PROCEDURE: equilibrium adsorption (ionic strength)

The ionic strength (IS) experiments will test adsorption when [NaCl] = 0.01M, 0.1M, 1.0M.
Procedure sections A, B, C, D will be done consecutively, for each experiment. Each experiment
has 3 triplicates and two controls (one with clay: BLK-clay, one without clay: BLK-no clay) in
50 mL tubes. For each IS experiment, the clay will be added first and rinsed with an NaCl solution
adjusted to the experimental IS.

Once the clay is rinsed, pH = _ Ga stocks (3000 μg/L Ga(NO3)3, at adjusted IS will be added to 3
triplicate tubes and BLK-no clay (for each IS). BLK-clay will only have IS adjusted NaCl solution
with no Ga. All tubes will be rotated in the shaker at 80 rpm for one week. A separate tube (15
mL) will contain only the acidified IS adjusted Ga stock sample.

Acid washed labware

• 50 mL centrifuge tubes: 15
• 15 mL centrifuge tubes: 3
• Syringes and filters: 15
• 500 mL HDPE bottles: 3

A) Preparation of tubes and rinsing solutions

1) Label 5 empty 50 mL centrifuge tubes (3 triplicates, 2 controls) with the sample name and
ionic strength you will test on both tube body and cap. Do this for all experiments. Weigh
& record their masses.
2) Using a metal spatula, weigh ~0.03 g Kga-2 using weighing paper, and add into 3 triplicate
tubes and BLK-clay. Record the mass.
3) Label 3 HDPE bottles with the ionic strength you will use and weigh. Record masses.
4) Add 500 mL of MQW to each bottle. Weigh and record masses.
5) Weigh desired NaCl using weighing paper and record the masses. Dissolve in each bottle.
For 0.01N, add 0.29222g. For 0.1N, add 2.9222g. For 1.0N, add 29.222g.

B) Clay rinse

6) Carefully pipette 30 mL of NaCl solution into the triplicates containing clay. Manually
shake and let rest for ~15 minutes.
7) Load tubes into centrifuge. Ensure the centrifuge is loaded symmetrically. Centrifuge at
4500 RPM for 12.5 minutes.
8) Measure pH.
9) Repeat steps 5-7 until the pH is stable (2x should be enough).
10) Control 1: Pipette 20 mL of the adjusted IS NaCl solution to the control tube WITH
CLAY. Weigh and record mass.
C) Neutral pH 3000 μg/L Ga stocks (Ga + NaCl)

11) Label 3 HDPE bottles with the IS you will adjust. Weigh the bottles with caps and record
their masses.
12) Into each bottle, add 199.4 mL of MQW.
13) Weigh desired mass of NaCl and record the masses. Dissolve in each bottle. For 0.01N,
add 0.11689 g. For 0.1N, add 1.11689 g. For 1.0N, add 11.1689 g.
14) Tare a clean 50 mL tube. Pipette 0.6 mL (600 μL) of single element Ga ICP standard into
the tube. Weigh and record the mass. Pour some IS adjusted NaCl solution from 13) to
dilute the Ga standard, and pour back into the bottle. Do this several times and make sure
none is left in the tube.
15) Measure the initial pH in the bottle. Add volume of 0.1N NaOH or HCl needed to adjust
to pH = 7. *After adding Ga ICP standard the pH should be <3.
16) Record the mass again after pH adjustment.

D) pH-adjusted Ga stock samples

17) Label and pre-weigh 15 mL tubes (need 1 for each IS)

18) Pipette 12 mL of the IS adjusted Ga stock from part C). Weigh and record mass.
19) Pipette 0.2 mL (200 μL) of 2x distilled HNO3 and weigh again. These samples can be
stowed, they are not part of experiments.

E) 50 mL tubes (adsorption), control 2, Ga stock sample

20) Tare the 50 mL triplicate tubes (containing rinsed clay). Pipette 20 mL of the Ga stock
from 15) into the tubes. Weigh and record masses.
a. Control 2: Tare the control tube WITHOUT CLAY. Pipette 20 mL of the Ga stock
from 15) into the tube. Weigh and record mass.
21) Once all the tubes are ready, secure them to the shaker and set to 60 rpm. Rotate for ~ 1
week. Record start and end date, time.
22) After contact time has elapsed, remove the samples and load them into the centrifuge
symmetrically. Centrifuge at 4500 RPM for 10 minutes.

F) 50 mL tubes (filtrate)

23) Label and weigh 15 mL tubes. Record the masses. Load HDPE syringes with 12 mL of the
supernatant solution from 22). Filter the solution into the 15 mL tubes using a 0.2 μm filter.
Weigh the 15 mL tubes again.
24) Pipette 0.2 mL (200 μL) double distilled HNO3 into each sample and weigh again. Record
masses. Samples are now ready for dilution and concentration analysis.