Phosphate Activation via Reduced Oxidation State Phosphorus (P). Mild Routes to Condensed-P Energy Currency Molecules
Abstract
:1. Introduction
2. Experimental Section
2.1. Materials and General Analytical Methods
2.2. Production of Pyrophosphite PPi(III)
pH | 4 Days | 5 Days | 6 Days |
---|---|---|---|
4.0 | 24(2) | 24(4) | 30(1) |
4.5 | 12(0) | 14(1) | 15(1) |
5.0 | 8(1) | 10(1) | 17(0) |
5.5 | 12(0) | 14(1) | 15(1) |
5.8 | 4(1) | 5(0) | 6(0) |
6.0 | 0 | 0 | 0 |
Time (h) | pH 3 | pH 4 | |
24 | 61(4) | 39(3) | |
48 | 61(3) | 16(1) | |
72 | 62(4) | 20(10) | |
336 | 35(5) | 38(0) |
2.3. Hveradalur Lake Geothermal Field Experiments: Site
2.4. Hveradalur Lake Geothermal Field Experiments: ICP-AES and ICP-MS-HPLC Analyses
- (i)
- Samples were pre-filtered using Whatman Number 1 filter papers.
- (ii)
- Samples were then diluted to 70 mL and re-filtered using Pall Corporation Acrodisc 32 mm 0.45 µm syringe filters to remove un-dissolved particulates.
- (iii)
- Nalgene bottles (30 mL capacity) were acid washed by filling with 50% HCl and leaving for 24 h. They were rinsed 3 times with tap water and 3 times with deionized water then left to air dry.
- (iv)
- Two portions of 35 mL of sample were placed in an acid-washed 30 mL Nalgene bottle.
- (v)
- Concentrated nitric acid (ca. 2 drops) was added to one of the portions and the lids screwed on tightly and the bottles labeled.
- (vi)
- Due to the concentration of sulphur, the acid treated samples were further diluted to allow accurate measurement of the sulphur content of each sample.
- (vii)
- Two 1.5 mL aliquots were taken from each of the acid treated samples. Two drops of toluene was added as an antibacterial agent. The sub-samples were subsequently submitted for ICP analysis.
Sample ζ | ICP-AES † (μgL−1) | ICP-MS ‡ (μgL−1) |
---|---|---|
Blank 1 | –0.04(1) | –0.02(0) |
A1 (KHL–UCL3; 40; 3.6) | 0.53(2) | 0.39(3) |
A2 (KHL–BPR; 79.5; 4.0) | 1.01(3) | 0.92(0) |
A3 (KHL–MP1; 87.4; 1.6) | 21.98(3) | 17.17(5) |
A4 (KHL–LP1; 93.5; 3.1) | 2.66(2) | 1.03(5) |
A5 (KHL–UCL5; 89.2; 4.7) | 1.20(2) | 1.50(4) |
A6 (KHL–LP3; 79.2; 2.5) | 0.62(0) | 0.47(1) |
A7 (KHL–LP4; 87.8; 3.3) | 0.77(2) | 0.70(2) |
A8 (KHL–MP3; 84.7; 2.7) | 2.28(6) | 2.00(3) |
2.5. Hveradalur Lake Geothermal Field Experiments: 31P-NMR Analyses
- (i)
- A 10 mL aliquot of the acidified sample (prepared as above) was taken in a 15 mL Falcon tube.
- (ii)
- Sample was treated with NaOH (1 M) to pH 12 and left for 1–2 min.
- (iii)
- Sample was gravity filtered to remove precipitate (hydrated ferrous oxides and hydroxides). These oxides were subsequently collected and shown to contain negligible amounts of phosphorus via EDX measurements.
- (iv)
- Sample was treated with HCl (1 M) to pH 4.
- (v)
- A 0.5 mL aliquot was taken and analyzed by 31P-NMR spectroscopy (500 MHz Bruker Avance, 320 scans, 300 K) using capillary D2O inserts.
- (vi)
- Sample was reduced to dryness and residues dried overnight in 50 °C oven.
- (vii)
- Residues were ground to fine powder in mortar and pestle.
- (viii)
- Residues were dry heated to ca. 90 °C for 72 h on a sand bath under flowing N2 (ca. 1 bubble per second).
- (ix)
- Residues were dissolved in deionized water (ca. 0.5 mL) and adjusted to pH 7.2 using aqueous Na2CO3 solution (1 M).
- (x)
- Sample was analyzed by 31P-NMR spectroscopy (500 MHz Bruker Avance, 2048 scans, 300 K) using capillary D2O inserts.
2.6. Conversion of PPi(III) to PPi(III–V)
2.7. Conversion of PPi(III–V) to PPi(V)
3. Results and Discussion
3.1. Pyrophosphite Formation and Geological Provenance
3.2. Phosphonylation of Pi(V) with PPi(III) in Aqueous Solution. Formation of PPi(III–V) and PPi(V)
Time (h) | Control [% total P] | MgCl2 [% total P] | CaCl2 [% total P] | |||
---|---|---|---|---|---|---|
PPi(III) | PPi(III–V) | PPi(III) | PPi(III–V) | PPi(III) | PPi(III–V) | |
0 | 98.6 | 0 | 98.6 | 0 | 98.6 | 0 |
48 | 95.7 | 13.8 | 68.5 | 66.2 | 36.2 | 82.3 |
168 | 89.0 | 27.7 | 42.5 | 78.1 | 20.2 | 65.4 |
336 | 82.5 | 36.8 | 30.3 | 81.8 | 18.4 | 45.9 |
504 | 78.2 | 41.6 | 23.4 | 81.1 | 5.6 | 23.9 |
4. Conclusions
Acknowledgments
Conflict of Interest
References
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Kee, T.P.; Bryant, D.E.; Herschy, B.; Marriott, K.E.R.; Cosgrove, N.E.; Pasek, M.A.; Atlas, Z.D.; Cousins, C.R. Phosphate Activation via Reduced Oxidation State Phosphorus (P). Mild Routes to Condensed-P Energy Currency Molecules. Life 2013, 3, 386-402. https://doi.org/10.3390/life3030386
Kee TP, Bryant DE, Herschy B, Marriott KER, Cosgrove NE, Pasek MA, Atlas ZD, Cousins CR. Phosphate Activation via Reduced Oxidation State Phosphorus (P). Mild Routes to Condensed-P Energy Currency Molecules. Life. 2013; 3(3):386-402. https://doi.org/10.3390/life3030386
Chicago/Turabian StyleKee, Terence P., David E. Bryant, Barry Herschy, Katie E. R. Marriott, Nichola E. Cosgrove, Matthew A. Pasek, Zachary D. Atlas, and Claire R. Cousins. 2013. "Phosphate Activation via Reduced Oxidation State Phosphorus (P). Mild Routes to Condensed-P Energy Currency Molecules" Life 3, no. 3: 386-402. https://doi.org/10.3390/life3030386