Elements v. x, issue y, month 2010 (corrected 150310) PERSPECTIVES SOME FUTURE RESEARCH PERSPECTIVES ON METAMORPHIC PROCESSES AND METAMORPHIC FLUIDS Alan Bruce Thompson*, ETH Zurich Metamorphic aqueous fluids makes things happen inside the Earth: they considerably speed up heat and mass transfer, they induce weakness and instabilities in rock masses, they are instrumental in localising deformation enabling tectonic response to plate motion, they markedly lower the melting temperature of silicate rocks, they noticeably lower the viscosities of silicate magmas, and they transport large quantities of dissolved materials in selected geological environments. In the future we need to determine what makes deep crustal fluids go where they go – in what quantity, with what speed? with what chemical effect? and with what consequence for mineralization? for rock deformation? Metamorphic petrology has developed much in the last twenty years. From laboratory and thermodynamic calibrations, the mineral assemblages in metamorphic rocks can be used to determine pressures (P) and temperatures (T) of equilibration. Some rocks containing chemically zoned minerals, or overgrown mineral assemblages, can reveal segments of PTt(time) paths of the rocks burial/exhumation history. These PTt paths can be related to structural features and tectonic indicators to estimate geodynamic evolution in distinct plate tectonic settings. Convergent plate settings include mountain building (orogenesis) above subduction zones or upon continental collision. Divergent plate settings include rifting in arcs, continental interiors or at mid ocean ridges. Careful comparison of deduced PTt paths with rheologically constrained geodynamic models is a developing field in each tectonic setting. This rich legacy of petrological methods is central to our understanding of plate-scale tectonic processes. The same methods will be vital to understanding nature when obtaining riches (fluids, minerals, heat) from the Earth’s crust There are now good criteria for indicating when such resources can be obtained and when they cannot. Heat sources for crustal metamorphism Metamorphism, the mineralogical transformation of rocks, occurs mainly by transposing rocks closer to a heat source - either by burial to depth where temperatures are higher, or next to a magmatic intrusion, or by concentrating radiogenic heat sources, or by locally converting work to heat during deformation. The latter two can refer to heat generation within the crust, the former two reflect the mantle as the ultimate heat source for crustal metamorphism. From heat balance considerations we are beginning to understand the extent of involvement of mantle heat in crustal metamorphism (oceanic and continental). Quantified heat balance required to induce particular metamorphic transformations has been determined from comparison of measured heat of specific metamorphic reactions compared to likely natural sources of heat (e.g. a selected magmatic intrusion) in selected terrains. Multiepisodic metamorphism of the lower crust As rock units from near the surface become tectonically buried, they transform their mineral assemblages in response to higher temperatures in the new surroundings at depth. Such metamorphic rock units are later returned to the surface by subsequent processes of tectonic exhumation. In many cases burial and exhumation do not occur in the same tectonic episode, sometimes being separated by tens of millions of years (10’s Ma). While multiplicity is suggested for many episodes of crustal tectonics, there is a sad paucity of geochronological data with which to evaluate the geodynamic evolution of most orogenic zones. Rates of burial/exhumation can proceed at plate velocities (1mm to 10 cm yr-1) or at much slower erosional velocities (0.01 to 0.5 mmyr-1). When correlated with available radiogenic geochronology it is clear that regional deformation proceeds in spurts of activity with pauses in between (episodic, punctuated). A region may suffer migrating orogenesis over 100’s of Ma, but individual episodes of tectonic activity within may be on a Ma timescale. The lack of age data (absolute or relative) means that we cannot say under which circumstances tectonic motion is continuous and controlled by large scale remote forces, and when it is perturbed by local adjustment to the changes in P (or depth), T, stress or fluid influx. We must consider multiple sequential separate episodes of deep crustal rock heating (which become recorded by new metamorphic minerals) and related fluid release. Slow fluid migration results in long-term mid crustal fluid storage. Stored metamorphic fluids become involved in regional (exhumation) or local (faulting, earthquakes) deformation only in a much later tectonic episode. Types of metamorphic fluids Deep metamorphic fluids are released beneath the continents through devolatilization reactions in response to tectonic transport towards a heat supply (products of prograde metamorphism). On the other hand metamorphic fluids on the ocean floor and in the continental crust are the cause of retrograde metamorphism, when drier hot rocks become infiltrated (making hydrated and carbonated minerals) next to fractures and in shear zones. Fluid production and fluid migration are very irregular events in the deeper Earth’s crust. Competition among the rates of these various processes generates the diversity seen in the patterns of microtexture and mineralogy in metamorphic rocks. We must never forget that exhumed deep crustal metamorphic rocks contain unstable mineral assemblages, which are very sensitive to destruction by fluids, especially where access is aided by penetrative deformation. We will discuss next the fate and effects of the fluids generated during metamorphism (more than rocks left behind). We consider that fluid-rock interaction at any PT involves “metamorphic” fluids, including shallow metamorphic fluids that have equilibrated with the atmosphere (meteoric, as in weathering). Stable isotope studies permit distinction of the loss of former meteoric signatures during fluid-rock interaction. Much of our understanding of redox reactions (and corrosion/erosion) between groundwaters, minerals and metals is being gained by geochemical observations - very important for construction, mineral processing, and deep engineering. Some metamorphic fluids, trapped in fluid inclusions, have geochemical signatures of equilibration with higher-grade metamorphic, mantle, or magmatic mineral assemblages. Mineral assemblages that have not been reset by retrograde reactions in the upper crust, indicate that fluid infiltration is rarely pervasive but rather focussed in spaced channelways. Related isotope studies indicate that retrograde fluid flow is usually focussed in regions of internal structural weakness, or in zones of external tectonic disturbance (rather than pervasively through all rock types). Particular elemental changes during metamorphism have been quantified from studies of mass-balance between mineral assemblages involved in specific rock transformation. These studies show which elements are sensitive to fluid migration near crystalline rock reservoirs and repositories. Ion microprobes able to analyse one micron sized spots in rock slices (eg, Gordon et al. 2009), are now providing necessary isotopic data relevant to the age, duration and intensity of fluid transport processes. Chemically concentrated metamorphic fluids Heating of buried rock units causes the volatile species in minerals (OH-, CO32-, 2H2O, S , SO42-, NH4-,) to be released as a metamorphic fluid phase. Metamorphic fluids are predominantly H2O, and CO2 is the prevalent carbon species (CO, CH4 are insignificant). CH4 is an important component of some ocean floor systems, indicating biological input or Fe3+ - Fe2+ redox control. Reduced nitrogen and sulfur gases (NH3, H2S, S2) are the stable species in metamorphic fluids when graphite or diamond is present. The fluids contain minor amounts of charged species, including Cl-, that bind with metal and other cations. Such fluids can become quite concentrated solutions at depth (e.g., Newton and Manning, 2010) especially close to the temperatures where crustal rocks melt (e.g., Hack et al, 2007). New work on understanding how metal and silicate solubility changes in natural fluids in the PTX(composition) gradients of the Earth, will help to understand the evolution of natural chemical concentration processes needed for mineral deposits. Timescales of metamorphism and fluid migration mechanisms Time-scales for prograde regional and contact metamorphic heating, are mainly determined by heat conduction from a finite heat source (distance to transposed asthenospheric mantle or to a magma body). The length- to time-scaling for solid heat conduction is as length squared proportional to к x time (where к ~10-6 m2 s-1). This proportionality directly controls the time-scales for fluid production. The rate at which minerals devolatilize is thus dependent upon the heat supply. In higher temperature regimes, natural compaction or shearing tend to govern fluid expulsion. Length-scales for fluid migration depend upon to what extent the fluid flow is focused for a given amount of fluid released by the devolatilization reactions. Focussing factors can be scaled to areas of porous media flow compared to a fracture, to obtain scaled fluxes. The lower density of metamorphic fluid (H2O, ca. 1 g cm-3) compared to rock (ca. 3 g cm-3) means that fluids tend to migrate upwards when they can. The rate of which metamorphic fluids migrate depends on whether the flow is dispersed or focused. Porous flow along grain boundaries is more typical for hotter (or more ductile) rheological behaviour, whereas fracture flow is expected in the brittle rock rheology PT-range. Hydrofracturing in response to rapid fluid release and fast strain rate deformation may occur in rocks even in the nominally ductile PT-range. The diverse factors controlling fluid flow can be quantified in forward models of metamorphism but are not easily recoverable from geological observations - which are inverse or “backwards oriented”. This reflects mainly the difficulty of obtaining three dimensional field coverage of actual metamorphic fluid channelways even from a mined ore deposit. It is not simple to know how much of specific fluid flow indicators belong to a particular episode which is to be identified with a given heat source. To attempt to quantify crustal-scale fluid migration thus requires new geochemical work using ratios of elements characteristic of the various fluid/melt/mineral partition characteristics. Massof-fluid fluxes so obtained with ion microprobes, help determine the real details of natural transport processes, and estimates of their magnitude and duration A vital aspect still to be resolved on all scales is how efficient is fluid recirculation within the lithosphere? In other words, when is fluid migration single- rather than multiple-pass (only upwards advection or more circular as in convection, e.g., Walther and Wood 1986)? Exhumation of metamorphic rocks Many crystalline rocks metamorphosed at depth stay there constituting the lower continental crust, if not exhumed by upwards oriented deformation processes. These rocks retain their higher grade metamorphic mineral assemblages and segregated ore deposits at depths inaccessible to our mining. Fuller understanding of the tectonic engines which lead to the exhumation of slices of metamorphosed lower crust, would certainly aid our prospecting initiatives in future years. Fluids go where they can travel fastest for a given pressure gradient, but become consumed where they can make volatilised minerals or hydrous melts, or enter magmas. In brittle rocks, fluids will tend to follow existing lithological/structural heterogeneities (as it is more difficult to make faults from scratch in homogeneous media). Thereafter the first heterogeneities tend to be continually reactivated and therefore localised in same place. Thus we would expect much continuous overprinting of isotopic signature, requiring careful separation of samples before measurement. Detailing the processes that lead to focussed rock weakening is also fundamental to understanding how deep metamorphic rocks become exhumed. Focused rock weakening is a vital part of the metamorphic cycle for mineralisation and for exhumation, and presumably involves the fluids released by deeper metamorphic reactions. Heat advection by metamorphic fluid The predominant mechanism of heat transfer during regional metamorphism is by conduction through minerals in rocks rather than by fluid advection through the porosity, simply because deep crustal fluid flow is naturally restricted. Fluid flow exceeding 10 -10 m3m-2s-1 is needed to permit any heat advection (eg. Bickle and McKenzie, 1987) and would be very rare in metamorphic settings (e.g., Brady 1988). Natural advective heating by rising fluids would be a faster mode of heat transfer than by conduction, but is restricted both in space and time. It is restricted geologically to natural convection (buoyant upflow and downflow) in hydrothermal - geothermal systems clearly related to magma intrusion at quite shallow depths. More themes for future research With the chemical and mineralogical background of metamorphic petrology well established, the next decade will see advances in scaled up (macroscopic) geophysical interpretations and field considerations, from regional to outcrop or hand-specimen scale. Scaling down, several detailed regions of microscopic chemical and isotopic study will be related to microstructures to establish diagnostics for time-dependent stress relaxation and mass transport. I have listed, some other areas of fluid-rock interaction research that I would certainly like to pursue, in decreasing scale of observation:1) quantifying the subducted flux of volatiles into deep earth compared to deep mineral storage of primordial volatiles, 2) mechanisms of access of H2O and CO2 from subducted slab into mantle wedge magmas, then from fractionated magma into the near -surface hydrothermal system, 3) specifics of role of water access in large-scale rock weakening leading to major tectonic processes (e.g., earthquake sources, crustal scale shear zones, thinning of lithosphere, promotion of subduction, aiding of magma intrusion). 4) mechanisms of transition from porous media flow in fluid source regions, to focussed flow in fractures or shear zones, 5) role of growth of hydrous/carbonate minerals in promoting rock failure. Such study is related to the CO2 -sequestration problem (see Elements v. 4, issue 5, October 2008), 6) the relative importance of oxidised versus reduced species of C, S and N in magmatic and hydrothermal processes in different fO2 ranges, migrating along natural gradients in pressure (driving fluid motion) and temperature (away from natural heat sources), 7) when do metamorphic fluids have catastrophic impact upon crustal heat transport or release of volatiles to crust (causing deep earthquakes?) or atmosphere (changing its composition?), or are such examples seldom? 8) depth of phase separation and relation to chemistry of fluids in ocean floor and landbased hydrothermal systems, 9) actual depth-temperature paths around natural critical points in liquid-vapour systems in hydrothermal systems and in fluid-melt systems (e.g., in subduction zones, Hack et al, 2007). Such study is also central to many chemical engineering projects for selective extraction or industrial concentration of particular elements in aqueous or carbonic fluids, 10) development of robotics in deep mining (which like space travel is not suited to the human body), 11) ways of determining the relative roles of sulfur and chlorine for metal transport in combined volatile systems, e.g., Seward and Barnes (1997), 12) mechanisms of proton weakening of mineral atomic bonding. I am grateful to James Connolly, Haakon Austrheim, Bjorn Jamtveit and Susan Stipp for comments. REFERENCES Bickle MJ and McKenzie DP (1987) The transport of heat and matter by fluids during metamorphism Contributions to Mineralogy and Petrology 95:384-392 Brady J B (1988) The role of volatiles in the thermal history of metamorphic terranes Journal of Petrology 29: 1187-1213 Gordon SM, Grove M, Whitney DL, Schmitt AK and Teyssier C (2009) Fluid-rock interaction in orogenic crust tracked by zircon depth profiling Geology 37: 735-738 Hack AC, Thompson AB and Aerts M (2007) Phase Relations Involving Hydrous Silicate Melts, Aqueous Fluids, and Minerals Reviews in Mineralogy and Geochemistry 65: 129-185 Newton, RC, and Manning, CE (2010) Role of saline fluids in deep-crustal and uppermantle metasomatism: insights from experimental studies. Geofluids 9: 1–15 Seward, TM and Barnes, HL (1997) Metal Transport by Hydrothermal Ore Fluids. In: Barnes, HL (ed) Geochemistry of hydrothermal ore deposits, Wiley New York, Chapter 9: 972 pp. Wood B J and Walther J V (1986) Fluid flow during metamorphism and its implications for fluid-rock ratios. In: Walther, J. V. & Wood, B. J. (eds) Fluid-Rock Interactions during Metamorphism, Springer, New York: 89–108 Footnote: *Alan B. Thompson is Professor of Petrology at ETH Zurich and at the University of Zurich, Switzerland. His research considers physical and chemical evolution of the Earths lithosphere, particularly the role of aqueous fluid and magma evolution in mass and heat transfer and tectonic processes.