Table 2.
Exploration of the role of the microfluidic pH gradient across the mineral precipitate in CO2 reduction
Experiment | Vent-side pH | Ocean-side pH | Vent-side postprecipitation solute* | Ocean-side postprecipitation solute/gas† | Formate concentration, μM‡ |
1§ | 12.3 | 3.9 | Na2S/K2HPO4/Na2Si3O7 | None/CO2 | 1.5 (1.66; 1.40) |
6 | 7.0 | 3.9 | None | None/CO2 | n.d. |
7¶ | 7.0 | 3.9 | Na2S/K2HPO4/Na2Si3O7 | None/CO2 | n.d. |
8¶ | 3.9 | 3.9 | Na2S/K2HPO4/Na2Si3O7 | None/CO2 | n.d. |
9 | 12.3 | 9.8 | Na2S/K2HPO4/Na2Si3O7 | Na2CO3/CO2 | n.d. |
10 | 12.3 | 3.9 | Na2S/K2HPO4 | None/CO2 | 1.5 (1.33; 1.69) |
11 | 12.6 | 3.9 | Na2S | None/CO2 | 1.8 (2.12; 1.44) |
12 | 9.1 | 3.9 | K2HPO4 | None/CO2 | (<0.37)# |
13 | 12.1 | 3.9 | K3PO4 | None/CO2 | 0.9 (1.04; 0.76) |
n.d., none detected.
Vent fluid concentrations for precipitation in all reactions were as follows: Na2S, 100 mM; K2HPO4, 10 mM; Na2Si3O7, 10 mM. The same concentrations were used postprecipitation, as relevant. K3PO4 (100 mM) was used postprecipitation in experiment 14. In all reactions, both during and after precipitation, vent fluids were driven by H2 at 1.5 bar and a flow rate of 5 µL/min.
Ocean fluid for precipitation was composed of FeCl2 (50 mM) and NiCl2 (5 mM) in H2O, pushed by CO2 (1.5 bar) at a flow rate of 5 µL/min. Following precipitation, the ocean fluid for reaction was changed to contain no solutes besides dissolved CO2 from the driving gas, except for experiment 9 with Na2CO3 (100 mM).
Average calculated concentrations listed, with results from duplicate samples in parentheses.
Same as in Table 1.
Vent fluid titrated with 1 M HCl to pH 7.0 (experiment 7) or pH 3.9 (experiment 8).
Peak was observable, but concentration was below the limit of quantification (0.37 µM; SI Appendix, Fig. S16).