REVIEWS OF MODERN PHYSICS, VOLUME 84, APRIL–JUNE 2012 Ice structures, patterns, and processes: A view across the icefields Thorsten Bartels-Rausch Laboratory of Radiochemistry and Environmental Chemistry, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland Vance Bergeron Ecole Normale Supe´rieure de Lyon, F-69007 Lyon, France Julyan H. E. Cartwright Instituto Andaluz de Ciencias de la Tierra, CSIC—Universidad de Granada, E-18071 Granada, Spain Rafael Escribano Instituto de Estructura de la Materia, CSIC, E-28006 Madrid, Spain John L. Finney Department of Physics and Astronomy, and London Centre for Nanotechnology, University College London, London WC1E 6BT, United Kingdom Hinrich Grothe Institute of Materials Chemistry, Vienna University of Technology, A-1060 Vienna, Austria Pedro J. Gutie´rrez Instituto de Astrofı´sica de Andalucı´a, CSIC, E-18080 Granada, Spain Jari Haapala Finnish Meteorological Institute, FIN-00100 Helsinki, Finland Werner F. Kuhs GZG Crystallography, University of Go¨ttingen, D-37077 Go¨ttingen, Germany Jan B. C. Pettersson Department of Chemistry, Atmospheric Science, University of Gothenburg, SE-41296 Go¨teborg, Sweden Stephen D. Price Department of Chemistry, University College London, London WC1H 0AJ, United Kingdom C. Ignacio Sainz-Dı´az Instituto Andaluz de Ciencias de la Tierra, CSIC—Universidad de Granada, E-18002 Granada, Spain Debbie J. Stokes FEI Company, Achtseweg Noord 5, 5651 GG, Eindhoven, The Netherlands Giovanni Strazzulla INAF—Osservatorio Astrofisico di Catania, I-95123 Catania, Italy Erik S. Thomson Department of Chemistry, Atmospheric Science, University of Gothenburg, SE-41296 Go¨teborg, Sweden 0034-6861= 2012=84(2)=885(60) 885 Ó 2012 American Physical Society 886 Thorsten Bartels-Rausch et al.: Ice structures, patterns, and processes: A ... Hauke Trinks Technical University Hamburg Harburg, D-21079 Hamburg, Germany Nevin Uras-Aytemiz Department of Chemistry, Suleyman Demirel University, TR-32260 Isparta, Turkey (published 24 May 2012) From the frontiers of research on ice dynamics in its broadest sense, this review surveys the structures of ice, the patterns or morphologies it may assume, and the physical and chemical processes in which it is involved. Open questions in the various fields of ice research in nature are highlighted, ranging from terrestrial and oceanic ice on Earth, to ice in the atmosphere, to ice on other Solar System bodies and in interstellar space. DOI: 10.1103/RevModPhys.84.885 PACS numbers: 33.15.Àe, 42.68.Ge, 83.80.Nb, 92.40.Vq CONTENTS 2. Glacial ablation 915 3. Sintering processes 915 I. Introduction 886 II. Ice Structures 887 B. Snow chemistry 916 A. Order and disorder in crystalline ice structures 887 1. Uptake of trace gases 917 1. Molecular structures of ices 887 2. Photochemistry of trace gases 919 VI. Sea Ice 920 2. Hydrogen disorder 887 A. Processes determining the evolution of pack ice 921 3. Ordering the familiar ice Ih 889 1. Initial formation of sea ice 922 4. Ordering high-pressure ices 889 2. Fracturing 922 5. Some outstanding questions 890 3. Redistribution 923 B. Cubic ice 890 4. Aging 923 C. Amorphous ices 891 B. A promoter of the emergence of the first life? 924 1. Crystalline and amorphous structures 891 VII. Perspectives 927 2. Formation and structures of amorphous ices 892 3. Some outstanding questions 893 D. Polycrystallinity and interfaces 894 1. Ice—e pluribus unum 894 I. INTRODUCTION 2. Surfaces and interfaces 894 III. Astrophysical Ice 896 The ice was here, the ice was there, A. Laboratory studies of astrophysical ices 898 the ice was all around. 1. Ice morphology on interstellar grain surfaces 899 Samuel Taylor Coleridge, 2. Mixed ices 900 The Rime of the Ancient Mariner B. Cometary ice 901 1. Amorphous versus crystalline ice 901 Ice is indeed all around us. As the cryosphere, ice or 2. Clathrates 902 snow covers a small but significant part of the Earth’s C. Heterogeneous chemical processes on interstellar surface, both land and sea, and it plays a similarly impor- surfaces 903 tant role in our atmosphere. Moreover ice is present on 1. Laboratory experiments 903 many other celestial bodies in our Solar System and surely 2. Desorption of ice-trapped molecules 904 beyond, and it coats grains of dust in interstellar space. Ice IV. Atmospheric Ice 904 is not a static medium but a dynamical one; it shows strong A. Measurement and simulation methods 906 variations of its characteristics with time and place, as we 1. Experimental techniques 906 may readily experience at a human scale on any ski slope. 2. Theoretical methods 907 A better understanding of ice structures, patterns, and B. Ice clouds in the mesopause region 908 processes is thus a topic of current research in physics. C. Polar stratospheric clouds 909 We show in the following how progress in understanding D. Ice-containing clouds in the troposphere 910 these questions is elemental in understanding current ques- 1. Ice morphology 910 tions in astrophysical, atmospheric, cryospheric, and envi- 2. Ice nucleation in the troposphere 911 ronmental science. 3. Cirrus clouds and the supersaturation puzzle 912 Ice research questions are not only tackled separately 4. Tropospheric chemistry 913 within distinct fields, in terrestrial, oceanic, atmospheric, V. Terrestrial Ice 913 planetary, and interstellar ice research, but also by researchers A. Glaciers 914 with disparate backgrounds: by modelers, field and laboratory 1. Glacier flow 914 experimentalists, and theoreticians from both physics and Rev. Mod. Phys., Vol. 84, No. 2, April–June 2012 Thorsten Bartels-Rausch et al.: Ice structures, patterns, and processes: A ... 887 chemistry. We work in these different fields and come from a degrees Fahrenheit, or, better still, a melting point variety of backgrounds. We came together, some of us ini- of one-hundred-and-thirty degrees.’’ tially for a Spanish national project supported by the Spanish CSIC, and then the majority of us for a workshop, Euroice Kurt Vonnegut, Cat’s Cradle 2008, sponsored by the European Science Foundation, which was organized to connect people working on structures and those working in applied icefields, to find common ground in A. Order and disorder in crystalline ice structures the physical and chemical processes at icy surfaces and the physics and chemistry of ice structures from the molecular Unlike Vonnegut’s fictional ice-nine, the real ice IX is scale to the macroscale, and to explore whether some of the not stable at ambient pressures and temperatures. But there questions we were asking and some of the answers we were are indeed many phases of ice. Although we normally seeking are the same. experience only one of these, the familiar ice Ih that forms During the workshop we found that, despite the diversity of in your freezer and makes up snowflakes and icebergs, ice research, a number of key themes are indeed common changing pressure and temperature can cause changes of between the different fields. The common ground in any field phase into other forms, as indicated in the phase diagram of of ice research is the urge to understand better its structure Fig. 1. Most of these phases are stable within a given range and dynamics. For example: What are the ordering mecha- of temperature and pressure, but some are only metastable; nisms of ice as it changes from one of its phases into another? for example, ice IV and XII, also indicated in Fig. 1, are What is the structure at its surface and how does this differ found within the regions of stability of other phases. from the bulk? What is the structure and microenvironment at the contact area of ice crystals? How does ice structure form 1. Molecular structures of ices initially? Are there metastable phases present in the environ- We now know the molecular structures of all of these ment? This work focuses on this common ground. It thus does phases, thanks largely to neutron-diffraction crystallographic not aim to be a comprehensive review; such a review of ice studies: These are indicated by the insets in Fig. 1. Further physics and chemistry would be a book, and indeed there are details and references can be found in Finney (2001, 2004) excellent books available (Hobbs, 1974; Petrenko and and Petrenko and Whitworth (1999). These structures can be Whitworth, 1999). However, many of the points raised in simply rationalized in terms of fully connected tetrahedral this work are issues of the 21st century that are not addressed networks of water molecules, with each molecule donating in the textbooks. This article provides a view of the way hydrogen bonds to two neighbors and accepting two hydro- ahead from some frontiers of research on ice. We set out the gen bonds from two others (Fig. 2). In the low-pressure ice Ih, main open physical and chemical questions on ice structures, the O–O–O angles are close to the ideal tetrahedral angle of patterns, and processes from the fields of ice research in 109.47. As pressure is increased, the molecules have to nature: from ice on Earth, in the oceans and the atmosphere, rearrange themselves to occupy less volume and this is to planetary and interstellar ice. done initially by both changes to the network structure (but We begin in Sec. II by introducing open questions in the still retaining four coordination) and increased distortion of molecular structures of ices; we then examine open issues on the O–O–O angles: for example, in ice II these angles vary dynamical patterns and processes in ice. Following this we between 80 and 129. As we increase pressure further, we look first, in Sec. III, at astrophysical ice. We then focus on come to a point at which the reduced volume available cannot ice on Earth, beginning with Sec. IV on atmospheric ice, be filled by merely increasing hydrogen-bond distortion: the whose precipitation leads to the subsequent formation of water molecules then form interpenetrating networks, as in terrestrial ice, Sec.