Subduction zone volcanoes are a major natural hazard, frequently endangering lives and livelihoods. The eruptive history of many subduction zone volcanoes includes the extrusion of blocky, silicic lava that forms domes or flows, but we do not yet understand what determines the duration of dome-forming behaviour, what path magma may take to the surface, or how these systems may change over time. This thesis presents an investigation of the Santiaguito complex of lava domes and flows in Guatemala, which has been erupting continuously since its inception in 1922. The Santiaguito lavas are predominantly dacitic to andesitic, with a gradual reduction in SiO2 content from ~66 wt% in the 1920s, to ~62 wt% in 2002. This is consistent with a ~15% decrease in the extent of fractional crystallization over that time. The compositions of plagioclase phenocryst cores indicate a diminished role for magma mixing after the 1940s. I model the Santiaguito system as progressively extracting magma from an extensive, chemically-stratified storage zone. Petrological data are consistent with a storage zone extending from ~25 to ~12 km depth, and magma storage temperatures of ~940 to ~980°C. Phenocryst-hosted apatites suggest melt in this storage zone contained 401 to 1199 ppm S, 600 to 1300 ppm F, and 4100 to 6200 ppm Cl. Ascending magma may pass slowly through a conduit bottleneck, or plug, at shallow depths; groundmass texture suggests that melt rigidifies at or near the base this plug. Pre-eruptive melt volatile concentrations suggest time-averaged fluxes of 40 to 263 Mg d-1 SO2, 32 to 145 Mg d-1 HF, and 247 to 708 Mg d-1 HCl, giving ratios of 0.6 to 0.8 HF/SO2, and 2.7 to 6.2 HCl/SO2. These results are consistent with the few direct measurements of SO2 at Santiaguito, and with measured halogen emissions from other silicic dome-forming systems.

After water vapour, CO₂ is the most abundant gas associated with magmatic hydrothermal systems. The detection of anomalous soil temperature gradients, and/or a significant flux of magmatic volatiles, is commonly the only surface signature of an underlying high temperature reservoir. For both heat (as water vapour) and gas to ascend to the surface, structural permeability must exist, as the unmodified bulk permeability of reservoir rock is too low to generate the focussed fluid flow typical of magmatic hydrothermal systems. This thesis reports the investigation into the surface heat and mass flow of the Ohaaki hydrothermal field using detailed surface measurements of CO₂ flux and heat flow. Detailed surface measurements form the basis of geostatistical models that quantify and depict the spatial variability of surface heat and mass flow, across the surface of both major thermal areas, as high resolution pixel plots. These maps, in conjunction with earlier heat and mass flow studies, enable: (i) estimates of the pre-production and current CO₂ emissions and heat flow for the Ohaaki Field; (ii) interpretation of the shallow permeability structures governing fluid flow, and; (iii) the spatial relationships between pressure-induced ground subsidence and permeability. Heat flow and CO₂ flux surveys indicate that at Ohaaki the soil zone is the dominant (≥ 70% and up to 99%) pathway of heat and mass release to the atmosphere from the underlying hydrothermal reservoir. Modelling indicates that although the total surface heat and mass flow at Ohaaki is small, it is highly focused (i.e., high volume per unit area) relative to other fields within the Taupo Volcanic Zone (TVZ). Normalised CO₂ emissions are comparable to other volcanic and hydrothermal fields both regionally and globally. Despite 20 years of production, there is little difference between pre-production and current CO₂ emission rates. However, the similarity of CO₂ emission rates masks a 40% increase in CO₂ emissions from new areas of intense steaming ground that have developed in response to production of the field for electrical energy production. This increase in thermal ground emissions is offset by emission losses associated with the drying up of all steam heated pools and alkali-Cl outflows from the Ohaaki West (OHW) thermal area, in response to production-induced pressure decline. The location of surface thermal areas is governed by the occurrence of buried or partially emergent lava domes, whereas the magnitude of CO₂ flux, mass flow, and heat flow occurring within each thermal area is determined by the proximity of each dome (thermal areas) to major upflow zones. Buried or partially emergent silicic lava domes act as cross-stratal pathways for fluid flow, connecting the underlying reservoir to the surface, and bypassing several hundred metres of the poorly permeable Huka Falls Formation (HFF) caprock. For each dome complex the permeable structures governing fluid flow are varied. At Ohaaki West, thermal activity is controlled by a deep-rooted concentric fracture zone, developed during eruption of the Ohaaki Rhyolite dome. Within the steam-heated Ohaaki East (OHE) thermal area, flow is controlled by a high permeability fault damage zone (Broadlands Fault) developed within the apex of the Broadlands Dacite dome. Structures controlling alkali-Cl fluid flow at OHW also iii appear to control the occurrence and shape of major subsidence bowls (e.g., the Main Ohaaki Subsidence Bowl), the propagation of pressure decline to surface, and the development and localization of pore fluid drainage. Across the remainder of the Ohaaki field low amplitude ground subsidence is controlled by the extent of aquifer and aquitard units that underlie the HFF, and proximity to the margins of the hot water reservoir. The correlation between the extent of low amplitude ground subsidence and the margins of the field reflects the coupled relationship between the hot water reservoir and reservoir pressure. Only where thick vapour-phase zones buffer the vertical propagation of deep-seated pressure decline to the surface (i.e., OHE thermal area), is ground subsidence not correlated with subvertical structural permeability developed within the HFF. This thesis makes contributions to regional and global research on geothermal and hydrothermal systems by: (i) quantifying the origin, mass, and upward transport of magmatic carbon from geothermal reservoirs; (ii) assessing the changes to the natural surface heat and mass flow of the Ohaaki Field following 20 years of production; (iii) establishing the utility of surface CO₂ flux and heat flow surveys to identify major upflow zones, estimate minimum mass flow, and determine the enthalpy of reservoirs; (iv) providing insight into the hydrothermal, structural and lithological controls over hydrothermal fluid flow; (v) demonstrating the influence of extinct silicic lava domes as important structural elements in the localisation of hydrothermal fluid flow; (vi) identifying the hydrostructural controls governing the spatial variability in the magnitude of pressure-induced ground subsidence, from which predictive models of subsidence risk may be defined, and; (vii) developing new technologies and characterising methods used for detailed assessment of surface heat and mass flow.