 The water bath should be preset to 85 C however insert thermometer and adjust if necessary Figure 3 To operate Blue M water bath turn on using toggle switch as shown on the left If necessary adjust the temperature setting using the large black knob as illustrated on the right 4 Filla 1 liter Nalgene bottle with 0 1M NaOH and insert the 50 ml Brinkmann Dispensette into bottle and set for 40 ml 5 Using the Brinkmann Dispensette add 40 ml to each labeled centrifuge tube cap tightly shake insert into 85 C water bath record time Fig 4 All of the tubes must be shaken every 30 minutes Fig 4 Figure 4 Prepare samples for biogenic silica analyses by adding 40 ml of NaOH to each centrifuge tube cap shake and place into the water bath at 85 C You will need to shake the samples every 30 minutes B Sampling Depending on the sample material being analyzed sediment trap or sediments your sampling time may vary For example when analyzing sediment trap samples we only sample the 2 and 3 hours all other sediments we sample hours through 5 The amount of solution taken on the selected hour can vary from 0
75. id per reaction vessel or let them go until they time out approximately 15 drops Do not leave this unattended because it is possible for the vials to fill and flood valve system if counter fails to work correctly Close acid valve 10 and 20 Click on TAKE MAG This will remove both reaction vessels Wait for both vessels to be removed before proceeding to Step 5 Click on LOAD MAG This will automatically load both reaction vessels Finished Figure P1 Finnigan Kiel III carbonate device oven and carousel assembly outside upper left photo and inside upper right photo In order to service the ports or to replace the carousel middle left photo it is necessary to remove vials from Port 1 middle right photo and 2 bottom left photo Once both vials are removed bottom right photo you can service ports Figure P2 Removing ice build up on the Finnigan Kiel II cold finger assembly It is normal for ice to build up around the cold finger valve assembly top left photo but too much ice can cause problems and damage Lower jack stand to expose cold finger assembly bottom left photo and then remove LN2 dewar Use the blow dryer to expedite removal of ice around the top top right photo and around the bottom of the cold finger assembly bottom right photo do not pry or force the removal of the ice this could damage components of the entire assembly Figure P3 Removing and installing the sample carousel on the Finnigan Kiel
76. inder 500 ml 1000 ml beaker hot plate or heating mantle with controller ring stand with clamp thermometer 200 C storage bottle flask with ground glass stopper 1 Calibrate 1000 ml flask or beaker to account for 15 75 ml loss of water during the heating process 2 Ina fume hood place 500 ml ACS grade 85 Phosphoric acid H3PO into a calibrated 1000 ml beaker or round flask 3 Insert thermometer and heat flask on hot plate or in heating mantle at 140 C for approximately 12 hrs or until enough water evaporates to reach the 15 calibration mark Note once temperature is stable at 140 C remove thermometer 4 When calibration make is reached turn of hot plate or heating mantle and allow to cool 5 Measure the density of the acid with a hydrometer The specific gravity is 1 89 1 90 This is adequate for the Kiel The acid resides in the oven at 70 C and flow well at this density If the acid is more dense the acid begins to polymerize and clog the capillaries and tubing The isotopic results are 0 03 o0 for 85 C and 0 05 oo for 8 8O on standards References Bowen R 1966 Paleotemperature analysis Elsevier Publishing Company New York Keish B J W Kennedy and A C Wahl 1958 The exchange of oxygen between phosphoric acid and water Anal Chem v 80 p 4778 4782 McCrea J M 1950 On the isotopic chemistry of carbonates and a paleotemperature scale Jour Chem Phys v 18 p 849 857 Wachter E A
77. king splits sum of the splits totaling half of the sample and an archive split remaining half of the sample Depending on the accumulation of material in the sample cup this split ratio can be modified to accommodate sample needs Safety Materials Gloves safety glasses lab coat or apron Caution Sediment trap samples contain about 5 formalin Therefore this procedure should be carried out in a fume hood Equipment Plankton splitter squeeze bottles 2 3 Nalgene bottles 125 mL and 250 mL sizes forceps Nuclepore or Milipore polycarbonate membrane filters 0 45um x 47mm Plastic media dishes 60 x 15mm Small trays 2 47 mm filtering rig and vaccuum line 2ml cryogenic vials Pipette and tips 50 mL centrifuge tubes II Preparation 1 Weigh out 4 Nuclepore filters for each sediment trap sample to be processed Place each in a small plastic media dish with the weight clearly labeled on the lid 2 On the log sheet Fig 1 record the name of the sample your progress through out this procedure any appropriate remarks and to keep track of splitting at the end of the procedure IID Procedure 1 Allow the sediment trap container to settle at least over night If possible longer is better This will allow the particulate matter in the container to settle and thereby maximizing the clarity of the liquid fraction supernatant 2 Open the sediment trap sample container usually 500ml and remove 2ml supernatant from the top
78. l display Locate the source of the error e g high voltage out Fix error then attempt to press ESC If the error display disappears and the instrument appears to be working watch it carefully because it may actually be hung up and just going through the motions It is best to just press TERMINATE and allow the sample that is in acquisition to finish If the error appeared a short time ago it is just a simple matter of restarting the sequence as follows 1 Si G3 Click on ALT T upper left screen This will exit CNF B ACON B 2 Click on CNF B ACON B 2 SEQUENCE ACQ Click on TABLE DIR Shift F10 pao gs g h TABLE NAME reselect the correct table name e g DM041702 START LINE begin where the error took place END LINE 46 if for a full carousel run MODE DAY FILENAME should be as follows Path D DA TA filename WKS Filename is 8 characters WKS The filename should have the format operators first initial date followed by a next letter in the sequence after the original that began A and followed by WKS e g D041702B WKS Type in the path and filename then press lt Enter gt e g the line should read as follows D DATA D041702B WKS LIST TYPE FORMAT3 ONLY FILE TYPE LOT SAVE DATA to database COL Click SAVE to save sequence Make sure there is plenty of paper in printer to complete the run Click MEASURE to begin run If you were able to escape from the error or the run was able to continue the d
79. label this with the sample name and 1 16 split this fraction will be used by A Leventer or another designated investigator Place this bottle in the refrigerator If the sample has moderate to a large amount of solid material you will need to continue splitting the sample Choose one of the sample splitter containers holding 1 8 and leave the other container in place Pour one 1 8 split into the sample splitter and split After splitting you will now have 1 16 in one of the splitter containers and 3 16 in the other 1 8 1 16 Continue splitting one side of the sample the necessary number of times until you feel it is near light enough for ease in filtering IMPORTANT Keep close track of the fractions you are working with It helps to make a diagram of the fractions that result from each successive split in each container When you have reached a point that your sample is fairly light on one side take the remaining side largest amount and decant this into a Nalgene bottle Label this bottle with the sample name the size of the fraction i e 3 16 7 32 15 64 etc and Extra Archive Place this bottle in the refrigerator 13 Split the remaining fraction again as in steps 10 and 11 but use the appropriate fractions not 1 8 or 1 16 Set on split aside in a bottle or beaker recording remembering the correct split fraction and other portion back into the samples splitter and split 14 a Place three weighed Nuclepore Milipore fi
80. leted Add 500 ml of each silica standard to a labeled vial This is only done after the first sampling Use the Repipet to introduce 4 5 ml of Nanopure water into each standard and sample vial All vials should now have 5 0 ml of liquid including either 250 ul of sample or 500 ul of standard Noting the time pipette in 2 ml of Molybdate reagent to each sample blank and standard After no less than 10 minutes and no more than 30 minutes go to the next step Noting the time pipette in 3 ml of Reducing solution to each sample blank and standard Remember to need to use the same timing as the Molybdate reagent Cap all vials and let stand for 3 hours no more than 5 hours before measuring their absorbance on the spectrophotometer at 812 nm VII References DeMaster D J 1981 The supply and accumulation of Silica in marine sediments Geochim Cosmochim Acta 45 1715 1732 Mortlock R A and P N Froelich 1989 A simple method for the rapid determination of biogenic opal in pelagic marine sediments Deep Sea Research 36 1415 1426 Strickland J D and T R Parsons 19728 Practical handbook of seawater analysis Bull 167 Fish Res Board Can Ottowa 31 1p Stanford University Stable Isotope Laboratory On line Manual Prepared by David A Mucciarone Section 6C Sediment Trap Split Procedure I Introduction This procedure is designed to split sediment trap samples usually 500ml collected in the field into wor
81. lick on BANK F7 and type BOPEN lt ENTER gt This will open all 12 ports to the selected bank including valve B The atmospheric pressure in the crackers will exit through valves B 12 13 39 T m PA E z SE i an z Figurel Schematic representation of the MAT252 inlet system and multiport manifold o9 10 11 12 13 Repeat Step 6a and 6c for the other bank Allow a minimum of 15 minutes for the crackers to evacuate before starting the run This can be monitored from the inlet screen display on CNF A SUPP A and 2 MULTIPORT CTRL Click on CNF A ACON A 2 SEQUENCE ACQ Click on TABLE DIR Shift F10 a TABLE NAME e g DM091702 b START LINE 1 c END LINE 12 make sure start and end line numbers are correct e g 1 and 12 for a full bank 1 and 24 for both banks d MODE DAY e FILENAME should be as follows Path D DATA filename WKS Filename is 8 characters WKS The filename should have the format operators first initial date followed by a letter beginning with A ending with WKS e g D091702A WKS Type in the path and filename then press lt Enter gt e g the line should read as follows D DATA D091702A WKS f LIST TYPE FORMAT ONLY g FILE TYPE LOT h SAVE DATA TO DATABASE COL Click SAVE F9 to save sequence To transfer the run data from hard disk to floppy disk you Press Ctrl and 2 from the number keypad Using DOS i e CD DATA and DIR and COPY commands go to the
82. lowed by a next letter in the sequence after the original that began A and followed by WKS e g D091702B WKS Type in the path and filename then press lt Enter gt e g the line should read as follows D DATA D091702B WKS D DATA D091700B WKS LIST TYPE FORMAT ONLY FILE TYPE LOT SAVE DATA TO DATABASE COL Click SAVE F9 to save sequence Make sure there is plenty of paper in printer to complete the run To transfer the run data from hard disk to floppy disk you Press Ctrl and 2 from the number keypad Using DOS i e CD DATA and DIR and COPY commands go to the directory D DATA and copy the file to floppy disk e g at prompt D DATA gt Type COPY D091702A WKS A or COPY D091702 A to copy all associated files Press Ctrl and 1 from keypad to return to ISODAT Click MEASURE F5 to begin run Stanford University MAT252 24x Multiport Operation III Run interrupted by error 1 PART 1 Able to escape out or error A Ifa gray window with at red bar will be displayed on the screen obstructing the normal display Locate the source of the error e g high voltage out Fix error then attempt to press ESC If the error display disappears and the instrument appears to be working watch it carefully because it may actually be hung up and just going through the motions It is best to just press ALT T to terminate the run If the error appeared a short time ago it is just a simple matter of restarting the sequence as follows 1
83. lters on the filter frits of the filter rig Use a little Nanopure water to keep the filters in place then use the clamps to secure the funnels in place Place the labeled empty media dishes in front of the appropriate filter Separately filter both 1 XXX splits using the first two filter rig setups Decant the remaining 1 XXX split from holding container bottle or beaker into sample splitter and split Take one 1 XXX split and decant this into the remaining filter rig Make sure to label the filter media dishes with the sample name and 1 XXX split and turn on the vacuum line to begin filtering Take the remaining 1 XXX split and decant into a small Nalgene bottle and label this with the sample name and 1 XXX split this fraction will be used by A Leventer or another designated investigator Place this bottle in the refrigerator As filtering progresses use a little Nanopure to clean off any sample that may accumulate on the side of the filter funnel glass and to wash salts off the filter Once filtering is completed remove filter from frit and place in the appropriate labeled media dish Place in the oven at 60 C to dry
84. ltiport Operation 2 PART 2 Unable to escape out or error A If a gray window with at red bar will be displayed on the screen obstructing the normal display If after looking for the fault and do not see one then attempt to press ESC If the error display does not disappear to the point where the screen freezes then you will have to reboot the computer by following the reboot sequence Ps en Press Ctrl Alt Del to reboot computer At the Load Real 32 prompt Type N lt Enter gt this will load Win95 At login prompt Type sil lt OK gt Click on Scan Disk on desktop Let the program delete any fragments DO NOT FIX THEM just delete them Restart the computer using the START button At the Load Real 32 prompt Type Y lt Enter gt this will load ISODAT v7 2 allow the microprocessor to reset before doing anything message is displayed at top of screen B Continue as follows to prepare the run 1 2 Click on ALT T upper left screen This will exit CNF A ACON A Click on CNF A ACON A 2 SEQUENCE ACQ Click on TABLE DIR Shift F10 TABLE NAME reselect the correct table name e g DM091701 START LINE begin where the error took place END LINE 24 if both banks are being run 12 if only 1 bank MODE DAY FILENAME should be as follows Path D DATA filename WKS Filename is 8 characters WKS The filename should have the format operators first initial date followed by a next letter in the sequence after
85. lve via a capillary To get an understanding on how this process works I will use calcium carbonate CaCO3 as an example and go from reaction of this material to mass spectrometer analysis When CaCO is reacted with purified phosphoric acid at 70 C in our lab CO and H 0 gas are produced Eq 1 2H3PO 3CaCO 3CO 3H 0 Ca PO Eq 1 The water is removed by a method called fractional freezing Since water has a freezing temperature warmer than CO the traps on the KCIII can heat or cool the trap as needed to control the transfer of CO2 The KCI works in the following manner see Fig 1 The sample is acidified with two drops of purified phosphoric acid Both CO and H O are frozen into Trap 1 at 196 C The reaction time is 470 seconds At the end of the reaction non condensable gases are pumped away for 30 seconds Trap 1 is then warmed to 115 C to keep the H O frozen but allows the CO to evolve as a gas Trap 2 is then cooled to 196 C to trap SUPPORT CASRGHATE HIT TRA 4 ub a J i p w Figure 1 Schematic diagram of Kiel III carbonate device The numbers denote valve identification T1 and T2 represent Traps 1 and 2 respectively HV represents high vacuum which includes roughing and 60L turbo pump FV is for fore vacuum which only has a roughing pump Turret indicates position of carousel VM1 and 2 monitor vacuum integrity MS indicates capillary attaching Kiel III carbonated device to changeover valve on the MAT2
86. magnet of strength B The MAT252 is equipped with an electromagnet with a maximum field strength of 0 77 Tesla providing a mass range up to 150 amu at full accelerating voltage Therefore the radius is fixed and the magnet is variable but constant for any given gas species At a constant accelerating voltage V and magnet strength the lighter mass will be deflected bend more than the heavier mass In the case of CO mass 44 is bent more than 45 and 46 However in order to analyze another gas such as N or SO with a fixed magnet the accelerating voltage needs to increase or decrease respectively or the accelerating voltage can remain the same and the magnetic field strength can be varied Therefore the relation of all these parameters is given as m z K H Where m z is the mass to charge ratio K R 2U constant H is the magnet strength R is the Radius of flight tube U is the acceleration voltage Figure 5 Schematic of MAT252 ion source Values are ion source potential in relation to ground at 10kV ion acceleration voltage After leaving the flight tube the separate ion beams of different masses are directed into 2 1 major and minor or 3 1 major and 2 minor collectors Faraday cups depending on the type of mass spectrometer Fig 6 These cups are grounded through high ohm resistors As the ion current passes to ground the drop in the resistor acts as a measure of the ion current There are two types of collectors major and
87. minor The major collector is larger and less sensitive than the minor collector These collectors can either be fixed to a correct spacing for a particular set of masses or adjustable In the case of COs a triple collector mass spectrometer can detect all three masses 44 major 45 minor and 46 minor and calculate 5 80 and 8 C in one run On a double collector with CO the accelerating voltage is changed to direct the appropriate masses into the 2 collectors in order to calculate tO and C 44 major 45 minor for C 44 amp 45 major 46 minor for 5 0O a A E j 4 Po l Pa f i a Li it 1 Pra Figure 6 Schematic representation of faraday cup collectors on the MAT252 The signals received by the collectors are amplified and transferred to voltage to frequency converters VFC on a system control board in a microprocessor This system board basically digitizes the analog signal for processing by an interfaced computer The analog and digital output is then sent to disk and a printer In the course of one analysis for 5 8O and 85 C on the MAT252 mass spectrometer 8 reference sample reference sets 8 traces or 24 changeover valve cycles are analyzed All of the data are expressed in conventional delta 5 notation where the isotopic ratios of 5 80 8 O and 8 C 8C are relative to the international PDB standard Eq 2 as defined by 8 oo RatiOsampie RatiOstandara RatiOstandara x 1000 Eq 2 PDB refe
88. n and exit the EA through stainless steel tubing attached to Vent M See Section 3 for a detailed explanation on the removal and separation of gases in the EA This tubing connects the EA to the ConFlolI interface At this point the gas enters an open split Within the open split are four 4 fused silica capillaries one for N3 reference gas one for CO reference gas one helium dilution of the sample coming from the EA and one connecting to the mass spectrometer The reference gas and helium dilution capillaries are attached to individual solenoids the mass spectrometer capillary is fixed The fixed mass spectrometer fused silica capillary is connected to a SGE on off valve mounted on top of the source housing Fig 1 Figure 1 Schematic representation of the Delta plus analyzer system and the arrangement of components Illustration is from Finnigan operations manual Once the gas passes through the SGE valves it enter the source through an inlet which simply directs the gas flow directly into the source block more precisely the ionization chamber see Fig 2 The gas flow in the ion source is always molecular Attached to the source block are the filament cathode trap ion extraction plates and focusing plates Fig 3 a The filament cathode often tungsten emits electrons in a helical orbit under the influence of small source magnets in which the CO gas molecules collide with the electron beam making a N or CO ion The electron beam
89. n the Carlo Erba NA1500 Series II elemental analyzer Figure P2 Switch stainless steel line exiting the elemental analyzer EA from Vent M on the left to Vent R in the middle The oxygen vent is on the right Figure P3 Turn down the oxidation oven from 1020 C to 320 C and the reduction oven from 650 C to 250 C Allow the ovens to cool before removing the reduction column You will have plenty of time to prepare a new column Figure P4 Preparing oxidation column Insert 3 5 to 4 0 cm of quartz wool into the bottom of the quartz tube upper left photo Gently tamp the quartz wool with the push rod upper middle photo Then add 6 0 to 6 5 cm of silvered cobalt II HI oxide upper right photo for a combined total of 10 cm Add 1 cm of quartz wool bottom left photo and again gently tamp using push rod bottom middle photo Next add 11 cm of chromium III oxide on top of the quartz wool Figure P5 Continued preparation of oxidation column Insert 1 0 to 1 5 cm of quartz wool on top of the chromium III oxide left photo Prepare a quartz insert by placing 5 to 7 mm of quartz wool in the bottom of the insert middle photo Slide the insert into the top of the oxidation column right photo The top of the insert should extend approximately to 2 mm above the top of the column If it falls below add an appropriate amount of quartz wool to compensate Figure P6 Install sealing ring on top of the reduction column left ph
90. ncentration and isotopic precision without compromising chromatography See Table for the configurations of the Delta plus EA A typical run for nitrogen and carbon on the Delta plus is as follows The run begins with a peak jump of the electromagnet current BDAC to N and centers the high voltage HVDAC on mass 29 or beam 2 When complete a new graphics display will appear on the screen A signal is sent to the EA to begin 1 second into the run and turn off at 25 seconds The ConFlolI solenoid will activate at approximately 14 seconds into the run indicated by the start of the LCD timer and the activation of the oxygen injection solenoid on the EA When the EA timer reaches 20 seconds the zero blank carousel will rotate one position dropping the sample into the combustion oxidation column At 90 seconds into the run a signal is sent to the ConFlol interface and N reference gas is injected into the mass spectrometer for 20 seconds The timer on the EA will reset at 120 seconds At about 175 seconds into the run the N peak from the sample will elute out of the 4 m GC column Depending on the amount of N in the sample the peak will have a retention time of approximately 50 to 80 seconds One second prior to the end of the nitrogen run the helium dilution solenoid is activated and at 275 seconds the nitrogen portion of the run is terminated Fig 1 Deltas ug EA Nitrogen Run N Std N SA He dilution on begin peak jump to C 0 50 100
91. nd standard vials Fig 11 Remember you have between 10 and 30 minutes from the time you start adding Molybdate reagent from the first to last vial before adding the Reducing solution Figure 11 Noting the time add 2 ml of Molybdate reagent to each 12 ml vial Then wait a minimum of 10 min but no more than 30 min before adding the reducing solution 2 Use the Oxford adjustable pipette and set to 3 ml Noting the time add 3 ml of Reducing solution Part II Number 6 in the Reagents section to each of the sample blank and standard vials Remember you have add the Reducing solution using the same timing as the Molybdate reagent Figure 12 Noting the time add 3 ml of reducing solution to each 12 ml vial using the same timing as the Molybdate solution 3 Cap all vials and let stand for 3 hours no more than 5 hours before measuring their absorbance on the Hitachi spectrophotometer Figure 12 When finished adding the reducing solution cap all vials and let stand a min of 3 hours but not more than 5 hours Standards are located in the front from 0 to 1200 uM left to right IV Hitachi U 2001 operational procedure The Hitachi U 2001 Fig 1 is a programmable spectrophotometer that uses a small volume sipper attachment for individual sample analysis This instrument has already been programmed for the analysis of biogenic silica You should also turn the instrument on approximately 20 to 30 minutes prior to sample analysis The in
92. nnections at the reactor column and the helium carrier line Fig 14 Carousel Operation Fig 15 a b Front panel Toggle switch up 32 hole sample drum Toggle switch down 50 hole sample drum Black push button advances drum forward 1 position Round switch up on red light on Round switch down off red light off Rear panel Switch on the rear panel is to align the carousel after swapping out sample drums Toggle switch up advance sample drum by steps Toggle switch down reverse sample drum by steps Load samples into carousel Fig 16 a b Loosen the 3 thumbscrews on the top of the carousel loosen back two first then front and fold out of the way Flip back the carousel lid to expose sample drum Using forceps carefully load samples into sample drum If first sample is not in hole 1 record start position on sample log sheet This will be helpful if there is a problem with the run e g sample capsule wedges in hole and does not drop samples need to be removed Once samples are loaded close lid and secure using the 3 thumbscrews Tighten back two first them front Allow carousel to purge for 2 minutes before closing purge valve on the top of carousel lid Figure 11 Switch stainless steel line exiting the elemental analyzer EA from Vent M on the left to Vent R in the middle The oxygen vent is on the right Figure 12 Removing the Costech Analytical zero blank carousel from EA reactor column
93. ockwise b If there is a leak the pressure on the M helium gauge will decrease If this occurs check for leaks The most common source of leaks will be at the carousel connection to the reactor column seals in water trap or the carousel lid seal Make sure to restore helium pressure to 90kPa before checking for leaks Repeat Steps 8a and 8b if necessary until leak is repaired c If there is no leak remove plug on Vent M and restore helium pressure to 90kPa 9 Select the helium dilution on ConFlolIl interface box top black knob Record helium dilution along with N and CO reference gas gauge pressures on sample log sheet Fig P9 10 Check tuning on Delta source and perform peak shape on CO3 a Click on CNF A SUPP A and 1 CONFLO II CTRL This will allow control of ConFlolII valves b Click on REF1 ON F6 or click on the REF 1 hourglass icon This will introduce CO into the mass spectrometer via the ConFlolI interface Fig 1 Click on CNF D ACON D and 1 INSTR CONTROL d Click on CUP CFG Shift F10 left click on CO2 CONF then right click or lt ENTER gt to select This will select the correct magnet and source voltage setting for CO e Click on CENTER F6 this will center the source voltage when finished click on SHAPE F8 followed by MEASURE F5 to perform a peak shape on mass 44 45 46 When complete click on EXIT F10 Now perform this same procedure on N gt 11 Check tuning on Delta source and perform pe
94. olumn right photo Figure P4 Leak checking the Carlo Erba NA1500 Move stainless steal line from Vent M to Vent R see Fig 2 and place plug left photo on Vent M Turn down counter clockwise rotation the helium pressure by using the knob labeled M on the EA right photo Observe the M helium gauge for leaks When finished restore helium pressure to 90kPa clockwise rotation Stanford University Stable Isotope Laboratory On line Manual Prepared by David A Mucciarone Section 6A Biogenic Silica Analysis Procedure I Introduction This procedure is designed to give weight percent biogenic silica using a small amount of sample material A total of 42 analyses 40 unknowns 1 blank 1 standard can be run using this procedure This procedure uses a 0 1M NaOH solution at 85 C to leach the silica from the sample This procedure has been modified from Strickland and Parson 1972 Materials Sodium hydroxide NaOH Sodium fluorosilicate Na SiF analytical grade reagent Oxalic acid dihydrate COOH 2H O Ammonium paramolybdate NH4 6 gt Mo7O 4H2O Hydrochloric acid HCI Sulfuric acid H2SO Anhydrous sodium sulfite Na SO3 Metol P methylaminophenol sulfate Nanopure water silica free Equipment Spectrophotometer 812nm constant temperature bath centrifuge adjustable pipette dispense 2 and 3 ml with disposable tips micro pipettes 250 amp 500 ul with disposable tips numbered Nalgene 12 ml vials with
95. or sample in memory or index of sample 1 200 Figure 10b EAGER 100 Recalculation Sub menu H Carousel Operation Changing Inserts and Loading Samples i Switch stainless steel line exiting the elemental analyzer EA from Vent M to Vent R Fig 11 Remove quartz insert from EA reactor column a b C Loosen purge valve on top of carousel Fig 12 Next open the purge valve on top of the carousel then loosen the fittings connecting the carousel to the reactor column and helium input line Move carousel to the side so the insert can be removed without obstruction Fig 12 Carefully remove insert from reactor Care should be taken when handling the insert because it is at 1020 C Place hot insert into waste beaker Fig 13 Install new quartz insert into EA reactor column a b C d Put approximately 7mm of quartz wool into the bottom of the insert Fig 13 Carefully slide the quartz insert into reactor column until it stops do not push or force insert Fig 3 The insert should stop approximately 5mm above top of reactor column If the insert falls below the top of the reactor column add an appropriate amount of quartz wool to the reactor column not the insert then slide the insert in again With the insert in the proper position gently push the insert down until it is flush with the top of the reactor column do not force Reposition the carousel onto the reactor column and secure both co
96. oto Clean the outside of the reduction column using a Kimwipe and 2 propanol Figure P7 Before you can service the columns you need to remove the oven cover to the elemental analyzer To accomplish this slide the cover up until it stops then pull it toward you Figure P8 Disassemble the coupling joining the bottom of the oxidation and reduction columns upper left photo Remove both supports upper middle photo to expose the coupling upper right photo Completely loosen the fitting to the reduction column middle left photo and the fitting to the reduction column center photo and remove coupling middle right photo Remove the sealing ring washer and nut from the bottom of the oxidation column bottom left photo so that the column is free bottom right photo Figure P9 Removing the Costech Analytical zero blank carousel from EA reactor column First open the purge valve on top upper left photo then loosen the connections to the oxidation column upper right photo and the helium line lower left photo Remove oxidation column lower right Caution Handle with care the oxidation column is still hot around 350 C to 400 C Place upright in a beaker until cool Figure P10 Leak checking the Carlo Erba NA1500 Move stainless steal line from Vent M to Vent R see Fig 2 and place plug left photo on Vent M Turn down counter clockwise rotation the helium pressure by using the knob labeled M on the EA right photo O
97. ousel to the side so the oxidation column can be removed without obstruction Fig P9 16 Carefully remove the used oxidation column and install the new one see caution note in Fig P9 17 Assemble in reverse order Attach the carousel first and then install the bottom nut washer and sealing ring on the bottom of the oxidation column Replace the coupling and secure both fittings Fig P8 18 Install both braces Fig P8 and perform a leak check EA Fig P10 a Place a plug over Vent M release pressure on M helium regulator on EA turn black silver knob counterclockwise b If there is a leak the pressure on the M helium gauge will decrease If this occurs check for leaks The most common source of leaks will be at the carousel connection to the reactor column seals in water trap or the carousel lid seal Make sure to restore helium pressure to 90kPa before checking for leaks Repeat 9 and 18b if necessary until leak is repaired c If there is no leak remove plug on Vent M and restore helium pressure to 90kPa 19 Turn up the oxidation oven to 1020 C and the reduction oven to 650 C Fig P3 When the ready light on the front panel illuminates the instrument is ready for use 20 It is common after an oxidation column change that you will need to change the water trap on the EA because of the moisture released from the column reagents See Section 3D for this procedure Figure P1 Material required to prepare oxidation column o
98. ow so allow at least 30 minutes This cannot be rushed The concentration of this standard is 3000 umoles Si liter Store in a 500 ml Nalgene bottle Standard is stable indefinitely a Dilution from primary standard when making a dilution use Nanopure water and store in Nalgene bottles Using a 50 ml Nalgene volumetric flask add the following amounts of primary silica standard and then bring the volume to 50 ml total 30 uM Si 0 5 ml of primary Si std 480 uM Si 8 0 ml of primary Si std 60 uM Si 1 0 ml of primary Si std 600 uM Si 10 0 ml of primary Si std 120 uM Si 2 0 ml of primary Si std 900 uM Si 15 0 ml of primary Si std 240 uM Si 4 0 ml of primary Si std 1200 uM Si 20 0 ml of primary Si std 360 uM Si 6 0 ml of primary Si std II Procedure A Sample and instrument preparation 1 Dry all samples in an oven at 60 C Use the Sartorius micro balance Fig 1 to weigh out sediments using a micro balance and then place material in numbered centrifuge tubes Fig 2 Remember to keep good records The amount of sample required depends on the amount of anticipated silica content A good starting point is between 8 15 mg for samples between 20 50 or 15 20 mg for samples in the range of 5 20 Figure 1 Sartorius micro balance operation Turn microbalance on by pressing the black button on the left To tare the micro balance press the red button on the right Figure 2 Weighing out samples for biogen
99. oxygen vent is on the right Figure P3 Checking and changing the magnesium perchlorate water trap on the Carlo Erba NA1500 Observe upper left portion of trap to see if magnesium perchlorate is sticking or degrading To remove the water trap loosen the red caps on both ends of the glass trap left and middle photo Remove Teflon silicon seals from both ends and check for cracking right photo Replace if necessary or reuse seals Make sure silicon portion of seal seats against the glass trap and the Teflon against the stainless steal flange Figure P4 Preparing new water trap Insert 5 to 7 mm of quartz wool into the bottom of the water trap tube left photo Use a funnel to add magnesium perchlorate to the tube middle photo make sure you gently tap the tube to slightly compact the magnesium perchlorate to avoid separation Make sure you leave a 5 to 7 mm space in the trap tube to insert quartz wool into the open end right photo Figure P5 Leak checking the Carlo Erba NA1500 Move stainless steal line from Vent M to Vent R see Fig 2 and place plug left photo on Vent M Turn down counter clockwise rotation the helium pressure by using the knob labeled M on the EA right photo Observe the M helium gauge for leaks When finished restore helium pressure to 90kPa clockwise rotation Figure P6 Cleaning water trap Remove quartz wool from one end left photo Use a spatula to loosen the magnesium perchlorate in the tr
100. pad to return to ISODAT 17 Click MEASURE to begin run Make sure there is plenty of paper in printer to complete the run es Got ODA Stanford University Stable Isotope Laboratory Finnigan MAT252 mass spectrometer with 24 port manifold and Kiel II carbonate device Stanford University MAT252 Kiel III Carbonate Device Operation II Run terminated with error l 2 3 00 Click on ALT T upper left screen This will exit CNF B ACON B Click on CNF B SUPP B 1 CARBONATE UNIT This will enter Kiel support screen Remove liquid nitrogen LN dewar and remove ice Fig P2 This is necessary if run was terminated by error and was sitting many hours If ice around cold traps has been removed and LN j is ready i e LS 160 dewars and small blue dewar replaced and small blue dewar is approximately 1 from top click on T1 then click on analog temperature bar at approximately 170 C to 180 C This will fill the blue LN dewar Remember as it begins to fill approximately 1 2 bring the and small blue dewar snug to the cold trap plate Click on CNF B EDIT B 2 SEQUENCE EDITOR Select table that was terminated by error and add and or delete reference refills RR 120 and make sure that the RR 120 are in the correct locations When finished save and exit Sequence Editor then Click on ALT T Return to CNF B SUPP B if acid temperature is at 69 C and LN dewar is filled and cold trap is at the temperature you selected above then
101. pe Laboratory Finnigan MAT Delta mass spectrometer Carlo Erba NA1500 Series II elemental analyzer Costech Analytical zero blank carousel and Finnigan MAT ConFlolI open split interface Stanford University Delta i Carlo Erba Elemental Analyzer Operation II Run terminated because of problem 1 Click on ALT T upper left screen This will exit CNF A ACON A Determine source of the problem and fix When problem is resolved begin run where it was terminated 3 Click on CNF A ACON A 2 SEQUENCE ACQ Click on TABLE DIR Shift F10 oaos f g h TABLE NAME reselect the correct table name e g ODP1098 1 START LINE begin where the error took place END LINE 31 MODE NIGHT FILENAME should be as follows Operators first initial date followed by a next letter in the sequence after the original that began with A and followed by WKS e g D091701B WKS The entire line needs to be typed in without mistakes You cannot edit the line it needs to be entered in one shot or press lt Enter gt and begin again e g the line should read as follows D DATA D091701B WKS LIST TYPE should be FORMAT3 FILE TYPE LOT SAVE DATA TO DATABASE NO 4 Click SAVE to save sequence Make sure there is plenty of paper in printer to complete the run on Click MEASURE to begin run 6 To transfer the run data from hard disk to floppy disk you Press Ctrl and 2 from the number keypad Using DOS i e CD DATA and DIR and CO
102. ple start time 15 seconds see 6 Fig 3 c Sample stop time 16 seconds see 7 Fig 3 d Oxygen injection stop time 70 seconds see 8 Fig 3 e Peak enable time 50 seconds see 9 Fig 3 NOTE The start and stop times can vary from 15 to 25 seconds However the two values should never be more than 1 second apart me He om ur Mime iC UTD Figure 3 Instrument control panel on the Carlo Erba NA1500 Series 2 elemental analyzer Numbers in photo are referenced in text 4 When the EA has obtained the preset temperatures you set above the ready light see 4 Fig 4 will illuminate 5 To check to see if the proper temperatures are correct press buttons 2 5 and or 6 Fig 4 The temperatures will be displayed above the buttons see 3 Fig 4 2 Gas Flow Rate Settings It is necessary to make sure all of the flow rates are set properly Normally nothing needs to be done however checking these prior to a run will insure proper operation Refer to Figure 5 when performing the following steps A Pressures and flow rates on the elemental analyzer should be set at the following 1 The helium flow should always be on However make sure helium flow is set to Flow not on Stand by see 1 Fig 5 Figure 4 Cycle timer and furnace oven temperature display panel on the Carlo Erba NA1500 Series 2 elemental analyzer Numbers in photo are referenced in text Figure 5 Regulator and flow control on the Carlo Erba N
103. pport screen Depending on where the carousel stopped rotating check to see its present position you will have to enter this value because the Turret position will default to 0 zero This must be reset e g the carousel failed at position 5 Using KBD INPUT Type P5 then Type P1 The carousel will not rotate at the first input but will rotate to position on the second If the carousel failed at position 1 then you only need to Type P1 the carousel will not rotate but the turret will be reset Remove liquid nitrogen LN dewar and remove ice This is necessary if run was terminated by error and was sitting many hours Fig P2 If ice around cold traps has been removed and LN is ready i e LS160 dewars and small blue dewar replaced and small blue dewar is approximately 1 from top Click on T1 then Click on analog temperature bar at approximately 170 C to 180 C This will fill the blue LN dewar Remember as it begins to fill approximately 1 2 bring the and small blue dewar snug to the cold trap plate Click on CNF B EDIT B 2 SEQUENCE EDITOR Select table that was terminated by error and add and or delete reference refills RR 120 and make sure that the RR 120 are in the correct locations When finished save and exit Sequence Editor then Click on ALT T Return to CNF B SUPP B if acid temperature is at 69 C or 70 C and LN dewar is filled and cold trap is at the temperature you selected above then Click ALT T Stanford Universi
104. processor to reset before doing anything message is displayed at top of screen Now continue as follows to prepare the run 1 Click on CNF A ACON A 2 SEQUENCE ACQ Click on TABLE DIR Shift F10 a TABLE NAME select the correct table name e g ODP1098 1 b START LINE begin where the error took place c END LINE 31 d MODE NIGHT e FILENAME should be as follows Operators first initial date followed by a next letter in the sequence after the original that began A and followed by WKS e g D091701B WKS The entire line needs to be typed in without mistakes You cannot edit the line it needs to be entered in one shot or press lt Enter gt and begin again e g the line should read as follows D DATA D091701B WKS f LIST TYPE should be FORMAT3 g FILE TYPE LOT h SAVE DATA TO DATABASE NO Click SAVE to save sequence Make sure there is plenty of paper in printer to complete run Click MEASURE to begin run To transfer the run data from hard disk to floppy disk you Press Ctrl and 2 from the number keypad Using DOS i e CD DATA and DIR and COPY commands go to the directory D DATA and copy the file to floppy disk e g at prompt D DATA gt Type COPY D091701A WKS A Press Ctrl and 1 from keypad to return to ISODAT Figure P1 Switch stainless steel line exiting the elemental analyzer EA from Vent M on the left to Vent R in the middle The oxygen vent is on the right Figure P2 Removing the
105. rameters for C and N analysis using the Carlo Erba Na1500 Series 2 elemental analyzer Instrument Temperatures C Combustion oven 1020 Reduction oven 650 Chromatographic column 60 Filament 190 Flow Rates ml min and gas pressures Helium carrier gas Grade 4 6 Zero 90 100kPa on EA 55 65 Oxygen Grade 4 3 UHP 100 105kPa on EA 25 30 Nitrogen Research Grade 6 0 100 105kPa on CFI Carbon dioxide Research Grade 4 6 100 105kPa on CFII Helium Grade 4 6 Zero 90 100kPa on CFII Element Retention Times seconds Nitrogen as N reference gas injection 80 100 Nitrogen as N 175 260 Carbon as CO 20 120 Carbon as CO reference gas injection 185 205 Additional Parameters on EA seconds Cycle time 110 Sample time begin end 20 amp 21 Oxygen injection 70 Run Parameters seconds Run time for N 265 Peak jump to C 90 100 Table 2 cont Set up parameters for C and N analysis using the Carlo Erba Na1500 Series 2 elemental analyzer Run time for C 225 Peak jump to N at end of run 30 Run time for N and C 630s 10 5 min Column Configuration cm Quartz combustion column 1 x w 45 0 x 1 8 From bottom to top Quartz wool 4 0 Silvered cobalic oxide Co30 Ag 6 0 Quartz wool 0 5 Chromium oxide Cr203 10 5 Quartz wool 0 5 Quartz reduction column 1 x w 45 0 x 1 8 From bottom to top Quartz wool 4 0 Reduced copper wires approx 150g 30 0 Quartz silica chips 9 0 Quartz wool 1 5 IID
106. rap containing soda lime or Ascarite would be added to remove the CO2 An adsorption trap containing magnesium perchlorate anhydrone must be installed for the removal of H2O The remaining N gt gas travels through a chromatographic column Porapak PQS and are detected with a thermal conductivity detector TCD See appendix for schematic diagram on N configuration of elemental analyzer Note Since we use the elemental analyzer coupled to the mass spectrometer Finnigan Delta plus via a continuous flow device Finnigan ConFlol we always use the water adsorption trap containing magnesium perchlorate anhydrone to remove the H2O However if only the elemental analyzer is used and H is desired then the adsorption trap containing magnesium perchlorate anhydrone can be removed Separation of N2 CO2 H20 and SO occurs within the GC column 4 m long with Porapak SQ 60 C various retention times for N2 CO2 H20 and SO with a He carrier flow between 55 and 65 ml min Figure 1 Carlo Erba NA1500 Series 2 Elemental Analyzer Number refers to the flow and pressure control panel 2 refers to the instrument control panel and 3 refers to furnace oven temperature control panel 100 105kPa Detection of these gases is by a thermal conductivity detector TCD at 190 C After detection N2 CO and SO exit through a He vent as a function of their individual retention times When the elemental analyzer is coupled to the mass spectrometer a
107. reduction column on the Carlo Erba NA1500 Series II elemental analyzer Figure P2 Switch stainless steel line exiting the elemental analyzer EA from Vent M on the left to Vent R in the middle The oxygen vent is on the right Figure P3 Turn down the oxidation oven from 1020 C to 820 C and the reduction oven from 650 C to 250 C Allow the ovens to cool before removing the reduction column You will have plenty of time to prepare a new column Note The reduction oven may only come down to the 300 C range because of the high temperature on the oxidation oven Caution Do not reduce the oxidation oven below 720 C because the quartz tube may become brittle and fail Figure P4 Preparing reduction column Insert 1 5 to 2 cm of quartz wool into the bottom of the quartz tube upper left photo Gently tamp the quartz wool with the push rod upper middle photo Then add 2 5 to 3 cm of quartz turnings upper right photo for a combined total of 5 cm Add 29 to 30 cm of pure copper wires on top of the quartz turnings bottom left photo Add 9 to 9 5 cm of quartz turnings on top of the copper wires bottom middle photo and finish with 1 to 1 5 cm of quartz wool bottom right photo The entire length of the reduction tube is 45 cm Figure P5 Install sealing ring on top of the reduction column left photo Clean the outside of the reduction column using a Kimwipe and 2 propanol Figure P6 Before you can service the col
108. romagnet on the Delta plus mass spectrometer to Carbon Configuration to detect the carbon dioxide from the unknown standard in the same manner as nitrogen X in Fig 5 A peak center is performed during the peak jump process a Helium injection begins and continues until end of run C in Fig 5 7 Carbon dioxide from the unknown standard elutes from the GC column and enters the mass spectrometer ion source and is later detected by the faraday cups 8 After CO from the unknown standard is complete CO reference gas is injected for 20 seconds D in Fig 5 9 Instrument software ISODAT peak jumps back to the Nitrogen Configuration a peak center is performed and the next sample in the sequence is run koto Mi SA CO SA CO STO 50 5A J F a he f Me 250 pec E l f L a ur L en aena _ i 55 7100 154 eo A BE Thr 180 220 25 min He ulian er ee Wa a AAG A B A c a e CO MS CO NS co MS oo ME 4 oT H ll BAT RALE MAD A A a a Ly RHF cr sath F a Le T F iini Alte fail LE jl H ii i I at id Ma iji iti C hal Ww Ll uj A E 5 Figure 5 Schematic of a C and N run on the Finnigan Delta plus EA illustrating the various configurations of the ConFlolI interface A denotes no injections B and D represents N and CO reference gases respectively and C is for helium dilution The X represents the point when the instrument soft
109. rotating it back and forth several time and pour into the splitter containers You now have two 1 4 splits Take each 1 4 split and decant into a tray or large petri dishes if necessary Use forceps to pick swimmers and other things particularly snotty things from the two 1 4 splits that might gum up the filtering process Be sure to pick each 1 4 split as evenly as possible Place the pickings in a plastic media dish on a pre weighed Nuclepore Milipore filer Label the media dish s the trap cup information and 1 2 split pick and the sample name and put it in oven 60 C to dry Take one of the 1 4 splits contents of one tray and decant into 50ml centrifuge tubes Run these in the centrifuge for 10 min at highest setting Fig 3 After the sample has been spun down once decant the liquid fraction from centrifuge tubes into your squirt bottle Consolidate the contents of all centrifuge tubes into one tube using Nanopure water and shake the sample until it is well mixed with the water Label the tube with the trap sample name and 1 4 split powder and centrifuge for another ten minutes Decant the remaining liquid fraction into a waste container and place the centrifuge tube with unscrewed cap in the oven at 60 C to dry This fraction will be used for chemical analyses such as carbon and nitrogen concentrations and isotopes weight percent biogenic silica phosphate and carbonate analyses NOTE You should carry out the remaining splitting
110. rs to a Cretaceous belemnite called Belemnitella americana from the Peedee formation in South Carolina and is defined as 0 for both 8 3C and 80 and has been exhausted however there may me a few labs that still have a small quantity remaining The carbonate standard NBS 19 or TS limestone NBS is an acronym for the National Bureau of Standards which was replaced by NIST is presently a substitute for PDB and has been given a fixed isotopic value for 5 C of 1 95 oo and for 8O of 2 2 oo Many laboratories use internationally known standards such as NBS 19 obtained from facilities such as the National Institute of Standards and Technologies NIST or from the International Atomic Energy Agency IAEA to calibrate their instruments and reference gases To reduce the possibility of exhausting these international standards laboratories establish working standards that have been calibrated against various known standards and with other laboratories to use routinely in the laboratory Although PDB is always used for reporting 5 C results in addition to PDB the term SMOW is also used when referring to 5 80 in carbonates and water SMOW is and acronym for Standard Mean Ocean Water introduced by H Craig 1961b Like PDB SMOW is defined as 0 for 5180 however SMOW does not equal PDB To convert PDB to SMOW or vice versa Friedman and O Neil 1977 generated the following equations 5180 sowy 03091 8 80 ppp 30 91 Eq 3 or 5180 ppp
111. s F8 If successful the following menu will display on the screen If you are not successful in you timing the following prompt LOAD Real 32 Y or N will display on the upper left of the screen If this happens you will have to Ctrl Alt Del again Microsoft Windows 95 Startup Menu Normal Logged BOOTLOG TXT Safe mode Safe mode with network support Step by step confirmation Command prompt only Safe mode command prompt only Previous version of MS DOS Oe Oy Oe bot Enter a choice At this prompt Enter a choice you can either enter 6 or 8 followed by lt ENTER gt You will then be give the C gt prompt Type STARTEA lt ENTER gt and follow the prompts This will load the Eager 100 software Now that you understand Step b continue by Pressing Ctrl Alt Del to reboot the computer When the AMIBIOS System Configuration screen is displayed as described in Step b Press F8 When the Microsoft Windows 95 Menu appears on the screen Type 6 or 8 lt ENTER gt At the C gt prompt type STARTEA lt ENTER gt and follow the prompts This will load the Eager 100 software mo ao 2 Ifthe C gt prompt is displayed on the screen the easiest way to rectify the situation is to type STARTEA press lt ENTER gt and follow the prompts This will load the Eager 100 software 3 Ifin Windows 95 select START restart computer then follow Steps 1c 1f 4 Nothing to do es Elemental Analyzer Operation
112. s containing sulfur and halogens and reduced copper wire for the reduction of nitrogen oxides to N2 N2 CO2 H20 and SO are then moved through the column and entire system by an ultra pure helium UHP grade 5 0 carrier gas An adsorption trap containing magnesium perchlorate anhydrone must be installed for the removal of H O The remaining N3 CO and SO gases travel through a chromatographic column Porapak PQS and are detected with a thermal conductivity detector TCD See appendix for schematic diagram on NCS configuration of elemental analyzer Example 2 If you want to analyze only NC two columns are used The reaction column would contain chromium oxide catalyst for oxidation and halogen removal and silvered cobaltous cobaltic oxide for removal of SO The reduction column would contain reduced copper wires for the reduction of nitrogen oxides to N2 Ny and CO and H O are then moved through the column and entire system by an ultra pure helium UHP grade 5 0 carrier gas An adsorption trap containing magnesium perchlorate anhydrone must be installed for the removal of H2O The remaining N and CO gases travel through a chromatographic column Porapak PQS and are detected with a thermal conductivity detector TCD See appendix for schematic diagram on CN configuration of elemental analyzer Example 3 If you only want N you would use the same setup in Example 2 where N and CO and H3O are carried through the columns An absorption t
113. s you have been trained and have a good understanding on operating the EA and the mass spectrometer Before you begin preparing the new Cu column you should first clear an area on the bench top obtain and organize all of the materials and equipment listed below Materials Costech Analytical grade pure copper Cu at 0 3mm mesh wire quartz turnings quartz wool and one 1 8 cm x 45 cm quartz tube Fig P1 Equipment Pliers funnel template ruler push rod and tray Fig P1 1 Switch the stainless steel line from Vent M to Vent R Fig P2 Turn down the left oxidation oven from 1020 C to 720 C and the right reduction oven from 650 C to 250 C Fig P3 Allow both ovens to cool before removing the reduction column While the ovens are cooling you can prepare a new reduction column Note The reduction oven may only come down to the 300 C range because of the high temperature on the oxidation oven Caution Do not reduce the oxidation oven below 720 C because the quartz tube may become brittle and fail 2 We have two types of quartz tubes opaque and clear It is easy to observe the packing and measure the amount of material added to a clear tube but more difficult to do the same on the opaque tubes When using the opaque tubes the push rod and template will assist you in determining the amount of material in the tube 3 Insert 1 5 to 2 0 cm of quartz wool into the bottom of the quartz reduction tube Fig P4 Place bottom of tube
114. strument needs time to stabilize Please treat the instrument with care and clean up your work area when finished Figure 1 Hitachi U 2001 Spectrophotometer 1 2 Remove instrument dust cover Turn the spectrophotometer on Switch is located on the front lower left The instrument will make some noise as it goes through several self check sequences that can be observed on the display When complete the main menu will appear on the instrument display with a cursor flashing at the lt SELECT OPTIONS at the bottom left Remember to turn the instrument on 20 to 30 minutes prior to analyzing samples At the SELECT OPTION prompt type 6 lt ENTER gt This is the TEST MENU routine At the SELECT OPTION prompt type 1 lt ENTER gt This is the LOAD TEST routine c At the SELECT OPTION prompt type 20 lt ENTER gt DUNBAR This is the preprogrammed routing for running biogenic silica The instrument will automatically tune the correct wavelength of 812nm SP Fill the reference cuvet 3 4 full with Nanopure water Slide the cover above the sipper back and insert cuvet into reference cell chamber Fig 2 The reference cuvet should be oriented so that the clear portions of the cuvet facing the sides i e frosted sides front to back Pull back the pump tube tensioning plate until you hear a click and the release button pops up Then slide the cover above the sipper closed Fig 3 Place the spectrophotometer drain line
115. taken from centrifuge tube in ml sample wt weight of sample in mg slope calculated from standards curve volume amount of NaOH solution added to centrifuge tube in ml y intercept calculated from standards curve 0 0001 1E 06 g ug 100 60 1 g Si mole amount of Si in one mole of SiO VI Quick reference guide 1 Day prior to analyzing samples a Dry samples in an oven at 60 C Weigh out samples using micro balance and place into numbered centrifuge tubes Leave in oven uncapped at 60 C to keep dry Fill water bath with water and heat to 85 C It is best to turn the water bath on the night before running to make sure it is up to temperature Run preparation Carefully pipette 40 ml of 0 1M NaOH into each centrifuge tube cab tightly shake and insert into the water bath set at 85 C Record time All tubes must be shaken every 30 minutes Depending on sampling time i e each hour for five hours 2 and 3 hour etc remove 8 centrifuge tubes and place into the centrifuge and spin for approximately 3 minutes Take 250 ul of sample from each tube using a pipette and place it into a labeled vial Rinse the pipette tip with Nanopure water then add 250 ul of Nanopure water to the sample for a total of 500 ul 0 5 ml Cap centrifuge tube tightly and place it back into the rack Continue until all tubes are sampled then shake all tubes and return them to the water bath Continue as needed until the sampling interval is comp
116. the original that began A and followed by WKS e g D091702B WKS Type in the path and filename then press lt Enter gt e g the line should read as follows D DATA D091702B WKS f List Type FORMAT1 ONLY g FILE TYPE LOT h SAVE DATA to database COL Click SAVE F9 to save sequence Make sure there is plenty of paper in printer to complete the run You need to remember that when a run is terminated by error in this way the data is saved to the database called Isobase only and not to the file you created in the SEQUENCE ACQ screen This file will only have 128K You will need to review the recover data section IV for instructions on how to obtain the run data Click MEASURE to begin run pee ge Stanford University MAT252 24x Multiport Operation IV Recover run data from database AUN 6 7 Click on CNF A EVAL A 1 OFF LINE 6 SEQUENCE NAME e g DM091701 Search by sequence name of run Click on DIRECTORY Shift F5 Click on TAG ALL F5 if all of the runs need to be transferred to disk or use TAG F6 to select the runs needed to be transferred Click on FORMAT F8 and then enter the following exactly OUTLIER TEST D2 STANDARD IDENT SIL 2 LIST TYPE NO GRAPHICS NO ALPHA CO3 CORRECTION NO ALPHA H20 CORRECTION NO ATOM APE REPORT NO FILENAME D DATA FILENAME WKS e g D041700A WKS Make sure the filename you select will not overwrite data on the disk The comput
117. the reduction column right and only loosen the fitting on the bottom of the oxidation column left enough so you can swing the coupling to the side Fig P7 Remove the bottom sealing ring washer and nut from the reduction column Fig P7 Loosen and remove the fitting at the top of the reduction column Fig P8 Carefully remove the used reduction column and install the new one see caution note in Fig P8 Assemble in reverse order Attach the top fitting first and then install the bottom nut washer and sealing ring on the bottom Swing the coupling into place and secure both fittings Fig P8 Install both braces Fig P7 and perform a leak check EA Fig P9 a Place a plug over Vent M release pressure on M helium regulator on EA turn black silver knob counterclockwise b Tf there is a leak the pressure on the M helium gauge will decrease If this occurs check for leaks The most common source of leaks will be at the carousel connection to the reactor column seals in water trap or the carousel lid seal Make sure to restore helium pressure to 90kPa before checking for leaks Repeat 9 and 18b if necessary until leak is repaired c If there is no leak remove plug on Vent M and restore helium pressure to 90kPa Turn up the oxidation oven to 1020 C and the reduction oven to 650 C Fig P3 When the ready light on the front panel illuminates the instrument is ready for use Figure P1 Material required to prepare
118. ting the carousel to the reactor column and helium input line Move carousel to the side so the insert can be removed without obstruction Fig P2 c Carefully remove insert from reactor Care should be taken when handling the insert because it is at 1020 C Place hot insert into waste beaker Fig P3 3 Install new quartz insert into EA reactor column a Put approximately 5 to 7 mm of quartz wool into the bottom of the insert Fig P3 b Carefully slide the quartz insert into reactor column until it stops do not push or force insert Fig 3 The insert should stop approximately 5mm above top of reactor column If the insert falls below the top of the reactor column add an appropriate amount of quartz wool to the reactor column not the insert then slide the insert in again c With the insert in the proper position gently push the insert down until it is flush with the top of the reactor column do not force d Reposition the carousel onto the reactor column and secure both connections at the reactor column and the helium carrier line Fig P4 e Let the carousel to purge for approximately 2 minutes to remove the atmosphere from the carousel headspace Then close the purge valve f Allow about 7 minutes for the air to purge the EA plumbing This can be monitored using the meter on the front panel of the EA g When the meter reaches baseline lt 750 you can perform a leak check II Perform a leak check EA Fig P5 1
119. tors and amplifiers Note that cup 2 is smaller than cups 1 and 3 but is more sensitive than cup 3 but less than cup 1 The resistor on cup 1 3 x 10 cup 2 3 x 10 and cup 3 3 x 10 for N and CO C is a detail representation of an individual collector The flight tube has a 90 deflection path Fig 1 having a radius of R fitted with a permanent magnet of strength B BDAC The Delta plus is equipped with an electromagnet with maximum field strength of 0 75 Tesla providing a mass range from 10 to 70 amu at full accelerating voltage of 3kV Therefore the radius is fixed and the magnet is variable but constant for any given gas species At a constant accelerating voltage V and magnet strength the lighter mass will be deflected bend more than the heavier mass In the case of CO mass 44 is bent more than 45 and 46 However in order to analyze another gas such as N or SO with a fixed magnet the accelerating voltage needs to increase or decrease respectively or the accelerating voltage can remain the same and the magnetic field strength can be varied Therefore the relation of all these parameters is given as m z K H Where m z is the mass to charge ratio K R 2U constant H is the magnet strength R is the Radius of flight tube U is the acceleration voltage After leaving the flight tube the separate ion beams of different masses are directed into 3 1 major and 2 minor collectors Faraday cups depending on the type of
120. transported by helium carrier gas flowing at 60 to 65 ml min and enter the open split Since the mass spectrometer capillary is so small 0 1mm ID only a small portion lt 10 of sample and carrier gas can enter the mass spectrometer The essentially reduces the flow to 0 3 ml min and allows the ion source to operate at a 10 Torr vacuum AL OG ariplar i O He Susp en Capiiary Bee a IRmMm Ho Flash of Combustion Dadalan eal Ce a Canfas ll ed tbe E Hill interface Wail te GE Coluim Oxidation Figure 1 Schematic representation of the Carlo Erba NA1500 setup for Nitrogen and Carbon connected to the Finnigan ConFloll interface IRMS refers to isotope ration mass spectrometer in our laboratory it is a Finnigan Delta plus Within the open split are four 4 fused silica capillaries one for N reference gas 0 025mm ID x 0 3mm OD one for CO reference gas 0 025mm ID x 0 3mm OD one for helium dilution 0 18mm ID x 0 27mm OD of the sample coming from the EA and one connecting to the mass spectrometer 0 10mm ID x 0 3mm OD The reference gas and helium dilution capillaries are attached to individual solenoids which allows for gas injection control The mass spectrometer capillary is fixed and is set below the non injected reference and helium dilution capillaries Without any injection of reference gas or helium dilution the flow of gas from the EA through the open split would be as illustrated in Fi
121. ttached to the He vent is a stainless steal line connecting the EA to the ConFloll The ConFlollI is a series of regulators and valves that control the introduction of gas es from the EA usually N and CO2 Nz and CO reference gases and helium dilution for CO2 The Nz and CO flow to the mass spectrometer through a fused silica capillary into the mass spectrometer ion source The N and CO are ionized to Nz and CO focused with numerous plates deflected through a flight tube surrounded by an electromagnet and detected by faraday cups collectors A Elemental Analyzer Computer Operation Usually the computer is running the Finnigan ISODAT software If this is the case you will need to follow Step 1 below in order to load the EAGER 100 software However there are other possibilities once the computer is rebooted Observe the screen and determine which situation applies and them follow that procedure outlined below 1 Finnigan ISODAT software running 2 C prompt 3 Computer is in Win95 4 Eager software is already running Depending on the condition above follow the corresponding procedure below 1 Ifthe Finnigan ISODAT software is running you will need to perform the following to load the EAGER 100 software a Press and hold the ALT key then type the letters Q U I T This will exit ISODAT and bring you to the REAL32 C gt b You will now have to reboot the computer Before doing this make sure you understand everything is this
122. tween peaks is needed so that them Delta plus mass spectrometer can peak jump from N to C Peak jumping involves changing the electromagnet current BDAC while maintaining the source voltage HVDAC constant This process takes time and therefore adequate time must be budgeted to allow completion of this task Second proper peak shape is needed to obtain accurate concentration and isotopic measurements Long tails on peaks will increase error in both calculations Our system is setup to perform a slow jump routine between the nitrogen and carbon run Our premise for using this routine is because it allows more maximum tuning of the source prior to analyses of N and C The fast peak jump routing requires the software to be instructed on how to change the electromagnet current This value will not be adjusted during the entire run sequence All things remaining equal this routine will perform satisfactory however through the course of a given run sequence the electromagnet and or source voltage can drift Thereby introducing the possibility of errors and instability If the retention times between peaks are close due to EA limitations or because of preference then the operator will benefit by using the fast peak jump routine In reality the mass spec will drift slightly over the course of a run sequence So by modifying the configuration and parameters of the EA we have created enough separation between the N and C peaks in a manner that we feel maximizes co
123. ty MAT252 Kiel III Carbonate Device Operation 2 PART 2 Unable to escape out or error CONTINUED 7 Click on CNF B ACON B 2 SEQUENCE ACQ Click on TABLE DIR Shift F10 eae oe f g h Click SAVE to save sequence Make sure there is plenty of paper in printer to complete the run Co TABLE NAME reselect the correct table name e g DM041702 START LINE begin where the error took place END LINE 46 if for a full carousel run MODE DAY FILENAME should be as follows Path D DA TA filename WKS Filename is 8 characters WKS The filename should have the format operators first initial date followed by a next letter in the sequence after the original that began A and followed by WKS e g D041702B WKS Type in the path and filename then press lt Enter gt e g the line should read as follows D DATA D041702B WKS LIST TYPE FORMAT3 ONLY FILE TYPE LOT SAVE DATA to database COL 9 You need to remember that when a run is terminated by error in this way the data is saved to the database called Isobase only and not to the file you created in the SEQUENCE ACQ screen This file will only have 128K You will need to review the recover data section IV for instructions on how to obtain the run data 10 Click MEASURE to begin run Stanford University MAT252 Kiel III Carbonate Device Operation IV Recover run data from database PUNG Sw E a s e E i Click on CNF A EVAL A 1 OFF LINE 6 SEQU
124. uite of unknowns ending with a suite of standards This run sequence can range in length depending on a number of different factors such as sample size type etc Since the injection of the helium dilution is consistent at a given pressure once set and standardized it is easy to account for this affect To standardize the unknown samples or standards a reference gas either N or CO is introduced via the ConFloll interface Fig 4 Like the helium dilution the pressure can be predetermined prior to a run sequence to be in the middle of the expected average unknown and standard range However unlike the helium dilution the isotopic composition will not change if the pressure is adjusted in between individual runs in a sequence You also need to keep in mind that the reference gases are always flowing When they are not in the injection position the gas es are simply venting out of the open slit position A in Fig 4 When the capillary is in the injection position position B in Fig 4 as with the gas es coming from the EA only a small portion of the reference gas enters the fixed mass spectrometer MS capillary the rest vents out of the open split In most cases an adjustment of these pressures is not necessary or encouraged because this is a means of monitoring any change in the sensitivity of the mass spectrometer ion source The pressures on the gauge are adjusted so that the voltage intensity on beam 2 on the mass spectrometer is set to appro
125. umns you need to remove the oven cover to the elemental analyzer To accomplish this slide the cover up until it stops then pull it toward you Figure P7 Disassemble the coupling joining the bottom of the oxidation and reduction columns upper right photo Remove both supports upper middle photo to expose the coupling upper right photo Completely loosen the fitting to the reduction column middle left photo then just loosen the fitting to the reduction column center photo and swing the coupling forward out of the way middle right photo Remove the sealing ring washer and nut from the bottom of the reduction column bottom left photo so that the column is free bottom right photo ve Figure P8 Remove coupling on top of reduction column Completely loosen both fittings on top of the reduction column upper right and left photos Remove coupling bottom left to expose reduction column and carefully remove the column bottom right photo Caution Handle with care the reduction column is still hot around 250 C to 300 C Place upright in a beaker until cool Figure P9 Leak checking the Carlo Erba NA1500 Move stainless steal line from Vent M to Vent R see Fig 2 and place plug left photo on Vent M Turn down counter clockwise rotation the helium pressure by using the knob labeled M on the EA right photo Observe the M helium gauge for leaks When finished restore helium pressure to 90kPa clockwise rotation
126. ust be switched from Vent M see 7 Fig 5 to Vent R see 8 Fig 5 Vent O see 9 Fig 5 is always open At the bottom of the main menu Fig 2 you will find 3 important status parameters Sample Index Status and Level Make sure the sample index corresponds with the position of the carousel the status should be STBY and the level around 1050 to 1150 Make sure the switch box behind the back right corner of the EA is switched to B Fig 19 Once you are confident all of the various run parameters and temperatures are correct and the ready light is illuminated on the front panel of the instrument see 4 Fig 4 you can begin the sample run by pressing lt F1 gt When the instrument starts you will hear a valve click which is the oxygen injection and then the clock on the front panel will start see 1 Fig 4 At the sample start time see 6 Fig 3 you will hear the carousel rotate at the time set for the oxygen injection see 8 Fig 3 you will hear the valve close and at the end of the run time see 5 Fig 3 the clock will reset to 000 Figure 19 Switching software control between ISODAT position A left photo and EAGER 100 position B right photo Remember to turn the switch back to position A when rebooting back to ISODAT The analysis can be stopped at any time by pressing lt F2 gt from the main menu either once run will terminate at end of sample analysis or twice run will stop This is handy if you encounter some kin
127. uy the purge on the elemental analyzer Fig P1 Make sure you replace the cap to the flask when you are finished The purpose of this section is to serve as a guide you should not attempt this unless you have been trained and have a good understanding on operating the EA and the mass spectrometer Before you begin preparing the new water trap you should first clear an area on the bench top obtain and organize all of the materials and equipment listed below Materials Costech Analytical grade magnesium perchlorate and quartz wool Fig P1 Equipment Forceps funnel spatula and tray Fig P1 I Removing water trap 1 Switch the stainless steel line from Vent M to Vent R Fig P2 2 Remove the magnesium perchlorate water trap Hold the glass tub and loosen red caps on both ends of trap and remove Teflon silicon seals usually stick to the glass trap Remove the seals and check for cracks Replace the seals if necessary otherwise clean and use Fig 3 3 Prepare water trap Clean water trap tubes are located in the stainless steel oven Use a funnel and put 5 to 7mm of quartz wool in one end of a clean trap tube and fill with magnesium perchlorate granules and gently tap trap on bench top to compact granules Be sure to leave approximately 5 to 7mm of space in order to insert quartz wool into the open end Fig 4 4 Install the newly prepared water trap in the reverse of Step 2 Fig 3 Remember the Teflon face of the seal goes against t
128. ware peak jumps from N to C It is necessary to review and understand the operation of the elemental analyzer and the mass spectrometer prior to operating these instruments This section was written as a guide that will help you better understand continuous flow mass spectrometry and how it relates to the instruments in the Stanford Stable Isotope Laboratory You can find more details on the mass spectrometer elemental analyzer and the ConFlolI interface in the sorted Finnigan Delta plus and Carlo Erba manuals Stanford University Stable Isotope Lab On line Manual Prepared by David A Mucciarone Section 2C Finnigan Delta Carlo Erba Elemental Analyzer Operation I Run terminated without error NORMAL 1 3 Click on ALT T upper left screen This will exit CNF A ACON A Switch stainless steel line exiting the elemental analyzer EA from Vent M to Vent R Fig P1 Remove quartz insert from EA reactor column a b c Loosen purge valve on top of carousel Fig P2 Next open the purge valve on top of the carousel then loosen the fittings connecting the carousel to the reactor column and helium input line Move carousel to the side so the insert can be removed without obstruction Fig P2 Carefully remove insert from reactor Care should be taken when handling the insert because it is at 1020 C Place hot insert into waste beaker Fig P3 Install new quartz insert into EA reactor column a b C d
129. xide Geochim Cosmochim Acta 12 133 149 Craig H 1961b Standard for reporting concentrations of deuterium and oxygen 18 in natural waters Science 133 1833 1834 Epstein S R Buchsbaum H Lowenstam and H C Urey 1953 Carbonate water isotopic temperature scale Geol Soc Am Bull 62 417 426 Friedman I and J R O Neil 1977 Complation of stable isotope fractionation factors of geochemical interest in Data Geochem 6 Ed U S Geol Surv Prof Pap 440 KK Gonfiantini R 1978 Standards for stable isotope measurements in natural compounds Nature 271 534 536 Hoefs J 1980 Stable Isotope Geochemistry Springer Verlag Berlin 208p McCrea J M 1950 On the isotopic chemistry of carbonates and a paleotemperature scale J Chem Phys 18 849 857 Shama T and R N Clayton 1965 Measurement of 89 O ratios in total oxygen of carbonates Geochim Cosmochim Acta 29 1347 1353 Swart P K S J Burns and J J Leder 1991 Fractionation of the stable isotopes of oxygen and carbon in carbon dioxide during the reaction of calcite with phosphoric acid as a function of temperature and technique Chem Geology 86 89 96 Walters Jr L J G E Claypool and P W Choquette 1972 Reaction rates and d180 variation for the carbonate phosphoric acid preparation method Geochim Cosmochim Acta 36 129 140 Stanford University Stable Isotope Lab On line Manual Prepared by David A Mucciarone Section 1B Finnigan
130. ximately 2 volts This works well for most run sequences Before making adjustment to reference gas pressures consult with the lab manager N raterence gas _ CO retarence gas an Position Ac wp no standard gas infected Postion B dean standard gas injected Figure 4 Schematic of the Finnigan ConFlolI interface injecting N and CO reference gases Position A and B represents the position of the reference gas capillaries without or with gas injection respectively Remember the reference gases from each of these capillaries are always flowing The position of the capillary determines whether or not gas is introduced into the fixed mass spectrometer MS capillary Now that we have an understanding on how the ConFlolIl operates let s take a look at an individual sample run and the position of each capillary in the open split Fig 5 For example with the EA setup to run carbon and nitrogen the following procedure happens 1 Instrument is in Nitrogen Configuration a peak center is performed prior to starting each run The EA is started and a sample is combusted A in Fig 5 3 While the sample is combusting and being filtered and separated in the GC column nitrogen reference gas is injected for 20 seconds B in Fig 5 4 Nitrogen from the unknown standard elutes from the GC column and enters the mass spectrometer ion source and is later detected by the faraday cups 5 The instrument software ISODAT then peak jumps the elect

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