Hướng dẫn sử dụng ICP Leemanlab

International Ocean Discovery Program
Leeman Prodigy ICP-AES:

User Guide
Manual Information
Author(s): D. Houpt (original version C. Bennight)

Reviewer(s): M. Bertoli, L. Brandt, R. Gray, E. Moortgat
Management Approval: D. Houpt (Supervisor of Analytical Systems)
Current Version: V1.0 | 7 August 2013
Revised: V1.1 | 6 Jan 2014 (IODP-II)
Domain: Chemistry
System: ICP-AES Elemental Analysis
Keywords: ICP, dissolved metals
Purpose and Audience

This user guide is intended for use by scientists and technical staff who have laboratory experience with analytical
instrumentation, preparing standards and samples, and data reduction and who have received an introduction and
demonstration of the laboratory instrumentation aboard the JOIDES Resolution. Good laboratory practices and
attention to laboratory safety is necessary while using the procedures described in this user guide.
In This User Guide
Topic See page…
Introduction 2
Apparatus, Reagents, & Materials 3
General ICP Operation 7
Methods 26
Solids Method 26
Interstitial Water Majors Method 29
Interstitial Water Minors 29
Quality Assurance/Quality Control 30
Data Reduction 35
Safety Considerations 43
ICP-AES User Guide 1 6 January 2014

Introduction
The methods in this manual are based on those described in ODP Technical Note 29, with updates for current
equipment, procedures, and analytics as used aboard the JOIDES Resolution in the International Ocean Discovery
Program.
Definitions
• Aliquot: A discrete, measured, representative portion of a sample taken for analysis.
• Analyte: Specific chemicals or components for which a sample is analyzed.
• Digestion: A process in which a sample is treated (usually in conjunction with heat) to convert the sample to a
more easily measured form.
• Duplicate: Analyses of the variable of interest performed identically on two subsamples of the same sample.
Results from duplicates are used to evaluate analytical/measurement precision but not the precision of sam-
pling, preservation, or storage internal to the laboratory.
• Interference, spectral: Occurs when particulate matter from atomization scatters the incident radiation from
the source or when the absorption or emission of an interfering species either overlaps or is so close to the
analyte wavelength that resolution becomes impossible (Skoog et al., 1992: Fundamentals of Analytical Chem-
istry).
• Internal Standard: A pure substance that is introduced in known amount into each calibration standard and
field and QC sample of the analyte. The ratio of the analyte signal to the internal standard signal can be then
used to determine the analyte concentration (Skoog et al., 1997: Principles of Instrumental Analysis).
• Matrix: Collection of all of the constituents making up an analytical sample (Skoog et al., 1997).
• Signal to Noise Ratio: Signal carries information about the analyte, whereas noise is made up of extraneous
information that degrades the accuracy and precision of an analysis and places a lower limit on the amount of
analyte that can be detected. Generally, the average strength of the noise is constant and independent of the
magnitude of the signal. Thus, the effect of noise on the relative error of a measurement increases as the
quantity being measured decreases in magnitude.
• Standard: Standard samples comprise a known amount of reference material in the matrix undergoing analy-
sis.
o A standard reference material (certified reference material) is produced by an authoritative source (e.g.,
NIST) and characterized for absolute content, independent of analytical method.
o Standards for which certified values do not exist can be used. Most of these have been analyzed repeat-
edly by multiple laboratories but can be quantified by IODP only. An example of this type of standard is
IAPSO seawater, which is certified only for salinity but for which the other constitutent values (e.g., sodi-
um, calcium, sulfate, chloride) have been determined by comparison to the literature values for those
constituents in reference seawater.
• LIMS
o General: Laboratory Information Management System, an integrated system to acquire and manage la-
boratory data.
o IODP-USIO: “LIMS” refers to the data-model, database, and systems that provide access to these re-
sources for IODP-USIO. The LIMS stores and provides access to analytical data collected.
• TextID (also Text_ID): A unique sample identification field that refers to a specific sample; it only points to one
sample.
• Sample Number: A unique numerical sample identification that refers to a specific sample.
Methods in this Manual

• Solids (Rock and Sediment), Major Element Oxides, and Minor Element Constituents: rock or sediment sam-
ples are fused with lithium metaborate (LiBO2) at a 1:4 ratio (sample:fluxing agent) and dissolved in 10% nitric
acid solution; dilution factor = 1:4000 (m/v).

• Interstitial Water, Major Elements: IW samples diluted in 2% nitric acid solution; dilution factor = 1:100 (v/v).
• Interstitial Water, Minor Elements: IW samples diluted in 2% nitric acid solution; dilution factor = 1:20 (v/v).
Apparatus, Reagents, & Materials

Hardware
ICP system hardware includes the following:
$ Teledyne-Leeman Prodigy Dual-View ICP-AES system (Figure 1)
$ Motion-compensated dual balance system (Figure 2)
$ Motion-compensated dual microbalance system (Figure 3)
$ Burrell wrist action shaker (Figure 4)
$ Muffle furnace (Figure 5)
$ Water chiller (Figure 6)
Figure 1. Teledyne-Leeman Prodigy Dual-View ICP-AES System.
Figure 2. Dual Balance System (Mettler-Toledo XS204).

Figure 3. Dual Microbalance System (Mettler-Toledo XP56).
Figure 4. Burrell Wrist Action Shaker Model 75.
Figure 5. Fisher Muffle Furnace.
Figure 6. Water Chiller.
Materials

All Methods: Personal Protective Equipment

$ Safety glasses
$ Nitrile gloves
$ Platinum-tipped tongs
$ Teflon tongs
$ Fume hood
Interstitial water
$ Pipettor, 100 µL
$ Sample tubes, 10 mL
$ Dispensette, 10 mL
$ Volumetric flask, 100 mL
Solids
$ Dispensor, 100 mL
$ Syringe, 20 mL
$ Acrodisc filter, 0.45 µm
$ Nalgene wide-mouth bottles, 60 mL and 125 mL
$ Scintillation vials, 20 mL
Reagents
• Reagent water: 18 MΩ deionized water
• Sodium chloride (NaCl), reagent grade
• Nitric acid (HNO3), trace metal grade, 70% (concentrated). Warning: Always add acid to water.
o 1% solution: 14 mL concentrated HNO3 per liter of reagent water.
o 4% solution: 57 mL concentrated HNO3 per liter of reagent water (make only ~500 mL).
• IAPSO standard seawater. Analyte concentrations in standard reference seawater are as follows:
1 2 3 4 5
Constituent Concentration Concentration Concentration Concentration
Lithium (µM) 27 25.7 N/A N/A
Sodium (mM) 480 480.2 480.2 480.7
Potassium (mM) 10.44 10.46 10.46 10.46
Magnesium (mM) 54 54.4 54.1 54.1
Calcium (mM) 10.55 10.54 10.54 10.54
Strontium (µM) 87 92 92.8 93.0
Chlorine (mM) 559 559.6 559.4 559.6
Sulfate (mM) 28.9 N/A 28.9 28.94
Alkalinity (mM) 2.325 N/A 2.38 N/A
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 of standard seawater at 15°C (1.025 kg/L) in order to match the standardized K15 value for IAPSO sea-
water. 2. Gieskes et al. (1991) already given in terms of molarity. 3. Summerhayes et al. (1996); also quoted by the OSIL
website as their reference for IAPSO constituents. 4. Pilson (1998). 5. Millero et al. (2008). N/A = not available from this
author.
IAPSO standard seawater is produced to have a specific conductivity, K15, referenced to a known concentration of
KCl at 15°C. It has been shown by Bacon et al. (2007) to be extremely consistent and stable over a reasonable peri-
od of time. It is assumed within this method that the concentration of the constituents in IAPSO standard seawater
is for all intents and purposes the same as that of standard reference seawater. Using the numbers found in Mil-
lero (2008), substituting the averaged value for Gieskes (1991) and Summerhayes (1996) for lithium and alkalinity,
the values are therefore:

Constituent Concentration
Lithium (µM) 26.4
Sodium (mM) 480.7
Potassium (mM) 10.46
Magnesium (mM) 54.1
Calcium (mM) 10.54
Strontium (µM) 93.0
Chlorine (mM) 559.6
Sulfate (mM) 28.94
Alkalinity (mM) 2.353
• Individual 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
• Internal standard stock solution (certified), 1000 ppm: Y
• Argon gas, instrument/analytical grade
Reagents for Interstitial Waters

$ IW matrix solution (2% HNO3/10 ppm Y): to make 20 L, add 570 mL concentrated HNO3 to 19.23 L reagent
water and 200 mL of 1000 ppm Y stock standard. Warning: Always add acid to water.
• Synthetic seawater (SSW): add 35 g NaCl per liter of reagent water.
• Acidified synthetic seawater (ASSW): add 35 g NaCl and 29 mL concentrated HNO3 per liter of reagent water.
• Rinse solution: 3% HNO3 (make 5–10 L at a time): 43 mL concentrated nitric acid per liter of reagent water.
Warning: Always add acid to water.
• Drift solution: 100% multielement standard curve solution (IW Majors standard curve below)
• Blank (10 mL):
o IW Majors: 100 µL reagent water + 9.9 mL IW matrix solution
o IW Minors: 500 µL SSW + 9.5 mL IW matrix solution
• IW Majors standard curve:
o NOTE: Although the solutions below will, upon final dilution, produce the same concentration range as
the original method, this version of the dilution scheme is quite different in order to acidify the stock
standards while preserving the acid strength. The 120% IAPSO standard has a slightly lower acid strength
(1.6% instead of 2%), but this difference will not be significant in the final dilution (1.98% HNO3 vs. 2.0%).
o IMPORTANT NOTE: The IW majors curve is diluted 1:50, not 1:100, in order to accommodate the acidifi-
cation of the stock standards.
o Serial dilutions of IAPSO standard seawater are made with reagent water and 4% HNO3 solution as in the
following table (store in a 100 mL Nalgene bottle; these standards are good for the entire expedition):
Standard conc. (%) Volume IAPSO (mL) Volume DI Water (mL) Volume 4% HNO3 (mL)
120% 36.0 0.0 24.0

100% 30.0 0.0 30.0
75.0% 22.5 7.50 30.0
50.0% 15.0 15.0 30.0
25.0% 7.50 22.5 30.0
10.0% 3.00 27.0 30.0
5.00% 1.50 28.5 30.0
2.50% 0.750 29.25 30.0

• IW Minors stock (100%):

o NOTE: The IW Minors primary stock solution is quite different from the previous version of this method to
bring the analyte ranges closer to those expected in a typical IW.
o Pipet 1000 ppm element stock solution into ASSW and bring up to 500 mL:
Minor element Volume 1000 ppm stock (mL)

B 7.50
Ba 2.50
Fe 0.500
Li 1.00
Mn 1.50
Si 15.0
Sr 10.0
• IW Minors standard curve: make serial dilutions of minor element stock standard in ASSW as follows:
Standard concentration Volume (mL) stock/30 mL ASSW
75% 22.5
50% 15
25% 7.5
10% 3
5% 1.5
2.5% 0.75
Reagents for Sediments/Hard Rocks

• Bead dissolution solution: 10% HNO3 + 10 ppm yttrium (make 5–10 L at a time):
For each liter of solution, add 143 mL concentrated nitric acid to 857 mL of DI water and 10 mL of 1000 ppm
Yttrium reference solution.
• Rinse solution: 10% HNO3 (make 5–10 L at a time):
Add 143 mL concentrated nitric acid per liter of reagent water.
• Drift solution: use one of the SRMs prepared as a sample (see Solid Standards)
• Blank: 100% SSW
• Standard reference materials (see Solid Standards)
ICP Alignment Solutions

• Mn solution, 100 ppm:
Volumetrically add 10 mL 1000 ppm Mn stock to 90 mL reagent water (stable indefinitely).
• Set 1 alignment solution, 10 ppm Al, B, Ba, Ca, Li, Mg, Na, P, S, Sc, Sr, Y:
Pipette 1 mL of 1000 ppm stock for each element into a 100 mL volumetric flask and bring up to volume with
1% HNO3 (stable indefinitely, store at 4°C).
• Set 2 alignment solution, 10 ppm Co, Cr, Cu, Fe, Ge, K, Mn, Nb, Ni, Si, Ti, V, Zn, Zr:
Pipette 1 mL of 1000 ppm stock for each element into a 100 mL volumetric flask and bring up to volume with
1% HNO3 (stable indefinitely, store at 4°C).
General ICP Operation

The Teledyne-Leeman Prodigy High Dispersion Inductively Coupled Plasma–Atomic Emission Spectrophotometer
(ICP-AES) on the JOIDES Resolution is equipped with a dual view torch and an 88-position autosampler. This in-
strument is henceforth referred to as the “ICP.”
This instrument is a simultaneous ICP-AES with an 800 mm focal length Echelle optical system coupled with a 28
mm × 28 mm megapixel Large Format Programmable Array Detector (L-PAD). The detector provides continuous
wavelength coverage from 165 to 1100 nm, allowing measurement over the entire spectrum in a single reading.
The ICP uses a 40.68 MHz free-running water-cooled oscillator. The torch is rigidly attached to the spectrometer
(Teledyne-Leeman refers to this as their “Image Stabilization System”), which minimizes the effect of instrument
movement/vibration. The sample introduction system consists of a 4-channel peristaltic pump, cyclonic spray
chamber with a knockout tube, single-piece quartz torch, and a Glass Expansion SeaSpray AR30 Nebulizer.
General ICP operation in this user guide covers the following procedures:
$ Starting the instrument (igniting the plasma)
$ Shutting Down the Instrument
$ Running a Method
$ Reporting Data
$ Managing Standards
$ Analyzing a Run
Starting the instrument (igniting the plasma)

1. Verify that sufficient Ar is connected.
(Gas supply bottles are located in the Lower Tween science pallet
stores.)
The instrument uses approximately 1 bottle of argon for every 6 hr of
operation.
2. a. Turn on the Ar flow.

b. Turn on the water chiller.
c. Power on the instrument.
IMPORTANT! Purge the optical chamber with Ar at 0.1 L/min

for at least 4 hr before turning on the camera. It is OK to run
the pre-run check during the purge, but do not engage the
camera cooler until the 4 hr period has passed. With the
camera cooled to –59°C moisture in the surrounding air will
cause ice crystals to form, seriously degrading the perfor-
mance of or damaging the detector.

3. Start the control software (SALSA) on

the computer and open the Instru-
ment Control screen.
4. When the prompt appears asking if the camera has

purged SELECT NO.
The autosampler will continue to initialize, and after

~30 s the software can be used.
5. If the Maintenance tab is red, click on the tab to see

what maintenance is required.
Typical maintenance includes checking and setting the
camera chiller water reservoir level, changing the peri-
staltic pump tubing, and cleaning/lubricating the au-
tosampler. The software provides instructional videos
on how to perform each maintenance procedure.
When maintenance is complete, select OK to exit the
screen.
Close SALSA.

6. Engage the peristaltic pump tubing:

Make sure the stops in both ends are engaged against the
frontmost grooves.
Make sure that the pump arms are locked in place.
7. Install/change glassware if needed. If removing an old torch that is still usable, place it in its box and indicate
on the box if the torch was used for flux-containing processes. Gas tubing disconnects from the torch via
quick-connect fittings.
Install the new torch, leaving a gap of 2–5 mm between the front of the torch and the ceramic view plate for
the air knife flow).
The frontmost gas sheath connector connects to the top quick disconnect in the optical chamber; the rear-
most connector attaches to the middle quick disconnect; and the nebulizer gas supply connects to the bottom-
most fitting.

8. Ensure that the condition of the O-rings for the nebulizer

sheath adapter is acceptable (no rubber fragments or visi-
ble degradation).
Replace the O-rings if needed.
9. Ensure that the peristaltic tubing is connected to the proper in-

puts and outputs.
Flow direction is:
• Sampling needle  nebulizer (black tubing),
• Spray chamber waste  waste bottle (red tubing),
• Wash bottle  wash vial (autosampler home) (red tubing).
The peristaltic pump turns in a counterclockwise direction: the
bottom tubing is the in-flow and the top tubing is the out-flow.
10. After at least 4 hr has passed since purging began, start SALSA
again and click YES when prompted for the status of camera
purging time.
The camera temperature readout will drop, and the au-
tosampler will perform initialization (~30 s), after which the
control software will be operable.

11. Select Instrument Control > Auto-Start.

After ~30 s the plasma torch will ignite. Let
the plasma flame stabilize (and the instru-
ment thermally equilibrate) for 45 min before
beginning analysis.
Shutting Down the Instrument
1. Let the instrument pump wash solution (2%–10% nitric acid, depending on sample type) for 10 min. Use the
lower concentration for IW analysis and the higher concentration acid for post-hard rock analysis rinsing.
2. Place a beaker of reagent water in place of the standards rack and move the probe to the
beaker.
Let the system run the water for 10 min.
3. Raise the probe out of the water and let the instrument aspirate air for 1 min (or until the spray-chamber is
dry). No solution should be visible in any of the sample induction lines.
4. Select Extinguish in the software instrument control

panel (top right).

5. Release the pressure from the peristaltic tubing by disengaging the arms
and disengaging the tension stops.
6. Shut down SALSA.3
7. Shut down the ICP (but leave Ar flowing).

Shut down the water recirculation pump.
IMPORTANT: Do not shut down the Ar flow before the
camera returns to room temperature (~15 min)!
After the waiting period, the Ar supply can be shut
down.
Running a Method
1. Select the method to run from

Method > Open at the top left.
2. After the method loads, open Element Selection and view the selected elements. To add lines or elements:

a. click Element Selected,

b. click the desired element from the
periodic table, then
c. select the line to analyze.
3. Once all desired lines are present, run Position Plasma by selecting In-
strument Control in the left tree menu, then looking in the top left of
the instrument control dialog box.
4. Perform a mercury lamp alignment: select View > Hg Lamp, then click
Position Plasma. The Hg lamp is internal to the ICP.
5. Select an Hg line from the window, and click Peak Plasma.
6. Pour some 100 ppm Mn solution into a sample tube, place the tube in the autosampler, and using
the dialog box on the instrument control panel move the autosampler probe to this solution. Wait
~30 s or until the nebulizer has been spraying the 100 ppm sample solution for 5 s.

7. Click Position Plasma on the Instrument Control screen. Select the first
Mn wavelength and click Peak Plasma. After ~5 min the operation will
be complete (when the values stop appearing on the screen).
8. Check the Total intensity of the alignment solution. If it is within an or-

der of magnitude of 1 million counts the result is fine. If the result is
lower, as shown here, there is likely a problem.
Check the nebulizer and sample induction path to ensure the correct
amount of sample is delivered to the torch.
9. To align each line to be analyzed, place Set 1 and Set 2 aligning solutions in a test tube and move the sample
probe to this tube (same as Step 6 above).
10. Click the Analysis tab to open the Analysis window, and then click Analysis > New Chapter from the top
menu. Give the chapter a name that is unique and meaningful for this particular run.

11. Click on the Echelle Spectrogram icon. Uncheck Extended Range and Wait 30 s for transport. Name the spec-
trogram based on the solution, a dash and the integration time, for example, “Soln848 – 1sec.” Click OK after
the solution has been spraying from the nebulizer for at least 5 s. See Tables 1 and 2 (below) for suggested
integration times for each element in Solutions 1 and 2.
If the peak (when aligning as detailed below) does not have a baseline visible in the image alignment window,
shorten the integration time. If the peak does not have a visible shape (center, shoulders, etc.), increase the
integration time.
Note that you do not specify an integration time per wavelength; rather take all wavelengths at each integra-
tion time and use the appropriate spectrogram for the wavelength in question when calibrating.
12. When the spectrogram is done, click the Image tab at the top to view the image. If only “snow” is visible, se-
lect a view in the instrument control menu and change the view to Axial.

13. Click the Analysis tab in the bottom menu, click on each element, and click Align Wavelength.
14. From the Echelle Images selection box, select the Echelle image just taken. Adjust these four parameters
when aligning the wavelength:
• Viewport offset (XY) – location of the view window on the L-PAD detector.
• Viewport height – height of the viewport window (width is fixed).

• Background – includes offset and width for both the left and right side. Adjust by clicking and dragging on
the visual representation, or by adjusting the slider bars.
• Peak – includes peak width and peak offset. Adjust by clicking and dragging on the visual representation,
or by adjusting the slider bars.
Caution: The slider bars for the left background, peak width, and right background settings are the same
color. Setting them in the wrong order causes odd results (e.g., negative peaks). Check this by looking at the
values for each region on the panel to the left of the Echelle image.
15. Use the arrow buttons in the right middle of the screen to adjust the viewport offset. Center the window
around the elemental signal of interest (yellow area). If other elements interfere, adjust the viewport height
(either 1, 3, or 5) to increase discrimination. Once the location is set, click OK below the arrow keys.
16. Set the peak offset and width using these guidelines:
• Left position: set at the peak to the left shoulder of the elemental peak
• Right position: set at the right shoulder of the peak
• Left baseline: set two squares immediately to the left of the peak
• Right baseline: set two squares immediately to the right of the peak
• Beginning and ending of the peak: set at the first and last squares that are noticeably higher than the
baseline.
If the element is in a noisy region, the width and location of the baseline may be adjusted as needed.
17. Repeat Steps 10–16 for each selected element.
18. Once peaks are defined, analysis is ready to proceed. Click on the Sequence tab in the bottom left to create a
sequence. (See Rules for Creating a Sequence).

19. Save the sequence using File > Save Rack.

20. Click Update and verify that the diagram showing the samples matches the samples prepared.
21. Click Run Sequence. Warning: Do not attempt to use any other functions in the software while the se-
quence is running. This may cause stability issues.
Table 1. Suggested approximate integration times per element/wavelength, Alignment Solution 1.

Element (Wavelength) 0.1 s 1s 2s 10 s
Al (308.215) X
Al (396.152) X
Ca (393.366) X
Ca (317.933) X
Mg (285.213) X
Mg (280.271) X
Na (588.995) X
Na (589.592) X
P (213.618) X
P (214.914) X
Ba (493.409) X
Sc (361.383) X
Y (360.073) X
Sr (407.771) X
Sr (421.771) X
Table 2. Suggested approximate integration times per element/wavelength for Alignment Solution 2.
Element (Wavelength) 0.5 s 1s 2s 5s
Fe (238.204) X
Fe (239.563) X
K (766.491) X
K (769.897) X
Mn (257.610) X
Mn (259.372) X
Si (251.611) X
Si (250.690) X
Ti (337.280) X
Cr (283.563) X
Ni (231.604) X
V (292.401) X
Zr (343.823) X
Zr (339.198) X
Zn (213.856) X
Cu (324.754) X
Co (228.615) X
Nb (309.418) X
Ge (265.117) X

Rules for Creating a Sequence

The following rules must be observed when creating a sequence for the ICP:
• Each sample name must be unique (e.g., Drift-1, Drift-2, Drift-3).
• “ – “ (space dash space) in sample names is reserved to indicate replicate runs. A dash without a space is fine.
• Drift(STD)* denotes drift samples. * = wildcard; any value can follow the close parens (e.g., Drift(BHVO-2)-1).
• Blank* denotes a blank sample.
• Use the name of a standard to denote a standard (e.g., BHVO-1, BIR-1, etc.). Standard names can be seen in
the Manage Standards window of the in-house ICP analysis software.
• CV-StandardName* denotes a calibration verification standard. This standard is not included in the instru-
ment calibration.
• Use the LIMS TextID (e.g., PWDR938493) for unknowns. Samples with invalid TextIDs will display in the work-
sheet but will not upload to LIMS. Use the barcode reader to transfer the TextID from the sample label.
• Run a drift sample every 5–7 samples, and begin and end each batch with a drift sample. Values outside of a
drift bracket will not be quantified.
• Run at least 5 standards for calibration. Run one standard as a calibration verification at least 3 times (exclude
from the curve) to determine precision/accuracy of each line.
• Run at least 2 blanks, one at the beginning and one at the end.
• Use a standard that has a high response in all measured lines (and low interference) for the drift solution.
Spikes or artificial solutions can be used/created as needed. Try to use the same drift for an entire expedition
(on a per-method basis).
• Sample order should not be depth-based—randomize samples to prevent data trends from being misinter-
preted.
• A typical sequence is as follows:
1. Blank-1
2. Drift(BHVO-2)-1
3. BIR-1
4. PWDR293984
5. PWDR848484
6. Drift(BHVO-2)-2
7. JGB-1
8. PWDR93984
9. PWDR938394
10. Drift(BHVO-2)-3
11. Blank-2
Reporting Data
After the analysis is complete (see warning above about attempting other functions while the sequence is run-
ning), export the data in a format that the data reduction software can work with.
1. Select the Analysis tab from the bottom of the screen and then select the Report tab at the top of the screen.
2. Select from the tree menu the red folder that contains all the analyses. If certain analyses cannot be selected
(e.g., samples) click on the Analysis > Reporting menu and make sure Samples is checked.

3. Load all lines: Click All > Load, and select the LIMS format definition. Click on Format 1 > Export. Give the file
the same name as the chapter.
Managing Standards
1. Ensure that all standards referenced in the run are already qualified in the LIMS database: in the ICPAnalyzer
software select Manage Standards.

2. The Manage Standards spreadsheet lists the following information:

• Name: name of the standard (the same name used when runs were set up)
• Type: Rock, Sediment, or Liquid
• Reference: authoritative source for standard values
• Description: lithology of the standard
• Sample Number: LIMS sample number for the standard (leave blank if creating one for the first time).
• Standard values: every column after this is a concentration value, with the header at the top of the page
indicating the element/molecule and the unit. If a standard doesn’t have a value for a particular moiety,
then leave the cell blank.
o IMPORTANT!!! At this time, a parsing error occurs for the element oxides and the element ox-
ide column header MUST be formatted as follows: <Element_symbol><space><remainder of
t
the header> [e.g., Al2O3 (%), Fe2O3 (%)]. If this format is followed, the element oxides will be
parsed correctly and the calibration curves for the elemental oxides will be calculated.
3. Add new standard lines by creating a new column header in the spreadsheet. The format is “Molecule (unit).”
Molecule is typically the element unless the values are reported as the oxide, then it is the molecular formula
for the oxide (e.g., Mn O), but note the warning above about the formatting.

4. Add new elements by adding the desired lines and leaving the sample number field blank.
5. Values can be changed for existing standards (but a full history of previous values and changes is kept).
6. When all values are entered, click Save—the data will be updated and the screen will close.
7. Restart the software for standard changes to take effect.
Analyzing a Run
1. Select Open, and browse to the CSV file that was exported from the ICP software (see Reporting Data). The
software will walk you through the following required steps (2–6):
• classify samples
• check drift
• check calibration
• generate the data spreadsheet
• upload data to LIMS

2. Classify Samples: presents software-determined sample classifications. The sample

type can be altered; however, it cannot be changed to standard. If the software
recognized it as a standard it would have been correctly classified. To use a sample
as a standard you must enter it as a standard (see Managing Standards). A stand-
ard can be changed to CV to use as a calibration verification (it will not be included
in the calibration).
3. Check Drift: view the drift on a per-line basis using the menu to control which lines are displayed. Hover over a
point to see information about that point.
4. Check Calibration: displays the calibration information for each line. Changes made in this window will be car-
ried through to the final calculations. In this window you can:
• Reject standard measurements from the calibration (enter a reason for the rejection).
• Determine if drift corrections are used (on a per-line basis).
• Reject an entire line.
• Choose either a first- or second-order curve fit.
• View the calibration, regression, and correlation.

5. Generate Spreadsheet: generates an Excel sheet that displays the data reduction values (Loading, Transposi-
tion, Blank Correction, Drift Correction, Calibration, Calculation, Averaging Calculations) as a labeled worksheet
in the final output. The final data is also marked as either the calculated average value, “bdl” (below detection
limit, in this case < 0), and marked with red background if the value is higher than the highest standard or lower
than the lowest standard (for a given line).
6. Upload Data to LIMS: Once the spreadsheet has been generated and the data looks acceptable, click Upload to
LIMS. This uploads all the data to LIMS, as well as generates peak profiles (graphical plots of the peak window)
for each element.

Methods
Three primary sample matrices are analyzed with the ICP:
• Solids (sediment and hard rock)
• IW Majors
• IW Minors
Solids Method
This method applies to matrices of rock or sediment samples. The samples are fused with lithium metaborate at a
1:4 ratio (sample:fluxing agent) and then dissolved in a 10% nitric acid solution for a total dilution factor of 1:4000
(m/v).
See the ICP-AES Hard Rock Preparation User Guide for specific instructions on preparing solid samples for ICP-AES.
This method can be used to analyze for any elements/wavelengths desired, typically those shown in Table 3.
Table 3. Elements analyzed by the ICP-AES solids method.
Element Measurement Unit Element Oxide Measurement Unit

Zn ppm CaO wt%
Zr ppm K2O wt%
V ppm MgO wt%
Cr ppm Al2O3 wt%
Ba ppm Fe2O3t wt%
Sc ppm SiO2 wt%
Ni ppm P2O5 wt%
Cu ppm TiO2 wt%
Co ppm MnO wt%
Sr ppm Na2O wt%

The major elements are reported in weight % (mass of oxide)/(mass of the sample) of the respective oxide, with
iron being normalized to Fe2O3 (the designation Fe2O3t is used, where t = total). The minor elements are reported
in units of ppm (mass of element/mass of sample).
Table 4 provides conversion factors between oxide and elemental concentrations (multiplicative factors; to con-
4
vert SiO2 to Si, multiply by 0.4675). The conversion from ppm to weight % (part per hundred) is division by 10 .
Table 4. Conversion factors between oxide and elemental concentrations.
Major element oxide Conversion factor Element

SiO2 0.4675 Si
Al2O3 0.5293 Al
Fe2O3 0.6994 Fe
FeO 0.7773 Fe
MnO 0.7745 Mn
TiO2 0.5995 Ti
CaO 0.7143 Ca
Na2O 0.7419 Na
K2O 0.8301 K
MgO 0.603 Mg
P2O5 0.4365 P
Flux-Fusion Preparation of Rocks

A typical flux-fusion hard-rock preparation procedure includes the following steps (see the Hard Rock ICP Sample
Prep guide for information on performing these steps):
1. Cutting the samples to size
2. Cleaning samples on a diamond wheel
3. Cleaning samples in methanol/DI
4. Drying samples
5. Crushing samples in the X-Press
6. Grinding samples in the shatterbox
7. Determining loss on ignition (LOI)
8. Making sample beads
Sample Dissolution and Dilution

Wear gloves when dissolving and diluting the sample bead for ICP analysis.
Dissolving the Sample Bead
1. Prime the 25 mL dispensette on top of the 1 L bottle to get rid of air.

2. Add 50 mL of 10% nitric acid solution to a 125 mL Nalgene wide mouth bottle by dispens-
ing two 25 mL aliquots from the 25 mL dispensette.
3. Drop the sample bead in the 125 mL Nalgene bottle, close the lid, and agitate with the
wrist-action shaker for 1 hr to dissolve the bead in the acid. Be sure to transfer all of the
glass (it may have chipped).
Filtering/Diluting the Sample
1. Using a new or acid-washed 20 mL syringe, extract 20 mL of solution at a time

from the 125 mL bottle (you can put the syringe directly in the 125 mL bottle).
2. Filter the 20 mL of solution extracted through a 0.45 µm Acrodisc into a clean

acid-washed 60 mL Nalgene wide mouth bottle.
Repeat this extraction process until all of the solution has been filtered.
Place the syringe in a tube for later acid-washing.
3. Pipette 1.25 mL of the filtered solution into a 20 mL scintillation vial and dilute it
with 8.75 mL (dispensed with 25 mL dispensette) of bead dissolution solution
(10% HNO3/10 ppm Y).

Characteristics of Flux Fusion Solutions

• Flux-fusion solutions become unstable over time; major and trace elements precipitate or form a gel, which is
not always visible (since it is clear), so inspect solutions prior to analysis.
• Discard the solution when it becomes unstable; the gel will strip dissolved trace metals from the analyte.
• The stability of a solution is proportional to the dilution factor and acid content and inversely proportional to
the SiO2 content. A dilute solution is more stable than a concentrated one.
• A solution with a 10% HNO3 matrix is more stable than one prepared at 1% HNO3.
• A flux-fusion solution enriched in SiO2 is likely to be more unstable than a basalt or shale solution. Analyze
samples on the ICP shortly after they are dissolved, ideally within 48 hours.
Interstitial Water Majors Method

This method applies to water samples in a 2% nitric acid solution at a 1:100 (v/v) dilution factor. Pore water and
rhizon samples are typically analyzed for the constituents Na, Ca, Mg, and K. Values are typically expressed in units
of millimoles per liter (i.e., millimolar, mM).
Sample Preparation
1. Acidify pore water, rhizon, or other aqueous samples with 5–10 µL of concentrated trace metal grade nitric
acid and keep in refrigerated storage in a sealed container until ready for analysis.
2. Pipette 100 µL of sample into a sample tube.
3. Using a dispensette, add 9.9 mL of IW matrix solution. This solution is ready to be analyzed
directly in the ICP.
Interstitial Water Minors

Method
This method applies to water samples in a 2% nitric acid solution at a 1:20 (v/v) dilution factor. Typically, B, Ba, Li,
Mn, Fe, and Sr are analyzed. Concentrations are typically reported in micromolar (µM).
Samples are usually the same split as is used for majors. As with the majors method, efforts are made to duplicate
sample preparation for both standards and unknowns.
The same IW matrix solution used for IW Majors is also used for IW Minors.

Sample Preparation
1. Acidify pore water, rhizon, or other aqueous samples with 5 µL of concentrated trace metal grade nitric acid
and keep in refrigerated storage in a sealed container until ready for analysis.
2. Pipette 500 µL of sample into a sample tube.
3. Using a dispensette, add 9.5 mL of IW matrix solution. This solution is ready to be analyzed directly in the ICP.
Quality Assurance/Quality Control
Sediment/Rock Samples
Solid Standards
ICP-AES is a comparative analytical technique, in that the instrument’s response (measured in intensity) is calibrat-
ed against standards in which the concentrations of the various elements are known. For rock analysis, calibration
is best achieved through comparison to internationally recognized and approved Standard Reference Materials
(SRMs). BIR-2, BHVO-2, and BCR-2 are typically included in every batch to allow for inter-run consistency checks.
Figure 1. Approved SRM Sediment/Rock Standards.
Other standards are selected by the science party based on the lithology of the samples being analyzed. Care
should be taken to try and match the matrix (base lithology) of the SRMs to that of the samples, as well as to en-
sure that the calibration range (least and most concentrated SRMs) brackets the expected range for the samples.
Figure 2. Other Solid/Rock Standards Available in the Chemistry Laboratory.
Commonly used standards are listed in the ICP Analysis software, and values can be viewed/reported from there.
As of 8/20/2010 standards with values in the software are include in Table 5.

Table 5. Standards with certified values in the software.

Standard Material
BCR-1 Basalt
BCR-2 Basalt, Columbia River
BHVO-1 Basalt, Hawaiian volcanic
BHVO-2 Basalt, Hawaiian volcanic
BIR-1 Basalt
DNC-1 Diabase
JA-3 Andesite
JG-2 Granite
JGB-1 Gabbro
JR-2 Rhyolite
LKSD-1 Lake sediment, Canadian shield
MAG-1 Marine mud
NBS-1C Limestone
RGM-1 Rhyolite
SCO-1 Cody shale
STM-1 Syenite
Solids Drift Solution

A drift solution is measured on the ICP multiple times during an analytical run to account and correct for instru-
mental drift. The drift solution must be of the same matrix as the samples and standards that are being analyzed.
For solids, typically, one of the SRMs will be used for a drift, though the only requirement is that the drift has a
strong response for the elemental lines being monitored. Standards used as drift cannot be used for any other cal-
culations (calibration, precision, etc.), as the drift calculations artificially normalize these results—so in the case
that a standard is used for a drift solution it should also be run in an additional aliquot(s) as a standard.
Figure 3. Drift Sample for Solids.

Solids Rinse Solution

It is necessary between each standard and each sample to rinse the sample uptake tubing and torch glassware to
remove carryover from the previous standard or sample. Rinsing also helps combat clogging of the nebulizer. For
LiBO2 matrix, a 10% nitric acid rinse solution is used. Rinse time should be set for a minimum of 60 s.
Tips for Checking Data Quality of Solid Samples
• Check the total major element wt%. Reasonable data typically totals 98.5–101.5 wt% when ignited powders
are used.
• Check the blanks for high background intensities. High background can be due to contamination or memory
effects.
• Compare drifts and BHVO-2 intensities; they should be very similar. If they aren’t, the data may be skewed
toward high or low totals.
• Check the drift intensities over the length of the run. They shouldn’t change much more than 10% in a typical
run; the instrument is usually very stable.
• The drift correction in the spreadsheet is based on the assumption of linear drift (over short periods of time),
so rapid or high-amplitude variations in intensity will cause high variability in the run and implies something
has gone wrong with the instrument.
Interstitial Water Majors

IW Majors Standards
Serial dilutions of IAPSO standard surface seawater are used to calibrate the ICP for major dissolved constituents.
IAPSO concentrations of 120%, 100%, 75%, 50%, 25%, 10%, 5%, 2.5%, and 0% are made, each at a 1:50 dilution.
The process for making each standard is designed to mimic the sample preparation as much as possible. The
standards are made by mixing IAPSO with 18 MΩ reagent water and 4% HNO3 to create a stock solution of the
desired amount. Use Table 6 as a guide for creating 30 mL of each stock solution (store in a 30 mL Nalgene bottle).
Table 6. Making IW Majors Stock Solutions.

Standard conc. (%) Volume IAPSO (mL) Volume DI Water (mL) Volume 4% HNO3 (mL)
120% 36.0 0.0 24.0

100% 30.0 0.0 30.0
75.0% 22.5 7.50 30.0
50.0% 15.0 15.0 30.0
25.0% 7.50 22.5 30.0
10.0% 3.00 27.0 30.0
5.00% 1.50 28.5 30.0
2.50% 0.750 29.25 30.0

Figure 4. Flowchart for Making the Standard and Sample Dilutions.
Running IW Majors IAPSO Standard Curve on the ICP

1. Pipette 200 µL of each level of the IW Majors standard curve into a sample tube.
IW Majors Drift Solution
Use the 100% IAPSO standard as a drift solution for majors analysis. Make a large dilution (enough for 10 mL for
each drift sample + 10%) and use aliquots of this dilution. For example, if there are 10 drift solutions in the run,
make 110 mL of drift solution in a large acid-washed beaker then pipette 10 mL (volume does not have to be exact)
of this drift solution into each of the drift test tubes.
IW Majors Blank
An analytical blank is composed of 100 µL of 18 MΩ water and 9.9 mL of IW matrix solution.
IW Majors Rinse Solution
Use a rinse solution of ~3% trace metal grade nitric acid. The strength should be slightly more concentrated than
the matrix. Mix enough rinse solution to last through the run (more is fine).

Interstitial Water Minors

IW Minors Standards
A synthetic set of standards are created from various multielement standards. A 100% stock solution of the stand-
ard is prepared, dilutions of 100%, 75%, 50%, 25%, 10%, 5%, and 2.5% are typically created in acidified synthetic
seawater (ASSW), and then the standards are subject to the same dilution procedure (using the same pi-
pette/dispensette as the samples).
Standard dilutions are stable indefinitely and should be stored at 4°C. Actual element concentrations in the stand-
ard curve are as shown in Table 7.
Table 7. Element concentrations in the IW minors standard curve.
Standard B (µM) Ba (µM) Fe (µM) Li (µM) Mn (µM) Si (µM) Sr (µM)
Concentration
100% 1387.5 36.41 17.91 288.1 54.6 1068.2 228.3
75% 1040.6 27.31 13.43 216.1 41.0 801.1 171.2
50% 693.7 18.20 8.95 144.1 27.3 534.1 114.1
25% 346.9 9.10 4.48 72.0 13.7 267.0 57.1
10% 138.7 3.64 1.79 28.8 5.46 106.8 22.8
5% 69.4 1.82 0.895 14.4 2.73 53.4 11.4
2.5% 34.7 0.910 0.448 7.20 1.37 26.7 5.71
1% 13.9 0.364 0.179 2.88 0.546 10.7 2.28
0% 0 0 0 0 0 0 0
Figure 5. IW Minor Standard Curve Workflow.

Running IW Minors Standard Curve on the ICP

1. Pipette 500 µL of each level of the IW minors standard curve into a sample tube.
IW Minors Drift Solution
Use the 100% IW Minors standard solution as a drift solution for minors analysis. Make enough volume for 10 mL
for each drift sample +10% and use aliquots of this dilution. For example, if there are 10 drift solutions in the run,
make 110 mL of drift solution in a large acid-washed beaker and pipette 10 mL (volume does not have to be exact)
of this drift solution into each of the drift test tubes.
IW Minors Blank
The analytical blank is composed of 500 µL of the SSW solution and 9.5 mL of IW matrix solution.
IW Minors Rinse Solution
Use a rinse solution of ~3% trace metal grade nitric acid. The strength should be slightly more concentrated than
the matrix. Mix enough rinse solution to last through the run (more is fine).
Data Reduction
Data reduction is handled by the ICP analysis software, which generates a spreadsheet showing each step of the
process.
The instrument software, SALSA, supplies a list of data from the instrument. For quantifying concentrations, the
primary values are intensity, element line, and sample identification—everything else is just metadata to qualify
those pieces.
The intensity derived from the software is not based on integration or a Gaussian curve fit. It is based on the aver-
age value of the intensities under the defined peak area.
If the series of intensities (from 1 to 15) are denoted as I1…I15, then the calculation is performed as
Background = Average (LBackgroundStart…LBackgroundStop + RBackgroundStart…RBackgroundStop)
ICorrectedn = In – Background
Intensity = Average(ICorrectedPeakLeft … ICorrectedPeakRight )
This makes it important to keep the peak width as narrow as possible when setting up a run.
Figure 6. Peak Background and Intensity.
Software Data Reduction

There are 6 distinct steps taken in the data reduction performed by the ICP Analysis software:
$ Result Transposition
$ Drift Correction
$ Blank Correction
$ Calibration
$ Calculation
$ Averaging

Result Transposition
The result data from the instrument is pivoted to provide a more useful, information-dense display. In the original
data each row contains intensity for one wavelength of one element. In the transposed data set each row corre-
sponds to one sample and each column corresponds to one wavelength. This is worksheet #2 available in the Excel
output from the analysis software.
Drift Correction
In this step the drift values are used to normalize the data set to the initial conditions. On a per-line basis, the drift
values are each normalized (divided) by the value for the first drift sample to provide a deviation factor at each
point.
A correction factor is then derived based on the distance of each sample from the drift values that bracket it and
the deviation factor of those drift samples. Drift is assumed to be related to time, so the closer a value is to a drift
sample the more weight it is given. Drift factor can be calculated as follows:
• DD (drift distance) = (drift 2 position – drift 1 position)
• Drift1Weight = Drift1Factor * [DD – (sample position – drift 1 position)]/DD
• Drift2Weight = Drift2Factor * [DD – (drift 2 position – sample position)]/DD
• Factor = Drift1Weight + Drift2Weight
Example Drift Correction
Take for instance the following run fragment
The drift values show a ~10% drift every 5 samples. Choosing the first drift measurement to normalize to is arbi-
trary—as long as all the drifts are normalized to one of the values the results will be the same since the correction
takes the form of a factor.
Taking the first drift interval from Drift 1 to Drift 2 and applying the calculations to the first sample (STD 1, position
2), we get the following values:
• DD (drift distance) = 5 – 1 = 4
• Drift1Weight = 1 × [4 – (2 – 1)]/4 = 1 × ¾ = 0.75
• Drift2Weight = 1.1 × [4 – (5 – 2)]/4 = 1.1 × ¼ = 0.25 × 1.1 = 0.275
• Factor = 0.75 + 0.275 = 1.025
Position Drift Factor
1 1
2 1.025
3 1.05
4 1.075
5 1.1
6 1.12
7 1.14

Position Drift Factor

8 1.16
9 1.18
10 1.2
We then take each of these factors on a per-sample, per-line basis and divide the original intensity by the calculat-
ed factor to determine the corrected intensity:
Position Sample Corrected Intensity
1 Drift 1 100.00
2 STD 1 82.93
3 Blank 1.90
4 Samp 1 104.19
5 Drift 2 100.00
6 Samp 2 85.71
7 Samp 3 72.81
8 STD 2 106.90
9 Samp 4 46.61
10 Drift 3 100.00
Blank Correction
Drift-corrected blank values are averaged (generally there are 2 blanks, one near the beginning and one near the
end of the run), and then on a per-line basis subtracted from each sample/standard. For example, given the follow-
ing drift corrected intensities:
1 Drift 1 100.00
2 STD 1 82.93
3 Blank 1 2.0
4 Samp 1 104.19
5 Drift 2 100.00
6 Samp 2 85.71
7 Samp 3 72.81
8 STD 2 106.90
9 Blank 2 4.0
10 Drift 3 100.00
Example Blank Correction
The average blank value is (4.0 + 2.0)/2.0 = 3.0. This value is subtracted from all drift-corrected intensities for the
same line, giving the following results:
1 Drift 1 97
2 STD 1 79.93
3 Blank 1 –1
4 Samp 1 101.19
5 Drift 2 97
6 Samp 2 82.71
7 Samp 3 69.81
8 STD 2 103.90
9 Blank 2 1

10 Drift 3 97
Calibration
The drift- and blank-corrected intensities are used to create a series of calibrations:
Figure 7. Calibration.
Each replicate (averaging is not done until the final step) is plotted as intensity (X-Axis) vs. Standard Concentration
(Y-Axis) (from the Standards Manager, i.e., LIMS). A first- or second-order best-fit regression is determined using
the least-squares method. This method finds the equation (constrained by first or second order) at which the
standard error is minimized. The vertical deviations are squared and summed, and the regression which gives the
lowest total error (deviation) is chosen.
Figure 8. Calibration Regression.
Calculation
The regression provides a function that transforms a drift- and blank-corrected intensity into a concentration on a
per-line basis. This function is applied to each intensity to create a corresponding concentration for each meas-
urement (replicates included). This data is represented in the All Measurements sheet.
Averaging
Replicates (typically 3 per sample) are averaged to a final concentration per sample, per element and shown in the
Final Measurements worksheet. Additionally, a warning is included (flag in LIMS upload or red cell backgrounds in
the worksheet) if the calculated values are lower than the lowest standard or higher than the highest standard for

a given line. This means that the concentration calculated extrapolated based on the data, but there is no standard
to confirm the validity of the extrapolation.
Uploading to LIMS
No data reduction occurs in this portion of the process—only the data in the spreadsheet is uploaded. A profile
plot (a plot of wavelength vs. intensity for each of the 3 replicates on a per-sample, per-line basis) is generated and
uploaded.
Figure 9. Example Profile Plot for Zinc.
Software
The ICP Analysis software is an in-house piece written in C# against the 3.5 version of the .NET runtime. Source
code is located at https://shiptest.ship.iodp.tamu.edu/svn/jr/NET/ICPAnalyzer (ship) and
https://build.iodp.tamu.edu/svn/jr/NET/ICPAnalyzer (shore).

Windows/XP, Windows/Vista, and Windows/7 in both x86 and x64 architectures are supported. Deployment is via
Click Once install, with the ship install location at http://web.ship.iodp.tamu.edu/tasapps/icp/.
If a developer is deploying to a location other than the ship the publish location should be changed to prevent the
querying of ship resources. Webserver default should be changed, this is located in the properties for the ICPAna-
lyzer project. Server location can be configured on a per-use basis.
For development work the FarPoint 4.0 library or newer is required to be installed on the development machine.
Libraries are included in the deployment so the end users do not need anything installed.
This software references the IODPutils, ZedGraph, and LIMS libraries. It makes use of resteasy-lims-webservices
and asman-webservices. This software allows the following interactions with LIMS:
• Creation of a subset of standards (children under the rock, sediment, or liquid chemistry categories)
• Addition, modification, and removal of certified standard values for new and existing standards under the
same scope as above (that is, modification of the EXPECTED analysis types for standards it can manage).
Note that no data is deleted or overwritten, when a standard value is edited the old value is canceled and
a new one logged – the change is fully qualified.
• Creation of new ICPAES (for the purpose of logging data)
• Logging of results under the ICPAES analysis created (and only under newly created ICPAES analysis)
This software has the following interactions with ASMAN:
$ Stores Excel files representing the original, reduced, and final data (LIMS asman prefix: excel)
$ Stores the raw data files obtained from the instrument (LIMS asman prefix: raw)
$ Stores an image of the drift calculations from the run (LIMS asman prefix: drift)
$ Stores an image of the peak profile for the measurement (LIMS asman prefix: profile)
Expected ASMAN space usage is ~7 MB per test, with 0.5–2 tests per hole being typical.
LIMS Definitions
This software populates the EXPECTED analysis (standard management – just one of many applications using this)
and is solely responsible for the ICPAES analysis. A valid LIMS username and account is required to upload data
with this software. By default, it will log on as guest/guest and prompt for an elevation of privileges when upload-
ing data. Table 8 lists the components in the ICP Analysis, properties, and descriptions.
Table 8. ICP-AES LIMS Components.
Component Alias Order Description

element_name Element Name 1 Name of element found in a sample
wavelength Wavelength 2 Wavelength used to measure concentration of an element found

in a sample (nm)
calibrated_name Name 3 Name of element or molecule actually calibrated
concentration Concentration 4 Concentration
profile_asman_id Peak Profile Plot 5 Plot of peak profile (intensity vs. wavelength)
calibration Calibration (Regres- 6 Regression (linear or quadratic) for the given line
sion)
correlation Correlation 7 Fit quality of calibration regression (r-squared)
in_calibration_range Value in calibrated 8 Indicates if this value falls within the highest and lowest calibra-
range tion standard
used_in_cal Calibration Stand- 9 Indicates if this sample analysis was used in construction of the
ard calibration

Component Alias Order Description

excel_asman_id Excel Data Reduc- 10 Excel data file containing the data reduction steps
tion
drift_asman_id Drift Plot 11 Graphical representation of the drift
raw_asman_id Raw Data File 12 Original data file from the instrument
batch_id Batch ID 17 Identifier for the analytical run; allows calibration and calibration
verification runs to be linked to samples
drift_corrected Drift Corrected 27 Indicates if the measurements are based on drift-corrected inten-
sities
drift_filename Drift Graph File- 29 Original filename of the drift graph
name
profile_filename Filename of profile 31 Filename of profile plot
plot
method Method name 32 Name of method used to perform analysis
corrected_intensity Corrected Intensity 33 Intensity after blank/drift corrections
raw_intensity Uncorrected Inten- 34 Uncorrected Intensity

sity
view Radial/Axial 36 Indicates the view used to perform thisi analysis
excel_filename Filename of Excel 39 Original filename of excel data reduction file

file
raw_filename Raw Filename 41 Original filename of raw file
Troubleshooting
The following common problems are addressed in this section:
$ Instrument Will Not Light
$ Cannot Select Samples to Report
$ Interlocks Light Turns on after Plasma Ignition
$ Alignment Image Does Not Give Good Peaks/Intensities Too Low
Instrument Will Not Light

1. Ensure that no interlock lights are lit on the Interlock screen except Air knife. This indicator will be red until
the Ar gas is flowing; this is normal.

2. Ensure that the torch is not chipped or flaking and that the distance from the outer wing of the view flange is
not greater than 1 cm. A larger distance will give better sensitivity and torch longevity but may cause issues
with torch lighting, especially with more concentrated matrices.
3. Ensure that nebulizer is not clogged and drain is not clogged.
Cannot Select Samples to Report

1. Make sure that you are on the Analysis > Report screen.
2. Make sure that the sample types you wish to report are selected under Analysis > ReportType.

Interlocks Light Turns on after Plasma Ignition

This is due to a pressure drop due to flow demand. Turn up the regulator slightly until the gauge reads 90 psi. The
light should go away.
Alignment Image Does Not Give Good Peaks/Intensities Too Low

It is likely there is an issue with the sample induction pathway. Do the following:
1. Check the nebulizer for clogs or restrictions.
2. View the spray chamber when in operation—is it fogging up properly/can you see a sample transport stream
to the torch? (If not it indicates a nebulizer issue)
3. Replace the black peristaltic pump tubing and ensure proper tension of the pump arms.
4. If you adjust anything with a large impact on sample uptake, you need to run the alignment procedure under
Running a Method.
Safety Considerations
The primary safety considerations for these procedures are physical, chemical, and heat based. Personal protective
equipment is required for some of the procedures described in this manual. Precautions should be taken in the
following areas:
 Acid dilutions: the samples are digested and diluted in a 10% nitric acid solution.
 Eye protection should be worn at all times when working with samples.
 Nitrile gloves should be worn when working with sample digests.
 Technicians should be aware of the location of spill control/neutralization items.
 Glassware in the ICP: the torch tubes are extremely hot after the plasma has been ignited.
References
Bacon, S., Culkin, F., Higgs, N., and Ridout, P., 2007. IAPSO standard seawater: definition of the uncertainty in the calibration
procedure, and stability of recent batches. J. Atmos. Oceanic Technol., 24(10):1785–1799. doi:10.1175/JTECH2081.1
Gieskes, J.M., Gamo, T., and Brumsack, H., 1991. Chemical methods for interstitial water analysis aboard JOIDES Resolution.
ODP Tech. Note, 15. doi:10.2973/odp.tn.15.1991
Millero, F.J., Feistel, R., Wright, D.G., and McDougall, T.J., 2008. The composition of Standard Seawater and the definition of the
Reference-Composition Salinity Scale. Deep-Sea Res., Part. I, 55(1):50–72. 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 inductively coupled plasma–atomic 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 Introduction to the Chemistry of the Sea. Upper Saddle River, NJ
(Prentice Hall).
th
Skoog et al. 1992 Fundamentals of Analytical Chemistry 7 Ed.
th
Skoog et al. 1997 Principles of Instrumental Analysis 5 Ed.
Summerhayes, C.P., and Thorpe, S.A., 1996. Oceanography An Illustrated Guide, Chapter 11, 165–181.

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International Ocean Discovery Program

Leeman Prodigy ICP-AES:

Author(s): D. Houpt (original version C. Bennight)

Purpose and Audience

In This User Guide

Topic See page…

ICP-AES User Guide 1 6 January 2014

Methods in this Manual

ICP-AES User Guide 2 6 January 2014

Apparatus, Reagents, & Materials

Figure 1. Teledyne-Leeman Prodigy Dual-View ICP-AES System.

Figure 2. Dual Balance System (Mettler-Toledo XS204).

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Figure 3. Dual Microbalance System (Mettler-Toledo XP56).

Figure 4. Burrell Wrist Action Shaker Model 75.

Figure 5. Fisher Muffle Furnace.

Figure 6. Water Chiller.

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All Methods: Personal Protective Equipment

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Reagents for Interstitial Waters

120% 36.0 0.0 24.0

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• IW Minors stock (100%):

Minor element Volume 1000 ppm stock (mL)

Reagents for Sediments/Hard Rocks

ICP Alignment Solutions

General ICP Operation

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Starting the instrument (igniting the plasma)

2. a. Turn on the Ar flow.

IMPORTANT! Purge the optical chamber with Ar at 0.1 L/min

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3. Start the control software (SALSA) on

4. When the prompt appears asking if the camera has

The autosampler will continue to initialize, and after

5. If the Maintenance tab is red, click on the tab to see

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6. Engage the peristaltic pump tubing:

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8. Ensure that the condition of the O-rings for the nebulizer

9. Ensure that the peristaltic tubing is connected to the proper in-

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11. Select Instrument Control > Auto-Start.

Shutting Down the Instrument

4. Select Extinguish in the software instrument control

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6. Shut down SALSA.3

7. Shut down the ICP (but leave Ar flowing).

1. Select the method to run from

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a. click Element Selected,

5. Select an Hg line from the window, and click Peak Plasma.

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8. Check the Total intensity of the alignment solution. If it is within an or-

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17. Repeat Steps 10–16 for each selected element.

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19. Save the sequence using File > Save Rack.

Table 1. Suggested approximate integration times per element/wavelength, Alignment Solution 1.

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