Timescales Of Storage Research Articles

A comparative analysis of the economic feasibility of reversible hydrogen systems based on time-resolved operation optimisation

The expansion of fluctuating renewable energy production, such as wind and PV, increases the mismatch to consumption. Power-to-Hydrogen-to-Power (PtHtP) systems are believed to be a key for balancing under and overproductions. PtHtP systems can provide temporal and spatial flexibilities and among them reversible solid oxide cells (rSOC) are a promising technology. They combine production of hydrogen and power in the same electrochemical stack. This generates a financial and environmental benefit since less resources are necessary for enabling both Power-to-Hydrogen and Hydrogen-to-Power. This work investigates the application of rSOC systems in comparison to reversible PEM systems consisting of electrolysis and fuel cell unit. In the present studies time-resolved optimization is employed for simulation of the optimal operation of the PtHtP technologies in different market price conditions for electricity, hydrogen and natural gas and with coupling to industry and district heat. Both systems have a zone of market prices, that allows for a positive economic performance over lifetime. The electricity‑hydrogen price difference in this zone is in the range from −83 €/MWh to 133 €/MWh depending on the scenario. Furthermore, the electricity price fluctuations are found to have the major impact on the profitability. By studying the influence of gas grid fees, one finds that local compressed hydrogen storages can be used only for very short storage timescales up to a few hours. Finally, the derivation of application conditions, that are suitable for the two different spatial kinds of reversible hydrogen systems – spatially concentrated and delocalized and the two technologies – rSOC and PEM, is made.

Effect of crustal stress state on magmatic stalling and ascent: case study from Puyehue-Cordón Caulle, Chile

The Southern Volcanic Zone (SVZ) in Chile is an active continental arc with a complex history of volcanism, where a range of magmatic compositions have been erupted in a variety of styles. In the Central SVZ, both monogenetic and polygenetic volcanoes exist, in close proximity to the Liquiñe-Ofqui Fault System (LOFS), but with variable local stress states. Previous studies have inferred varying crustal storage timescales, controlled by the orientation of volcanic centres relative to the N-S striking LOFS and σHMax in this region. To assess the relationship between volcanism and crustal stress states affected by large-scale tectonic structures and edifice controls, we present whole rock geochemical data, to ensure consistency in source dynamics and crustal processing, mineral-specific compositional data, thermobarometry, and Fe–Mg diffusion modelling in olivine crystals from mafic lavas, to assess ascent timescales, from the stratovolcanic edifice of Puyehue-Cordón Caulle and proximal small eruptive centres. Textural observations highlight differences in crystal maturation timescales between centres in inferred compression, transpression, and extension, yet source melting dynamics remain constant. Only samples from the stratovolcanic edifice (in regional compression) preserve extensive zonation in olivine macrocrysts; these textures are generally absent from proximal small eruptive centres in transtension or extension. The zonation in olivines from stratovolcanic lavas yields timescales on the order of a few days to a few weeks, suggesting that even in environments which inhibit ascent, timescales between unrest and eruption of mafic magmas may be short. Significantly, high-resolution compositional profiles from olivine grains in the studied samples record evidence for post-eruptive growth and diffusion, highlighting the importance of careful interpretation of diffusion timescales from zoned minerals in more slowly cooled lavas when compared with tephra samples.

Remobilization and eruption of an upper crustal cumulate mush at the Singkut caldera (North Sumatra, Indonesia)

Understanding the conditions and timescales of storage and remobilization of magma bodies in the upper crust is key to interpreting the signals of potential reawakening at active volcanoes. In this paper, we provide the first volcanological and petrochronological characterization of the Singkut caldera, a young volcanic system located in northern Sumatra (Indonesia), in close proximity to Medan, one of the country's most popoluous cities. Singkut formed at ∼44 ka during a VEI 6 explosive eruption that deposited at least ∼26 km3 of tephra (dense rock equivalent, DRE). The cataclysmic eruption was preceded by >200 ky of mostly effusive pre-caldera activity and followed by effusive to mildly explosive post-caldera activity. The lavas and pumices have high crystallinity (up to 62% crystals) with andesitic to dacitic bulk-rock composition and rhyolitic glass. Mineral textures and matrix glass compositions indicate resorption of quartz, plagioclase and zircon. Zircon crystallization ages show a complete overlap with the eruption ages in pre-caldera lavas, while a time gap in zircon crystallization (>50 ky) is identified in the caldera-forming tuff and post-caldera lavas. Ti-in-zircon thermometry shows that the Singkut magma body experienced a temperature increase starting approximately upon eruption of the pre-caldera lavas (∼254 ka). Such thermal perturbation determined progressive melting of mineral phases in the cumulate crystal mush, caused the resorption of the youngest zircon domains before the caldera-forming eruption, and hampered zircon crystallization between the caldera-forming eruption and the effusion of the post-caldera lavas (∼16 ka). Our data demonstrate how cumulate melting processes played a key role in leading the volcanic system towards a caldera-forming eruption and controlled the transitions in eruptive style between the effusive phases and the explosive climactic eruption.

Benefit-cost ratios of carbon dioxide removal strategies

All pathways to achieving the Paris Agreement target of limiting global warming to 1.5 ∘C or 2 ∘C require the large-scale removal of carbon dioxide (CO2) from the atmosphere. Many CO2 removal (CDR) strategies have been proposed, which vary widely in both price per ton of CO2 removed and storage timescale of this removed CO2, as well as mechanism, maturity, scalability, and other factors. However, it has not yet been thoroughly assessed whether the benefits, in terms of climate change-related damages avoided, of CDR deployment exceeds their cost at current reported prices and storage timescales, or what cost is required for CDR strategies with a given storage timescale to provide net benefits and how these depend on socioeconomic assumptions. For CDR strategies that have long storage (500 year) timescales, these questions reduce to whether its price is lower than the social cost of carbon, but here we show for CDR strategies that operate over shorter timescales they also depend on the duration of storage. We demonstrate that for CDR strategies with reported storage timescales of decades to centuries, the benefits of their deployment outweigh their reported costs under middle-of-the-road socioeconomic assumptions, and in some cases their benefits still outweigh their costs under optimistic socioeconomic assumptions. Overall, the benefit-cost ratios of the evaluated CDR strategies vary by more than an order of magnitude, and are strongly influenced by both price and storage timescale. Our results provide a framework that can be used to assess and compare different CDR strategies quantitatively to help guide future research, development, and policy efforts.

Isotopic approach to linking landscape and catchment storage across multiple spatial scales

Catchment heterogeneity leads to uncertainty about estimating timescales of storage and difficulty in extrapolating to larger scales. A heterogeneity-independent storage index (SI) was employed to build a connection with catchment characteristics, especially for landscapes, over six humid, forestry catchments. The SI is derived from the amplitudes of tracer cycles in precipitation and ephemeral/intermittent streamflow. The SI was significantly correlated with landscape metric (R2 = 0.81 and p = 0.014), specifically the fractal dimension index (FRAC) indicating the shape complexity of the landscape. Meanwhile, the topographic wetness index (TWI) (R2 = 0.77, p = 0.021) showed a close connection with the storage index as well. Close correlations suggested that the FRAC and TWI regulate the timescale of storage over the range of spatial scales, in particular the young water fraction in streams, because the SI is a heterogeneity-independent metric derived from seasonal tracer cycle amplitudes, which has a close relation to young water fraction. This also indicated the SI can be treated as an alternative travel-time metric and a reflection of the hydrological nature. Moreover, the findings implied the possibility of hydrological modeling over multiple spatial scales. The linkage between SI and landscape and topography provides insight into the mechanism of streamflow generation. Based on ephemeral streams, the crucial control of landscape and topography on the timescale of storage contributes to available water assessment and sustainable ecosystem management.

Thermal storage conditions and origin of compositional diversity of plagioclase crystals in magmas from the 1980 and 2004-2005 eruptions of Mount Saint Helens

Abstract The thermal histories of upper crustal magma reservoirs place important constraints on the formation, evolution, and remobilization of crustal magmas, yet quantifying thermal histories remains challenging. We report new in-situ plagioclase trace-element data, Sr in plagioclase diffusion timescales, and plagioclase 238U-230Th-226Ra disequilibria data from Mount Saint Helens (MSH) 1980 cryptodome and 2004-2005 dacite domes to evaluate the thermal storage conditions and compositional diversity of recent MSH magmas. This approach allows us to more directly link the thermal (and therefore physical) conditions within the MSH magma reservoir to timescales of storage, thereby constraining the fraction of time 1980-2005 MSH magmas have spent in a mobile state. Plagioclase trace-element data and U-series characteristics reveal a compositionally heterogenous magmatic system beneath MSH and also require multi-stage plagioclase growth histories. The data also show that 2004-05 dacites contain a different plagioclase population relative to the 1980 cryptodome dacite, comprised of either a compositionally (and possibly temporally) distinct plagioclase component or composed of the same plagioclase components but in significantly different proportions. Discordant plagioclase 238U-230Th and 230Th-226Ra apparent ages require a mixture of young (likely eruption related) and old (>20-40 ka) plagioclase crystals in both 1980 and 2004-05 dacites. The low (230Th)/(232Th) in all measured 1980 and 2004-05 plagioclase requires a significant fraction (>10-30%) of the plagioclase to be old (>10s kyr). Maximum modeled Sr diffusion timescales at 750oC range from decades to centuries for both eruptions, with a maximum of ~600 years found in 1980 cryptodome plagioclase. However, partially equilibrated Sr in the innermost exposed parts of some crystals found in both 1980 and 2004-05 plagioclase indicate that a fraction (>20%) of plagioclase may have experienced a total of >10 kyrs at temperatures ≥750oC. Coupling Sr diffusion timescales with U-series measurements indicates that significant fraction (at least ~40%) of modeled MSH plagioclase spent <5% of their storage time at temperatures ≥750oC and thus in an easily mobilized rheological state. In contrast, the fraction of partially equilibrated plagioclase possibly spent >25-50% of their storage time at hotter conditions. Our data combined with data from other arc magmatic systems (e.g., Mt. Hood) imply that the process of remobilizing magma in arc systems towards successive eruptions requires thermally rejuvenating largely crystalline material, as opposed to sequential tapping of a persistent liquid-dominated magma body, even if successive eruptions are spaced closely in time (decades). In addition, rejuvenation events responsible for successive eruptions may sample spatially localized, but potentially overlapping, portions of the broader magma reservoir.

Analyzing Recharge Dynamics and Storage in a Thick, Karstic Vadose Zone

AbstractKarst vadose zone heterogeneity creates complex transmission and storage dynamics that affect the timing and magnitude of aquifer recharge. Young, high‐matrix permeability eogenetic karst aquifers may have significantly higher matrix storage than older, lower matrix permeability counterparts. In vulnerable and water‐limited karst regions, the timescales of storage may be important for seasonal and sub‐seasonal water resource management. We create a framework to quantify storage dynamics in karst aquifers using high‐resolution precipitation and groundwater levels from the Northern Guam Lens Aquifer in the US territory of Guam. We estimate recharge using the Water Table Fluctuation method, and then develop transfer functions between precipitation and recharge to quantify storage and release of water from the vadose zone. The transfer functions are partitioned into different flow pathways including conduit, conduit/matrix, and slowly draining matrix. Probability distributions are fit to each pathway to determine the average travel times of infiltrated waters. The results show that aquifer recharge through secondary porosity features typically occurs within a few hours of a rainfall event, but this rapid recharge accounts for only 12%–28% of total recharge. The majority of aquifer recharge (>70%) occurs within a month of a contributing storm event. An additional 10% of recharge, on average, took longer than a month to reach the water table. The framework established can help improve the hydrological modeling and freshwater management for karst aquifers.

Quantitative relationships between river and channel-belt planform patterns

Abstract Channel planform patterns arise from internal dynamics of sediment transport and fluid flow in rivers and are affected by external controls such as valley confinement. Understanding whether these channel patterns are preserved in the rock record has critical implications for our ability to constrain past environmental conditions. Rivers are preserved as channel belts, which are one of the most ubiquitous and accessible parts of the sedimentary record, yet the relationship between river and channel-belt planform patterns remains unquantified. We analyzed planform patterns of rivers and channel belts from 30 systems globally. Channel patterns were classified using a graph theory-based metric, the Entropic Braided Index (eBI), which quantifies the number of river channels by considering the partitioning of water and sediment discharge. We find that, after normalizing by river size, channel-belt width and wavelength, amplitude, and curvature of the belt edges decrease with increasing river channel number (eBI). Active flow in single-channel rivers occupies as little as 1% of the channel belt, while in multichannel rivers it can occupy >50% of the channel belt. Moreover, we find that channel patterns lie along a continuum of channel numbers. Our findings have implications for studies on river and floodplain interaction, storage timescales of floodplain sediment, and paleoenvironmental reconstruction.

Spatially averaged stratigraphic data to inform watershed sediment routing: An example from the Mid-Atlantic United States

Abstract New and previously published stratigraphic data define Holocene to present sediment storage time scales for Mid-Atlantic river corridors. Empirical distributions of deposit ages and thicknesses were randomly sampled to create synthetic age-depth records. Deposits predating European settlement accumulated at a (median) rate of 0.06 cm yr–1, range from ∼18,000 to 225 yr old, and represent 39% (median) of the total accumulation. Sediments deposited from 1750 to 1950 (“legacy sediments”) accumulated at a (median) rate of 0.39 cm yr–1 and comprise 47% (median) of the total, while “modern sediments” (1950–present) represent 11% of the total and accumulated at a (median) rate of 0.25 cm yr–1. Synthetic stratigraphic sequences, recast as age distributions for the presettlement period, in 1900 A.D., and at present, reflect rapid postsettlement alluviation, with enhanced preservation of younger sediments related to postsettlement watershed disturbance. An averaged present age distribution for vertically accreted sediment has modal, median, and mean ages of 190, 230, and 630 yr, reflecting the predominance of stored legacy sediments and the influence of relatively few, much older early Holocene deposits. The present age distribution, if represented by an exponential approximation (mean age ∼300 yr), and naively assumed to represent steady-state conditions, implies median sediment travel times on the order of centuries for travel distances greater than ∼100 km. The percentage of sediment reaching the watershed outlet in 30 yr (a reasonable time horizon to achieve watershed restoration efficacy) is ∼60% for a distance of 50 km, but this decreases to <20% for distances greater than 200 km. Age distributions, evaluated through time, not only encapsulate the history of sediment storage, but they also provide data for calibrating watershed-scale sediment-routing models over geological time scales.

Floodplain Sediment Storage Timescales of the Laterally Confined Meandering Powder River, USA

AbstractAs sediment is transported through river corridors, it typically spends more time in storage than transport, and as a result, sediment delivery timescales are controlled by the duration of storage. Present understanding of storage timescales is largely derived from models or from field studies covering relatively short (≤102 year) time spans. Here we quantify the storage time distribution for a 17 km length of Powder River in Montana, USA by determining the age distribution of eroded sediment. Our approach integrates surveyed cross‐sections, analysis of historical aerial imagery, aerial LiDAR, geomorphic mapping, and age control provided by optically stimulated luminescence (OSL) and dendrochronology. Sediment eroded by Powder River from 1998 to 2013 ranges from a few years to ∼5,000 years in age; ages are exponentially distributed (r2 = 0.78; Anderson‐Darling p value 0.003). Eroded sediment is derived from Powder River's meander belt (∼900 m wide), which is only 1.25 times its meander wavelength, a value reflecting valley confinement rather than free meandering. The mean storage time, 824 years (95% C.I. 610–1030 years), is similar to the time required to rework deposits of Powder River's meander belt based on an average meander migration rate of ∼1 m/yr, implying that storage time distributions of confined meandering rivers can be quantified from remotely sensed estimates of meander belt width and channel migration rates. Heavy‐tailed storage time distributions, frequently cited from physical and numerical modeling studies, may be restricted to unconfined meandering rivers.

The fate of fluvially-deposited organic carbon during transient floodplain storage

CO2 release from particulate organic carbon (POC) oxidation during fluvial transit can influence climate over a range of timescales. Identifying the mechanistic controls on such carbon fluxes requires determining where POC oxidation occurs in river systems. While field data show POC oxidation and replacement moving downstream in lowland rivers, flume studies show that oxidation during active fluvial transport is limited. This suggests that most fluvial POC oxidation occurs during transient floodplain storage, but this idea has yet to be tested. Here, we isolate the influence of floodplain storage time on POC oxidation by exploiting a chronosequence of floodplain deposits above the modern groundwater table in the Rio Bermejo, Argentina. Measurements from 15 floodplain cores with depositional ages from 1 y to 20 ky show a progressive POC concentration decrease and 13C-enrichment with increasing time spent in floodplain storage. These results from the Rio Bermejo indicate that over 80% of fluvially-deposited POC can be oxidized over millennial timescales in aerated floodplains. Furthermore, POC in the oldest floodplain cores is more 14C-enriched than expected based on the independently-dated floodplain ages, indicating that a portion of this oxidized POC is replaced by autochthonous POC produced primarily by floodplain vegetation. We suggest floodplain storage timescales control the extent of oxidation of fluvially-deposited POC, and may play a prominent role in determining if rivers are significant atmospheric CO2 sources.

Preliminary analysis of long‐term storage requirement in enabling high renewable energy penetration: A case of East Asia

Integrating a high penetration of renewable energy for developing sustainable and low-carbon electric energy system is becoming a common trend around the world. Many studies have evaluated the energy storage requirement for accommodating variable renewable energy (VRE). However, in the situation of high renewable penetration, there will be a huge potential requirement of long-term energy storage for addressing the seasonal energy imbalance between VRE and load demand. Thus, a key element of evaluating the storage demand in enabling high VRE penetration is identifying the timescales of storage needed and the economic combination of long-term and short-term energy storages. This is neglected in existing researches. In this study, we quantitatively analyse the role of long-term seasonal storage in enabling high VRE penetration. A generation expansion planning model is formulated to optimise the least-cost generation portfolio with a renewable penetration target. Based on the proposed model, an empirical analysis for East Asia in 2050 is performed. The results indicate that (1) long-term storage contributes to addressing the long-term energy imbalance issue, (2) the optimal duration time of long-term storage is around 720 h (a month), and (3) the long-term storage becomes economical when the renewable penetration is above 70% (54.2% VRE penetration).

Millennial soil retention of terrestrial organic matter deposited in the Bengal Fan

The abundance of organic carbon (OC) in vegetation and soils (~2,600 PgC) compared to carbon in the atmosphere (~830 PgC) highlights the importance of terrestrial OC in global carbon budgets. The residence time of OC in continental reservoirs, which sets the rates of carbon exchange between land and atmosphere, represents a key uncertainty in global carbon cycle dynamics. Retention of terrestrial OC can also distort bulk OC- and biomarker-based paleorecords, yet continental storage timescales remain poorly quantified. Using “bomb” radiocarbon (14C) from thermonuclear weapons testing as a tracer, we model leaf-wax fatty acid and bulk OC 14C signatures in a river-proximal marine sediment core from the Bay of Bengal in order to constrain OC storage timescales within the Ganges-Brahmaputra (G-B) watershed. Our model shows that 79–83% of the leaf-waxes in this core were stored in continental reservoirs for an average of 1,000–1,200 calendar years, while the remainder was stored for an average of 15 years. This age structure distorts high-resolution organic paleorecords across geologically rapid events, highlighting that compound-specific proxy approaches must consider storage timescales. Furthermore, these results show that future environmental change could destabilize large stores of old - yet reactive - OC currently stored in tropical basins.

Timescales of pre-eruptive magmatic processes at Vulcano (Aeolian Islands, Italy) during the last 1000 years

An integrated petrological and geochemical study on plagioclase crystals erupted at Vulcano Island (Aeolian Islands, Southern Italy) over the past 1000 years allowed us to draw a detailed model of the internal structure of the volcanic system, in which modes of magma interaction and timescales of storage at crustal depth are shown. The integration of compositional, textural and temporal record preserved in plagioclase crystals provides evidence for an articulated plumbing system constituted by several reservoirs connected at the crust-mantle boundary. Here, a basaltic-shoshonitic magma resides and is thought to feed the shallow magma reservoir of both La Fossa and Vulcanello centers, finally triggering eruptions throughout injections from depth. Textural and micro-compositional data on plagioclase crystals suggest the presence of three main magma levels located between ca. 17 and 2 km of depth beneath La Fossa Cone, which were intermittently reactivated over the whole period of activity considered. Plagioclase textures and compositional zoning indicate that the shallow (<11 km bsl) portions of the La Fossa plumbing system were particularly active over the last 1000 years, as crystals record the ascent and continuous episodes of magma recharge and mixing that affect the shallower reservoirs. The first stage of activity at Vulcanello (i.e. Vulcanello I eruption) was fed by slightly differentiated melts that directly rose from the deep basaltic-shoshonitic reservoir, residing for a short period of time into the crust before the eruption. Indeed, diffusion modeling calculations on Sr zoning in plagioclase indicate shorter timescales of residence (<2 years) for crystals erupted at Vulcanello compared to those of the La Fossa Cone eruptions (ca. 2–10 years). If compared with the time span between eruptions occurred at La Fossa, our time estimations may suggest that magma feeding the activity at La Fossa resides most of the time in reservoirs located below the plagioclase nucleation depth (~11 km of depth), finally rising up only few years before the eruption onset. According to our model, magmatic eruptions at Vulcano Island are related to the ascent of deep basic (basaltic/shoshonitic) magmas that trigger a sort of “reaction chain” through subsequent episodes of recharge and mixing toward the upper magmatic reservoirs.

Rapid mixing and short storage timescale in the magma dynamics of a steady-state volcano

Steady-state volcanic activity implies equilibrium between the rate of magma replenishment and eruption of compositionally homogeneous magmas, lasting for tens to thousands of years in an open conduit system. The Present-day activity of Stromboli volcano (Aeolian Islands, Southern Italy) has long been recognised as typical of a steady-state volcano, with a shallow magmatic reservoir (highly porphyritic or hp-magma) continuously refilled by more mafic magma (with low phenocryst content or lp-magma) at a constant rate and accompanied by mixing, crystallisation and eruption. Our aim is to clarify the timescale and dynamics of the plumbing system at the establishment of the Present-day steady-state activity (<1.2 ka) to pinpoint the onset of the steady-state regime. We investigated the Post-Pizzo (PP) pyroclastic sequence (∼1.7–1.5 ka) and one of the Early Paroxysms (EP) of the Present-day activity, focusing on the clinopyroxene population.Whole rock and clinopyroxene compositional variation among the PP and EP magmas is consistent with the time progression of the Stromboli system towards more mafic and lower 87Sr/86Sr compositions, pointing to the chemical and isotopic signature of the Present-day activity. Clinopyroxenes from both PP and EP record a complex history with compositional zoning that reflects growth in three different melt domains: a high-Mg# proto-lp recharging magma, a low-Mg# proto-hp resident magma, and a transient intermediate-Mg# magma. These are the result of complex turbulent flow fields and mixing regimes produced by repeated injections of the proto-lp magma in the shallow proto-hp magma reservoir. During the PP period the magmatic system was already able to regain the pre-input proto-hp composition, gradually changing toward a less evolved signature after the injection(s) of the more mafic proto-lp magma, owing to efficient (days to a few years) stirring and melt homogenisation (i.e., homogenisation time < residence time).Based upon Fe–Mg diffusion in clinopyroxene the total residence time during PP and EP periods, from the arrival of the mafic magma in the shallow system until the eruption, ranges from 1 to ∼50 years. Longer residence times (up to 150 years) have been recorded in the initial phase of the PP sequence, possibly testifying to the transition from a closed- to the open-conduit, steady-state regime of the Present-day activity.Some clinopyroxenes from the PP recorded the mafic triggering event of the feeding proto-lp magma occurring within few months to a few days before eruption. Remarkably, other clinopyroxene portions crystallised and captured the rapid timescales (a few days) of the on-going mixing and homogenisation process between the proto-lp and the proto-hp magmas leading to the eruption.The modelling of clinopyroxene zoning events at Stromboli provides evidence for growth and storage in three different melt domains, and sets robust constraints on their residence time from lp-magma recharge(s) to eruption, along with the timescales of melt homogenisation and triggering events. The lifetime history captured by Fe–Mg zoning of Stromboli clinopyroxenes suggests that the interplay between rapid mixing and short storage timescales can be a key parameter controlling the dynamics of the plumbing system of steady-state volcanoes.

Timescales of storage and recycling of crystal mush at Krafla Volcano, Iceland

Processes in upper-crustal magma reservoirs such as recharge, magma mixing, recycling of previously crystallized material, and eruption affect both the physical state and the chemical composition of magmas. A growing body of evidence shows that crystals in intermediate or silicic volcanic rocks preserve records of these processes that may be obscured due to mixing in the liquid fraction of magmas. Fewer studies have focused on crystals in basaltic lavas, but these show evidence for a more subtle, but still rich record of magmatic processes. We present new 238U–230Th–226Ra data for plagioclase, combined with δ18O and trace-element measurements of the same crystal populations, from basalts erupted at Krafla Volcanic Center, Iceland. These data document the presence of multiple crystal populations within each sample, with chemical and oxygen isotope heterogeneity at a variety of scales: within individual crystals, between crystals in a given population, between crystal populations within the same sample, and between crystals in lavas erupted from different vents during the same eruption. Comparison to whole-rock or groundmass data shows that the majority of macroscopic crystals are not in trace-element or oxygen isotope equilibrium with their host liquids. The most likely explanation for these data is that the macroscopic crystals originated within a highly heterogeneous crystal mush in the shallow magma reservoir system. U-series and diffusion data indicate that the crystals (and therefore the mush) formed recently (likely within a few thousand years of eruption, and with a maximum age of 8–9 ka), and that the crystals resided in their host magma prior to eruption for decades to a few centuries at most. These data, in conjunction with other recent studies, suggest a model where erupted Icelandic magmas are the result of diverse magmas entering the crust, followed by complex interactions between melts and previously crystallized material at all crustal levels.

Time scales of magma transport and mixing at Kīlauea Volcano, Hawai’i

Modeling of volcanic processes is limited by a lack of knowledge of the time scales of storage, mixing, and final ascent of magmas into the shallowest portions of volcanic plumbing systems immediately prior to eruption. It is impossible to measure these time scales directly; however, micro-analytical techniques provide indirect estimates based on the extent of diffusion of species through melts and crystals. We use diffusion in olivine phenocrysts from the A.D. 1959 Kīlauea Iki (Hawai’i, USA) eruption to constrain the timing of mixing events in the crustal plumbing system on time scales of months to years before eruption. The time scales derived from zonation of Fe-Mg in olivines, combined with contemporaneous geophysical data, suggest that mixing occurred on three time scales: (1) as much as 2 yr prior to eruption in the deep storage system; (2) in a shallow reservoir, between incoming hot melts and resident melt for several weeks to months prior to eruption; and (3) in the conduit and summit reservoir, between the resident magma and cooled surface lava, draining back into the vent on time scales of hours to several days during pauses between episodes. Synchronous inflation of the shallow reservoir with deep earthquake swarms and mixing suggests an intermittently open transcrustal magmatic system.

The magmatic and eruptive response of arc volcanoes to deglaciation: Insights from southern Chile

In tectonic settings where decompression melting drives magmatism, there is compelling evidence that changes in ice loading or water loading across glacial-interglacial cycles modulate volcanic activity. In contrast, the response of subduction-related volcanoes remains unclear. A high-resolution postglacial eruption record from a large Chilean stratovolcano, Mocho-Choshuenco, provides new insight into the arc magmatic response to ice-load removal. Following deglaciation, we identify three distinct phases of activity characterized by different eruptive fluxes, sizes, and magma compositions. Phase 1 (13–8.2 ka) was dominated by large dacitic and rhyolitic explosive eruptions. During phase 2 (7.3–2.9 ka), eruptive fluxes were lower and dominated by moderate-scale basaltic andesite eruptions. Since 2.4 ka (phase 3), eruptive fluxes have been elevated and of more intermediate magmas. We suggest that this time-varying behavior reflects changes in magma storage time scales, modulated by the changing crustal stress field. During glaciation, magma stalls and differentiates to form large, evolved crustal reservoirs. Following glacial unloading, much of the stored magma erupts (phase 1). Subsequently, less-differentiated magma infiltrates the shallow crust (phase 2). As storage time scales increase, volcanism returns to more evolved compositions (phase 3). Data from other Chilean volcanoes show a similar tripartite pattern of evacuation, relaxation, and recovery, suggesting that this could be a general feature of previously glaciated arc volcanoes.

Aggregation in environmental systems – Part 1: Seasonal tracer cycles quantify young water fractions, but not mean transit times, in spatially heterogeneous catchments

Abstract. Environmental heterogeneity is ubiquitous, but environmental systems are often analyzed as if they were homogeneous instead, resulting in aggregation errors that are rarely explored and almost never quantified. Here I use simple benchmark tests to explore this general problem in one specific context: the use of seasonal cycles in chemical or isotopic tracers (such as Cl−, δ18O, or δ2H) to estimate timescales of storage in catchments. Timescales of catchment storage are typically quantified by the mean transit time, meaning the average time that elapses between parcels of water entering as precipitation and leaving again as streamflow. Longer mean transit times imply greater damping of seasonal tracer cycles. Thus, the amplitudes of tracer cycles in precipitation and streamflow are commonly used to calculate catchment mean transit times. Here I show that these calculations will typically be wrong by several hundred percent, when applied to catchments with realistic degrees of spatial heterogeneity. This aggregation bias arises from the strong nonlinearity in the relationship between tracer cycle amplitude and mean travel time. I propose an alternative storage metric, the young water fraction in streamflow, defined as the fraction of runoff with transit times of less than roughly 0.2 years. I show that this young water fraction (not to be confused with event-based "new water" in hydrograph separations) is accurately predicted by seasonal tracer cycles within a precision of a few percent, across the entire range of mean transit times from almost zero to almost infinity. Importantly, this relationship is also virtually free from aggregation error. That is, seasonal tracer cycles also accurately predict the young water fraction in runoff from highly heterogeneous mixtures of subcatchments with strongly contrasting transit-time distributions. Thus, although tracer cycle amplitudes yield biased and unreliable estimates of catchment mean travel times in heterogeneous catchments, they can be used to reliably estimate the fraction of young water in runoff.

Development of a Thermostable Microneedle Patch for Influenza Vaccination

The goal of this study is to develop thermostable microneedle patch formulations for influenza vaccine that can be partially or completely removed from the cold chain. During vaccine drying associated with microneedle patch manufacturing, ammonium acetate and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffer salts stabilized influenza vaccine, surfactants had little effect during drying, drying temperature had weak effects on vaccine stability, and drying on polydimethylsiloxane (PDMS) led to increased stability compared with drying on stainless steel. A number of excipients, mostly polysaccharides and some amino acids, further stabilized the influenza vaccine during drying. Over longer time scales of storage, combinations of stabilizers preserved the most vaccine activity. Finally, dissolving microneedle patches formulated with arginine and calcium heptagluconate had no significant activity loss for all three strains of seasonal influenza vaccine during storage at room temperature for 6 months. We conclude that appropriately formulated microneedle patches can exhibit remarkable thermostability that could enable storage and distribution of influenza vaccine outside the cold chain.