In Situ Geochemical Analysis of Organics in Growth Lines of Antarctic Scallop Shells: Implications for Sclerochronology
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Methods
2.2.1. General Sample Preparation and Selection of Regions of Interest
2.2.2. Scanning Electron Microscopy (SEM) Imaging
2.2.3. Focused Ion Beam (FIB) Work
2.2.4. Local Electrode Atom Probe (LEAP) Work and Data Analysis
3. Results
4. Discussion
4.1. Chemical Composition of Growth Lines
4.2. APT Geochemical Data: Implications for Sclerochronology in the Context of Diagenesis
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Specimen/Data Set | Scallop-W7 | Scallop-W8 | |||||
---|---|---|---|---|---|---|---|
Reference | 4173-M13 | 4174-M19 | 4175-M20 | 4176-M21 | 4149-M3 | 4150-M4 | 4198-M10 |
Instrument Model | LEAP 5000 XS | LEAP 5000 XS | LEAP 5000 XS | LEAP 5000 XS | LEAP 5000 XS | LEAP 5000 XS | LEAP 5000 XS |
Instrument settings | |||||||
Laser wavelength | 355 | 355 | 355 | 355 | 355 | 355 | 355 |
Laser pulse energy | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
Pulse frequency (kHz) | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
Evaporation control | Detection rate | Detection rate | Detection rate | Detection rate | Detection rate | Detection rate | Detection rate |
Target detection rate (ions/pulse)% | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
Nominal fligth path (mm) | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
Set point temperature (K) | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
Chamber pressure (torr) | 3.00E-11 | 4.00E-11 | 4.60E-11 | 5.60E-11 | 4.90E-11 | 4.10E-11 | 5.30E-11 |
Data summary | |||||||
Analysis software | IVAS 3.8.4 | IVAS 3.8.5 | IVAS 3.8.6 | IVAS 3.8.7 | IVAS 3.8.8 | IVAS 3.8.9 | IVAS 3.8.10 |
Total ions: | 12,070,475 | 5,258,176 | 9,251,680 | 7,502,224 | 16,213,824 | 12,223,734 | 4,878,030 |
Sigle (%) | 75.5 | 74.2 | 74.5 | 75.5 | 77.8 | 74.2 | 73.4 |
Multiple (%) | 23.4 | 24.3 | 24.5 | 23.2 | 21.2 | 24.2 | 25.5 |
Partial (%) | 1.1 | 1.4 | 1 | 1.3 | 1 | 1.1 | 1.1 |
Reconstructed ions: | 7,042,775 | 3,170,254 | 5,374,711 | 4,496,256 | 13,933,458 | 9,839,070 | 3,699,975 |
Ranged (%) | 50.9 | 48 | 51.6 | 47 | 35 | 39 | 41.7 |
Unranged (%) | 49.1 | 52 | 48.4 | 53 | 65 | 61 | 58.3 |
Mass calib. (peaks/interp.) | Lin. Method | Lin. Method | Lin. Method | Lin. Method | Lin. Method | Lin. Method | Lin. Method |
(M/∆M) for 40Ca++ | 261 | 149 | 388 | 282 | 435 | 208 | 294 |
(M/∆M10)c | 122 | 77 | 172 | 112 | 196 | 90 | 109 |
Time indipendent background (ppm/ns) | 115 | 143 | 110 | 97 | 22 | 37 | 42 |
Recontruction | |||||||
Final speciment state | fractured | fractured | fractured | fractured | unsure | fractured | fractured |
Pre-/post-analysis imaging | SEM/n.a. | SEM/n.a. | SEM/n.a. | SEM/n.a. | SEM/n.a. | SEM/n.a. | SEM/n.a. |
Radius evolution model | Shank | Shank | Shank | Shank | Shank | Shank | Shank |
Field factor (k) | 3.5 | 3.3 | 3.3 | 3.3 | 3.3 | 3.3 | 3.3 |
Image compression factor | 1.3 | 1.3 | 1.3 | 1.3 | 1.3 | 1.3 | 1.3 |
Assumed E-field (V/nm) | 18 | 18 | 18 | 18 | 18 | 18 | 18 |
Detector efficiency (%) | 80 | 80 | 80 | 80 | 80 | 80 | 80 |
Avg. atomic volume (nm3) | 0.0435 | 0.0435 | 0.0435 | 0.0435 | 0.0435 | 0.0435 | 0.0435 |
Vinitial; Vfinal (V) | 2500; 5800 | 1800; 3500 | 2400; 5400 | 2000; 4700 | 2200; 5300 | 3200; 3900 | 3400; 4900 |
Peaks (Da) | Peaks (Da) | ||
---|---|---|---|
Mg++ | 12,12.5,13 | CO2+ | 44,45,46 |
Mg+ | 24,25,26 | Ca2O++ | 48,49,50 |
NH+ | 15 | CaO+ | 56,58,60 |
O+ | 16 | CH3NO+ | 57 |
OH+ | 17 | C3H6OH+ | 59 |
H2O+ | 18 | CH3NS+ | 61 |
Fe+++ | 18.6 | C4N+ | 62 |
H3O+ | 19 | HNO3+ | 63 |
Ca++ | 20,21,21.5,23 | unknown | 67.5 |
Ca+ | 40,42,43 | C5H9 | 69 |
N2+ | 28 | Ca2CO3++ | 70 |
N2H+ | 29 | CaO2+ | 72,74,75,76 |
N2H2+ | 30 | unknown | 80 |
O2+, S+ | 32 | CaCO3+ | 100 |
SH+, S+ | 33,34 |
Reference | W7-4175-M20 | W8-4149-M3 | ||||
---|---|---|---|---|---|---|
Ion | Counts | Atomic % | Atomic Error % | Counts | Atomic % | Atomic Error % |
S | 14,759 | 0.36 | 0.082 | 14,531 | 0.25 | 0.154 |
H | 658,324 | 15.90 | 0.002 | 711,148 | 12.08 | 0.010 |
Ca | 2,244,793 | 54.21 | 0.030 | 3,400,315 | 57.78 | 0.030 |
C | 160,130 | 3.87 | 0.008 | 149,473 | 2.54 | 0.005 |
N | 39,504 | 0.95 | 0.002 | 48,173 | 0.82 | 0.001 |
O | 1,012,163 | 24.44 | 0.002 | 1,547,706 | 26.30 | 0.002 |
Fe | 298 | 0.01 | 0.002 | - | - | - |
Mg | 10,821 | 0.26 | 0.008 | 13,296 | 0.23 | 0.018 |
Scallop W7 | Scallop W8 | ||||||
---|---|---|---|---|---|---|---|
Reference | 4173-M13 | 4174-M19 | 4175-M20 | 4176-M21 | 4149-M3 | 4150-M4 | 4198-M10 |
Volume (nm3) | 116,376 | 56,368 | 86,300 | 70,661 | |||
Mg | 0.37% | 0.31% | 0.44% | 0.17% | 0.36% | 0.51% | 0.25% |
N compounds | 0.68% | 0.58% | 1.47% | 0.59% | 1.17% | 0.85% | 0.97% |
C compounds | 0.72% | 0.33% | 0.74% | 0.46% | 0.14% | 0.27% | 6.23% |
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Pérez-Huerta, A.; Walker, S.E.; Cappelli, C. In Situ Geochemical Analysis of Organics in Growth Lines of Antarctic Scallop Shells: Implications for Sclerochronology. Minerals 2020, 10, 529. https://doi.org/10.3390/min10060529
Pérez-Huerta A, Walker SE, Cappelli C. In Situ Geochemical Analysis of Organics in Growth Lines of Antarctic Scallop Shells: Implications for Sclerochronology. Minerals. 2020; 10(6):529. https://doi.org/10.3390/min10060529
Chicago/Turabian StylePérez-Huerta, Alberto, Sally E. Walker, and Chiara Cappelli. 2020. "In Situ Geochemical Analysis of Organics in Growth Lines of Antarctic Scallop Shells: Implications for Sclerochronology" Minerals 10, no. 6: 529. https://doi.org/10.3390/min10060529