Digestion Method

Digestion solution: 10% HF/50% HNO3 (v/v) higher concentrations of HNO3 have
no effect on particulate digestion effectiveness, but can increase filter blank.
2ml should be sufficient for a 47mm filter.

0.2ml HF (Con) +
1.0 ml HNO3 +
0.8ml DI Water
= 2ml
Close cap tightly and place on Teflon hotplate 130 degC for 4 hours we dont
have screw lids for these so reflux for longer. It should be apparent when all the
material has dissolved.
After cooling collect all drops at bottom of vial by tapping. Dry down the solution
and carefully watch for ~ 5ul of solution remaining, i.e. not burnt and crispy. Add
100ul conc HNO3 and dry down again to ~5ul droplet (to remove any residual
HF).
CRM
50mg GBW07315
Anything organic/more appropriate in the CRM cupboard Gangi?
Blanks
(we have 2 or 3 blanks already in the samples).
Sample Volume
Take up samples by washing down the sides of the vials in 14ml 5% HNO 3 (leave
over night to dissolve all solutes) and decant into pre acid washed 15ml sample
tubes with stoppers.
Analytes.
Order of importance: Fe (!) Rare Earth Elements, Al, Transition metals + the
usual elements.
Based on a rough estimate of Fe concentration in loch Etive particulate material
from Tims REES program, the conc of a 14ml solution will be between 0 and
3000ppb (mean ~600ppb).
ICPMS analysis 1
3ml taken from sample In and Rh added (dilution factor applied to final conc
calc) Direct measurement of solution 0 100ppb with calibrator concentrations
increased at the low end 0-10ppb (upper standards to be removed where
appropriate off line) using 5% matrix match standards. Target analyte any low
conc Fe and REE. This will also give us rough Fe concs for dilution calculations
(step 2 below). Monitor counts on Fe57 normal mode and Fe56 collision cell to
remove ArO interference. Tune collision cell on Fe56 for maximum stability vs
intensity. Tune out the nitric blank Fe56 signal (mostly ArO) by increasing
collision cell gas. REE measured in standard mode.
If the Fe signal from samples is massive do a second run of these samples in
high resolution mode to reduce the number of counts and get a better idea of
conc for analysis 2.

Potential problems High salt content on filters. If the samples were not DI rinsed
may need to think about doing this prior to digestion?
ICPMS analysis 2. Most important.
Take <1 ml and as appropriate dilute to get ~50ppb Fe in final sample (~3ml) for
analysis. Adding internal standards may not be possible if all the vials have wildly
different volumes. We will see it may be possible depending on the concentration
range. Suggest adding more check standards (with In and Rh) to sample run
which will monitor instrument drift, but not matrix effects. Take three samples
with high conc Fe and make a second sample and spike with In and Rh to monitor
internal standard recovery.
ICPMS analysis 3. As appropriate.
Subsequent dilution to obtain any other analytes within the 100 ppb range
ICPOES
~10ml sample will remain for direct ICPOES analysis.
Fe and Al most important (but do the usual run).
Hopefully a few samples will have high enough Fe that we can compare OES Fe
with MS Fe (that has an isobaric interference).
The Al will give us a lithogenic signal if high enough conc.