PROCEDURE: 50 μg/L Ga goethite adsorption experiments (pH = 7)

Summary:
Experiment [Ga], Adsorbent Ga/adsorbent pH Duration,
ug/L (wt. ratio) day
GT-pH7 50 Goethite 1500 7 7
These experiments will test Ga adsorption on goethite at pH = 7. This procedure will be applied
on other minerals. Procedure sections A, B, C, D will be done consecutively for each experiment.
This experiment has 3 triplicates and two controls (one with goethite: Blk-GT, one without
goethite: Blk-NO GT) in 500 mL bottles.
pH = 7 Ga stocks (50 μg/L Ga, 0.01M NaCl) will be added to the 3 triplicate bottles and Blk-NO
GT. Blk-GT will only have 0.01M NaCl solution with no Ga. A separate tube (15 mL) will contain
only the acidified Ga stock sample.

Acid washed labware and chemicals

• 2L HDPE bottle: 1
• 500 mL HDPE bottles:10→ 5(experiment) + 5(filtrate)
• 10 mL HDPE bottles: 5
• 15 mL centrifuge tubes: 1
• Syringes and filters: 10
• 1L volumetric flask: 1
• 500 mL volumetric flask: 1
• Solutions for pH adjustment: 1M NaOH, 1M HCl
• Thermo-Scientific pH meter
• Sartorius (or other brand) scale (>1kg capacity)
• Precision balance

A) Rinse solution and tubes

1) Label 5 empty 50 mL centrifuge tubes (3 triplicates, 2 blanks) with the sample name on
both tube body and cap. Name the triplicates GT-A, GT-B, GT-C.
2) Name the blanks Blk-GT, Blk-NO GT. Use these experiment IDs for the remainder of this
procedure. Weigh & record the masses of the tubes with cap on.
3) Using a metal spatula, weigh ~0.017xx g goethite using weighing paper, add into triplicate
tubes and Blk-GT. Re-weigh the tubes with goethite in them. Record the masses.
4) Weigh and label a 2L HDPE bottle for the pH = 7, 0.01M NaCl solution. Weigh ~1.17 g
NaCl using a tared, clean centrifuge tube, record the mass and add to the bottle.
5) Fill a 1L volumetric flask to the mark with MWQ, then pour about 40 mL of this MQW
into the centrifuge tube to rinse off any salt residue, then pour the solution in the 2L HDPE
bottle. Pour the rest of the MQW in the volumetric flask into the 2L HDPE bottle.
6) Using a 1L volumetric flask, add another 1L MQW into the 2L HDPE bottle which now
contains 2L of 0.01M NaCl solution. This solution will be used for rinse, Blk-GT and
future experiments.
7) Adjust solution in 6) to pH = 7 using 1M NaOH or HCl. Record the pH value.
B) Mineral rinse
8) Carefully pipette 30 mL pH 7 adjusted 0.01M NaCl solution from Procedure A) into the
triplicates and Blk-GT 50mL centrifuge tubes. Manually swirl, then let rest for 15 minutes.
9) Load tubes into centrifuge, ensuring symmetrical loading. Centrifuge at 4500 RPM for 15
minutes.
10) Always calibrate the pH meter the day you will use it. Measure and record the pH for
GT-A and both blanks to observe pH change. Clean and dry the pH probe thoroughly with
MQW in a wash bottle and 500mL rinse bottle before and after measuring each sample.
11) Discard the supernatant rinse solution from the tubes to a waste container and discard.

C) Preparing Blk-GT control solution

1) Label a 500 mL bottle for Blk-GT, weigh and record mass.
2) Pour pH 7 0.01M NaCl solution prepared in the Procedure A) into a 500 mL volumetric
flask to the mark.
3) Into the Blk-GT tube, pour about 30 mL of the pH adjusted NaCl solution from Procedure
A). Manually shake vigorously until the mineral powder is totally reincorporated into the
solution with no clumps. Transfer this solution containing the mineral into the 500 mL
bottle prepared in Step 1). Use the solution in the volumetric flask to rinse the centrifuge
tube to ensure that the entire mineral powder is transferred into the 500 mL HDPE bottle.
4) Pour the rest of the pH 7 0.01M NaCl solution into the 500 mL HDPE bottle. Weigh and
record mass.
5) Blk-GT control solution can be sealed with Parafilm and is now done.
The triplicates will also be transferred to their respective 500 mL bottles after being
homogenized with the Ga stock solution prepared in D).

D) pH = 7, 50 μg/L Ga stocks (Ga + NaCl)

1) Clearly label a 2 L HDPE bottle for the Ga stock. Weigh and record the mass.
2) Weigh and record mass of ~1.17 g NaCl using a tared, clean centrifuge tube.
3) Fill a 1L volumetric flask to the mark with MWQ
4) Pour about 40 mL of this MQW into the centrifuge tube to rinse off (dissolve) any salt
residue, then pour the solution in the 2L HDPE bottle. Repeat this step as needed to make
sure NaCl is completely dissolved.
5) Pour the rest of the MQW in the volumetric flask into the 2L HDPE bottle.
6) Using a 1L volumetric flask, add another 1L MQW into the 2L HDPE bottle which now
contains 2L of 0.01M NaCl solution.
7) Tare a clean 7 mL Teflon vial with the cap. Remove the vial from the scale and pipette 0.1
mL (100 μL) of single element Ga ICP standard into the vial. Weigh and record mass.
8) Pour Ga ICP standard into solution prepared in Step 6). You should be able to pour this
into the 2 L bottle as a single drop with no residue left. If there is residue in the vial, pipette
a few mL of the NaCl solution you just prepared, swirl gently, and pour back in.
Gently shake the bottle, flipping several times to make sure Ga solution is well mixed.
9) Measure the initial pH in the bottle and adjust solution to pH = 7 using 1M NaOH or
HCl. Since the probe doesn’t reach the bottom of the bottle, close with lid and gently
shake after adjusting periodically. Ensure the pH is stable and record the pH. You will
have to repeatedly measure pH while shaking bottle in between.
 pH is very sensitive between 6-9 so you will use smaller volumes (<1 mL) of
NaOH and HCl to adjust while in this range. If you add too much reagent
while in this range, you will over/undershoot the pH and will have to readjust.
Experiment with 100 µL or less (NaOH b/c solution will begin as slightly
acidic), see the response, and you can go from there. (see example) →

Ex. If the solution starts out around pH 5-6, you know you will not be using
much reagent to adjust the pH. Just keep these points in mind.

Lumen learning (web)

E) pH-adjusted Ga stock sample

1) Weigh a 15 mL tube and label body and cap with 7GaSTK50ppb

2) Pipette 12 mL of the Ga stock from part D). Weigh and record mass.
3) Pipette 0.2 mL (200 μL) of concentrate Trace Metal Grade HNO3 into the tube and weigh
again. This sample can be stowed.

F) Preparing Triplicates and Blk-NO GT control

1) Weigh and label 500 mL HDPE bottles for triplicates and Blk-NO GT.
2) For Blk-NO GT, fill a 500 mL volumetric flask with the pH adjusted Ga stock prepared in
Procedure D). Add to the bottle, weigh and record mass, and then set aside. This sample
can be Parafilm and is now done.

Do the following steps (steps a to d) from each triplicate (three tubes containing the mineral
rinsed in the Procedure A):
a. Pour the pH adjusted Ga stock solution into a 500 mL volumetric flask to the mark.
b. Into each triplicate tube, pour about 30 mL of the pH adjusted Ga stock solution
from Procedure A). Manually shake vigorously until the mineral powder is totally
reincorporated into the solution with no clumps. Transfer this solution containing
the mineral into the 500 mL bottle prepared in the Step 1) in this procedure. Use
the solution in the volumetric flask to rinse the centrifuge tube to ensure that the
entire mineral powder is transferred into the corresponding 500 mL HDPE bottle.
For example, mineral in the GT-A tube must be transferred to the GT-A 500 mL
HDPE bottle.
c. Pour the rest of the pH adjusted Ga stock solution into the 500 mL HDPE bottle.
d. Cap on, weigh and record mass.
3) Once all the bottles are ready, tighten the cap and seal with Parafilm. Gently shake the
bottles twice per day and maintain contact time for 1 week.
4) (1 week later) Label five 10 mL HDPE bottles. Calibrate the pH meter. pipette 5 mL of the
supernatant into corresponding 10 mL HDPE bottles; measure and record the pH. After
doing this, discard the 10 mL bottles and the solution inside. Thoroughly rinse the probe
before and after measuring each sample.
G) Processing sample filtrate

1) Label and weigh five 500 mL HDPE bottles, recording masses.

Do the following for each sample, one experiment at a time:

a. Carefully pour the sample into EIGHT (8) clean 50 mL centrifuge tubes to 50mL
mark.
b. Centrifuge the samples at a time (4500 RPM, 15 minutes).
c. Using 60mL syringes with filter attached, filter the supernatants in these eight tubes
into the new bottle. You can use one filter/syringe for filtering a whole sample
(~495 mL) but use a fresh pair of filter and syringe for different sample. Weigh
and record masses.
d. Into each filtrate bottle, add 8 mL Trace Metal Grade HNO3 and weigh again,
recording masses. Gently flip the bottles 5 times to mix the acid well. Tighten the
cap and cover with Parafilm. Samples are ready.