Sulfur Deposition Research Articles

Delayed recovery of surface water chemistry from acidification in subtropical forest region of China

The three largest acid rain regions of current earth are located in northern and western Europe, eastern North America, and East Asia. Sulfur and nitrate concentrations in headwater streams in Europe and North America decreased as atmospheric sulfur and nitrogen deposition decreased, albeit with a considerable delay. However, how water chemistry responds to the declining sulfur and nitrogen deposition in China is unclear. The regional survey of surface water chemistry during 2010 and 2018 within the Sichuan Basin in southwestern China showed that the recovery of the surface water chemistry was delayed for at least 5 years owing to the release of previously deposited sulfur and nitrogen stored in the soil. After sulfur deposition declined from its peak value, the subregions of purplish soil with low sulfate adsorption capacity still exhibited a net sulfur release in 2010, but this release was no longer evident by 2018. The subregions with the red and yellow soils, which have a high sulfate adsorption capacity, operated as sulfur sinks during 2010 and 2018, indicating a continuous immobilization process through sulfate reduction despite a decrease in sulfur deposition. Additionally, this sulfate reduction countered the release of sulfate caused by sulfur desorption. There was a substantial nitrogen sink within the Sichuan Basin. Nitrogen leaching decreased slowly with the declined nitrogen deposition, except in regions where nitrogen deposition exceeded the critical threshold. Compared to temperate forest regions in Europe, the Sichuan Basin and its surrounding areas have experienced higher decline rates in the leaching of sulfur and nitrogen, highlighting that the subtropical forest region undergoes a faster restoration of surface water chemistry.

A pXRF‐based geochemical dataset of typical boreholes in Xuancheng Qiaomaishan copper–sulphur deposit

AbstractDrilled cores provide first‐hand data for deposit research. The element compositions at different depths of cores are an important basis for evaluating the reserves of mineral deposits. Therefore, a dataset containing a complete drill core element content has great value on practicality. In this study, a pXRF analyser was used to measure the element contents in eight cores of the Xuancheng Qiaomaishan copper–sulphur deposit ZK16 + 02, ZK16 + 03, ZK16 + 04, ZK1804, ZK18 + 02, ZK1403, ZK1602, and ZK1604, and a geochemical dataset was obtained. The dataset includes Cu, S, Fe, W, Mg, Al, Si, As, Mn, Co, Ni, Zn, Se, Ti, V, Cr, Ca, Cl, P, Sr, Y, Zr, Nb, Mo, Pb, Th, U, and other 27 major and trace elements. Based on this dataset, the vertical variation pattern of main and trace element content in drill cores can be examined, the distributions of elements in full hole or exploration line profile can be drawn, and element correlation analysis and principal component analysis can be performed.

Prominent Role of Sulfate Reduction in Considerable Sulfur Retention in a Subtropical Soil

AbstractThe sulfur biogeochemical cycle controls the sulfur dynamics in the soil. In contrast to almost all deposited sulfur leaching out in temperate catchments, approximately 80% of the deposited S is retained in the catchments in subtropical regions. However, the mechanisms for sulfur retention were unclear, hindering the understanding of potential threats of legacy sulfur with environmental changes. Here, we demonstrated that sulfate reduction (as sulfide fixed in soil) was a prominent yet overlooked mechanism for sulfur retention in addition to the widely recognized sulfate adsorption in soil, based on a study on soil sulfur storage and stable isotope signatures within entire soil profiles in a typical subtropical catchment in China. Using a dual‐isotopic model, the sulfate reduction flux was further determined to be 30% of the S deposition. Due to a lot of deposited sulfur fixed via sulfate reduction, the release of soil legacy sulfur would be less in response to decreasing sulfur deposition compared to the projections only considering adsorption. However, the remobilization of large amounts of reduced S should be regarded as a threat to the environment under climate change in the future.

The Effect of Sr<sup>2+</sup> and Fe<sup>3+</sup> Cations and the Stirring Speed on The Precipitation of Barium Sulfate in a Batch System

The batch system investigation explored the effect of Sr2+ and Fe3+ cations and the stirring speed on the characteristics of precipitated barium sulfate. A series of experiments were conducted to evaluate the rate of barium sulfate precipitation in laboratory equipment from brines containing barium ions (3500 ppm) and varying amounts of Sr2+ and Fe3+ ions (10 and 20 ppm). Kinetic analysis was also performed to explore how stirring speeds (240 and 480 rpm) affect barium sulfate scales' crystallization by increasing the stirring speed and promoting Sr2+ and Fe3+-cation solubility while decreasing the precipitation rate. All solid crystals obtained were mostly pure barite, as the X-ray diffraction (XRD) method confirmed. The SEM micrograph of barite morphology revealed particles with tablet-shaped crystals 2 to 5 nm in size. With the presence of Sr2+ and Fe3+-cation, the shape of barium sulfate was modified into spherical tablets or flower-like clusters of tablets. Meanwhile, the morphological changes could result from increased stirring rates. Moreover, the kinetic results yielded a general reaction rate equation that might be used to estimate barium sulfate deposition in pipelines for various brine, supersaturation, and mixing time durations.

Boosting SO2‑tolerant oxidation of Hg0 and chlorobenzene over MnCo2O4@TiO2 catalyst via constructing shielding effects

Currently, it was still challenging to improve the SO2-tolerant catalytic oxidation of Hg0 and chlorobenzene in flue gas. Herein, we developed a MnCo2O4@TiO2 core–shell material that employed a self-shielding mechanism to prevent sulfate deposition. The optimal MnCo2O4@TiO2-2 catalyst achieved 100 % Hg0 removal efficiency at 250 °C under 150–600 ppm SO2, and also showed enhanced SO2 resistance during chlorobenzene conversion at 275 °C. The strong interaction between MnCo2O4 and TiO2 facilitated the electronic transfer from MnCo2O4 to TiO2, thereby producing more Co3+ and maintaining the high reactivity. Further, the mesoporous TiO2 layer facilitated the generation of moderate acid sites, improved the distribution of surface oxygen species, and weakened SO2 adsorption on catalyst. Under the protection of mesoporous TiO2 layer, the generation of Mn/Co sulfates could be inhibited effectively. In particular, the suitable TiO2 shell balanced the chemical adsorption and oxidation processes of Hg0 on the catalyst. This enhancement led to improved single Hg0 removal efficiency and SO2-tolerant Hg0 removal performance. During chlorobenzene degradation in presence of SO2, the oxidation path of chlorobenzene on MnCo2O4@TiO2 occurred via chlorobenzene → phenolates → maleates → formates/acetates → CO2 and H2O. Although sulfate formation would cover the active surface and inhibit the reaction path, the TiO2 shell could attenuate this negative effect. This study provided a new approach for the development of SO2-tolerant transition metal oxide with superior performance, holding significant academic and practical value.

Wet deposition of sulfur and nitrogen in the Jiuzhaigou World Heritage Site, China: Spatial variations, 2010–2022 trends, and implications for karst ecosystem conservation

Excessive sulfur and nitrogen deposition is a threat to natural ecosystems. This study investigated the spatio-temporal changes of wet sulfur and nitrogen deposition in Jiuzhaigou to understand the responses of wet deposition chemistry to local and national air pollutant emission changes and to assess relevant ecological risks. The results show that local emission sources (e.g., tourism, post-earthquake reconstruction, and vegetation damages) largely elevated the concentrations of SO42−, NO3−, NH4+, and Ca2+ at the non-background sites during 2021–2022; However, the gaps of annual sulfur and nitrogen wet deposition fluxes among the background, semi-background, and non-background sites were reduced by annual precipitation. The pH was also higher at the non-background sites due to stronger acid neutralization capacities from crustal dust there, and acid precipitation (pH < 5.6) was not detected at all the sites. During the 2010 to 2022 period, the wet deposition of SO42− and TIN (i.e. total inorganic nitrogen) and the equivalent ratio of SO42−: NO3− generally presented a declining trend at the background and semi-background sites, as a result of regional and national emission reductions. The TIN reduction from 2015 to 2016 to 2021–2022 at the background site was more from wet NH4+ deposition and the site's NO3− concentrations and fluxes were relatively stable. Compared to the critical loads (CLs) of sulfur and nitrogen for acidification and eutrophication, the annual wet and wet+dry deposition fluxes of sulfur and nitrogen were lower in almost the entire watershed, except for the CLmin of nitrogen for acidification in considerable areas. However, all the wet deposition samples were calcite-unsaturated and had annual TIN concentrations higher than the national environmental standard of total nitrogen for surface water. More field investigations are needed to better assess the ecological risks.

The changing nitrogen landscape of United States streams: Declining deposition and increasing organic nitrogen.

Air quality regulations have led to decreased nitrogen (N) and sulfur deposition across the conterminous United States (CONUS) during the last several decades, particularly in the eastern parts. But it is unclear if declining deposition has altered stream N at large scales. We compared watershed N inputs with N chemistry from over 2,000 CONUS streams where deposition was the largest N input to the watershed. Weighted change analysis showed that deposition declined across most watersheds, especially in the Eastern CONUS. Nationally, declining N deposition was not associated with significant large-scale declines in stream nitrate concentration. Instead, significant increases in stream dissolved organic carbon (DOC) and total organic N (TON) were widespread across regions. Possible mechanisms behind these increases include declines in acidity and/or ionic strength drivers, changes in carbon availability, and/or climate variables. Our results also reveal a declining trend of DOC/TON ratio over the entire study period, primarily influenced by the trend in the Eastern region, suggesting the rate of increase in stream TON exceeded the rate of increase in DOC concentration during this period. Our results illustrate the complexity of nutrient cycling that links long-term atmospheric deposition to water quality. More research is needed to understand how increased dissolved organic N could affect aquatic ecosystems and downstream riverine nutrient export.

Sulfate sources, biologic cycling, and mobility in Atacama Desert soils revealed by isotope signatures

A set of 55 surface samples from Atacama Desert gypsisols was collected along four altitude transects and analyzed for ∆17OSO4, δ18OSO4, δ34SSO4, and 87Sr/86Sr in order to identify the main depositional mechanisms and quantify the proportional contribution of sulfate sources across the desert's main topographic units – the Coastal Cordillera, the Central Depression, and the Precordillera. Sulfate deposited at any location in the Atacama Desert may derive from up to five different source and process endmembers that can principally be identified by their isotopic composition. Three aerosol sources dominate sulfate deposition and accumulation in gypsisols throughout the Atacama. These are secondary atmospheric Ca- and Na-sulfate derived from global volcanic SO2 oxidized by ozone and its derivates, and a marine sulfate aerosol that is roughly a 9:1 mixture of sea salt (primary) sulfate from evaporated sea spray, and secondary non-sea salt sulfate, i.e., dimethyl sulfide (DMS) mainly oxidized by ozone. These marine sources dominate sulfate deposition in the Coastal Cordillera. Unlike in most places on Earth, the positive mass-independent ∆17OSO4 signature of secondary atmospheric sulfate is ubiquitous in Atacama Desert soils and is never completely erased by biologic cycling. Hence, biologic cycling of the sulfate inventory – i.e., the reduction of sulfate, subsequent oxygen isotope exchange with water, and re-oxidation – is apparently not quantitative in any of the Atacama Desert environments sampled here, including the most biologically active permanent salt lakes. The preservation of highest ∆17OSO4 values (∼ 1.0‰) at altitudes of the Coastal Cordillera above the 1200 m altitude cut-off level of fog advection suggest that episodic rainfall events are insufficient for significant in situ biologic sulfate turnover. At lower altitudes and regular fog advection, moisture supply appears to be sufficient for limited in situ biologic sulfate turnover. Overall, biologically recycled sulfate constitutes a fourth major contributor to the desert's gypsisol sulfate inventory. This may comprise fluvially redeposited sulfate from older sediments, particularly on the debris fans protruding from the Precordillera into the Central Depression. In the Central Depression, Sr-isotopes may allow for a further distinction between redeposition-dominated and aerosol-dominated sedimentation environments. On the Precordillera, rainfall and run-off provide sufficient moisture for significant but still incomplete in situ biologic sulfate cycling. Hydrothermal non-evaporitic Na-sulfate – the fifth potential source – likely originates from larger outflow events or mobilization from rock veins over the course of the Atacama's geologic history may contribute locally to the sulfate inventory. The degree of bio-cycling and mobility of sulfate likely reflects a balance between overall water availability and the mixing proportion of very soluble (mobile) Na-sulfate and less soluble Ca-sulfate inherent in the various sulfate sources.

Micro-mesoporous carbon nanofibers loaded with sulfur as a self-supported cathode for high-performance Li-S batteries

Self-supported carbon fibers with hierarchical porous structures regulated by zinc salt and copper salt were prepared through electrospinning technology, and sulfur loaded carbon fibers were obtained through sulfur vapor deposition method. Small molecular sulfur (S2-S4) and cyclic sulfur (S8) were encapsulated effectively in hierarchical pores by this way, both of them could run stably in carbonate electrolyte. Due to the three-dimensional conductive structure and suitable pore structure of the carbon fibers, the self-supported S/MCNF-ZnCu cathode exhibits high capacity, excellent cycling stability and out-standing rate capacity. The reversible capacity after 100 cycles at 0.2 A g−1 based on the mass of cathode is 520 mAh g−1, corresponding to the capacity retention rate of 98.4 %. The reversible capacity after 1000 cycles at 1.0 A g−1 is 429 mAh g−1, with a capacity loss of approximately 0.01 % per cycle. Even at the sulfur loading of 4 mg cm−2, the cathode shows a stable capacity of nearly 500 mAh g−1 at 0.1 A g−1, provides a novel and efficient strategy for the next generation of high-performance batteries.

Transferrin Receptor-Targeted Iduronate-2-sulfatase Penetrates the Blood-Retinal Barrier and Improves Retinopathy in Mucopolysaccharidosis II Mice.

Mucopolysaccharidoses (MPSs) make up a group of lysosomal storage diseases characterized by the aberrant accumulation of glycosaminoglycans throughout the body. Patients with MPSs display various signs and symptoms, such as retinopathy, which is also observed in patients with MPS II. Unfortunately, retinal disorders in MPS II are resistant to conventional intravenous enzyme-replacement therapy because the blood-retinal barrier (BRB) impedes drug penetration. In this study, we show that a fusion protein, designated pabinafusp alfa, consisting of an antihuman transferrin receptor antibody and iduronate-2-sulfatase (IDS), crosses the BRB and reaches the retina in a murine model of MPS II. We found that retinal function, as assessed by electroretinography (ERG) in MPS II mice, deteriorated with age. Early intervention with repeated intravenous treatment of pabinafusp alfa decreased heparan sulfate deposition in the retina, optic nerve, and visual cortex, thus preserving or even improving the ERG response in MPS II mice. Histological analysis further revealed that pabinafusp alfa mitigated the loss of the photoreceptor layer observed in diseased mice. In contrast, recombinant nonfused IDS failed to reach the retina and hardly affected the retinal disease. These results support the hypothesis that transferrin receptor-targeted IDS can penetrate the BRB, thereby ameliorating retinal dysfunction in MPS II.

The Shoshone Canyon Conduit Cave: A Greater Yellowstone Ecosystem Sulfur Cave

Fve miles west of Cody, Wyoming and ~25 miles east of Yellowstone National Park lies the Shoshone Canyon Conduit Cave (Fig. 1, Suppl. material 1). Bisecting Cedar Mountain, an irrigation tunnel built by the Bureau of Reclamation (BoR), managed by the Heart Mountain Irrigation District, delivers water from the BoR Buffalo Bill Reservoir to more than 30,000 acres of irrigated lands in and around Cody. During the construction of that tunnel in the late 1940’s, a cave was discovered and the tunnel was made to travel though the cave with only light disturbance to the cave. The cave can only be accessed with permission in the non-irrigation time of year. The cave is rich in sulfides and sulfur deposits with unique speleothems. To date, we have conducted a preliminary geobiological survey of the geochemistry, microbiology and mineralogy of this sulfur cave on its speleothems, mineral deposits and waters. Sampled waters, of which there is little, were all highly acidic (pH &amp;lt; 2). Microbiologically, an analysis of microbial communities present in approximately 25 sample locations (Fig. 1) to answer the question of—who is there?—was conducted via small subunit ribosomal 16S rRNA gene (for Bacteria and Archaea) and 18S rRNA (for Eukarya) analyses, prepared using a polymerase chain reaction (PCR) primer-pair that allows for the even amplification of all three domains of life. All samples were relatively low in biomass and resultant community analysis indicates a variety of Bacteria and Archaea phyla are represented with a dominance of known sulfur metabolizers. Mineralogically, petrography reveals a variety of crystal growth and habit in this sulfur-dominated, calcium carbonate-driven karstic ecosystem. X-ray diffraction analysis (XRD) was used to better determine the kinds and extant of mineral morphotypes and were surprisingly variable. The Shoshone Canyon Conduit Cave is a most intriguing sulfur cave to reveal what is known of the geobiology of sulfur caves in the Rocky Mountain Region. Findings from this work will likely apply to other cave systems such as Villa Luz (Mexico) and the Frasassi system (Italy). Finally, to learn about the Cedar Mountain Caves will inform on how either or both the National Park Service (NPS) and Bureau of Land Management (BLM) may better manage them as a meaningful component of the Greater Yellowstone Ecosystem.

N-Alkane Biosignatures in a High Arctic Mars Analogue Gossan Deposit

If past life ever existed on Mars, what are the multiple ways it could have been preserved in the Martian geological record? This crucial question is becoming especially relevant the more we uncover about the planet’s ancient wet history. Different acidic and sulfur rich analog environments have been proposed that are comparable to the alteration environments of iron oxides and sulfate minerals on Mars. However, some authors have hypothesized that these past Martian environments might have been cold and semi-dry, similar to polar regions on Earth. As part of the T-MARS team, we studied reactive gossans in the Canadian High Arctic, on Axel Heiberg Island, as an analog environment to similar deposits on Mars. We hypothesized that n-alkane lipids could potentially be an important form of molecular fossils entombed in varying mineral assemblages of sulphates, iron oxides, and phyllosilicates in Arctic gossans, because of their excellent preservation potential relative to most other forms of organic molecules. To determine the preservation potential of lipids in mineralogically varying acidic sulfur rich gossan deposits, this study extracted and quantified n-alkane biomarkers from three different Arctic gossans with gas chromatography–mass spectrometry (GC-MS). Total organic carbon, pH, and mineralogy were also determined. Organic matter was found to be very low in all samples (&amp;lt;1% wt.%). N-alkane analysis also revealed preserved even-over-odd distribution patterns in short chain n-alkanes, most likely from a microbial source, along with evidence for long-chain n-alkanes with odd-over-even distribution from higher plant sources. The presence of these unique chemical biosignatures in low organic, highly acidic, and sulfur rich Mars analog gossans of varying maturity provides evidence that sulfur deposits linked to paleo hydrothermal systems on Mars can be promising targets for preserved organic biosignatures, specifically lipid n-alkanes. The significant diversity in biosignature patterns across samples of varying mineralogy, pH, and oxidation levels within each gossan suggests that n-alkane preservation varies on a small scale in these environments. These factors alone do not definitively account for the variability of n-alkane concentrations and distributions in this study, and additional investigations of these and other influencing factors are needed to determine which specific targets to choose for biosignature search on Mars in future space missions. This exploratory study provides novel insights into the lipid biosignature content in high Arctic Mars analogue gossan deposits.

In Situ Rb‐Sr Dates of Muscovite and Sulfur Isotope of Pyrite from the Yangshan Gold Deposit in Western Qinling, China

AbstractLocated along the southern part of the West Qinling orogenic belt, the Yangshan gold deposit is one of the largest in China. The major gold ores of Yangshan are disseminated in metasedimentary host rocks with minor native gold amounts in stibnite‐gold quartz veins. Pyrite and arsenopyrite are the major Au‐bearing minerals. Hydrothermal muscovite from gold‐bearing quartz veins was dated using the in situ Rb‐Sr method to determine the formation age of the Yangshan gold deposit. The Rb‐Sr isochron date of the muscovite yielded 210.1 ± 5.6 Ma (MSWD = 1.2). This date is near the lower end of the period of the mineralized granitic dykes (210.49–213.10 Ma). Two stages of gold enriching process are recognized in the gold‐bearing pyrite: the first is incorporated with the Co, Cu, As, Ni enrichment; and the second is accompanied by Bi, Co, Ni, Pb, Cu, Sb concentration. The in‐situ sulfur isotopic values of pyrites show a restricted Δ34s range of –1.43 ‰ to 2.86 ‰ with a mean value of 0.43 ‰. Trace‐element mapping and in‐situ sulfur isotopic analysis of pyrite suggest that the sulfur deposits are likely derived from a magmatic source and likely assimilated by sulfur from the sedimentary bedrock. Thus, magmatism plays a critical role in the formation of the Yangshan gold deposit.

Influence of anthropogenic activities and loess dusts on the rainwater hydrochemistry in the Chinese Loess Plateau

Rainwater hydrochemistry is an important indicator for tracing anthropogenic input on air quality. As the fastest economically developing city in the northwestern China and the Chinese Loess Plateau, rainwater chemistry, sources of dissolved solutes, and the influence of loess dust on rainwater chemistry in Xi'an city is unclear. Inorganic ions, δD and δ18O of two years' rainwater samples were measured to decipher the above issues. Rainwater samples were weakly alkaline (pH = 7.2) with the mean total dissolved solids (TDS) values of 43 mg/L. NH4+ and Ca2+ dominated in the cations and SO42− and NO3− dominated in the anions. The wet deposition of sulfur (S) and nitrogen (N) was 70.9 ± 67 mg·(m2·month)−1 and 244.8 ± 270.9 mg·(m2·month)−1, respectively. The meteoric water line in Xi'an was δD = 7.29δ18O+3.72 (R2 = 0.99). δD, δ18O, and d-excess analysis indicated the influence of evaporation on the dissolved solutes in rainwater, especially in the dry season. Rainwater acidity in the Xi'an city was mainly neutralized by Ca2+ and NH4+, and the neutralization ability in Xi'an city is higher than the southern China cities. Correlation analysis (CA), positive matrix factorization (PMF), and the backward air masses trajectory model identified high NH4+ and Ca2+ in rainwater were mainly originated from local agricultural activities and loess dust, while NO3− and SO42− were associated with local coal combustion and vehicle exhaust sources. High inputs of dusts and coal combustion in spring and winter resulted in elevated values of pH and major ions in Xi'an. Due to the air pollution control policy, air quality in Xi'an is getting better in recent years. Our study highlights the influence of anthropogenic activities and loess dusts on the rainwater hydrochemistry in Xi'an and provides important dataset for air pollution control for other cities in semi-arid and arid regions.

Impact of Air Refreshing and Cloud Ice Uptake Limitations on Vertical Profiles and Wet Depositions of Nitrate, Ammonium, and Sulfate

AbstractThe impacts of cloud mixing and uptake on wet scavenging are not adequately resolved in global models which can lead to an overestimation of the removal of water‐soluble gases and aerosols from the atmosphere. To address this issue, we develop and implement novel parameterizations to consider the impacts of these processes. Our analysis of vertical profiles of nitric acid, inorganic nitrate, ammonium, and sulfate concentrations during the Atmospheric Tomography Mission periods indicates that air refreshing limitation has a significant impact above 800 hPa, while cloud ice uptake limitation plays an important role above 500 hPa. Incorporating these two processes resulted in a reduction of wet depositions of these species across source regions and a slight increase in their downwind regions. Wet depositions of nitrate, ammonium, and sulfate were reduced in source regions by 22.7%, 8.4%, and 8.3%, respectively and increased in downwind regions by 10.1%, 7.0%, and 4.3%, respectively.

Origin and mineralization processes of REE during magmatic-hydrothermal evolution: Insights from in-situ geochemistry of calcite from the Weishan REE deposit, eastern North China Craton

The Weishan REE deposit, hosting more than one million tons of light REE oxides (LREE2O3), is one of the largest LREE deposits in China. It has been considered to be a carbonatite-related REE deposit, but whether carbonatites occurred or not is still controversial, leading to the confusions of how the LREE originated and mineralized. Here, we conducted in-situ elemental and Sr-Nd isotopic analyses on different stages of calcite from the Weishan REE deposit, combined with petrographic and bulk C-O isotopic studies, with the aim to unravel the origin and mineralization processes of REE. Four stages of calcite (Cal-1, Cal-2, Cal-3 and Cal-4) were identified, of which the Cal-1 typically coexists with K-feldspar and quartz while the Cal-2 and Cal-3 coexist with sulfates and REE minerals (e.g., bastnäsite and parisite), respectively. The Cal-4 occurs in the post-ore veinlets and coexists with sulfides. The Cal-1 is characterized by exsolution of carbocernaite along its cleavage planes with highest Na, K, Sr, Ba and LREE contents. The other stages of calcite show continuous decrease of the above elements. Combined with petrographic features and elemental discrimination diagrams, it is concluded that the Cal-1 is magmatic while the others are hydrothermal. These calcites thus indicate a continuous magmatic-hydrothermal evolution. The four stages of calcite show similar isotopic compositions, which are consistent with those of the alkaline silicate rocks in the ore district, suggesting an uniform source or magma chamber for their derivation. Considering the magmatic features of Cal-1, it is inferred that carbonate melts coupled with abundant alkaline fluids were exsolved from the alkaline magmas. Alkalis (e. g., K and Na) were enriched in the magmatic-hydrothermal system with potassic metasomatism being more prevalent, which might play an important role in REE exsolution and transportation. Focused REE deposition occurred shortly after massive deposition of sulfates, indicating that REE-sulfate complexes might be the dominant transporting ligands of REE. The deposition of REE was mainly induced by fluid boiling, as indicated by the boiling/unmixing features of fluid inclusions. The Sr-Nd isotopic compositions of ores and associated alkaline rocks show affinities to the enriched lithospheric mantle (EM) beneath the study region, but are more depleted. Because subduction of the Paleo-Pacific oceanic plate beneath the eastern Asian occurred since the Jurassic, it is inferred that CO2- and REE-rich melts/fluids released from the subducted oceanic slab metasomatized the EM, leading to a REE-rich carbonated mantle. Rollback of the subducted slab occurred during the early Cretaceous, resulting in partial melting of the EM and thus generating the CO2- and REE-rich alkaline magmas. This deposit shows significant hydrothermal features with poorly-developed carbonatites, distinct from the typical carbonatite-related REE deposits in the other places. The REE mineralization is thus considered to be basically controlled by the alkaline magmas rather than the carbonatites.

Hydrolysis of Carbonyl Sulfide in Blast Furnace Gas Using Alkali Metal-Modified γ-Al2O3 Catalysts with High Sulfur Resistance.

A carbonyl sulfide (COS) hydrolysis catalyst can play an efficient role in blast furnace gas (BFG), but the life of the catalyst is greatly shortened due to the presence of O2 and H2S in the atmosphere, so improving the sulfur resistance of the catalyst is the key to application. In this work, alkali metals Na and K modified γ-Al2O3 catalysts to improve COS hydrolysis efficiency and sulfur resistance by adding an alkaline center. Compared with γ-Al2O3 catalysts, the COS hydrolysis efficiency of the modified catalysts in the experiment was improved by 12% in the presence of H2S and O2. The main cause of catalyst sulfur poisoning is the presence of O2, which intensifies both the total amount of sulfur deposition and the proportion of sulfate. It is found that the NaOH/Al2O3 catalyst shows better sulfur resistance than the KOH/Al2O3 catalyst for two reasons: first, the support of Na can significantly improve the medium-strong alkaline site, which is the adsorption site of H2S. This is equivalent to increasing the "sulfur capacity" of H2S adsorption and reducing the impact of sulfur deposition on the main reaction. Second, the elemental sulfur is more easily produced on the NaOH/Al2O3 catalyst, but the sulfur is further oxidized to sulfate and sulfite on the KOH/Al2O3 catalyst. The molecular diameter of elemental sulfur is smaller than that of sulfate. Therefore, the NaOH/Al2O3 catalyst has better sulfur resistance.

A YSZ-based mixed potential sensor achieving fast detection and complete recovery to SO2 through combining a high-temperature pulse and Pd catalyst in sensing electrode

Detection and prevention of some hazardous gas pollutants has always been a challenging problem. SO2, as a typical toxic and dangerous gas, is extremely difficult to be monitored stably because of its toxicity to gas detecting equipment. In this work, we report a high-performance YSZ-based mixed potential sensor to realize continuously on-line detection of SO2. In view of shortcomings of high temperature SO2 sensors such as poor stability, slow response and recovery rate and easy deterioration, Pd/Al2O3 catalyst was mixed thoroughly with Mn/Ce composite oxide and sintered to construct sensing electrode and an improved scheme combining high-temperature pulse and catalyst was proposed to decompose sulfate deposit and improve recovery characteristics. EDS and XPS measurements were used to verify the reason for improvement of SO2 sensing performance. Through the strategy proposed in this study, recovery time of the high temperature SO2 sensor to 5 ppm SO2 was reduced from 665 s to 73 s, indicating its fast-detecting ability. The detection range is 0−20 ppm (resolution ratio:1 ppm), meeting SO2 detection requirement. Moreover, stability of SO2 sensor during 10 days was significantly enhanced. This SO2 sensor is suitable for application in hazardous gas detection field due to its miniaturized, cost-effective, satisfying stability and selectivity, and fast response and recovery features.

Assimilation of POLDER observations to estimate aerosol emissions

Abstract. We apply a local ensemble transform Kalman smoother (LETKS) in combination with the global aerosol–climate model ECHAM–HAM to estimate aerosol emissions from POLDER-3/PARASOL (POLarization and Directionality of the Earth's Reflectances) observations for the year 2006. We assimilate aerosol optical depth at 550 mnm (AOD550), the Ångström exponent at 550 and 865 nm (AE550–865), and single-scattering albedo at 550 nm (SSA550) in order to improve modeled aerosol mass, size and absorption simultaneously. The new global aerosol emissions increase to 1419 Tg yr−1 (+28 %) for dust, 1850 Tg yr−1 (+75 %) for sea salt, 215 Tg yr−1 (+143 %) for organic aerosol and 13.3 Tg yr−1 (+75 %) for black carbon, while the sulfur dioxide emissions increase to 198 Tg yr−1 (+42 %) and the total deposition of sulfates to 293 Tg yr−1 (+39 %). Organic and black carbon emissions are much higher than their prior values from bottom-up inventories, with a stronger increase in biomass burning sources (+193 % and +90 %) than in anthropogenic sources (115 % and 70 %). The evaluation of the experiments with POLDER (assimilated) and AERONET as well as MODIS Dark Target (independent) observations shows a clear improvement compared with the ECHAM–HAM control run. Specifically based on AERONET, the global mean error in AOD550 improves from −0.094 to −0.006, while absorption aerosol optical depth at 550 nm (AAOD550) improves from −0.009 to −0.004 after the assimilation. A smaller improvement is also observed in the AE550–865 mean absolute error (from 0.428 to 0.393), with a considerably higher improvement over isolated island sites at the ocean. The new dust emissions are closer to the ensemble median of AEROCOM I, AEROCOM III and CMIP5 as well as some of the previous assimilation studies. The new sea salt emissions have become closer to the reported emissions from previous studies. Indications of a missing fraction of coarse dust and sea salt particles are discussed. The biomass burning changes (based on POLDER) can be used as alternative biomass burning scaling factors for the Global Fire Assimilation System (GFAS) inventory distinctively estimated for organic carbon (2.93) and black carbon (1.90) instead of the recommended scaling of 3.4 (Kaiser et al., 2012). The estimated emissions are highly sensitive to the relative humidity due to aerosol water uptake, especially in the case of sulfates. We found that ECHAM–HAM, like most of the global climate models (GCMs) that participated in AEROCOM and CMIP6, overestimated the relative humidity compared with ERA5 and as a result the water uptake by aerosols, assuming the kappa values are not underestimated. If we use the ERA5 relative humidity, sulfate emissions must be further increased, as modeled sulfate AOD is lowered. Specifically, over East Asia, the lower AOD can be attributed to the underestimated precipitation and the lack of simulated nitrates in the model.

Electrochemical Hydrogen Sulfide Decomposition Using Proton Conducting Ceramic for Pure Hydrogen Production

Hydrogen sulfide (H2S) is a substance that occurs during the process of processing sulfur, which is abundant in fossil fuels such as oil and natural gas, into high-quality fuel. Due to its high toxicity, it is classified as harmful industrial waste and removal in the process of discharging is essential. Until now, refiners have used the Claus process and the Wet Sulfuric Acid (WSA) process, which reacts hydrogen sulfide with oxygen to release it in the form of water or sulfuric acid. These processes require a huge amount of heat energy and only aim to remove hydrogen sulfide, so they emit hydrogen atoms contained in hydrogen sulfide in the form of water and sulfuric acid. Because hydrogen is an eco-friendly energy source that has recently been in the spotlight, hydrogen sulfide can be a valuable resource if hydrogen can be extracted from hydrogen sulfide. In this study, an electrochemical process that decomposes hydrogen sulfide and obtains hydrogen from hydrogen sulfide, replacing the conventional hydrogen sulfide removal process was proposed. To achieve this goal, thermodynamics of this reaction was analyzed and a solid oxide electrochemical cell based on proton conducting ceramic was fabricated for operating at high temperature and using perovskite structured electrodes. Experiments were then conducted to decompose hydrogen sulfide using fabricated cells and found that about 40 ppm, 100 sccm of hydrogen sulfide was decomposed at 600 oC by applying 0.5 V, 0.57 mA/cm2. Through this, the feasibility of the process was confirmed, and the durability test and regeneration process of the anode electrode were proceeded to solve degradation caused by sulfur deposits. In this study, a process has been proposed to effectively produce hydrogen of high value as an energy source, as well as to remove industrial waste hydrogen sulfide. It is expected that waste disposal and energy source production can be simultaneously produced in a clean and efficient way if cell performance improvement, removal of sulfur poison, and large systemization are applied to oil refiners' processes.