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RE S EAR CH | R E P O R T S
(529.1 eV) has been ascribed to O-Ce, the com- J. A. Rodriguez, J. C. Hanson, P. J. Chupas, Eds. (Wiley, 20. X. Peng, Q. Pan, G. L. Rempel, S. Wu, Catal. Commun. 11,
ponent at 530 eV to O-metals (Rh and/or Pd), New York, 2013), pp. 315–343. 62–66 (2009).
4. D. E. Starr, Z. Liu, M. Hävecker, A. Knop-Gericke, H. Bluhm, 21. J. C. Garcia-Martinez, R. M. Crooks, J. Am. Chem. Soc. 126,
and the component at 531.8 eV to –OH groups Chem. Soc. Rev. 42, 5833–5857 (2013). 16170–16178 (2004).
present on the surface of the catalyst (Fig. 4, D to 5. C. Escudero, M. Salmeron, Surf. Sci. 607, 2–9 (2013). 22. See the supplementary materials.
F, O 1s) (28, 29). The ratio between the area of 6. F. Tao et al., Science 322, 932–934 (2008). 23. Y. Qi et al., Nanoscale 6, 7012–7018 (2014).
the O-Ce peak and the –OH peak increases as the 7. H. Idriss et al., ChemSusChem 1, 905–910 (2008). 24. C. Wheeler, J. Catal. 223, 191–199 (2004).
8. N. J. Divins, E. López, Á. Rodríguez, D. Vega, J. Llorca, 25. V. Pérez-Dieste et al., J. Phys. Conf. Ser. 425, 072023 (2013).
photon energy increases; i.e., as the sampling Chem. Eng. Process. Process Intensif. 64, 31–37 (2013). 26. C. J. Powell, A. Jablonski, NIST Electron Inelastic-Mean-Free-
depth increases, which highlights the sensitivity 9. G. A. Deluga, J. R. Salge, L. D. Schmidt, X. E. Verykios, Science Path Database - Version 1.2 (National Institute of Standards
to different depths of the chosen photon energies 303, 993–997 (2004). and Technology, Gaithersburg, MD, 2010).
and the presence of the –OH groups on the sur- 10. J. Llorca, V. Cortés Corberán, N. J. Divins, R. O. Fraile, 27. Y. Zhu et al., ACS Catal. 3, 2627–2639 (2013).
E. Taboada, in Renewable Hydrogen Technologies, L. M. Gandía, 28. M. M. Natile, A. Glisenti, Surf. Sci. Spectra 13, 17–30 (2006).
face of the Rh0.5Pd0.5/CeO2 catalyst. The same G. Arzamendi, P. M. Diéguez, Eds. (Elsevier, Amsterdam, 2013), 29. C. Force, E. Roman, J. M. Guil, J. Sanz, Langmuir ACS J. Surf.
trend is observed for the unsupported NPs, where pp. 135–169. Colloids 23, 4569–4574 (2007).
the ratio between the O-metal peak and the –OH 11. F. Aksoy et al., Nucl. Instruments Methods Phys. Res. Sect. 30. H. Sánchez Casalongue et al., Nat. Commun. 4, 2817 (2013).
peak also increases when the photon energy is A Accel. Spectrometers Detect. Assoc. Equip. 645, 260–265
(2011). AC KNOWLED GME NTS
increased (Fig. 4, A to C, O 1s). In this case, the O 1s 12. K. Mudiyanselage et al., Angew. Chem. Int. Ed. Engl. 52, This work has been funded through grant MINECO
high-binding-energy component could be related 5101–5105 (2013). ENE2012-36368. J.L. is grateful to the ICREA Academia program.
to hydroxyl groups interacting with water mole- 13. C. Wen et al., ACS Nano 6, 9305–9313 (2012).
cules (30), because they almost do not participate 14. A. Caballero et al., Chem. Commun. (Camb.) 46, 1097–1099
(2010). SUPPLEMENTARY MATERIALS
in the ESR reaction (fig. S1), and the –OH groups 15. C. Mattevi et al., J. Phys. Chem. C 112, 12207–12213 www.sciencemag.org/content/346/6209/620/suppl/DC1
do not affect the oxidation state of the metals (2008). Materials and Methods
(Fig. 2 C), because the inner shells are the most 16. A. Bruix et al., J. Am. Chem. Soc. 134, 8968–8974 (2012). Figs. S1 to S5
oxidized ones. 17. A. Trovarelli, Catal. Rev. 38, 439–520 (1996). References (31–33)
18. H. Song, L. Zhang, R. Watson, D. Braden, U. Ozkan,
Finally, the oxidation state of both metals in Catal. Today 129, 346–354 (2007). 30 June 2014; accepted 2 October 2014
the Rh0.5Pd0.5/CeO2 catalyst very nearly recov- 19. H. Idriss, Platin. Met. Rev. 48, 105–115 (2004). 10.1126/science.1258106
ered the values of the first reducing treatment at
lower temperature (Fig. 3A) during the reduction
with pure H2 at the reaction temperature (823 K,
Fig. 3C and fig. S5), unlike the model NPs, and EARLY SOLAR SYSTEM
again this points to the stabilizing effect of the
ceria support. Analysis of the oxidation state of
cerium (performed only with hu = 1150 eV, fig.
S3) reveals variations depending on the gaseous
Early accretion of water in the inner
environment and temperature (22). Under H2
and 573 K, the Ce3+/Ce4+ atomic ratio was 0.63. solar system from a carbonaceous
The ratio decreased to 0.58 during the ESR reac-
tion at 823 K, in accordance with the oxidation
experienced by the noble metals, and it strongly
chondrite–like source
increased up to 0.83 under H2 at 823 K. Adam R. Sarafian,1* Sune G. Nielsen,1 Horst R. Marschall,1,2,3
In the absence of a support, the model NPs Francis M. McCubbin,4 Brian D. Monteleone1
were more strongly reduced for all the environ-
ments tested, and the reduction temperature af- Determining the origin of water and the timing of its accretion within the inner solar system
fected the amount of metallic phase found in Rh is important for understanding the dynamics of planet formation. The timing of water
and Pd. Compared with the unsupported NPs, accretion to the inner solar system also has implications for how and when life emerged
the capability of CeO2 as a support to activate wa- on Earth. We report in situ measurements of the hydrogen isotopic composition of the
ter and to donate oxygen atoms determined the mineral apatite in eucrite meteorites, whose parent body is the main-belt asteroid 4 Vesta.
oxidation states of the noble metals under the These measurements sample one of the oldest hydrogen reservoirs in the solar system
same reaction conditions. In addition, the inter- and show that Vesta contains the same hydrogen isotopic composition as that of
action between the ceria support and the metal carbonaceous chondrites. Taking into account the old ages of eucrite meteorites and their
nanoparticles prevented reorganization of the similarity to Earth’s isotopic ratios of hydrogen, carbon, and nitrogen, we demonstrate
Rh and Pd atoms. We have thus demonstrated that these volatiles could have been added early to Earth, rather than gained during a late
the pivotal role of the metal-support interaction accretion event.
in the reorganization of metal atoms in supported
H
bimetallic catalysts under operating conditions
and shown that this effect has a strong influence ydrogen is vitally important in cosmochem- water on the Moon, Mars, and the asteroid 4
on the catalytic performance. Keeping this in ical and geochemical processes. For ex- Vesta (2–4), these planetary bodies are often
mind, it should be noted that AP-XPS studies (and ample, water (H2O) plays a critical role in thought to have accreted dry (5–8). This prompts
other studies) carried out on unsupported model plate tectonics on Earth (1) and has likely two key questions: Where did the water come
systems may not provide reliable information on shaped the surface of Mars (2). Despite the from? And when was it present in the inner solar
supported real catalysts. For this reason, it is very abundance of water on Earth and evidence of system? The answers may reveal information
important to also take into account the influence about accretion processes in terrestrial planets.
of the support in spite of the experimental diffi- 1
Department of Geology and Geophysics, Woods Hole
Additionally, the extent and importance of lat-
culties often encountered. Oceanographic Institution, Woods Hole, MA 02543, USA. eral water transport throughout the history of
2
Department of Earth and Planetary Sciences, American the solar system are debatable (9, 10).
RE FE RENCES AND N OT ES Museum of Natural History, New York, NY 10024, USA.
3
The source of water in planetary bodies can be
1. F. F. Tao, M. Salmeron, Science 331, 171–174 (2011). School of Earth Sciences, University of Bristol, Bristol BS8
2. S. Zafeiratos et al., J. Catal. 269, 309–317 (2010). 1RJ, UK. 4Institute of Meteoritics, University of New Mexico,
investigated by measuring the ratio between the
3. D. E. Starr, H. Bluhm, Z. Liu, A. Knop-Gericke, M. Hävecker, Albuquerque, NM 87131, USA. isotopes of hydrogen (deuterium, D or 2H, and
in In-situ Characterization of Heterogeneous Catalysts, *Corresponding author. E-mail: asarafian@whoi.edu hydrogen, 1H) because different regions of the
solar system vary widely in measured D/H ratios Table 1. Hydrogen isotope and water analyses of apatite and epoxy.
(11). Thus, determining D/H ratios in meteorites
with well-known ages and planetary origins can Sample dD (‰) T 2s H2O (mg/g) T 2s
help constrain the timing of water delivery to PCA 91078 ap1 –141 T 40 804 T 60
accreting planetary bodies. Such analysis pro- PCA 91078 ap2 –109 T 53 668 T 52
vides an ideal opportunity to study the prove- Pasamonte ap1 –53 T 29 2207 T 153
nance of water in bodies throughout the solar Pasamonte ap2 –216 T 25 1630 T 584
system, including Earth, the Moon, Mars, and Pasamonte ap3 –200 T 34 1545 T 295
the asteroid belt (12–14).
Juvinas ap1 –223 T 21 1781 T 152
Eucrites, a class of asteroidal basaltic meteor-
Juvinas ap2 –179 T 29 1594 T 107
ites, can provide unique information about the
Stannern ap1 –107 T 38 2624 T 182
timing of water delivery to planets because most
of these rocks crystallized 4559 to 4547 million Stannern ap2 –37 T 68 2390 T 157
years ago (Ma), or ~8 to 20 million years after Stannern ap3 –75 T 36 1595 T 107
the first solids in the solar system, calcium- and Cachari ap1 –158 T 24 932 T 62
aluminum-rich inclusions (CAIs) (15, 16). Eucrites PCA 91078 epoxy –174 T 9 140,000 T 9000
belong to the howardite-eucrite-diogenite group Weighted mean apatite –162 T 127 1748 T 1689
of meteorites (HEDs) that are derived from the
asteroid belt, dominantly from the asteroid
Vesta (17–19). Determining the source of water
Fig. 1. Hydrogen isotopes
in eucrites can constrain the time at which water
versus water content of
existed in the inner solar system, because these
eucrite apatites. Note the
ancient rocks are some of the oldest igneous rocks
large variation in water con-
in the solar system. However, until recently it
tent that contrasts with a
was believed that eucrites were completely anhy-
small range in the hydrogen
drous and therefore could provide no insight
isotopic compositions. Error
into the D/H ratio of Vesta (4, 6).
bars are 2s; where error bars
Here, we report the concentration and isotopic
are not present, they are
composition of structurally bound water in the
smaller than the symbol.
mineral apatite [Ca5(PO4)3(OH,F,Cl)] from five differ-
ent basaltic eucrite samples: Juvinas, Pasamonte,
Cachari, Stannern, and Pecora Escarpment (PCA)
91078 (figs. S1 and S2). We measured the D/H
and water contents simultaneously in situ using
a Cameca 1280 ion microprobe. The water con-
centration in these apatites ranges from 668 to
2624 mg/g, which agrees with calculated water
contents from electron probe measurements (table
S1) (4, 20). We measured dD values ranging from
–231 per mil (‰) to –37‰ (Table 1) (21). No
systematic variation in D/H exists between sam-
ples or between different apatite grains in the
same meteorite (Fig. 1). The weighted mean
hydrogen isotopic composition for eucritic apa-
tite from the five different investigated samples
is dD = –162 T 127‰ (2s; n = 11).
There are three processes that could have mod-
ified the hydrogen isotopic composition of the
apatite we analyzed from that of the parental
magma: (i) hydrous degassing before or during
apatite crystallization, (ii) equilibrium stable iso-
tope fractionation between hydrous phases and
melt, and (iii) contamination or assimilation of
exogenous H or D, presumably from the regolith
of Vesta. Degassing is unlikely due to the small
observed spread in dD with the relatively large
spread of water contents of the analyzed apatite
(22, 23). Apatite is the only hydrous mineral
phase in eucrites, and stable isotope fractiona-
tion between apatite and melt is expected to be
small (~20‰) at high temperature; thus, apatite- Fig. 2. Nitrogen isotopes versus hydrogen isotopic compositions of objects in the Solar System.
melt fractionation should be minor relative to Note that the fields for the Moon and Mars are large; these represent all D/H data because of a lack of
the variation in dD observed (24). Contamination consensus about the hydrogen isotopic compositions for the bulk Moon and Mars. For carbonaceous
by exogenic H from solar wind and/or by D pro- chondrites, ice in equilibrium with bulk clays has dD values of ~ –400‰ to 100‰ (12). Early car-
duced during spallation processes is unlikely, be- bonaceous chondrite ice could be another source of water for the inner solar system.The degassing model
cause apatites have young exposure ages, high line originating at protosolar values does not intersect Vesta, Earth, or the Moon. See (20) for details and
water contents, and a small range of dD across data. [Figure modified from (3, 28)]
10. H. King et al., Earth Planet. Sci. Lett. 300, 11–18 (2010). 21. dD = {[(D/Hunknown)/(D/HVSMOW)] – 1} × 1000, where Cosmochemistry Program award NNX11AG76G (F.M.M.).
11. F. Robert, D. Gautier, B. Dubrulle, Space Sci. Rev. 92, 201–224 VSMOW = Vienna standard mean ocean water. Secondary ion mass spectrometry analyses were made at the
(2000). 22. Z. D. Sharp, F. M. McCubbin, C. K. Shearer, Earth Planet. Sci. Lett. Northeast National Ion Microprobe Facility (NENIMF) at the Woods
12. C. M. Alexander et al., Science 337, 721–723 (2012). 380, 88–97 (2013). Hole Oceanographic Institution (WHOI). NENIMF acknowledges
13. F. Robert, Science 293, 1056–1058 (2001). 23. R. Tartèse et al., Geology 42, 363–366 (2014). support from the NSF Instrumentation and Facilities Program,
14. L. Hallis, G. Taylor, K. Nagashima, G. Huss, Earth Planet. Sci. Lett. 24. T. Chacko, D. R. Cole, J. Horita, Rev. Mineral. Geochem. 43, Division of Earth Sciences, and from WHOI. Data are presented in
359–360, 84–92 (2012). 1–81 (2001). the main text of the manuscript and the supplementary materials.
15. Q. Zhou et al., Geochim. Cosmochim. Acta 110, 152–175 25. Y. Miura, N. Sugiura, Antarctic Meteor. Res. 6, 338 (1993).
(2013). 26. A. Morbidelli et al., Meteorit. Planet. Sci. 35, 1309–1320
16. K. Misawa, A. Yamaguchi, K. Hiroshi, Geochim. Cosmochim. Acta (2000). SUPPLEMENTARY MATERIALS
69, 5847–5861 (2005). 27. D. P. O’Brien, K. J. Walsh, A. Morbidelli, S. N. Raymond, www.sciencemag.org/content/346/6209/623/suppl/DC1
17. R. N. Clayton, N. Onuma, T. K. Mayeda, Earth Planet. Sci. Lett. A. M. Mandell, Icarus 239, 74–84 (2014). Materials and Methods
30, 10–18 (1976). Supplementary Text
18. T. B. McCord, J. B. Adams, T. V. Johnson, Science 168, ACKN OWLED GMEN TS
Figs. S1 and S2
1445–1447 (1970). We thank the anonymous reviewers; K. Righter, D. Ebel, C. Agee, Table S1
19. H. Y. McSween Jr., D. W. Mittlefehldt, A. W. Beck, R. G. Mayne, and T. McCoy for sample allocations; and N. Shimizu and References (28–81)
T. J. McCoy, in The Dawn Mission to Minor Planets 4 Vesta and G. Gaetani for their immense help. Supported by NASA graduate
1 Ceres (Springer, New York, 2012), pp. 141–174. fellowship NNX13AR90H (A.R.S.), an Andrew W. Mellon 30 May 2014; accepted 29 September 2014
20. See supplementary materials on Science Online. Foundation Award for Innovative Research (S.G.N.), and NASA 10.1126/science.1256717
NEURODEVELOPMENT
apparently affected by sparse trkC removal
(figs. S2 and S3A), consistent with previous ob-
Dendrite morphogenesis servations (6, 7), we observed a distinctive Purkinje
cell dendrite phenotype (Fig. 1).
Both trkC+/+ and trkC+/– Purkinje cells ex-
depends on relative levels of tended complex dendritic arbors that spanned
the entire molecular layer of the cerebellum
NT-3/TrkC signaling (Fig. 1A, left and middle). In contrast, arbors
from trkC–/– cells failed to reach the pial surface
(65 out of 72 cells; Fig. 1A, right). These stunted
William Joo,1,2 Simon Hippenmeyer,1* Liqun Luo1,2† arbors exhibited normal dendritic spine density
(fig. S3B), but spanned only ~75% of the mo-
Neurotrophins regulate diverse aspects of neuronal development and plasticity, but their lecular layer (Fig. 1B). To determine when the
precise in vivo functions during neural circuit assembly in the central brain remain unclear. trkC–/– dendrite phenotype emerges, we com-
We show that the neurotrophin receptor tropomyosin-related kinase C (TrkC) is required pared trkC+/+ and trkC–/– cells between post-
for dendritic growth and branching of mouse cerebellar Purkinje cells. Sparse TrkC natal day 7 (P7) and P21, when Purkinje cells
knockout reduced dendrite complexity, but global Purkinje cell knockout had no effect. normally elaborate their dendrites and begin
Removal of the TrkC ligand neurotrophin-3 (NT-3) from cerebellar granule cells, which to form synapses (Fig. 1C and fig. S4). Although
provide major afferent input to developing Purkinje cell dendrites, rescued the dendrite indistinguishable from control cells at P7 and
defects caused by sparse TrkC disruption in Purkinje cells. Our data demonstrate that P10, trkC–/– cells exhibited reduced dendritic
NT-3 from presynaptic neurons (granule cells) is required for TrkC-dependent competitive arbor height, branch number, and total den-
dendrite morphogenesis in postsynaptic neurons (Purkinje cells)—a previously unknown drite length compared to trkC+/+ cells by day 14
mechanism of neural circuit development. (Fig. 1, C and D, and fig. S4). Growth and branch-
N
ing phenotypes persisted in 3-month-old animals
eurotrophins regulate the survival, differ- patterning (8–10). However, evaluating the roles (Fig. 1, C and D, and fig. S4), indicating that loss
entiation, and plasticity of peripheral and of NT-3/TrkC signaling in the central brain in of TrkC caused a morphogenesis defect rather
central neurons (1–3). The mammalian neu- vivo has been hindered by the early postnatal than a developmental delay. Furthermore, the
rotrophin family signals through three lethality of NT-3 or TrkC knockout mice and the most distal dendritic branches were preferen-
tropomyosin-related kinase (Trk) recep- limited cellular resolution of phenotypic analyses tially lost in trkC–/– cells (fig. S3C). Uniparental
tors, as well as the p75 neurotrophin receptor (7, 11). disomies (13) (fig. S5) and fluorescent markers
(p75NTR). Whereas brain-derived neurotrophic To study the cell-autonomous function of (fig. S6) did not affect Purkinje cell dendrite phe-
factor (BDNF) has been intensely studied, much TrkC in mouse neural development, we used notypes. Thus, our mosaic analysis suggested that
less is known about neurotrophin-3 (NT-3) and mosaic analysis with double markers (MADM) TrkC is required cell-autonomously for proper
its receptor, TrkC, despite their widespread ex- (12, 13) with a null allele of trkC that removes all Purkinje cell dendrite growth and branching.
pression in the developing and adult brain (4, 5). isoforms of the receptor (14), and a pan-neural Although Trk signaling normally requires the
The lack of central brain cell death in mice lack- Nestin-Cre line (15) to drive recombination through- tyrosine kinase domain (16), TrkC also has a
ing NT-3 and TrkC contrasts starkly with the out the brain. Thus, in an otherwise heterozy- kinase-independent role in synaptogenesis (17).
severe reductions in sensory and sympathetic neu- gous animal (trkC+/–), Cre/loxP-mediated mitotic To determine whether dendritic arborization re-
rons and suggests survival-independent functions recombination between homologous chromo- lies on kinase activity, we examined MADM mice
(6, 7). NT-3 functions in dendrite morphogenesis somes sparsely labels wild-type (trkC+/+) and harboring a conditional allele in which loxP
in brain slice culture and in proprioceptive axon homozygous mutant (trkC–/–) cells in distinct sites flank an exon encoding part of the TrkC
colors (figs. S1A and S2). In these animals, kinase domain (18). Here, Nestin-Cre mediated
1
Howard Hughes Medical Institute and Department of sparse trkC–/– cells were labeled with green flu- interchromosomal recombination within the
Biology, Stanford University, Stanford, CA 94305, USA. orescent protein (GFP) (green), trkC+/+ cells with MADM cassettes, and also excised this exon to
tdTomato (red), and trkC+/– cells with both GFP generate a “kinase-dead” allele (trkCKD; fig. S1B).
2
Neurosciences Program, Stanford University, Stanford, CA
94305, USA.
*Present address: Institute of Science and Technology Austria,
and tdTomato (yellow). Cells without recombina- At P21, Purkinje cells homozygous for this allele
3400 Klosterneuburg, Austria. †Corresponding author. E-mail: tion, which remained colorless, were all trkC+/–. (trkCKD/KD) exhibited dendrite height, branch
lluo@stanford.edu Although survival of central brain cells was not number, and total dendritic length phenotypes