Mass Balance Calculations Research Articles

Bio-methanol with negative CO2 emissions from residual forestry biomass gasification: Modelling and techno-economic assessment of different process configurations

The paper presents a techno-economic comparison among five alternative process configurations for bio-methanol production from the gasification of residual forestry biomass. Process design and simulations are performed in Aspen Plus for mass and energy balance calculation, followed by preliminary sizing and economic analysis. Process schemes include a gasification island (state-of-the-art low-pressure gasification compared against a high-pressure gasifier) with syngas conditioning and compression, heat recovery, syngas composition adjustment (by CO2 capture or addition of hydrogen produced by electrolysis), methanol synthesis and purification and a heat recovery cycle for power generation. CO2 capture is performed with conventional chemical absorption in the benchmark cases, while low-temperature partial condensation of CO2 is modeled in the advanced scenario. Methanol output is 14–15 kt/y in the CO2 capture cases and 36 kt/y in the H2 addition option.Configurations with a pressurized gasifier and phase-change-based CO2 separation are the most efficient ones, with a primary energy efficiency of 50 % and a Levelized Cost of Methanol (LCOM) of 700 €/tMeOH. In comparison, LCOM increases to 730 €/tMeOH in the case with conventional capture or between 792 €/tMeOH and 831 €/tMeOH (depending on the CCS technology) if the gasification pressure is conservatively reduced to 2.5 bar. In the H2 addition scenario, LCOM increases to 821 €/tMeOH due to the significant impact of the electricity consumption for H2 production, (only partly compensated by the increased methanol production). Scenarios with CO2 capture feature negative CO2 emissions, in the range −1.64 to −1.84 tCO2eq/tMeOH, as a result of the capture and storage of biogenic CO2 (BECCS approach).

Isotope hydrology of the intermontane Elk Valley, British Columbia: an assessment of water resources around coal mining operations

ABSTRACT This study aimed to synthesise and interpret stable isotopic data (δ 2H and δ 18O) from various sources to understand the isotope hydrology around coal mine operations in Elk Valley, B.C., Canada. The data, including precipitation, groundwaters, seeps, and mine rock drains, were used to construct a local meteoric water line (LMWL) for the Elk Valley, evaluate the spatiotemporal isotopic composition of its groundwater, and assess mine seepage and mine rock drain discharge. The study revealed a robust LMWL relation (δ 2H = 7.4 ± 0.2 · δ 18O – 4.3 ± 4.1). The groundwater and seep data indicated a winter season bias and a north–south latitudinal gradient, suggesting rapid near-surface groundwater flow without significant post-precipitation evaporation. Porewater isotope samples from unsaturated mine rock piles (MRPs) showed site-specific evaporation patterns, potentially due to convective air flows or exothermic sulphide oxidation. This research revealed the influence of groundwater and meltwater on rock drain discharge. Based on evaporative mass balance calculations, MRPs seasonally contributed ca. 5 %(December base flow) and 22 % (snowmelt) to drain discharge. The findings underscore the value of stable isotope data collections in the Elk Valley to help better define and quantify the hydrology–hydrogeology, including a better understanding of evaporative conditions in MRPs.

Enhancing fluidity and mechanical properties in Limestone Calcined Clay cements with one-third Portland clinker content

Limestone Calcined Clay Cements (LC3) are attracting considerable attention due to their low CO2 footprints and relatively fast hydration kinetics. LC3-50 formulations (approximately 50 % Portland clinker, 30 % kaolinitic calcined clay, 15 % limestone and 5 % gypsum) are being extensively investigated and the hydration chemistry, rheology, mechanical strength developments and durability performances are starting to be well established. LC3 binders with lower clinker factors are possible, offering an opportunity for further CO2 footprint reduction. However, these blends have been much less studied. This work contributes to fill this gap. Here, a LC3-35 binder (i.e. 35 % Portland clinker content) is investigated and its performances are compared to those of the original Portland cement (PC) and a standard LC3-50 binder. The effects of two superplasticizers and a strength-enhancing admixture are thoroughly investigated in mortars and pastes. Larger calcined clay contents result in an exacerbation of the slump retention problem, but this issue is solved by the use of a new superplasticizer. Moreover, the low mechanical strengths at early ages can be partly mitigated with a C-S-H nucleation seeding admixture. Employing the right admixtures, LC3-35 binders can develop strength values similar to those of neat PC and LC3-50 at 7 and 28 days. The laboratory X-ray powder diffraction results for LC3-35 pastes, when using the strength-enhancing admixture, show that C4AF exhibits an accelerated reaction rate, leading to the formation of larger amounts of AFt and AFm phases. Approximate mass balance calculations are carried out to estimate the metakaolin reaction degree. Finally, an environmental performance indicator is used to place the footprints of the reported binders within the LC3 landscape.

New insights into the metallogenic genesis of the Xiadian Au deposit, Jiaodong Peninsula, Eastern China: Constraints from integrated rutile in-situ geochemical analysis and machine learning discrimination

The genesis of the Mesozoic Au deposit within the Jiaodong Peninsula is debated, with vague connections to magmatism, deep-source metamorphic devolatilization, or the involvement of mantle materials over the long term. This study presents an integrated investigation involving textures, in-situ geochemical analysis, and machine learning discrimination of the rutile of the Xiadian Au deposit at the northwest Jiaodong Peninsula, aiming to provide metallogenic insights. Rutile is distinguished into three types: Type 1 rutile formed in the pre-ore stage is fine-grained and replaces and coexists with relict titanite, with euhedral crystal and being homogeneous and dark BSE response. Type 2 and type 3 rutile exhibit subhedral and anhedral crystals and are associated with quartz-sericite-pyrite alteration. The former has low W contents and is dark BSE response, while the latter is brighter in BSE and exhibits pronounced fragmentation and erosion. Chemical trends indicate the elemental substitution mechanism within rutiles from early to later stages: (Nb, Ta)5+ + (V, Fe, Al, Cr)3+ ↔ 2Ti4+ to 2(V, Fe, Al, Cr)3+ + W6+ ↔ 3Ti4+. Elevated concentrations of trivalent iron ions due to elevated oxygen fugacity of the ore-forming fluids are more likely to have contributed to this change, rather than the increment of W content. This may induce the destabilization of gold-sulfur complexes and contribute to gold mineralization. Machine learning models, including Extreme Randomized Tree (ET), Support Vector Machine, and Naive Bayes classifiers, were trained using a collected dataset containing 6598 rutile geochemistry data. These models consistently classify Xiadian rutile as the hydrothermal origin and having affinity to orogenic Au deposit. The SHapley Additive exPlanation (SHAP) framework was used to explain the discrimination criteria for the best-performing ET models. It revealed that elements such as Y, Ta, Mo, Sn, W, and Nb significantly contribute to classifying Xiadian rutile as affiliated with orogenic Au deposit. Further mass balance calculations with titanite, the predominant precursor Ti-bearing mineral of rutile, suggest that the W content in rutile is controlled by ore-forming fluids, likely having a deep source. In contrast, elements like Y, Mo, Cr, Nb, and Ta are influenced by leaching or re-equilibration with host rocks. Collectively, deep geodynamic processes likely provide major Au mineralization-related materials and fluids, while elemental leaching or re-equilibration with shallow crust rocks near fluid pathways influences the geochemical characteristics of the Xiadian gold system.

Rare-metal halos of lithium pegmatite at the Wolfsberg deposit, Austria, and their implications for exploration

The Austroalpine Unit Pegmatite Province (AUPP) in the eastern European Alps hosts abundant Permian-aged, variably rare-metal-enriched pegmatite bodies. However, only a small number containing spodumene [LiAlSi2O6] have been discovered. Here, we characterize three drill cores from the AUPP’s largest spodumene pegmatite resource, the Wolfsberg deposit (Austria), to determine the extent of rare-metal halo formation within different host rock types generated by pegmatite-derived fluids and their applicability to spodumene pegmatite exploration. The halos in both mica schist and amphibolite host rocks, as quantified via whole-rock mass-balance calculations, are characterized by enrichments in Li, Cs, Sn, Rb and Tl, amongst others, elements which were highly mobile during initial interactions between pegmatite-derived fluids and host rocks. The concentrations of these elements within the halos can be several times that present in unaltered host rock. They are most enriched in altered host rock interbedded or at the contacts with pegmatite, and decrease with distance from pegmatite to a distance of at least 4 m in mica schist and <3 m in amphibolite. Lithium, and in mica schist, Cs, have the most consistent and furthest extending halos, with respective concentrations of >590 ppm and >40 ppm in mica schist, and >390 ppm Li in amphibolite indicating proximity to spodumene pegmatite. An ID-TIMS U-Pb titanite age of ca. 103 Ma derived from a rare-metal-enriched amphibolite within the alteration halo reflects recrystallization of the Permian protolith during the Cretaceous Alpine orogeny and indicates preservation of the original pegmatite signature through eclogite-facies metamorphism. Recognition of rare-metal halos surrounding pegmatite at Wolfsberg serves as a potential geochemical exploration tool for spodumene pegmatite within the AUPP and may be applicable to other regions.

Relict soil evidence for post-Miocene aridification in the Atacama Desert of South America

Deep exposures of soil profiles on Miocene or Mio-Pliocene alluvial deposits were studied along a 500 km N-S transect in the Atacama Desert. These ancient deposits, with excellent surface preservation, now stand many meters above a broad incised Plio-Pleistocene alluvial terrain. Total geochemical analyses and mass balance calculations allowed the establishment of elemental gains, losses, and redistribution in the soils. From north to south (presently hyperarid to arid), the ancient soils reveal an increase in losses of rock-forming elements (Si, Al, Fe, K, Mg). Additionally, rare earth elements (REE) show losses with increasing southerly latitude and systematic patterns with soil depth. Some REEs appear to be unique chemical tracers of exogenous dust and aerosol additions to the soils. The removal of major elements and REEs is impossible in the present climate (one of salt and dust accumulation), revealing that for a significant period following the deposition of the alluvium, soils were exposed to rainfall, chemical weathering, and mass loss—with a geographical pattern that mirrors the present rainfall gradient in the region. Following the cessation of weathering, the pre-weathered soils have undergone enormous dust and salt accumulations, with the rates and types of salt accumulation consistent with latitude: (1) carbonate in the south and (2) sulfate, chlorides, and nitrates to the north. The quantity, and apparent rates, of salt accumulation have a strong latitudinal trend. Isotopes of sulfate have predictable depth patterns based on isotope fractionation via vertical reaction and transport. The relict hyperarid soils are geochemically similar to buried Miocene soils (ca. 10−9 Ma) in the region, but they differ from older Miocene soils, which formed in more humid conditions. The overall soil record for the Atacama Desert appears to be the product of changes in Pacific Ocean sea surface temperatures over time, and resulting changes in rainfall. The mid-Miocene was relatively humid based on buried soil chemistry and evidence of fluvial activity. The mid to late Miocene cooling (ca. 10−5.5 Ma) appears to have aridified the region based on paleosol soil chemistry. Pliocene to earliest Pleistocene conditions caused weathering of the relict soils examined here, and regional fluvial activity. Since the earliest Pleistocene, the region has largely experienced the accumulation of salts and, except for smaller scale oscillations (glacial-interglacial), has experienced protracted hyperaridity.

Position-Specific Oxygen Isotope Analysis in Inositol Phosphates by Using Electrospray Ionization-Quadrupole-Orbitrap Mass Spectrometry.

Conventional isotope-ratio mass spectrometry measurements obscure position-specific isotope distributions in molecular compounds because these measurements require an initial step that converts compounds into simple gases by combustion or pyrolysis. Here, we used electrospray ionization (ESI)-based Orbitrap mass spectrometry to measure oxygen isotope ratios in the phosphate and hydroxyl moieties of inositol phosphates. A thermal hydrolysis experiment was conducted using 18O-labeled water to examine the position-specific oxygen isotope exchange in inositol hexakisphosphate (IP6) as well as its hydrolysis products IP5, IP3, and PO3 fragments. Measurement precisions of the position-specific and molecular-average oxygen isotope values of inositol phosphates were better than ±1.1‰ and ±0.5‰, respectively. Under optimized ionization and Orbitrap parameters, this level of precision was obtained within 30 min of run time at 60 μM initial concentration of inositol phosphate. The ability to measure phosphate-specific oxygen isotopes in inositol phosphate enabled the quantification of isotope exchange, which did not occur in phosphate on IP6, IP5, IP3, and PO3 fragments, meaning that the change in isotopes should have resulted from hydroxyls in the ring. Isotope mass balance calculations corroborated that hydroxyl oxygens are derived from 18O-labeled water. With the observed sensitivity and precision achieved in this study, Orbitrap IRMS proved to be a promising tool for investigating the position-specific oxygen isotopes in organophosphorus compounds. These outcomes open up numerous potential applications that can expand our understanding of phosphorus cycling in the environment.

Lithium isotopic records of anthropogenic activity in the Xiaoqing River basin, eastern China

The environmental impact of the discharge of lithium (Li) by anthropogenic activity has been overlooked. By analyzing Li concentrations and isotope compositions (δ7Li) of water and sediment samples, this study evaluates the influence of anthropogenic Li discharge on the Xiaoqing River and Laizhou Bay, which are heavily polluted areas in China. High Li concentrations of the river water (up to 7.8 μmol/L) should be linked to anthropogenic Li discharge. However, no profound δ7Li anomalies were observed, preventing identification of the exact discharge sources. In the river sediments, Li concentrations (19.0–45.0 μg/g) were weakly correlated with Zn, Cu, and Cr concentrations, whereas δ7Li values ranged from 0.6 ‰ to 13.9 ‰ with high values being accompanied by high contents of total organic carbon and heavy Cr isotope compositions (δ53Cr). All these point to significant influence of anthropogenic activity on the Li budget of river sediments. A simple mass balance calculation indicates that smelters, Li-bearing therapeutic drugs, and secondary Li-ion batteries are the main anthropogenic Li sources. In contrast to river sediments, marine sediments in the Laizhou Bay were broadly homogeneous at both spatial and temporal scales, indicating no significant influence of anthropogenic Li discharge. Overall, our data indicate that Li isotope systematics in river sediments, especially sediments near intense anthropogenic activity, are effective at tracing potential Li pollution and can help obtain accurate results for environmental inspection.

Geochemistry and mineralogy of the shale-hosted vanadium Van Property deposit, Mackenzie Mountains, Northwest Territories

Abstract Shales and mudstones are fine-grained rocks formed in sedimentary basins throughout Earth’s history. These lithologies are increasingly important targets for mineral deposit exploration since they can have economic resources of critical minerals including vanadium (V), an essential component of redox-flux batteries in solar cells. However, many Paleozoic shale-hosted V deposits are metamorphosed and deformed. This commonly obscures primary features including V-bearing host phases and the original composition of organic material. In this study, we present geochemical and mineralogical data from the Paleozoic Van Property deposit, Northwest Territories, Canada, to show that V can be released from organic matter during metamorphism and incorporated in clay phases such as illite. The siliceous argillites at the Van Property hosts up to 0.69% V2O5 and were metamorphosed to (sub-)greenschist facies. Their mineralogy is dominated by quartz with minor graphite, illite, muscovite, pyrite, sphalerite, rutile, and carbonates. Although, some illite (i.e., high-V illite) can have up to 13 wt% V2O3 and rutile can have up to 4.4 wt% V2O3, mass balance calculations are insufficient to explain V enrichment at the Van Property utilizing only illite and rutile. The third V host is inferred to be carbonaceous matter in which V accumulated syn-deposition on the seafloor. Subsequent metamorphism led to the demetallation of V-bearing geoporphyrins and the release of vanadyl ions (VO2+), some of which were then incorporated into high-V illite and rutile. This process of V enrichment highlights the role of organic matter in scavenging V from superficial reservoirs and the importance of metamorphism on subsequent V release and its incorporation into inorganic phases. The geochemistry of siliceous, V-rich argillites at the Van Property is also compared to other V-enriched shale and mudstone deposits, highlighting the diversity of shale-hosted V deposits, and emphasizing the need for further research to close the knowledge gaps related to variations in composition, mineralogy and V enrichment processes.

ICP-MS As a Contributing Tool to Nontarget Screening (NTS) Analysis for Environmental Monitoring.

Due to the increasing number of chemicals released into the environment, nontarget screening (NTS) analysis is a necessary tool for providing comprehensive chemical analysis of environmental pollutants. However, NTS workflows encounter challenges in detecting both known and unknown pollutants with common chromatography high-resolution mass spectrometry (HRMS) methods. Identification of unknowns is hindered by limited elemental composition information, and quantification without identical reference standards is prone to errors. To address these issues, we propose the use of inductively coupled plasma mass spectrometry (ICP-MS) as an element-specific detector. ICP-MS can enhance the confidence of compound identification and improve quantification in NTS due to its element-specific response and unambiguous chemical composition information. Additionally, mass balance calculations for individual elements (F, Br, Cl, etc.) enable assessment of total recovery of those elements and evaluation of NTS workflows. Despite its benefits, implementing ICP-MS in NTS analysis and environmental regulation requires overcoming certain shortcomings and challenges, which are discussed herein.

Mix and measure II: joint high-energy laboratory powder diffraction and microtomography for cement hydration studies.

Portland cements (PCs) and cement blends are multiphase materials of different fineness, and quantitatively analysing their hydration pathways is very challenging. The dissolution (hydration) of the initial crystalline and amorphous phases must be determined, as well as the formation of labile (such as ettringite), reactive (such as portlandite) and amorphous (such as calcium silicate hydrate gel) components. The microstructural changes with hydration time must also be mapped out. To address this robustly and accurately, an innovative approach is being developed based on in situ measurements of pastes without any sample conditioning. Data are sequentially acquired by Mo Kα1 laboratory X-ray powder diffraction (LXRPD) and microtomography (µCT), where the same volume is scanned with time to reduce variability. Wide capillaries (2 mm in diameter) are key to avoid artefacts, e.g. self-desiccation, and to have excellent particle averaging. This methodology is tested in three cement paste samples: (i) a commercial PC 52.5 R, (ii) a blend of 80 wt% of this PC and 20 wt% quartz, to simulate an addition of supplementary cementitious materials, and (iii) a blend of 80 wt% PC and 20 wt% limestone, to simulate a limestone Portland cement. LXRPD data are acquired at 3 h and 1, 3, 7 and 28 days, and µCT data are collected at 12 h and 1, 3, 7 and 28 days. Later age data can also be easily acquired. In this methodology, the amounts of the crystalline phases are directly obtained from Rietveld analysis and the amorphous phase contents are obtained from mass-balance calculations. From the µCT study, and within the attained spatial resolution, three components (porosity, hydrated products and unhydrated cement particles) are determined. The analyses quantitatively demonstrate the filler effect of quartz and limestone in the hydration of alite and the calcium aluminate phases. Further hydration details are discussed.

Watching the Grand Ethiopian Renaissance Dam from a distance: Implications for sustainable water management of the Nile water.

Increased demands for sustainable water and energy resources in densely populated basins have led to the construction of dams, which impound waters in artificial reservoirs. In many cases, scarce field data led to the development of models that underestimated the seepage losses from reservoirs and ignored the role of extensive fault networks as preferred pathways for groundwater flow. We adopt an integrated approach (remote sensing, hydrologic modeling, and field observations) to assess the magnitude and nature of seepage from such systems using the Grand Ethiopian Renaissance Dam (GERD), Africa's largest hydropower project, as a test site. The dam was constructed on the Blue Nile within steep, highly fractured, and weathered terrain in the western Ethiopian Highlands. The GERD Gravity Recovery and Climate Experiment Terrestrial Water Storage (GRACETWS), seasonal peak difference product, reveals significant mass accumulation (43 ± 5 BCM) in the reservoir and seepage in its surroundings with progressive south-southwest mass migration along mapped structures between 2019 and 2022. Seepage, but not a decrease in inflow or increase in outflow, could explain, at least in part, the observed drop in the reservoir's water level and volume following each of the three fillings. Using mass balance calculations and GRACETWS observations, we estimate significant seepage (19.8 ± 6 BCM) comparable to the reservoir's impounded waters (19.9 ± 1.2 BCM). Investigating and addressing the seepage from the GERD will ensure sustainable development and promote regional cooperation; overlooking the seepage would compromise hydrological modeling efforts on the Nile Basin and misinform ongoing negotiations on the Nile water management.

Hydrothermal alteration and its geochemistry of the Xiadian gold deposit, Jiaodong Peninsula, China: Implications for fluid-rock interaction processes and mineral exploration

The interaction between hydrothermal fluids and host rocks, along with associated alteration geochemistry within the Mesozoic Jiaodong gold system, presents significant gaps in our understanding. This study systematically examines the petrographic, mineralogical, and geochemical characteristics of alteration at the Xiadian gold deposit, including comprehensive whole-rock geochemistry analyses, mass balance calculations, and phase equilibria modeling. The alteration history of Xiadian could be divided into four stages. Amid Stage 1, the predominant process involves the replacement of plagioclase by K-feldspar-albite, accompanied by the simultaneous bleaching of amphibolite and associated significant depletion of MgO (ΔCi/CiO = −21.2 %) and Fe2O3 (−27.2 %) owing to the decomposition of mafic minerals. Stage 2a involves sericitization of albite and continued mafic mineral decomposition, resulting in the lowest recorded MgO (avg. 0.23 wt%) and Fe2O3 (avg. 0.92 wt%) contents in all alteration lithologies. Stage 2b is characterized by abundant chlorite vein formation, corresponding to the proximal enrichment of MgO (158.1 %) and Fe2O3 (108.2 %), accompanied by aMg2+/(aH+)2 decreased in the fluid. Stage 3, the main stage of gold mineralization, involves chlorite substitution with sericite during quartz-sericite-pyrite (QSP) alteration, suggesting mild acidification of the ore-forming fluid. Insights from phase equilibrium modeling suggest that sulfidation has contributed to gold precipitation, leading to increased fO2 and reduced fH2S (extending into quartz-carbonate alteration of stage 4). Mass balance calculations indicate gold is enriched compared to protolith at all stages, with the most intense enrichment in stage 3. This suggests that hydrothermal fluids at Xiadian were auriferous throughout their evolution. The process may induce fluid modifications, particularly through the dissolution of mafic minerals, more so in mafic mineral-rich rocks (e.g., amphibolite) than in granite, promoting the incorporation of hydrothermal chlorite into the Au system to contribute to sulfidation. Our results provide insights into lithology controls on gold mineralization at Xiadian, indicating that felsic rocks (Linglong granite and quartz porphyry) with lower initial CaO contents often develop K-metasomatism and Au-bearing QSP alteration, while mafic rocks (amphibolite and lamprophyre) with higher CaO contents develop carbonization. This is likely due to the influence of lower CaO contents on alteration minerals, which promote rock porosity, affecting rock deformation, pore-fluid flow, and reacting with wall rocks. Principal component analysis (PCA) results indicate that elements including Au, Ag, As, Bi, W, and Cu are proxies for Au mineralization, suggesting their mobilization and deposition together during the gold mineralization process. This highlights their significance as a proxy for gold exploration.

Stable isotope hydrology of a polymictic lake: Capturing transience of groundwater interactions

Although there have been many studies of groundwater inflow to small lakes, no systematic attention has been paid to the role of the time interval in the reliability of transient flow analysis. We addressed this issue in a two-year study of the isotope hydrology and water budget of a small lake in eastern Washington State (USA) that has been subject to limited management over several decades. The weighted local meteoric water line is δ2H = 7.14 δ18O – 5.22, reflecting the impact of convective recycling in this semi-arid region of inland northwestern North America. Groundwater inflow to the lake was quantified over two years using a short-interval isotopic transient mass balance approach. Calculated inflow was less than a fifth of the lake’s total water budget. Unrealistic temporal fluctuation of the calculated inflow was apparently correlated with fluctuation of the observed isotopic ratio of lake water (δL). We obtained realistic lake fluctuation and groundwater–lake exchange estimates by experimenting with the time interval of the isotope mass balance. It is crucial to acknowledge that each lake possesses unique characteristics that influence hydrologic and isotopic variations. Therefore, the optimal time interval for sampling and calculating mass balance may vary among different small lakes. Our findings have implications for long-term studies with frequent interval sampling.

CONTROL OF BIOMASS BOILER WATER TEMPERATUR USING SLIDING MODE CONTROL SYSTEM

Medium scale biomass temperature control is aspecific field of control issues where one of the most important features is cost effectiveness. It means that anykind of control system improvement should be done withthe lowest possible additional costs. Generally, the basiccontrol of such kind of boiler regulates temperature ofoutlet heating water. This control can be also performed bya conventional or advanced control. Although the main problem of this study is the constructionof the model of biomass boiler for control purposes, our taskdeals with technology of boilers and principles of its innerprocesses as well. Creation of the model comes out not onlyfrom these important findings, but also from experimentaldata collected during measurements in real operation. Heatand mass balance calculations were made according to thesedata and they serve to precise dynamic properties ofexperimental unit for biomass combustion.Based on the derived mathematical model of the biomassboiler, here is possibility to enhance the control byadditional algorithms that are responsible for extendedoptimization functions. In this paper, an advanced processcontrol such as sliding mode control system (SMC) is usedto control the temperature of the boiler water. The resultsshow that SMC has strong immunity for the disturbanceand the varying of process parameters.

The Role of Latent Heat Buffering in the Generation of High-Silica Rhyolites

Abstract The physical process of crystal-melt separation is responsible for the accumulation of small to very large volumes (&amp;gt;100 km3) of eruptible rhyolitic melt in the shallow crust. Granitic intrusions, although providing a terminal, time-integrated image of melt segregation processes, host an unmatched record of the physical properties controlling mechanisms and rates of interstitial melt extraction from a crystal-rich source. We applied mass balance calculations and thermodynamic modeling simulations to an extensive bulk rock geochemistry dataset (&amp;gt;150 samples) collected in a Permian upper-crustal granitoid intrusion of the Italian Southern Alps. Textural and geochemical evidence indicate that this intrusion constituted a single, zoned magma body, with a crystal-rich base and a thick (~2 km), high-silica cap (75–77 wt% SiO₂). The large compositional variability of the crystal-rich materials suggests variable degrees of melt extraction efficiency and corresponding terminal porosities. Specifically, the loosely bimodal distribution of porosity values (φ) indicates that at least two distinct melt segregation mechanisms were operating in this system, which produced both high (0.65–0.45) and low terminal porosities (0.45–0.25) in the crystal-rich, cumulate materials. Modeling of latent heat budget shows that coexistence of cumulate products with differing terminal porosity signature can be explained by melt segregation processes taking place at different depths across a thick, interconnected magmatic reservoir with an initial homogenous water content (~4 wt% H2O). Deep in the mush column, low water activities (aH₂O &amp;lt; 0.5) promoted thermal buffering of cooling magma at high crystallinities, enabling residual melt extraction by percolation through a crystalline framework accompanied by compaction. Instead, at shallower depths, high water activities (aH₂O &amp;gt; 0.5) ensured prolonged magma residence at porosities that promoted crystal melt separation via hindered settling. Distinct melt extraction processes, acting synchronously but at different depths in vertically extensive silicic mush columns, can account for the large volumes of residual, haplogranitic melt mobilized during the relatively short lifespan of upper crustal magma reservoirs (~105 years).

Albitization related U and Th mobilization under reducing conditions

Hydrothermally altered quartzofeldspathic gneisses, granites and pegmatites of the West Garo Hills, Shillong Plateau (eastern India) preserve alteration assemblages of monazite, xenotime and zircon comprising thorite and coffinite in the altered domains. Albitization of muscovite and K-feldspars, sericitization of K-feldspar and albite, alteration of biotite to hydrobiotite, and crystallization of tourmaline is suggestive of the involvement of acidic fluids. The microtextural relations and the mineral assemblages indicate prevalence of low-temperature (T < 300 °C) conditions during hydrothermal alteration. The light δ11B values of tourmaline (–15.1 to –13.5 ‰) suggests derivation/interaction of the fluids from/with metapelitic rock and/or S-type granite. Low ‘inferred’ Fe3+/Fe2+ ratio in tourmaline (based on high Al content in Y-site, 0.16–0.56 apfu, avg. 0.36 apfu), estimated excess charge (0.22–0.47, avg. 0.35 apfu) and lack of any Fe–Al relation support a reduced nature of the hydrothermal fluid. Mass balance calculations reveal that Th and U required for the formation of thorite and coffinite, respectively were likely derived from monazite and xenotime, and zircon. Significantly lower Cl─ contents in hydrobiotite (avg. 0.03 wt%) compared to the unaltered biotite (avg. 0.13 wt%) suggests release of Cl─ to the hydrothermal fluid during alteration. Textural evidences of albitization together with Cl─ release from biotite suggest increased Cl─ concentrations in the fluid during hydrothermal alteration. Based on solubility calculations for various U and Th species, we propose that high Cl─ content in the fluid aided mobilization of Th and U as ThCl40 and UCl40/UO2Cl20 complexes from accessory radioactive phases under reducing conditions. These results suggest that significant mobility of U and Th can be achieved in acidic high salinity fluid even under reducing conditions. Thermodynamic calculations for the solubility of Th- and U-chloride complexes and stability of monazite/xenotime in a range of pH and temperature suggest that thorite and coffinite precipitation was the result of an increase in pH.

Safety and transfer of veterinary drugs from substrate to black soldier fly larvae

There is an increasing interest in edible insects in Europe for feed and food purposes. Quantitative information on the transfer of chemical hazards from substrates to larvae is needed to evaluate food and feed safety aspects. This evaluation is especially needed when organic substrates or residual streams such as manure will be applied as substrate, contributing to a circular food system. This study investigated the transfer of veterinary drugs from spiked substrate to black soldier fly larvae (Hermetia illucens). Veterinary drugs that are commonly administered to chicken, fattening pigs, and cattle and regularly detected in manure were included: three different antibiotics (enrofloxacin, oxytetracycline, sulfamethoxazole), three coccidiostats (narasin, salinomycin, toltrazuril) and one antiparasitic drug (eprinomectin). The chemicals were spiked to insect substrate to reach final concentrations of 0.5 and 5 mg/kg for the antibiotics and the antiparasitic drug, and 5 and 50 mg/kg for the coccidiostats. Black soldier fly larvae were reared for 1 week on the spiked substrates, and the transfer of the veterinary drugs to the larvae and frass was quantified using liquid chromatography coupled with tandem mass spectrometry. Only oxytetracycline and eprinomectin reduced the average weight and/or survival of the black soldier fly larvae. The transfer of the veterinary drugs to the larvae was on average 19.2% for oxytetracycline, 12% for enrofloxacin, 9.5% for narasin, 8.1% for eprinomectin, 3.9% for salinomycin, 4.2% for toltrazuril, and 0.2% for sulfamethoxazole, relative to concentrations in the substrate. Mass-balance calculations revealed that the larvae seem to metabolise veterinary drugs, and indeed, metabolites of enrofloxacin, sulfamethoxazole, and toltrazuril were detected in the larvae and frass. In conclusion, insect-rearing substrates should be evaluated for the presence of veterinary drug residues to ensure feed (and food) safety, as well as because of possible effects on insect growth.

Quantification of Methane Emissions from Cold Heavy Oil Production with Sand Extraction in Alberta and Saskatchewan, Canada.

Cold heavy oil production with sand (CHOPS) is an extraction process for heavy oil in Canada, with the potential to lead to higher CH4 venting than conventional oil sites, that have not been adequately characterized. In order to quantify CH4 emissions from CHOPS activities, a focused aerial measurement campaign was conducted in the Canadian provinces of Alberta and Saskatchewan in June 2018. Total CH4 emissions from each of 10 clusters of CHOPS wells (containing 22-167 well sites per cluster) were derived using a mass balance computation algorithm that uses in situ wind data measurement on board aircraft. Results show that there is no statistically significant difference in CH4 emissions from CHOPS wells between the two provinces. Cluster-aggregated emission factors (EF) were determined using correspondingly aggregated production volumes. The average CH4 EF was 70.4 ± 36.9 kg/m3 produced oil for the Alberta wells and 55.1 ± 13.7 kg/m3 produced oil for the Saskatchewan wells. Using these EF and heavy oil production volumes reported to provincial regulators, the annual CH4 emissions from CHOPS were estimated to be 121% larger than CHOPS emissions extracted from Canada's National Inventory Report (NIR) for Saskatchewan. The EF were found to be positively correlated with the percentage of nonpiped production volumes in each cluster, indicating higher emissions for nonpiped wells while suggesting an avenue for methane emission reductions. A comparison with recent measurements indicates relatively limited effectiveness of regulations for Saskatchewan compared to those in Alberta. The results of this study indicate the substantial contribution of CHOPS operations to the underreporting observed in the NIR and provide measurement-based EF that can be used to develop improved emissions inventories for this sector and mitigate CH4 emissions from CHOPS operations.

Understanding the Fate of H2S Injected in Basalts by Means of Time‐Domain Induced Polarization Geophysical Logging

AbstractTo help meet emission standards, hydrogen sulfide (H2S) from geothermal production may be injected back into the subsurface, where basalt offers, in theory, the capacity to mineralize H2S into pyrite. Ensuring the viability of this pollution mitigation technology requires information on how much H2S is mineralized, at what rate and where. To date, monitoring efforts of field‐scale H2S reinjection have mostly occurred via mass balance calculations, typically capturing less than 5% of the injected fluid. While these studies, along with laboratory experiments and geochemical models, conclude effective H2S mineralization, their extrapolation to quantify mineralization and its persistence over time leads to considerable uncertainty. Here, a geophysical methodology, using time‐domain induced polarization (TDIP) logging in two of the injection wells (NN3 and NN4), is developed as a complementary tool to follow the fate of H2S re‐injected at Nesjavellir geothermal site (Iceland). Results show a strong chargeability increase at +40 days, interpreted as precipitation of up to 2 vol.% based on laboratory relationships. A uniform increase is observed along NN4, whereas it is localized below 450 m in NN3. Changes are more pronounced with larger electrode spacing, indicating that pyrite precipitation takes place away from the wells. Furthermore, a chargeability decrease is observed at later monitoring rounds in both wells, suggesting that pyrite is either passivated or re‐dissolved after precipitating. These results highlight that a sequence of overlapping reactive processes (pyrite precipitation, passivation, pore clogging and possibly pyrite re‐dissolution) results from H2S injection and that TDIP monitoring is sensitive to this sequence.