Coal fly ash has long been considered a potential resource for recovery of valuable elements, such as rare earth elements (REE), which are retained and concentrated upon combustion of coal feedstocks. Understanding REE occurrence within fly ash is a key to developing possible recovery methods. Recent results using modern analytical approaches shed light on the distribution REE in fly ash and the approaches required for their recovery. Some of the highest REE contents occur in fly ash derived from U.S. Appalachian Basin coals, and among these, coals influenced by input volcanic ash (Fire Clay coal, Kentucky) are especially enriched. Leaching studies of bulk fly ash show that, as a proportion of the total REE present, samples from eastern U.S. coals are generally less readily extractible than fly ash derived from western U.S. coals having lower REE contents. Direct determinations by ion microprobe show that REE in a range of fly ash samples are partitioned into aluminosilicate glasses formed during melting at boiler temperatures. These glasses comprise the largest mass fraction of coal fly ash. REE-enriched domains are present locally in fly ash at the nanometer scale (as shown by TEM), and these REE coexist with the glass phase. To enable systematic study of these REE, Ce has been proposed as a proxy for the trivalent lanthanides, as supported by speciation determinations demonstrating that Ce occurs in the trivalent form in fly ash. Despite a decreasing proportion of coal use for electric power generation in the U.S. and elsewhere, annual fly ash production, combined with coal ash already in storage, make up a large resource for potential recovery of rare earths and associated critical elements. Further developments in extraction technologies are needed to overcome difficulties in REE concentration and purification to produce REE materials of saleable purity derived from coal ash.
In karst environments, typically characterized by peculiar hydrogeological features and high heterogeneity and anisotropy, the connection between the recharge areas and the springs is often not straightforward. Rapid infiltration underground, and the resulting network of karst conduits, are frequently at the origin of a lack of correspondence among topographic divides and underground watersheds. As a consequence, in many karst areas there is still much work to do to fully understand the groundwater flow, with the only “underground truth” often being provided by cave data. In this contribution we start from general considerations about the difficulty in comprehending hydrogeology in karst, and use them to analyze one of the most important karst areas of southern Italy, the Alburni Massif in Campania (Italy). In detail, we present data about the main karst features at the surface (dolines, endorheic basins, etc.), the most important cave systems (reaching maximum depth of about 450 m below the surface), and the main basal springs coming out at the massif borders. Integration of the different sources of data allows to hypothesize the main directions of groundwater flows, and to perform the first attempts in correlating recharge and discharge data, but such hypothesis then often prove to be wrong by data from cave and diving explorations.
The solar corona, the outer atmosphere of the Sun, is heated to millions of degrees. This is several orders of magnitude hotter than the photosphere, the optical surface of the Sun, below, and a mystery that has baffled scientists for centuries. The answer to the question of how the solar corona is heated lies in the crucial magnetic connection through the atmosphere of the Sun. The magnetic field that threads the corona extends below the solar photosphere, where the convective motions drag the magnetic field footpoints, tangling and twisting them. The chromosphere is the atmospheric layer above the photosphere, below the corona, and the magnetic field provides an important connection between these layers. The exchange of mass and energy between the chromosphere and corona is an essential piece of this puzzle. The connection between the chromosphere and the corona is a challenging piece of the puzzle both observationally and computationally, as it is highly complex in space and time. We describe the history of the observations and theoretical understanding of the heating of the solar atmosphere, and end with future prospects of the coronal heating problem.
Iron is present in magmas at concentrations ranging from less than 1 wt% to more 8 than 10 wt% in two valence state. In general, Fe2+ is a network modifier in the melt structure while Fe3+ is a weak network former. The ratio Fe3+/(Fe3+ + Fe2+) depends on temperature, pressure, oxygen fugacity and melt composition. Parametric models allow its calculation, but the complex links between melt composition, iron oxidation state and coordination can be further rationalized using a ionic-polymeric model. Constraining concentration and oxidation state of iron is critical for determining magma density and viscosity, which drive exchanges of matter and heat in the Earth. At high pressures, changes in the coordination of elements, including iron, yield a stiffening and densification of magmas, potentially influencing dynamic and geochemical processes. Near surface, crystallization of Fe-bearing phases changes the residual melt composition, including iron content and oxidation state as well as volatile concentration, ultimately driving large changes in density and viscosity of magmas, and, hence, in the dynamic of fluid flow in volcanic systems. The complex interplay between magma iron content and oxidation state, major element chemistry, crystal and volatile content thus can play a large role on the dynamic of volcanic systems.
Time-related information of pre-eruptive magmatic processes is locked in the chemical profile of compositionally zoned minerals and can be retrieved by means of elemental diffusion chronometry. However, only the timescale of the outermost rim is commonly resolved, limiting our knowledge of timescales to those directly preceding the eruption. A major obstacle is the need to accurately constrain temperatures at which diffusion occurred. This is particular difficult for multiple zoned minerals where the different compositional boundaries indicate multiple physicochemical changes of melt environments during the lifetime of a crystal. Here, we argue that elemental diffusion chronostratigraphy can be fully resolved for crystals that have spent their lifetime in hot storage. Under this condition, crystals will be kept at the temperature of the eruptible magma(s), and diffusion timescales approximate the storage of the crystal in question in different melt environments. We further argue that hot storage conditions are typical of open-conduit systems in steady-state and are driven by the regular supply of fresh hot magmas determining the constant presence of eruptible magma. Fe-Mg interdiffusion in pyroxenes from Stromboli and Popocatepetl volcanoes are used as examples to reconstruct the time-dependent elemental diffusion chronostratigraphy of single crystals and discuss magma dynamics implications. Uncertainties introduced by temperature estimates and other input data, including experimentally derived values for the activation energy E and the pre-exponential factor D0, have large effects on the accuracy of modelled timescales, which need to be correctly evaluated and mitigated. Elemental diffusion chronostratigraphy is an extremely powerful tool to obtain time-related temporal information on the dynamics and histories of volcanic plumbing systems, which can lead to an in-depth knowledge of the magmatic system far beyond late-stage pre-eruptive processes. Combined with monitoring data and other petrological, geological and geophysical constraints at active volcanoes, they can greatly enhance our capability to inform volcanic hazard assessments.
Perhaps the least ambiguous signal that the mantle is convecting comes from observations of seismic anisotropy---the variation of wave speed with direction---which must arise due to the ordering of material as deformation occurs. Therefore significant effort has been made over many years to infer the direction and nature of mantle flow from these data. Observations have focussed on the boundary layers of the mantle, where deformation is expected to be strongest and where anisotropy is usually present. While prospects for mapping flow seem good, the lack of knowledge of several key issues currently holds progress back. These include the cause of anisotropy in the lowermost mantle, the causative material's response to shear, and the single-crystal or -phase seismic properties of the causative materials. In this chapter we review recent observations of lowermost mantle anisotropy, constraints on mineral elasticity and deformation mechanisms, and challenges in linking geodynamic modelling with seismic observations.
Due to the awareness of degrading groundwater quality in Florida’s freshwater 7 springs and beginning in the early 1990s, the state’s water management districts, the Florida 8 Department of Environmental Protection, and the U.S. Geological Survey began efforts to 9 coordinate monitoring of Florida’s first-and second-magnitude springs. This study investigates 10 changes in spring discharge and the concentrations of two saline indicators sodium (Na +) and 11 chloride (Cl-) from 1991 through 2020 (30 years) in the Floridan aquifer system (FAS). Data were 12 obtained from 32 major springs and three additional discharge gaging stations. Spring discharge 13 was observed to decrease, while concentrations of sodium and chloride increased. As a group, the 14 FAS springs experienced passive saline encroachment. Not only did encroachment occur along 15 Florida’s coasts, but also in the interior. Median concentrations of sodium and chloride increased 16 by an estimated range of 7 to 11% per decade. Evidence suggests the major driver is decreasing 17 rainfall and subsequent declines in recharge to the FAS, followed by sea-level rise. The sources 18 of the saline water are from salt water near Florida’s coasts and relict sea water from the deeper 19 portions of the FAS. The observed changes agree with those predicted by the Ghyben-Herzberg 20 principle for coastal, carbonate aquifers. 21
A variety of smoke model frameworks are used to simulate smoke for research and forecast applications. Here, a comprehensive summary is provided which covers the many different smoke models that are available, while simultaneously highlighting some of the strengths and weaknesses of each model, along with the uncertainties surrounding each of these frameworks. This review also provides an in-depth discussion on coupled wildfire-atmosphere models, which is a relatively newer smoke modeling tool not previously discussed in other review papers. Key processes related to smoke transport and dispersion, such as the wildfire plume rise, are also discussed in length. This review wraps up with a discussion of future smoke modeling needs and potential new research directions for smoke transport and dispersion models.
The Tropical Rainfall Measuring Mission (TRMM) daily (3B42) and monthly (3B43) rainfall products are evaluated relative to synoptic weather station observations in Cameroon and according to the main agro-climatic regions. In order to achieve this goal, deterministic and categorical metrics were used, as well as inter annual variability and seasonnal distributions. Outcomes of the comparison showed that synoptic weather station data are strongly correlated with the TRMM 3B43 data and that rainfall distribution is characteristic for each agro-climatic region. The highest skill scores were observed in the Sudano-sahelian, High Savannah, and Western Highlands zones, while the Uni-modal Equatorial zone displayed the lowest correspondence scores between TRMM rainfall estimates and station-based observations. Daily TRMM 3B42 showed good performance in detecting rainy events, especially for light and moderate intensity rainfall events. TRMM 3B42 overestimates rainfall intensities except in the uni-modal region where rainfall intensities are underestimated. Rainfall seasonnality, as well convective zone are well reproduced by the TRMM datasets. Overall, the skill of TRMM 3B42 decreases for increasing precipitation intensities.
The Cape Verde archipelago is a group of Ocean Islands in the Central Atlantic that forms two chains of islands trending Northwest and Southwest. Several of the islands are considered to be volcanically active, with frequent eruptions on Fogo. We examine the mineral chemistry and thermobarometry of the southern islands; Santiago, Fogo and Brava together with the Cadamosto Seamount. Our objective is to explore the magmatic storage system and implications for volcanic eruptions and associated hazards at Cape Verde. The volcanic rocks at Cape Verde are alkaline and dominantly mafic, whereas the island of Brava and the Cadamosto Seamount are unusually felsic. Clinopyroxene compositions range from 60 to 90 Mg# at Santiago and Fogo. In contrast, at Brava and the Cadamosto Seamount the clinopyroxene compositions are 5 to 75 Mg#. Mineral chemistry and zonation records fractional crystallization, recharge, aggregation of crystals, magma mixing and variations in thermal conditions of the magma at temperatures from 925 to 1250C. Magma storage depths at Santiago, Fogo, Brava and the Cadamosto Seamount are between 12 and 40 km, forming deep sub-Moho magma storage zones. Transient magma storage in the crust is suggested by fluid inclusion re-equilibration and pre-eruption seismicity. A global compilation of magma storage at Ocean Islands suggests deep magma storage is a common feature and volcanic eruptions are often associated with rapid magma ascent through the crust. Shallow magma storage is more variable and likely reflects local variations in crustal structure, sediment supply and tectonics. Petrological constraints on the magma plumbing system at Cape Verde and elsewhere are vital to integrate with deformation models and seismicity in order to improve understanding and mitigation of the volcanic hazards.
This chapter describes the variability of rainfall and river discharges in the Ogooué River basin (ORB) in recent decades (since 1940). Due to its location crossing the Equator, the ORB receives abundant precipitation that maintains one of the world’s best-preserved ecosystems. In contrast to neighboring forest basins that have been severely degraded because of deforestation, mining resources extraction, extensions of agricultural areas, and river transport, which is a crucial alternative to the cruel lack of road infrastructures, the ORB is experimenting with an exceptional conservation policy in the region. For example, the rural penetration rate in Gabon is about 1 inhabitant per km² and many studies report a deforestation rate close to 0%, with even full natural regeneration. However, the fluctuations of the standardized anomaly index of rainfall in the ORB show three main phases of variations: the first wet phase was characterized by abundant precipitations from 1940 to 1970, the second phase of the long-term mild drought was extended in the 1970s and 1980s and the final third phase presented a slight return of abundance in precipitation. Even though drought severity in the ORB was mainly weak, its effects in river discharges were very sensitive on seasonal and inter-annual scales. The pure equatorial regime of the ORB characterized by equal maximum floods in spring and autumn changed significantly from the difference between both maximum discharges of 13.5 % during the 1960s to 27.0 %, 38.4 %, 33.9 %, and 26.7 % for the 1970s, 1980s, 2000s and 2010s respectively. A brief comparison between the ORB and the Congo River basin showed that changes in the ORB are part of a regional process that Central Africa is undergoing with some spatial heterogeneities.
Elements with variable valence state (i.e. redox-sensitive) often show contrasting mineral/melt partition coefficients as a function of oxygen fugacity (fO2) in magmatic systems. This is because trace-element incorporation into crystal lattices depends on the charge, size, and crystal-field stabilization energy of atoms, all of which differ greatly between oxidized and reduced species of the same element. This has two critical implications: (1) petrologic/ geochemical modelling of partitioning behavior of redox-sensitive trace-elements in magmatic systems requires some knowledge of their oxidation state, and (2) the oxidation state of magmatic systems may be inferred from partitioning relations of redox-sensitive trace elements preserved in mineral and melt phases of rapidly cooled magmas. The advantage of this oxybarometric approach is that mineral/melt partitioning relations are not sensitive to late stage degassing, charge-transfer on quenching, or surficial alteration. In this chapter we discuss the theoretical treatment of experimental mineral/melt partitioning data of redox-sensitive trace elements, and review aspects concerning the partitioning behavior of well-known redox-sensitive elements, including transition metals (Ti, V, Cr, Fe), rare earth elements (Ce, Eu), U, and siderophile elements (Mo, W, Re, and platinum group elements) under planetary magmatic fO2 conditions.
The latest work on the main African rivers on the Atlantic coast has made it possible to subdivide the multi-year streamflow records into several homogeneous phases. The year 1970 seems to mark both for West and Central Africa the major hydroclimatic event of the 20th century, heralding its main period of deficit flow. For the first time, this article presents a comparative study of the hydro-rainfall records of five drainage systems (those of the Congo River and its main tributaries Lualaba, Kasai, Sangha, Oubangui) based on field data, obtained on both the left and right banks of the Congo River. A reconstitution of the Cuvette Centrale regime is proposed. The 1970 hydro-rainfall disruption is common in most tributaries of the Congo River basin, with significant reductions in flows depending on various factors (geographical location, vegetation cover, surface conditions and land use, etc.). The Oubangui is the most fragile northern tributary that continues to suffer from flow deficits, with an increase in the duration and intensity of its low flows. Since 1995, flows of the Congo River at its main station in Brazzaville/Kinshasa seem to have returned to the interannual average since 1903. However, from the same year onwards, an increase in seasonal variability and a decrease in spring flood flows can also be observed for its bimodal tributaries. This article explains some of the hydrological paradoxes specific to this basin, which illustrate the complexity of its hydrological functioning. Finally, it shows that the period of excess flow in the 1960s is the major hydrological anomaly of the Congo River over a continuous 116-year history. For the whole basin, hydrological variations are attenuated compared to those of precipitation. Finally, the hydrometric regimes reconstructed by spatial altimetry and modelling are compared with those from in situ data.
15 The increasing pressure on wetland resources continues to threaten the role wetlands play in 16 maintaining the ecological balance of watersheds. The Cuvette Centrale of the Congo is the 17 greatest intertropical peatland in the world. To fully understand its role in water resources and 18 ecological services linked to the quality of water and life in the basin, we first need to quantify 19 its role in the hydrological dynamics. To achieve this aim, we used the Soil and Water 20 Assessment Tool model (SWAT)-modified for tropical environments-in combination with 21 monthly discharge data. We analyzed water fluxes entering and flowing out of the Cuvette 22 Centrale of the Congo River Basin on a monthly time scale for the 2000-2012 period. The 23 model was calibrated, validated, and compared with discharge from gauging stations and 24 surface water elevation from radar altimetry. Results showed that upland runoff from the 25 Congo River was the highest contributor to the Cuvette Centrale (33 percent) followed closely 26 by efficient precipitation inside the Cuvette Centrale (31 percent) with right bank and left bank 27 tributaries contributing 25 percent and 11 percent respectively. We simulated monthly mean 28 interannual inflows of approximately 34,150 m 3 s-1 (88 billion m 3) with the main flood peaking 29 in November (45,310 m 3 s-1) and total outflows averaging around 39,860 m 3 s-1 (100 billion 30 m 3) peaking at 52,430 m 3 s-1 in December for the simulation period. We subsequently estimated 31 a negative monthly mean interannual variation of storage in the Cuvette Centrale wetlands in 32 the order of 5,700 m 3 s-1 suggesting that the Cuvette Centrale supplies the river during low 33 water periods. This highlights the important regulatory function of the Cuvette Centrale and 34 the need for protection of groundwater resources in order to maintain wetland water quantities 35 and quality. 36
Many rivers systems of the world are super-saturated in dissolved CO2 (pCO2) relative to equilibrium with the atmosphere — why? Here we compare the coupled organic matter and pCO2 dynamics of the world’s two largest river systems, the Amazon and Congo, where data sets enable insights into the overall functioning of the respective basins. Discharge is the primary control on particulate (POC) and dissolved organic carbon (DOC) export in both the Amazon and Congo Rivers. Total suspended sediments (TSS) yield from the Amazon is twenty times greater per unit area than the Congo. However, despite low TSS concentrations, the Congo has a POC content approximately five times higher than the Amazon. The organic rich character of both watersheds is reflected in the DOC export, with the Amazon exporting ~ 11% and the Congo ~ 5% of the global land to ocean flux, based on measurements from the last discharge gauging stations. But care should be taken when describing estimates of TSS and carbon to the ocean. Processing and sequestration in tidal and coastal areas can significantly alter TSS and carbon delivery, and last discharge gauging stations are typically hundreds of kilometers from the sea. pCO2 in the Amazon mainstem ranges from 1,000 to 10,000 μatm, with floodplain lakes ranging from 20 to 20,000 μatm. Concentrations in the Congo mainstem are lower, with maximum values of ~5,000 μatm observed. The elevated level of pCO2 even as far as the mouth of such major rivers as the Amazon and Congo, up to thousands of kilometers from CO2-rich small streams, poses a most interesting question — what set of processes maintains such high levels? The answer is presumably some combination of instream metabolism of organic matter of terrestrial and floodplain origin, and/or injection of very high pCO2 water from local floodplains or tributaries.
The spatiotemporal evolution of droughts in the Congo River Basin (CRB) from 1981–2018 was investigated using the Standardised Precipitation Index (SPI) and Standardised Precipitation–Evapotranspiration Index (SPEI) to assess the roles of precipitation and potential evapotranspiration. The results confirmed a notable trend toward drier conditions, particularly in parts of the northern and central basin, as well as in the south of the CRB, which was associated with increases in potential evapotranspiration and declining rainfall. Global outputs of the Lagrangian model FLEXPART were used to model air masses over four important climatological regions considered to be the main sources of precipitation in the CRB, and their contributions to precipitation over the basin were computed. These analyses confirmed that moisture in the CRB is ~60% self-sourced; African lands were the next greatest contributor, followed by the Indian and Atlantic Oceans. It was found that a reduction in contributions of the sources prevailed during 53 meteorological drought episodes that affected the CRB during the study period and it could be inferred that a reduction in moisture supplied from the Atlantic and Indian Oceans played an important role in the onset of drought episodes. It was also observed that the contribution of moisture from all sources to the CRB decreased during the study period, especially over the northern half of the basin, where the main humid forest of the CRB is located, confirming the importance of water transport and local hydroclimatological dynamics on the hydrological conditions, ecosystems, and local communities of the CRB.
The dynamic topography of the core-mantle boundary (CMB) provides important constraints on dynamic processes in the mantle and core. However, inferences on CMB topography are complicated by the uneven coverage of data with sensitivity to different length scales and strong heterogeneity in the lower mantle. Particularly, a trade-off exists with density variations, which ultimately drive mantle flow and are vital for determining the origin of mantle structures. Here, I review existing models of CMB topography and lower mantle density, focusing on seismological constraints. I develop average models and vote maps with the aim to find model consistencies and discuss what these may teach us about lower mantle structure and dynamics. While most density models image two areas of dense anomalies beneath Africa and the Pacific, their exact location and relationship to seismic velocity structure differs between studies. CMB topography strongly influences the retrieved density structure, which helps to resolve differences between recent studies based on Stoneley modes and tidal measurements. Current CMB topography models vary both in pattern and amplitude and a discrepancy exists between models based on body-wave and normal-mode data. As existing models feature elevated topography below the Large-Low-Velocity Provinces (LLVPs), very dense compositional anomalies may currently be ruled out as possibility. To achieve a similar consistency as observed in lower mantle models of S-wave and P-wave velocity, future studies should combine multiple data sets to break existing trade-offs between CMB topography and density. Important considerations in these studies should be the choice of theoretical approximation and parameterisation. Efforts to develop models of CMB topography consistent with body-wave, normal-mode and geodetic data should be intensified, which will aid in narrowing down possible explanations for the LLVPs and provide additional insights into mantle dynamics.
Fragments of former oceans are commonly observed in mountain belts: blueschists and eclogites, on the one hand, and ophiolites, on the other hand, are all that remains of ancient oceanic lithosphere. Though volumetrically subordinate, they provide essential insights into past geodynamics and into the processes involved in the formation and destruction of oceanic lithosphere. This contribution apprehends these two types of oceanic fragments jointly and shows the advantage of doing so for understanding the dynamics of oceanic convergence, i.e. subduction and obduction. We examine the intimate relationships between blueschists/eclogites and ophiolites, as well as the similarities and differences in the mechanisms leading to their preservation. While the extensive, unmetamorphosed true ophiolites markedly differ from fragments of oceanic lithosphere offscraped from the slab during subduction, at shallow or great depths, both types record the mechanical behavior and ‘hiccups’ of the subduction plate boundary. Their preservation also highlights the importance of the evolution of the subduction regime through time, from the onset of intra-oceanic subduction to the cessation of continental subduction.