Agilent ICP-OES 5110 User Guide (2024)

This user guide is intended for use by scientists and technical staf=f who have laboratory experience with analytical instrumentation, preparing= standards and samples, and data reduction; who have received an introducti=on and demonstration of the laboratory instrumentation aboard the JOIDES Re=solution. Good laboratory practices and attention to laboratory safety are =necessary while performing the procedures outlined in this user guide.
<=br> The user guide is to be used in conjunction with the Agil=ent 5100 and 5110 ICP-OES User=E2=80=99s Guide and the ICP Expert Help, both of which provide clear, detailed =walkthroughs of instrument setup, operation, maintenance and troubleshootin=g procedures. Brief procedural videos are accessible through IC=P Expert Help which demonstrate proper techniques when dealin=g with instrument components. The Agilent For Your Safety User==E2=80=99s Guide details additional safety information. Becom=e acquainted with these resources before proceeding through this user guide=.

The JRSO wishes to thank Raymond M. Johnston and Jeff Ryan for their =help and advice in fleshing out the solids methodology in this User Guide, =as originally presented in the Exp. 366 IODP Proceedings Methods chapter. T=he JRSO also thanks Hans Brumsack for refining the interstitial water metho=dology as described on the Exp. 369 IODP Proceedings Methods chapter. The J=RSO also thanks all of the many other geochemists who have provided help an=d advice over the many years of elemental analysis on the JOIDES Resolution=.

Inductively-coupled plasma optical emission spectrometry is a techni=que used to measure the elemental composition of a material by evaluating c=haracteristic elemental spectra emitted during plasma heating. Dissolved sa=mple flows through an introduction system in which the component molecules =are desolvated, atomized and excited within an argon plasma. The transfer o=f energy from electronic and atomic collisions within the plasma excites el=emental valence electrons across various atomic and ionic orbitals, which i=n turn release characteristic photons during electron de-excitation. Portio=ns of these photons are directed through an optical chamber and ultimately =fall upon a diffraction grating where they are reflected at angles determin=ed by their wavelengths, separating them, like a prism, into discrete spect=ral orders. The photons impinge on an accurately aligned CCD or CMOS detect=or chip, and thus are mapped to a 2-D pixel array. A given element concentr=ation is determined by locating its spectra within the array (i.e. on the c=hip), integrating the spectral intensity over a short time interval and com=paring the results against a calibration curve of certified reference mater=ial.

The Agilent 5110 ICP-OES is used for routine shipboard measurement o=f interstitial water and hard rock matrices. The Waters method allows for s=imultaneous determination of major and minor dissolved elements. The Hard R=ock method yields elements making up the major oxides, minor elements, and =several trace metals that surpass the limits of detection. ICP-OES analytic=al results are heavily matrix dependent, thus the suite of elemental analyt=es may be altered on a per expedition basis depending upon the material col=lected.

Before conducting an analysis for the first time, consult the Agilen=t Technologies Agilent 5100 and 5110 ICP-OES User=E2=80=99s Gui=de and For Your Safety =User=E2=80=99s Guide for a detailed review of safety issues. =Listed below is a succinct overview of several important safety issues whic=h are flagged, when appropriate, within the text:

• Ensure there is adequate storage space and ventilation for high-pr=essure argon gas bottles. Bottles must be secured to a rack, and the racks =must be secured to the ship. The steel cap for each bottle must be in place= whenever the bottles are not connected to the gas manifold. Use Swagelok S=noop Liquid Leak Detector to ensure proper seals at argon bottle and gas ma=nifold connections.
• Samples and standards are made up in dilute solutions of concentra=ted nitric acid. Use proper PPE (nitrile gloves and eye protection) when ha=ndling acids. Always add acid to water. Be aware of the location of acid sp=ill control and neutralization kits.
• Ensure the fume hood ventilation above the instrument is operation=al before igniting the plasma.
• The plasma torch is extremely hot during operation (6000 K). Do no=t handle the torch, RF coil, or other items within the torch compartment un=til ample time (>5 mins) has been given for the glassware to cool after =operation. Wear heat resistant gloves if necessary.

The plasma emits ultraviolet and intense visible light. Ensure the t=orch compartment door is closed and sealed whenever igniting the plasma. In=strument safety interlocks will extinguish the plasma If the door is opened= during operation, however, do not attempt to open the door while the plasm=a is active.

• Empty the waste container of acid residue after every batch analys=is.

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Hardware

The complete Agilent 5110 ICP-OES system includes:

• Agilent 5110 Single View/Dual-View (SVDV) ICP-OES system equipped =with the Automatic Valve Switching (AVS 6/7) option
• Agilent SPS4 4-rack autosampler
• Agilent G8481A Recirculating Chiller
• Mettler Toledo XS204 motion-compensated dual balance system
• Cahn Microbalance motion-compensated dual balance system
• Barnstead Reverse Osmosis Water Purification System
• Burrell Wrist-Action Shaker
• Thermolyne Muffle Furnace

Consumables

Reagents

• Reagent Water: 18 M=CE=A9 deionized water
• Sodium Chloride: Trace metal clean
• Nitric Acid (HNO₃): Trace metal grade,= 70% concentrated. Warning: Always add acid to water.
• Element Stock Solutions: Certified 1000 ppm: Al, =Ba, Ca, Co, Cr, Cu, Fe, Ge, K, Mg, Mn, Na, Nb, Ni, P, Sc, Si, Sr, Ti, V, Y,= Zn, Zr
• Element Internal Standards: Certified 1000 ppm: B=e, In, Sb, Sc, Y
• Argon Gas: Ultra high purity (UHP) grade
• IAPSO standard seawater is produced to have a spe=cific conductivity, K₁₅, referenced to a known concentration of =KCl at 15=C2=B0C. It has been shown by Bacon et al. (2007) to be extremely =consistent and stable over a reasonable period of time. It is assumed withi=n this method that the concentration of the constituents in IAPSO s=tandard seawater is, for all intents and purposes, the same as tha=t of standard reference seawater. Using the numbers found in Millero (2008)=, substituting the averaged value for Gieskes (1991) and Summerhayes (1996)= for lithium and alkalinity, the working concentrations are therefore:
  <=br>

1. The molarity values in this table except for Gieskes et al. (1991=) were calculated from the g/kg values in the reference using the density o=f standard seawater at 15=C2=B0C (1.025 kg/L) in order to match the standar=dized K₁₅ value for IAPSO seawater. 2. Gieskes et al. (1991) alr=eady given in terms of molarity. 3. Summerhayes et al. (1996); also quoted =by the OSIL website as their reference for IAPSO constituents. 4. Pilson (1=998). 5. Millero et al. (2008). N/A =3D not available from this author.

=Preparing the Calibration Standards

Preparing and Measuring Major Cation Salt Solutions:

Frequently, dissolved major cations increasing downhole surpass the =upper bound of IAPSO concentrations and the certified 1000 ppm standards at= working dilutions. These elements may be constrained within calibration cu=rves by increasing the dynamic range of the calibration solutions with majo=r cation salt doping. Primary salt solutions are prepared and concentration=s are determined by ICP once at the beginning of an expedition and carried =through further standard co*cktails. There is no need to heat salts in the o=ven to desiccate. Note: magnesium chloride hexahydrate dec=omposes to magnesium tetrahydrate at 116.6=C2=B0C:

• 1% Potassium: Make up 1.94 g of potassium chlorid=e (KCl, 74.5513 g/mol) in 100 mL MQ water
• 1% Magnesium: Make up 9.13 g of magnesium chlorid=e hexahydrate (MgCl₂H₁₂O₆, 203.31 g/mol) i=n 100 mL MQ water
• 1% Calcium: Make up 3.8 g of calcium chloride dih=ydrate ( CaCl₂H₄O₂, 147.008 g/mol) in 100 =mL MQ water
• 3.5% NaCl: Acidified Synthetic Seawater reagent=li>

Measure each solution against certified reference standards to acqui=re accurate concentrations for further standard dilutions.

• Working salt solutions: Pipette 1 mL of each 1% K=, Mg, and Ca salt solution, and 286 =C2=B5L of 3.5% NaCL into a single 100 =mL volumetric flask and make up with 2% trace metal HNO₃. With t=his solution, prepare 5-7 replicates of a 1:10 dilution (1 mL solution + 9 =mL 2% HNO₃) to be run by ICP. Vortex mix the aliquots. Each yiel=ds roughly a 10 ppm solution containing each major cation.
• Primary Certified Standard: Pipette 5 mL of each =the 1000 ppm Ca, K, Mg, and Na standards into a 50 mL volumetric flask and =make up with 2% trace metal HNO₃.

Make up 6 calibration standards according to the following scheme:=p>

Use the template IODP_STANDARD_SALTSOLUTIONS_TEMPLATE to evaluate the 5-7 replicates against the above calibration st=andards. For each wavelength used, average the concentrations for the 5-7 r=eplicates. Multiply the Ca, K, and Mg concentrations by a factor of 1000, a=nd Na by a factor of 3500 to give the original 1% salt concentrations in pp=m. In judging each element=E2=80=99s concentration, average all samples acr=oss all wavelengths after removing any erroneous/problematic lines. To star=t this analysis follow the steps given in Performing an ICP-OES= Analysis. Adjust and update the concentrations of Na, Mg, Ca=, and K listed in Table 1 to reflect the values m=easured in the 1% salt solutions.

Preparing Interstitial Water Working Standards:

Prepare a primary co*cktail standard according to the recipe shown in= columns 2 and 3 of Table 1. Pipette all individu=al standards into a single 100 mL volumetric flask and bring to volume with= 2% trace metal HNO₃. Na, Mg, Ca, and K values are from the majo=r salt solutions which are determined in the preceding step, the remaining =standards are 1000 ppm SPEX CertiPrep reference standards.

Table 1: Recipes of the primary co*cktail and IAPSO =(highlighted in blue) used to create working standards, and final concentra=tions of the working standards. Serially dilute the in-house co*cktail and I=APSO according to the scheme given in Table 2. Na, Mg, Ca, and K are from t=he major salt solutions. Adjust concentrations accordingly. Iron and mangan=ese values were excluded from IAPSO due to their low concentrations, and ba=rium due to its precipitation with sulfate. Be wary of silicon concentratio=ns in IAPSO due to its storage in glass containers.

As listed in Table 2, create one set of working standards by making serial dilutions of the= in-house synthetic co*cktail (Table 1) using sepa=rate 100 mL volumetric flasks, adding the required amount of 3.5% sodium ch=loride, 100 ppm internal standard and bringing to volume with 2% trace meta=l HNO₃. Prepare a set of IAPSO serial dilutions in the same fash=ion (do not add 3.5% sodium chloride). Note: Both sets of =standards are analyzed in order to constrain Ba and S (predominately SO₄^2-) which precipitate if present in the same vial (even =if acidified), and to measure Na=E2=80=94which is necessarily kept constant= to be used as an ionization buffer for the minor elements in the synthetic= standards.

Table 2: Recipes for two sets of standard serial di=lutions, one of the synthetic standard co*cktail and the other of IAPSO. Pre=pare each standard in a 10 mL nalgene bottle, make up to volume with 2% tra=ce metal nitric acid for IAPSO standards, and make up to volume with acidif=ied synthetic seawater for In-House working standards. The final concentrat=ions are listed in Table 1. Note: The left three columns indicate the recip=e for the 10 ml In-House working standards and the three columns to the rig=hts are the 10 ml IAPSO standards recipe.

Alternate Method for Interstitial Water Standards

The aim of this method of preparing standards is to reduce error. In=stead of standards and samples being prepared differently for analysis, the=y will all be prepared the same. In addition there will only be two solutio=ns being pipetted for sample dilutions instead of three. This method also m=imics prior methods used with the previous ICP where large batches of a mat=rix solution were made. Internal standard amounts were selected to remain c=lose to the concentrations used in the above preparations.

• Matrix Solution: Pipette 2.25mL each of Be, In, S=c, and 4.5 mL Sb, along with 28.3 mL trace metal HNO3 to 1L of nanopure wat=er.

Preparing Hard Rock and Sediment Standards:

Hard rock and sediment standards are prepared according to the ICP-OES Hard Rock Preparation User Guide. Standards ar=e fused with lithium metaborate (LiO₂) at a 1:4 sample:flux rati=o and then dissolved in a 10% trace metal HNO₃ solution (Optiona=l: doped with Li₂CO₃) for a total dilution factor of =1:2000. Lithium carbonate may be employed as an ionization buffer to mainta=in a relatively constant number of free electrons in the plasma to mitigate= ionization and matrix effects and enhance peaks intensities of minor eleme=nts (not part of the routine analysis).

Major elements are reported in weight % (mass of oxide/mass of sampl=e) of the respective oxide, with iron species being normalized to Fe_{2<=/sub>O3 (the designation Fe2O3t is used, w=here t =3D total). Minor elements are reported in units of ppm (mass of ele=ment/mass of sample).}

An analytical procedural blank= is prepared identically to the samples, with the exception that only 0.4 g= of flux is fused and dissolved. An additional 0.1 g of flux is not added t=o mimic the TDS of the 0.5 g mix of sample + flux because this would provid=e an inaccurate quantitation of the impurities introduced by the amount of =flux used in preparation of the unknowns.

Flu=x-Fusion Preparation of Rocks

Consult the IODP Hard Rock ICP Sample Preparation Guide<=/em> for a complete, in-depth explanation of the hard rock and sed=iment sampling procedure. The amount of time necessary to prepare a single =sample for analysis according to Table 4 is appro=ximately 48 hours.

Table 3: ICP hard rock and sediment sampling and be=ad preparation timeline

Dilution =of Sediment/Hard Rock standards

Choose a suite of hard rock or sediment standards which matrix-match= and span the range of expected concentrations within the samples. Consult =Appendix 4: Table of Values for Hard Rock and Sediment Certifie=d Reference Materials when choosing analytic=al standards. Standards are prepared in the same fashion as samples, as des=cribed in the proceeding section (see Hard Rock and Sediment (S=olids Method)).

Characteristics of Flux Fusion Solutions

Flux fusion solutions become unstable over time; major and trace ele=ments precipitate or form a gel, which is not always visible (since it is c=lear), so inspect solutions prior to analysis. The stability of the solutio=n is proportional to the dilution factor and acid content and inversely pro=portional to the SiO₂ content. A dilute solution is more stable =than a concentrated one, and a solution becomes more stable with higher HNO=₃ presence. A flux-fusion solution enriched in SiO₂ i=s likely to be more unstable than a basalt or shale solution. Analyze sampl=es on the ICP shortly after they are dissolved.

I=nterstitial Water (Waters Method)

This method applies to water samples in a 2% nitric acid solution at= a 1:10 (v/v) dilution factor.

1. Acidify pore water, rhizon or other aqueous samples with 5-10 uL o=f concentrated trace metal grade nitric acid and store refrigerated in seal=ed vials.
2. When preparing an analytical batch, pipette 500 =C2=B5L of sample =(using an Eppendorf set-volume pipette) + 100 =C2=B5L internal standard + 4=.4 mL of matrix solution into a 15 mL vial. Cap and mix using a vortex stir=rer for 10 seconds.

Hard Rock and Sediment (Solids Method)

This method applies to hard rock and sediment samples in a 10% trace= metal nitric acid solution at a 1:2000 (m/v) dilution factor

1. Prime the 50 mL dispensette atop a 1 L bottle containing&nbs=p;10% nitric acid solution. Ensure there are no air bubbles present in the spigot.
2. Add 50 mL of10% nitric acid solutionto a 125 mL HNO_{3<=/sub>acid-cleaned Nalgene wide-mouthed bottle.}
3. Carefully place the sample bead (and all chipped pieces) in the 12=5 Nalgene bottle, close the lid, and agitate with the Burrell wrist-action =shaker for 1 hr.
4. Using a new or acid-washed 20 mL syringe, extract solution from th=e sample bottle and then using a 0.45 =C2=B5m Acrodisc syringe filter, filt=er the solution into a 60 mL acid-cleaned Nalgene wide-mouth bottle. Repeat= until the entire sample is filtered.
5. Pipette 500 =C2=B5L of the filtered solution into a 15 mL scintill=ation vial and dilute it with 100 =C2=B5L hardrock internal standard + 4.4 =mL dissolution solution. Cap and mix using a vortex stirrer for 10 seconds.=
6. Analyze samples within 48 hours of dilution.

Pre=paring an Analytical Sequence

Correct setup of the analytical sequence is integral to monitoring a=nd troubleshooting the analytical results. Adhere to the following scheme i=n all cases:

1. Bracket samples and with check standards. Use the 100% Level (IAPS=O and the In-house) standards as checks. Prepare a large volume of the chec=k standards in a volumetric flask and, after mixing, decant it into several= aliquots to be analyzed intermittently every 8-10 samples.
2. IMPORTANT: Analyze a blank before runnin=g the calibration standards, and periodically throughout a run. The blank m=ust be diluted in the same fashion as the samples. It must contain the same= amount of internal standard. The blank must be analyzed first.
3. Analyze the standards at the beginning of a sequence. They can be =in a random order.
4. Always analyze the samples in a random order, do not sequence them= by depth in hole.

Figure 1: ICP Expert instrument dashboard.

Starting th=e Instrument

1. Verify that the instrument is connected to the electrical mains (v=oltage requirement: 200 V), and that instrument is connected to the PC and =network via Ethernet.
2. Verify the Ar line is connected and the wall-mounted pressure gaug=e reads 90 psi. In the Upper Tweens ensure that two Ar gas manifold lines a=re each connected to a series of four Ar bottles. Open the manifold valve t=o only one set of four bottles. A fresh rack yields a pressure of ~2200-240=0 psi=E2=80=94displayed on the pressure gauge connected in-line to the mani=fold above the Ar bottle racks. The regulator should be set around ~400 psi=. The Ar usage is ~100 psi/hour with the plasma on, and ~2.5 psi/hr during =standby. Use the Gas Status Monitor (http://eiger.ship=.iodp.tamu.edu/GASSTATUS/) to monitor gas levels during an analysis. Note: Ar leaks may cause asphyxiation by displacing oxygen. =Notify a coworker when manipulating gas lines in the Upper Tweens.
3. Open the wall-mounted Ar valve above the ICP workstation.
4. Power on the instrument by first enabling the kill-switch located =on the rear-left, then press the power button located on the front-left of =the instrument. The LED for the power button will flash green for a few sec=onds before steadying.
5. Start the ICP Expert software.
6. Wait approximately 30-45 minutes for the polychromator temperature= to stabilize at 35.0=C2=B0C. The temperature may periodically fluctuate by= 0.1=C2=B0C. If measuring wavelengths below 189 nm it is best to allo=w the polychromator to purge for a total time of 2-3 hours with Boost purge enabled.
7. Turn on the water chiller. The default temperature setpoint should= be at 20=C2=B0C and the pressure setpoint at 59 psi. Turning on the instru=ment alone does not require the water chiller to be on, but you would want =to have the chiller on for 30 minutes before igniting the plasma. The Pelti=er cooling temperature should be at -40=C2=B0C.
8. In ICP Expert click the ICP instrument b=utton located on the top tool bar to bring up the instrument parameters men=u. Click Plasma on. Over the next 60 seconds the =plasma will ignite. If the plasma suddenly extinguishes during ignition, it= is usually due to air drawn up through the tubing for the spray chamber ri=nse solution. Repeat this step while covering the end of the tubing with a =gloved finger. The peristaltic pump comes on when the plasma ignites. Once =the plasma is on, place the spray chamber rinse tubing in the 3% TM HNO₃ bottle. Allow the plasma to stabilize for more than 20 minutes.
9. Important: Ensure the peristaltic pump tubing is correctly seated.= Place the tubing collars within the beams located above and below the pump= wheel. Seat the collars within the beam grooves, not stretched along the o=utsides. Allow the pump to turn several times (enabling fast pump helps) fo=r the tubing to work itself into position, then engage the pressure bars an=d if necessary adjust the tension of each. Bands of air or sample flowing t=hrough the lines leading to the pump should be unvarying in speed. If there= is a chugging motion in fluid flow the pressure bars are too tight. If the=re is no flow, the pressure bars are too loose or there is blockage.

Selecting Elements, Wavelengths and Internal Stan=dards to Measure

The ICP Expert software is designed in suc=h a way that a method =E2=80=9Ctemplate=E2=80=9D may be set up and re-used =for any number of subsequent analyses. When a run commences, the template f=ile is converted to an ICP ExpertWork=sheetFile (.esws)=E2=80=94which is =identical to the template file except that it stores analysis results and a=rchives instrument measurement conditions. It is important to keep in mind =that all updates must be applied to the template file in order to be presen=t in future runs. Altering the worksheet file (e.g. changing a calibration =type, internal standard, removing or adding new lines, adjusting the standa=rds table, etc) only applies to the respective worksheet.

Figure 2: ICP Expert Elements Menu =for selecting analytical lines and assigning internal standards

Specifying Instrument Measurement Conditions

A considerable amount of finesse is required to improve elemental re=sults by changing the measurement conditions. By default, use the method de=veloped on x369. It is stored under the name ICP-Template-Master on the ICP= host PC. Table 5 lists the parameter values nece=ssary to recreate the measurement conditions. If certain instrument compone=nts or parameters are changed, then all conditions must again be optimized =as they are interlinked. In particular, adjust measurement conditions if:=p>

• The sample isolation loop or any of the sample introduction lines= are exchanged for one of different length and/or internal diameter.
• The pump rate is altered, or any time events are changed (e.g. va=lve uptake delay, rinse time, etc).

• The number of condition sets changes from two, or SVDV is used.
  
  Figure 3: ICP Expert Conditions Menu for specifying instrument mea=surement parameters, assigning condition sets to individual lines, and sett=ing integration areas. Note: These parameters cannot be changed once the se=quence has started.

  Table 4: List of standard measurement parameters for ICP-OES anal=ysis of interstitial water, sediment and hard rock. The firstconditio=n set to be run must include a 30 second plasma stabilization time, the pla=sma will remain stabilized for all subsequent condition sets provided the R=F power and Ar flows are the same.

  Parameter	Common Conditions	Condition Set 1	Condition Set 2
  Replicates	3
  Pump Speed (rpm)	12
  Pump Rate =E2=80=93Uptake (mL/min)	28
  Pump Rate =E2=80=93Inject (mL/min)	0.5
  Valve uptake delay (s)	18.0
  Bubble Injection Time (s)	2.0
  Pre-emptive Rinse Time (s)	2.0
  Rinse Time (s)	5
  Read Time (s)	5	5
  RF Power (kW)	1.20	1.20
  Stabilization Time (s)	30
  Viewing mode	Axial	Radial
  Viewing Height (mm)	8	8
  Nebulizer Flow (L/min)	0.70	0.70
  Plasma Flow (L/min)	12.0	12.0
  Auxiliary Flow (L/min)	1.00	1.00
  Make up Flow (L/min)	0.00	0.00

  Parameters for Common Conditions:

  Replicates: The number of integrations for each =condition set per sample.

  Pump speed (rpm): The instrument peristaltic pum=p speed.

  Pump rate =E2=80=93 Uptake (mL/min): The r=ate at which sample is drawn through the sample isolation loop connected to= the AVS.

  Pump rate =E2=80=93 Inject (mL/min): The rate at= which sample is pumped into the nebulizer/spray chamber from the sample is=olation loop.

  Valve uptake delay (s): The length of time sampl=e is pumped from the sample vial into and through the sample isolation loop=.

  Bubble injection time (s): The amount of time Ar= is pumped into the sample isolation loop after sample uptake but before ri=nse uptake. This allows a bubble to separate the sample and standard within= the uptake lines.

  Pre-emptive Rinse Time (s):

  Rinse time (s): The amount of time rinse solutio=n is drawn through the sample lines after a sample uptake.

  Par=ameters for Condition Sets

  Read time (s): The length of time for a single r=eplicate integration.

  RF Power (kW): The forward power supplied by the= RF coil to maintain the plasma.

  Stabilization Time (s): The amount of time allot=ted for sample to be introduced from the AVS sample isolation loop to the p=lasma before performing integrations.

  Viewing Mode: The angle from which the plasma is= viewed. In =E2=80=9CAxial=E2=80=9D view the instrument views the pla=sma from the top facing downwards. In radial view, the instrument views the= plasma from the side.

  Viewing Height (mm): 8: The position of the radi=al optics when viewing the plasma from the side.

  Nebulizer Flow (L/min): The argon flowrate intro=duced to the nebulizer which carries sample through the spray chamber

  Plasma Flow (L/min): The argon flowrate introduc=ed to the outer sheath of the torch in order to contain the plasma.

  Aux flow (L/min): The argon flowrate intro=duced to the torch to maintain the plasma

  Make up flow (L/min):

Creating a =Standards Table

By following the standards di=lution recipe given in this guide and using the default ICP Expert Templates (IODP_STANDARD_IW_MAJORS_MINORS_TEMPLATE.ests, IODP_STANDARD_HARDR=OCK_TEMPLATE_.ests), t=he standards table will not require major adjustment. In the case additiona=l or different standards must be run:

• 1. Click on the Standards menu located o=n the left side of the ICP Expert window
  2. Increase the Number of Standards to t=he desired quantities. Adjust the decimal places for the desired leve=l of precision.
  3. Ensure Include Blank in Calibration i=s checked, and Correlation coefficient limit is s=et to 0.5000
  4. Within the table enter the standard names under Sol=ution Label and enter the concentrations within the pertinent= element columns. Attribute units to the concentrations by selecting from t=he dropdowns located immediately below the element header row.
  5. Adjust the =E2=80=9CCalibration Fit=E2=80=9D table so that the =Calibration Error for each line is at 1000%. Unch=eck Through Origin for each line.

Figure 4: ICP Expert Standards Menu where the numbe=r and concentrations of analytical standards may be edited. The user may sp=ecify the type of calibration fit=E2=80=94which may be altered before, duri=ng and after an analysis

Creating =a Sample Sequence

1. Open the sample Sequence menu located on= the left side of the ICP Expert window.
2. Increase the Number of Samples to the de=sired quantity.
3. In the sample table, enter the sample names and/or TextIDs and any= dilution factors which deviate from the usual method dilution (dilution fa=ctors may likewise be adjusted after a run). Insert check standards every 8=-10 samples. If necessary, change the values in the Rack:Tube=em> column to designate each sample placement within the autosampl=er rack.
4. Under the End of Run Actions, ensure the= pump speed is set to 12 rpm and the rinse is set to 10 minutes.
5. Next, open the Autosampler menu located =below the Sequence menu. Notice the orientation o=f the autosampler displayed on the screen versus the autosampler placement =on the countertop. Assign a rack for the standards by right-clicking on a r=ack, highlighting Rack Use and selecting =Standards. Right-click on a single vial within the rack t=o set it as the Start Tube. Perform the same acti=ons for samples by assigning sample racks and sample start tubes. The defau=lt rack types are 60 samples x 16 mm OD.

Figure 5: ICP Expert Sequence Menu for setting up a= sample sequence and designating vial positions within the autosampler rack=s.

Figure 6: ICP Expert Autosampler Menu for assigning= racks and vials to positions within the autosampler. The autosampler probe= may be manually controlled from this menu.

Startin=g and Monitoring a Run

Within the Analysis menu, located on the l=efthand side of the ICP Expert window (Figure 3), occasionally monitor the results during acquisit=ion.

1. Begin an analysis only after the standards and samples have been p=repared and placed in the autosampler (with caps off), a standards table an=d sequence have been created in ICP Expert, and t=he correct measurement conditions have been applied on the Cond=itions tab. Press the Run button lo=cated on the top menu bar of ICP Expert. A messag=e will appear asking to save the template as a worksheet file (.esws). Save= to an expedition related data directory on the PC.
2. As the instrument measures, periodically click on cells within the= Results table to display the scan profile, calib=ration curve, and measurement statistics for each sample=E2=80=99s replicat=e integrations.
3. In the spectrum window, move the dotted red vertical hash line so =that it coincides with a peak maximum (Note: the adjustmen=t propagates through all scans of the respective line). Ensure the entire p=eak is within the integration area. Click and drag the background points so= there is minimal overlap with any spectral interferences. The type of back=ground correction may be changed by right-clicking on the spectrum graph, h=ighlighting Background fit and changing the selec=tion.
4. Ensure that the RSDs for each element are within the acceptable ra=nge. For values above the instrument detection limits, expect most RSDs to =be below 1-2%. Values above but near the LOD will typically have an RSD of =5%, whereas values below the LOD will typically return RSD=E2=80=99s of 5%+=. After measuring the standards, if there is a systematic increasing/decrea=sing trend in intensity for the three replicate integrations, stop the run =and troubleshoot. (See Section Troubleshooting for help).
5. Outliers may be removed by selecting a sample in the results table= and unchecking the boxes for Replicate located o=n the pane at the bottom of the screen. The software disregards a sample/st=andard if all replicates are removed.
6. If necessary, change the calibration type (linear, quadratic, rati=onal) by navigating to the Standards menu and cha=nging the selection within the Calibration Fit me=nu.
7. On an element case-by-case basis, remove the replicates for high-e=nd standards which greatly over range the sample concentrations.

Figure 7: ICP Expert Analysis window. User may view= analytical results during acquisition, dynamically change background corre=ctions and integration areas, flag outliers, and view calibrations

Exporting, Vetting and Uploading Data

Follow the subsequent steps only after a run has completed, the cali=brations have been verified, dilutions have been taken into account, values= below LODs have been disregarded and results are ready for upload. Follow =the guidelines in the Quality Assurance and Data Reduction section when vet=ting ICP-OES results.

1. For each element wavelength in the results table, right-click on t=he column header, select Column Properties and to=ggle off all result flags (Figure 6).
2. Left-click the empty cell on the left-most column of the Results t=able (left of the Rack:Tube header) to select all= the results. Right-click the same cell then select =E2=80=9CExport selecte=d solutions.=E2=80=9D Save the file to an expedition specific directory.
3. Open the AIDR-ICP Data Reduction.xlsm. On the Raw Data= worksheet open the user menu (CTRL+SHIFT+W) and select Import Data. Follow the prompts.
4. Manually Copy the Condition Sets and Element Lists tables from ICP= Expert to the appropriate tables located on the Condition Set =and Element List tab in the Agilent Data Reduction Program. O=pen the user menu on the Raw Data worksheet and <=strong>Format Data.
5. (Optional) Download a curatorial report from LORE and paste it to =the table on the Curatorial Report tab.
6. On the Reduced Data tab, open the menu (=CTRL+SHIFT+W) and click Refresh PivotTable.
7. Use the slicers to filter out undesired elemental wavelengths. Por=ewater graphs may be generated by opening the menu and selecting Show Concentration Plots.
8. At this point, pass the workbook over to the geochemists. After th=e data has been vetted, open the menu (CTRL+SHIFT+W) on the Red=uced Data tab and select Spreadsheet Uploader For=mat. The data will be formatted for upload.
9. Paste into Spreadsheet uploader, validate the sheet, then upload t=o LIMS. Data must be pasted into Spreadsheet Uploader in chunks of 500 rows= or less.

Instr=ument Shutdown Procedure

1. Cycle the nitric acid rinse solution for 10 minutes, followed by D=I water for 5 minutes, then remove the sample uptake tubing from solution a=nd allow air to purge the lines and introduction system for 10 minutes or t=o dryness.
2. Extinguish the plasma by clicking Plasma off from the ICP Expert menu.
3. Disengage the peristaltic pump tubing on both the instrument and a=utosampler.
4. After 10 minutes necessary for the RF coil to fully cool, switch o=ff the water cooler.
5. If another analysis will be conducted within the following week, l=eave the instrument on with Ar flowing (usage is ~2.5 psi/hr in standby). I=f it is the end of expedition or there will be a long interval between the =next analysis, turn off the Ar gas inlet by closing the wall-mounted valve =located above the instrument. Turn off the power using the switch on the fr=ont left, wait for the green LED to stop blinking, then turn off the mains =power switch located on the rear left of the instrument.
6. Leave the vials in the autosampler rack until the results have bee=n inspected to ensure no two vials were misplaced during the analysis. Remo=ve the labels from the vials, empty the contents into the waste container, =and rinse the vials with tap water. Soak them in 10% HNO₃ for 12= hours.
7. If proceeding to an interstitial water analysis after performing a= hard rock analysis change all the sample introduction tubing and glassware= to prevent Li and B contamination. These include the autosampler probe, sa=mple uptake tubing, sample introduction loop, nebulizer and spray chamber.<=/li>

Cleaning Instrument Components:

Follow the routine cleaning procedure outlined in the Ag=ilent 5100 and 5100 ICP-OES User=E2=80=99s Guide when cleanin=g or servicing any instrument components. Walkthrough videos and step-by-st=ep instructions are accessible through the ICP Expert Help menu, underneath the =E2=80=9CHow to,=E2=80=9D =E2=80=9CTroublesh=ooting,=E2=80=9D and =E2=80=9CMaintenance=E2=80=9D folders.

Daily= Cleaning and Maintenance

• Check the torch for cleanliness. To clean the torch, soak the end =in a small volume of 50% aqua regia. For 200 mL, combine 100 mL DI water, 2=5 mL of concentrated HNO₃, and 75 mL of concentrated HCl in a gl=ass beaker. Fresh aqua regia has a darkish orange-brown hue that gradually =becomes lighter as the nitrogen degasses as nitrogen dioxide, at which poin=t it should be replaced. Caution: Always add acid to= water. Aqua regia is more corrosive than its components taken separately. =Wear proper PPE, including a face shield and lab coat. Work in a fume hood.= Store aqua regia in a glass or Teflon container as it will corrode regular= LDPE or HDPE bottles.
• Inspect the elasticity of the peristaltic pump and AVS tubing, rep=lace if necessary.
• Flush the sample flow paths with DI water to remove any acidic sol=ution and ensure there are no blockages.
• Wrap the CRM bottle necks and caps in Parafilm to prevent evaporat=ion.

Week=ly Cleaning and Maintenance

• Clean the torch, cone, snout, spray chamber and nebulizer. Consult= ICP Expert Help Menu for in-depth videos of remo=val, cleaning, and installation procedures.

Figure 8: Cone before cleaning &nb=sp; Figure 9:= Cone after cleaning with a non-metal scouring pad in DI water.Figur=e 8: Cone before cleaning

Mon=thly Cleaning and Maintenance

• Clean the inlet filter for the cooling air
• Perform an ICP-OES calibration
• Remove and clean the water filter
• Inspect the axial and radial optics windows, replace if necessary<=/li>
• Check the water level in the water chiller
• Clean the water chiller radiator of dirt and dust build-up
• Drain the water chiller and either refill or treat with algaecide<=/li>

=Interstitial Waters Standard Report

• Exp:expedition number
• Site:site number
• Hole:hole number
• Core:core number
• Type:type indicates the coring= tool used to recover the core (typical types are F, H, R, X).
• Sect:section number
• A/W:archive (A) or working (W)= section half.
• Top offset on section (cm):pos=ition of the upper edge of the sample, measured relative to the top of the =section.
• Bottom offset on section (cm):=position of the lower edge of the sample, measured relative to the top of t=he section.
• Top depth CSF-A (m):position o=f observation expressed relative to the top of the hole.
• Top depth [other] (m):position= of observation expressed relative to the top of the hole. The location is =presented in a scale selected by the science party or the report user.
• Sampling tool:tool used to col=lect sample
• Data columns:header lists para=meter measured and concentration units, followed by wavelength (for ICP-AES=) and then analysis method.

Expa=nded ICPAES Report

• Exp:expedition number
• Site:site number
• Hole:hole number
• Core:core number
• Type:type indicates the coring= tool used to recover the core (typical types are F, H, R, X).
• Sect:section number
• A/W:archive (A) or working (W)= section half.
• text_id:automatically generated uniqu=e database identifier for a sample, visible on printed labels
• sample_number:sample number of= sample. text ID with sample type prefix removed.
• label_id:id combining exp, sit=e, hole, core, type, sect, A/W, parent sample name (if any), sample name
• sample_name:name of sample
• x_sample_state:
• x_project:expedition project t=he sample is uploaded under. typically the same as Exp.
• x_capt_loc:
• location:location sample was t=aken
• x_sampling_tool:tool used to c=ollect sample
• changed_by:name of person who =uploaded sample
• changed_on:date and time sampl=e was uploaded
• sample_type:type of sample. ty=pically LIQ, for liquid.
• x_offset:top offset of parent sample where =sample was taken in m
• x_offset_cm:top offset of pare=nt sample where sample was taken in cm
• x_bottom_offset_cm:bottom offset of parent =sample where sample was taken in cm
• x_diameter:
• x_idmp:
• x_orig_len:
• x_length:length of sample in m
• x_lengeth_cm:length of s=ample in cm
• status:
• old_status:
• original_sample:
• parent_sample:
• standard:
• login_by:name of person logged into LIMS ap=plication used for this test
• sampled_date:
• legacy:
• test changed_on:date of last edit of analys=is
• test date_started:date analysi=s was started
• test group_name:
• test status:
• test old_status:
• test test_number:unique number= associated with the instrument measurement steps that produced these data<=/li>
• test date_received:date analysis was upload=ed to LIMS
• test instrument:instrument used to perform =analysis
• test analysis:analysis type
• test x_project:project test was assigned to=
• test version:
• test order_number:
• test replicate_test:
• test replicate_count:
• rest sample_number:sample number for sample= the analysis was performed on

• Top depth CSF-A (m):position of observation= expressed relative to the top of the hole.

• Bottom depth CSF-A (m):position of observat=ion expressed relative to the top of the hole.

• Top depth CSF-B (m):

• Bottom depth CSF-B (m):

• batch_id:
• calibrated_name:element analyzed along with= concentration unit
• calibration:
• concentration:measured concentration of ana=lyzed element
• corrected_intensity:
• correlation:
• drift_asman_id:
• drift_corrected:
• drift_filename:
• element_conc_dissolved (uM)
• element_name: name of analyzed element
• ssup_asman_id:download link for the batch o=f data uploaded through spreadsheet uploader
• ssup_filename:filename of spreadsheet uploa=der batch
• view:view mode that analysis was performed =in (axial, radial, svdv)
• wavelength:wavelength that element was meas=ured at

• sample description:observation=s recorded about the sample itself

• test test_comment:observations= about a measurement or the measurement process; some measurement observati=ons may be under Result comments

• result comments:observations a=bout a measurement or the measurement process; some measurement observation=s may be under Test Comments

Note:Iron is expressed as Fe₂O₃t, or total Iron (III) oxi=de.

Aside from performing drift corrections, the Agilent ICP= Expert software accounts for all data reduction. The option =to normalize to any analyzed internal standard wavelength is available befo=re, during and after a run. Additionally, quality control specifications ma=y be changed to flag troublesome data. The following quality controls ultim=ately fall under the purview of the geochemists.

Implement the following steps to vet the data:

1. Ensure there are no spectral interferences overlapping the peaks o=f interest.=20
   1. If spectral interferences are present, inspect the interference =level in the blank versus the level in the standards. If the interference i=s not constant between all standards, disregard the line.
2. Ensure the linear/quadratic/rational relationship of each waveleng=th calibration curve.
3. Ensure the sample concentrations are less than the greatest calibr=ation point. Remove standards from the calibration which greatly over range= elemental abundances in the samples as they may bias the calibration curve= slope.
4. Do not remove a point from the calibration unless:=20
   1. The RSD % is outside of the allowable.
   2. A student T-Test or Grubbs Outlier Test has been performed on th=e point. Use the signal intensity-to-concentration ratios to compare the po=int against the mean and standard deviation of the population of the other =points making up the calibration curve.
   3. The liquid level of the vial in the autosampler rack indicates s=ome sample volume was not introduced.
5. For each line, verify that the accuracy (% difference) of any chec=k standards is within tolerance.
6. Ensure the % change in drift standards throughout the course of th=e analytical run is insignificant, or, if it is not, take into account drif=t with linear drift factors. If the drift is random (non-systematic), then =ignore drift corrections and consider troubleshooting precision issues.
7. Ensure there is not a significant deviation in the slopes of calib=ration curves as compared to the same curves in previous runs.
8. Before uploading to LIMS, flag values below detection limit, highe=r than the highest calibration point, or have poor %RSD. AIDR has capabilit=ies for this.

Sediment/R=ock Standards

1. For a given sample/standard, ensure that the total % recovery of m=ajor oxides is 100 =C2=B1 2 wt%.
2. Periodically ensure that sediment and rock standard certified refe=rence material values are up to date with the literature.

Pl=asma Extinguishes upon Startup:

This occurs when air contaminates the torch box or the torch is not =dry. Verify the torch is dry. Allow Argon to purge the torch box for 10 min=utes or so. When igniting the plasma, press a glove finger against the end =of the rinse uptake tubing connected to the spray chamber to cut off it fro=m drawing in air or solution.

• Attempt to implement the SVDV dual view mode for simultaneous axia=l and radial measurement. This will reduce analysis time, argon usage, and =the amount of pore water required per sample analysis.

1. Adapt the current ICP Template by changing the number of condition= sets to 1 (SVDV).
2. Adjust the Common Conditions so there is at least a 30 second dela=y after sample initially reaches the torch for the plasma to stabilize. It =is easiest to time this by running a sample containing sodium as it emits a= bright orange color within the plasma.
3. Adjust the pump conditions so that the sample isolation loop fills= with enough sample for each replicate integration. Watch the fluids flow t=hrough the lines to aid in timing. If the measurement finishes before all t=he sample has been ejected from the sample loop, then on the next run incre=ase the =E2=80=9CPre-emptive rinse time=E2=80=9D so that rinse solution is =drawn into the sample isolation loop in place of the tail-end volume of sam=ple.
4. After optimization, run a calibration curve. Ensure there are no s=ystematic increases or decreases in intensities across each replicate. RSD =should be below 2%. Inspect the calibration curves for linearity (or quadra=tic fits). The squared correlation coefficient must be greater than 0.90 in= order to be acceptable.
5. Compare spectral interferences for each element wavelength between= the current Axial/Radial method and SVDV. Investigate the presence or abse=nce of interferences and each interference intensity in relation to the ana=lyte peak intensity. Calculate detections limits. Compile the data into a t=able and compare against the Axial/Radial method.=20
   1. Headers: Analytical Wavelengths
   2. Rows: Detection Limits, % RSD (low and high sample), % Accuracy =(Low and High sample), squared correlation coefficient, calibration curve s=lope and intercept, dynamic range, internal standards used, spectral interf=erences.

• Attempt to optimize the RF forward power and viewing height parame=ters in Axial/Radial mode. This may improve analytical measurement and dete=ction of minors elements such as Fe and P. Keep in mind that the plasma mus=t stabilize for a period if the RF forward power is altered.
• Purchase and implement an Argon Humidifier to help reduce precipit=ate buildup in the nebulizer.
• Create a generic report template using the ICP report designer tha=t includes all the measurement parameters, calibration information, sequenc=e information, results and statistics using the ICP Expert= Report Designer. Reports are exported as pdfs. Store the reports =to Uservol and to the instrument host PC. Move towards implementing an uplo=ader in MUT which captures reports.
• Create an Excel script (or other) to aid in quickly visualizing da=ta downhole from the data exported after a run.
• Create an Excel script to apply a linear drift correction to selec=t lines.
• Create a Database (Excel or other) which captures calibration info=rmation for future reference.
• Revisit whether or not sample/standard residues from LOI yield val=id measurements, or instead, direct fluxing of standards before combustion =should be performed.=20
  • Certified reference materials are only valid for drying at 120==C2=B0C.
  • LOI is loss of H₂O, CO₂ but also gain of O=₂ from oxidation products, which complicates the final mass valu=e
  • Nearly 20 hrs of sample preparation time may be saved.

Agilent Technologies, ICP Expert Software, Version 7.3.1.9507, 2017<=/p>

Agilent Technologies =E2=80=9CAgilent 5100 and 5110 ICP-OES User=E2==80=99s Guide,=E2=80=9D Manual # G8010-90002, October 2016, 4^th =Ed, Malaysia

Agilent Technologies =E2=80=9CFor Your Safety User=E2=80=99s Guide,==E2=80=9D Manual # 5971-6636, February 2014, 2^nd Ed, Malaysia

Agilent Technologies =E2=80=9CAgilent SPS 4 Autosampler User=E2=80==99s Guide,=E2=80=9D Manual # G8410-90000, May 2015 Revision A, Malaysia

Bacon, S., Culkin, F., Higgs, N., and Ridout, P., 2007. IAPSO standa=rd seawater: definition of the uncertainty in the calibration procedure, an=d stability of recent batches. J. Atmos. Oceanic Technol., 24(10):=1785=E2=80=931799. doi:10.1175/JTECH2081.1

Gieskes, J.M., Gamo, T., and Brumsack, H., 1991. Chemical methods for interstitial water analysis aboard JOID=ES Resolution. ODP Tech. Note, 15. doi:10.2973/odp.tn.15.1991=

Houpt, D., 2013. Leeman Prodigy ICP-AES User Guide. International Oc=ean Discovery Program.

Millero, F.J., Feistel, R., Wright, D.G., andMcDougall, T.J., =2008. The composition of Standard Seawater and the definition of the Refere=nce-Composition Salinity Scale. Deep-Sea Res., Part. I, 55(1):50==E2=80=9372. doi:10.1016/j.dsr.2007.10.001

Murray, R.W., Miller, D.J., and Kryc, K.A., 2000. Analysis of major =and trace elements in rocks, sediments, and interstitial waters by inductiv=ely coupled plasma=E2=80=93atomic emission spectrometry (ICP-AES). ODP =Tech. Note, 29. doi:10.2973/odp.tn.29.2000

Pilson, M.E.Q., 1998. Major Constituents of Seawater. In: An Int=roduction to the Chemistry of the Sea. Upper Saddle River, NJ (Prentic=e Hall).

Skoog et al. 1992 Fundamentals of Analytical Chemistry 7th Ed.

Skoog et al. 1997 Principles of Instrumental Analysis 5^th Ed.

Summerhayes, C.P., and Thorpe, S.A., 1996. Oceanography An Illus=trated Guide, Chapter 11, 165=E2=80=93181.

The following tables detail analytical wavelengths, internal standar=ds, and viewing modes for elements measured in the Hardrock/Sediment and In=terstial Waters methods. Each table is followed by a list of similar line c=ombinations, which have been rejected for various reasons listed in each ta=ble. An Excel spreadsheet (Hardrock-Sediment_Interstital Waters_Default Ana=lytical Wavelengths Library.xlsx) containing this information is available =on the desktop of the ICP host computer. If should be periodically updated =as lines are added or removed.

Interst=itial Waters Method:

Use the analytical lines, internal standards and torch views listed =in Table 5 to recreate the default instrument con=dition set for analysis of dissolved elements in pore waters. These values =are appropriate for the interstitial water dilution scheme given in the tex=t above. Altering the dilution scheme by changing the concentrations of ana=lytical standards or diluting samples and standards by a ratio other than 1=:10, may affect the respective calibration curves, in which case, these con=ditions may need to be adjusted.

Table 5: List of instrument conditions to recreate the method for me=asurement of major and minor elements in interstitial water.

Element Wavelengths Excluded from the Inte=rstitial Waters Analysis and Why

Hardro=ck and Sediments Method

Use the following elemental lines to recreate the method used for an=alysis of rocks and sediments. Several lines for each element are included =to bracket a wide range of concentrations (low concentrations need lines wi=th large instrument responses, and vice-versa for high concentrations), and= to provide a larger selection of alternative lines in the case of interfer=ences. This custom list of wavelengths is based on the hard rock dilution s=cheme detailed in the text.

Table 6: List of instrument conditions to recreate =the method for measurement of rocks and sediments.

Element Wavelengths Excluded from the Hardrock Analy=sis and Why

Table 6: Elemental units and conversion factors fro=m major oxides to element wt%

Most LIMS components are directly saved as a pair of components: a R=ESULT table name for the name of the parameter, and RESULT.entry for the te=xt or numeric result. For the Inductively-Coupled Plasma=E2=80=94Optical Em=ission Spectrometer however, it was necessary to create a different structu=re. Three of the name fields in the RESULT table are analyte, concentration=, and wavelength. Any given result is a marriage of these three fields (e.g=., analyte =3D Mg, concentration =3D 51.060 mM, and wavelength =3D 257.61 n=m). These are organized on the RESULT table by use of the RESULT.replicate_=count field, so a given analyte entry, concentration entry, and wavelength =entry have the same replicate_count (e.g., /0, /1).

Although the ICP is used for both solid and liquid samples, the comp=onent table is common between them. The reports separate them by use of the= SAMPLE.sample_type field; all LIQ sample are considered to be interstitial= water sample, and all other sample types are lumped into the solids ICP re=port.

ICP-OES User Guide: 29th September 2022

=LMUG-ICP_User Guide-230220-1914-156.pdf