Soil Geobacteraceae are the key predictors of neurotoxic methylmercury bioaccumulation in rice.

Contamination of rice by the potent neurotoxin methylmercury (MeHg) originates from microbe-mediated Hg methylation in soils. However, the high diversity of Hg methylating microorganisms in soils hinders the prediction of MeHg formation and challenges the mitigation of MeHg bioaccumulation via regulating soil microbiomes. Here we explored the roles of various cropland microbial communities in MeHg formation in the potentials leading to MeHg accumulation in rice and reveal that Geobacteraceae are the key predictors of MeHg bioaccumulation in paddy soil systems. We characterized Hg methylating microorganisms from 67 cropland ecosystems across 3,600 latitudinal kilometres. The simulations of a rice-paddy biogeochemical model show that MeHg accumulation in rice is 1.3-1.7-fold more sensitive to changes in the relative abundance of Geobacteraceae compared to Hg input, which is recognized as the primary parameter in controlling MeHg exposure. These findings open up a window to predict MeHg formation and accumulation in human food webs, enabling more efficient mitigation of risks to human health through regulations of key soil microbiomes.

Narrow-Band Green-Emitting Hybrid Organic-Inorganic Eu (II)-Iodides for Next-Generation Micro-LED Displays.

Low-dimensional metal halide perovskites are an emerging class of light-emitting materials for LED-based displays; however, their B-site cations are confined to ns2, d5, and d10 metals. Here, the design of divalent rare earth ions at B-site is presented and a novel Eu(II)-based iodide hybrid is reported with efficient (PLQY ≈98%) narrow-band (FWHM ≈43 nm) green emission and high thermal stability (97%@150 °C). Owing to reduced lattice vibrations and shrunken average distance of Eu(II)-iodide bonds in the face-sharing 1D-structure, photoluminescence from Eu(II) 4f-5d transition appears along with elevated crystal-field splitting of 5d energy level. The Eu(II)-based iodide hybrid is further demonstrated for color-pure green phosphor-converted LEDs with a maximum brightness of ≈396 000 cd m-2 and photoelectric efficiency of 29.2%. High-resolution micrometer-scale light-emitting diode (micro-LED) displays (2540 PPI) via the solution-processed screen is also presented. This work thus showcases a compelling narrow-band green emitter for commercial micro-LED displays.

Crystal Plane Regulation Promotes the Oriented Conversion of Radicals in Heterogeneous Persulfate Catalyzed Oxidation Process.

In heterogeneous persulfate-catalyzed oxidation systems, the mechanism underlying the crystal plane effects of the catalyst on the selective conversion of reactive oxygen species (ROS) remains ambiguous. In this study, nano-Co3 O4 catalysts with varying crystallinity and exposure levels of (111) crystal planes are prepared via a hydrothermal method. Compared to low crystalline catalysts, high crystallinity catalysts predominantly expose (111) planes containing higher concentrations of Co2+ and oxygen vacancies (Ov), resulting in an increase degradation efficiency of p-nitrobenzaldehyde (4-NBA) from 74.5% to 100%. Radical quenching experiments and EPR characterization reveal that the degradation of 4-NBA occurs through a radical pathway, and quantification of radicals demonstrates that increasing exposure levels of (111) planes effectively promote radical yield (CSO4•- increase from 18.2 to 172.8 µm and C•OH increase from 1 to 58.9 µm). Furthermore, XPS and DFT calculations indicate that high crystallinity catalyst possesses more Ov active sites on (111) planes. The presence of Ov not only facilitates the adsorption of PMS molecules but also enhances electron transfer from Co2+ to PMS, leading to directed formation and efficient transformation of radicals. This study presents a novel strategy for promoting efficient radical formation in persulfate-activated systems.

Labile carbon inputs boost microbial contribution to legacy mercury reduction and emissions from industry-polluted soils.

Soils is a crucial reservoir influencing mercury (Hg) emissions and soil-air exchange dynamics, partially modulated by microbial reducers aiding Hg reduction. Yet, the extent to which microbial engagements contribute to soil Hg volatilization remains largely unknown. Here, we characterized Hg-reducing bacterial communities in natural and anthropogenically perturbed soil environments and quantified their contribution to soil Hg(0) volatilization. Our results revealed distinct Hg-reducing bacterial compositions alongside elevated mercuric reductase (merA) gene abundance and diversity in soils adjacent to chemical factories compared to less-impacted ecosystems. Notably, solely industry-impacted soils exhibited increased merA gene abundance along Hg gradients, indicating microbial adaption to Hg selective pressure through quantitative changes in Hg reductase and genetic diversity. Microcosm studies demonstrated that glucose inputs boosted microbial involvement and induced 2-8 fold increments in cumulative Hg(0) volatilization in industry-impacted soils. Microbially-mediated Hg reduction contributed to 41.6% of soil Hg(0) volatilization in industry-impacted soils under 25% water-holding capacity and glucose input conditions over a 21-day incubation period. Alcaligenaceae, Moraxellaceae, Nitrosomonadaceae and Shewanellaceae were identified as potential contributors to Hg(0) volatilization in the soil. Collectively, our study provides novel insights into microbially-mediated Hg reduction and soil-air exchange processes, with important implications for risk assessment and management of industrial Hg-contaminated soils.

Assessing microbial degradation potential of methylmercury in different types of paddy soil through short-term incubation.

The neurotoxic methylmercury (MeHg) in paddy soils can accumulate in rice grains. Microbial demethylation is an important pathway of MeHg degradation in soil, but the effect of soil type on microbial degradation of MeHg remains unclear. Therefore, we investigated MeHg degradation in eight typical paddy soils and analyzed the associations between soil physiochemical properties and microbial degradation efficiencies of MeHg. Results showed that MeHg was significantly degraded in unsterilized paddy soils, and the microbial degradation efficiency ranged from 10.8% to 64.6% after a 30-day incubation. The high microbial degradation efficiency of MeHg was observed in the soils with high levels of clay content, whereas relatively low degradation efficiency was found in the red paddy soils. We identified that Paenibacillaceae was the most important microbial predictor of MeHg degradation and was positively correlated with the degradation efficiency in the soils. The abundances of these microbial taxa associated with MeHg degradation were positively correlated with clay content. In addition, Eh, pH, and SOC could influence microbial degradation of MeHg by regulating certain microbial communities. Our results indicate that soil type is crucial in driving MeHg degradation, which has important implications for the mitigation of MeHg pollution in various croplands.

Soil contamination in nearby natural areas mirrors that in urban greenspaces worldwide.

Soil contamination is one of the main threats to ecosystem health and sustainability. Yet little is known about the extent to which soil contaminants differ between urban greenspaces and natural ecosystems. Here we show that urban greenspaces and adjacent natural areas (i.e., natural/semi-natural ecosystems) shared similar levels of multiple soil contaminants (metal(loid)s, pesticides, microplastics, and antibiotic resistance genes) across the globe. We reveal that human influence explained many forms of soil contamination worldwide. Socio-economic factors were integral to explaining the occurrence of soil contaminants worldwide. We further show that increased levels of multiple soil contaminants were linked with changes in microbial traits including genes associated with environmental stress resistance, nutrient cycling, and pathogenesis. Taken together, our work demonstrates that human-driven soil contamination in nearby natural areas mirrors that in urban greenspaces globally, and highlights that soil contaminants have the potential to cause dire consequences for ecosystem sustainability and human wellbeing.

Methylmercury Degradation by Trivalent Manganese.

Methylmercury (MeHg) is a potent neurotoxin and has great adverse health impacts on humans. Organisms and sunlight-mediated demethylation are well-known detoxification pathways of MeHg, yet whether abiotic environmental components contribute to MeHg degradation remains poorly known. Here, we report that MeHg can be degraded by trivalent manganese (Mn(III)), a naturally occurring and widespread oxidant. We found that 28 ± 4% MeHg could be degraded by Mn(III) located on synthesized Mn dioxide (MnO2-x) surfaces during the reaction of 0.91 µg·L-1 MeHg and 5 g·L-1 mineral at an initial pH of 6.0 for 12 h in 10 mM NaNO3 at 25 °C. The presence of low-molecular-weight organic acids (e.g., oxalate and citrate) substantially enhances MeHg degradation by MnO2-x via the formation of soluble Mn(III)-ligand complexes, leading to the cleavage of the carbon-Hg bond. MeHg can also be degraded by reactions with Mn(III)-pyrophosphate complexes, with apparent degradation rate constants comparable to those by biotic and photolytic degradation. Thiol ligands (cysteine and glutathione) show negligible effects on MeHg demethylation by Mn(III). This research demonstrates potential roles of Mn(III) in degrading MeHg in natural environments, which may be further explored for remediating heavily polluted soils and engineered systems containing MeHg.

Energy-Trapping Management in X-Ray Storage Phosphors for Flexible 3D Imaging.

X-ray imaging has received sustained attention for healthcare diagnostics and nondestructive inspection. To develop photonic materials with tunable photophysical properties in principle accelerates radiation detection technologies. Here the rational design and synthesis of doped halide perovskite CsCdCl3 :Mn2+ , R4+ (R = Ti, Zr, Hf, and Sn) are reported as next generation X-ray storage phosphors, and the capability is greatly improved by trap management via Mn2+ site occupation manipulation and heterovalent substitution. Specially, CsCdCl3 :Mn2+ , Zr4+ displays zero-thermal-quenching (TQ) radioluminescence and anti-TQ X-ray-activated persistent luminescence even up to 448 K, further revealing the charge-carrier compensation and redeployment mechanisms. X-ray imaging with the resolution of 12.5 lp mm-1 is demonstrated, and convenient 3D X-ray imaging for the curved objects is realized in a time-lapse manner. This work demonstrates efficient modulation of energy traps to achieve high storage capacities and promote future research into flexible X-ray detectors.

Potential for mercury methylation by Asgard archaea in mangrove sediments.

Methylmercury (MeHg) is a potent neurotoxin that bioaccumulates along food chains. The conversion of MeHg from mercury (Hg) is mediated by a variety of anaerobic microorganisms carrying hgcAB genes. Mangrove sediments are potential hotspots of microbial Hg methylation; however, the microorganisms responsible for Hg methylation are poorly understood. Here, we conducted metagenomic and metatranscriptomic analyses to investigate the diversity and distribution of putative microbial Hg-methylators in mangrove ecosystems. The highest hgcA abundance and expression occurred in surface sediments in Shenzhen, where the highest MeHg concentration was also observed. We reconstructed 157 metagenome-assembled genomes (MAGs) carrying hgcA and identified several putative novel Hg-methylators, including one Asgard archaea (Lokiarchaeota). Further analysis of MAGs revealed that Deltaproteobacteria, Euryarchaeota, Bacteroidetes, Chloroflexi, and Lokiarchaeota were the most abundant and active Hg-methylating groups, implying their crucial role in MeHg production. By screening publicly available MAGs, 104 additional Asgard MAGs carrying hgcA genes were identified from a wide range of coast, marine, permafrost, and lake sediments. Protein homology modelling predicts that Lokiarchaeota HgcAB proteins contained the highly conserved amino acid sequences and folding structures required for Hg methylation. Phylogenetic tree revealed that hgcA genes from Asgard clustered with fused hgcAB genes, indicating a transitional stage of Asgard hgcA genes. Our findings thus suggest that Asgard archaea are potential novel Hg-methylating microorganisms and play an important role in hgcA evolution.

Soil biodiversity supports the delivery of multiple ecosystem functions in urban greenspaces.

While the contribution of biodiversity to supporting multiple ecosystem functions is well established in natural ecosystems, the relationship of the above- and below-ground diversity with ecosystem multifunctionality remains virtually unknown in urban greenspaces. Here we conducted a standardized survey of urban greenspaces from 56 municipalities across six continents, aiming to investigate the relationships of plant and soil biodiversity (diversity of bacteria, fungi, protists and invertebrates, and metagenomics-based functional diversity) with 18 surrogates of ecosystem functions from nine ecosystem services. We found that soil biodiversity across biomes was significantly and positively correlated with multiple dimensions of ecosystem functions, and contributed to key ecosystem services such as microbially driven carbon pools, organic matter decomposition, plant productivity, nutrient cycling, water regulation, plant-soil mutualism, plant pathogen control and antibiotic resistance regulation. Plant diversity only indirectly influenced multifunctionality in urban greenspaces via changes in soil conditions that were associated with soil biodiversity. These findings were maintained after controlling for climate, spatial context, soil properties, vegetation and management practices. This study provides solid evidence that conserving soil biodiversity in urban greenspaces is key to supporting multiple dimensions of ecosystem functioning, which is critical for the sustainability of urban ecosystems and human wellbeing.

Molten-salts assisted preparation of iron-nitrogen-carbon catalyst for efficient degradation of acetaminophen by periodate activation.

Highly efficient and stable heterogeneous catalysts were desired to activate periodate (PI) for sustainable pollution control. Herein, iron-nitrogen-carbon catalyst was synthesized using a facile molten-salts mediated pyrolysis strategy (denoted as FeNC-MS) and employed to activate PI for the degradation of acetaminophen (ACE). Compared with iron-nitrogen-carbon catalyst prepared by direct pyrolysis method (marked as FeNC), FeNC-MS exhibited superior catalytic activity due to its large specific surface area (1600 m2 g-1) and the abundance of FeNx sites. The batch experiments revealed that FeNC/PI process achieved 37 % ACE removal within 20 min, while ACE removal in FeNC-MS/PI process was 98 % under the identical conditions. Integrated with electron paramagnetic resonance tests, quenching experiments, chemical probe identification, and electrochemical experiments, we demonstrated that FeNC-MS-PI complexes-mediated electron transfer was the predominant mechanism for the oxidation of ACE. Further analysis disclosed that FeNx sites in FeNC-MS were the main active sites for the activation of PI. Additionally, FeNC-MS/PI process exhibited significant resistance to humic acid and background electrolyte, and avoided the secondary pollution imposed by Fe leaching. The possible degradation pathways of ACE were proposed. The germination experiments of lettuce seeds showed that the ecotoxicity of ACE solution was significantly reduced after treatment with FeNC-MS/PI process. Overall, this study provided a facile strategy for the synthesis of efficient iron-nitrogen-carbon catalysts and gained fundamental insight into the mechanism of PI activation by iron-nitrogen-carbon catalysts for pollutants degradation.

Interplay of defect levels and rare earth emission centers in multimode luminescent phosphors.

Multimode luminescence generally involves tunable photon emissions in response to various excitation or stimuli channels, which demonstrates high coding capacity and confidentiality abilities for anti-counterfeiting and encryption technologies. Integrating multimode luminescence into a single stable material is a promising strategy but remains a challenge. Here, we realize distinct long persistent luminescence, short-lived down/upconversion emissions in NaGdTi2O6:Pr3+, Er3+ phosphor by emloying interplay of defect levels and rare earth emission centers. The materials show intense colorful luminescence statically and dynamically, which responds to a wide spectrum ranging from X-ray to sunlight, thermal disturbance, and mechanical force, further allowing the emission colors manipulable in space and time dimensions. Experimental and theoretical approaches reveal that the Pr3+ ↔ Pr4+ valence change, oxygen vacancies and anti-site TiGd defects in this disordered structure contributes to the multimode luminescence. We present a facile and nondestructive demo whose emission color and fade intensity can be controlled via external manipulation, indicating promise in high-capacity information encryption applications.

Global hotspots for soil nature conservation.

Soils are the foundation of all terrestrial ecosystems1. However, unlike for plants and animals, a global assessment of hotspots for soil nature conservation is still lacking2. This hampers our ability to establish nature conservation priorities for the multiple dimensions that support the soil system: from soil biodiversity to ecosystem services. Here, to identify global hotspots for soil nature conservation, we performed a global field survey that includes observations of biodiversity (archaea, bacteria, fungi, protists and invertebrates) and functions (critical for six ecosystem services) in 615 composite samples of topsoil from a standardized survey in all continents. We found that each of the different ecological dimensions of soils-that is, species richness (alpha diversity, measured as amplicon sequence variants), community dissimilarity and ecosystem services-peaked in contrasting regions of the planet, and were associated with different environmental factors. Temperate ecosystems showed the highest species richness, whereas community dissimilarity peaked in the tropics, and colder high-latitudinal ecosystems were identified as hotspots of ecosystem services. These findings highlight the complexities that are involved in simultaneously protecting multiple ecological dimensions of soil. We further show that most of these hotspots are not adequately covered by protected areas (more than 70%), and are vulnerable in the context of several scenarios of global change. Our global estimation of priorities for soil nature conservation highlights the importance of accounting for the multidimensionality of soil biodiversity and ecosystem services to conserve soils for future generations.

Efficient removal of mercury and chromium from wastewater via biochar fabricated with steel slag: Performance and mechanisms.

Biochar derived from biomass is regarded as a promising adsorbent for wastewater treatment, but the high cost of modification is still a challenge for its large-scale practical applications. In this study, we employed steel slag as a low-cost fabricant and synthesized hydrothermally carbonized steel slag (HCSS), as a stable environmentally functional material for heavy metal removal. Typically, positively and negatively charged heavy metal contaminants of Hg2+ and Cr2O7 2- were employed to testify the performance of HCSS as an adsorbent, and good capacities [(283.24 mg/g for Hg (II) and 323.16 mg/g for Cr (VI)] were found. The feasibility of HCSS on real wastewater purification was also evaluated, as the removal efficiency was 94.11% and 88.65% for Hg (II) and Cr (VI), respectively. Mechanism studies revealed that the modification of steel slag on bio-adsorbents offered copious active sites for pollutants. As expected, oxygen-containing functional groups in HCSS acted as the main contributor to adsorption capacity. Moreover, some reactive iron species (i.e., Fe2+) played an essential role in chemical reduction of Cr (VI). The adsorptive reactions were pH-dependent, owing to other more mechanisms, such as coprecipitation, ion-exchange, and electrostatic attraction. This promising recycling approach of biomass waste and the design of agro-industrial byproducts can be highly suggestive of the issues of resource recovery in the application of solid waste-derived environmentally functional materials for heavy metal remediation.

Increased water inputs fuel microbial mercury methylation in upland soils.

Mercury (Hg) can be converted to neurotoxic methylmercury (MeHg) by certain microbes typically in anaerobic environments, threatening human health due to its bioaccumulation in food webs. However, it is unclear whether and how Hg can be methylated in legacy aerobic uplands with increasing water. Here, we conducted a series of incubation experiments to investigate the effects of increased water content on MeHg production in two typical upland soils (i.e., long-term and short-term use). Results showed that marked MeHg production occurred in water-saturated upland soils, which was strongly correlated with the proportions of significantly stimulated Hg methylating taxon (i.e., Geobacter). Elevated temperature further enhanced MeHg production by blooming proportions of typical Hg methylators (i.e., Clostridium, Acetonema, and Geobacter). Water saturation could also enhance microbial Hg methylation by facilitating microbial syntrophy between non-Hg methylators and Hg methylators. Taken together, the present work suggests that uplands could turn into a potential MeHg reservoir in response to water inputs resulting from rainfall or anthropogenic irrigation.

Understanding the nonradical activation of peroxymonosulfate by different crystallographic MnO2: The pivotal role of MnIII content on the surface.

Manganese oxide-activated persulfate plays a critical role in water purification and in situ chemical oxidation processes, but the underlying mechanism needs to be further revealed. Herein, the detailed mechanism of MnO2 with various crystallographic structures (α-, ß-, γ-, and δ-MnO2) towards peroxymonosulfate (PMS) activation was investigated. PMS activated by tunnel structured α-, ß-, and γ-MnO2 showed higher acetaminophen (ACE) removal than layer structured δ-MnO2 with the removal efficiency following an order of α-MnO2 (85%) ≈ Î³-MnO2 (84%) > ß-MnO2 (65%) > Î´-MnO2 (31%). Integrated with chemical quenching experiments, electron paramagnetic resonance, Raman spectra, X-ray photoelectron spectroscopy, and Langmuir-Hinshelwood model on kinetic data, both surface-bound PMS complexes and direct oxidation by surface manganese species (Mn(Ⅳ, Ⅲ)(s)) were disclosed as the dominant oxidation mechanism for ACE degradation in α-, ß-, and γ-MnO2/PMS, which were rarely observed in previous reports. Moreover, the catalytic activity of α-, ß-, and γ-MnO2 was positively correlated to the MnIII(s) content on the catalyst surface. Higher content of MnIII(s) would stimulate the generation of more oxygen vacancies, which was conducive to the adsorption of PMS and the formation of reactive complexes. Overall, this study might provide deeper insight into the nonradical activation mechanism of PMS over different crystallographic MnO2.

[Characteristics and Assessment of Heavy Metal Contamination in Soils of Industrial Regions in the Yangtze River Economic Belt].

The Yangtze River Economic Belt is one of the areas with rapid economic development in China, although the intensive industrial activities have aggravated the emissions of soil pollutants in this area. Industrial activities are important sources of soil heavy metal contamination; however, the spatial distribution and main emission sources of soil heavy metal contamination in industrial regions of the economic belt remain unclear. Here, we collected data on the concentrations of eight heavy metals (Cd, Cr, Cu, Pb, Ni, Hg, As, and Zn) in the surface soils of 193 industrial regions covering 11 provinces and cities of the Yangtze River Economic Belt from China National Knowledge Infrastructure (CNKI), Web of Science, and other public databases. On this basis, we analyzed the spatial distribution characteristics of heavy metals and the contamination characteristics of typical industries. The results showed that the heavy metal contamination in agricultural land was more serious than that in industrial land. A total of 58.49%, 39.53%, and 22.64% of the agricultural land, respectively, contained levels of Cd, Zn, and Pb that exceeded the screening values of the Soil Environmental Quality Control Standard for Soil Pollution Risk of Agricultural Land (GB 15618-2018). The results of geo-accumulation index analysis showed that the contamination degree of the eight heavy metals was in the order of Cd (2.52)>Hg (1.17)>Pb (1.00)>Zn (0.90)>Cu (0.72)>As (0.02)>Cr (-0.40)>Ni(-0.48). As for the spatial distribution, Hg, Cd, As, Cu, Pb, and Zn were the main pollutants in the upstream and middle reaches of the industrial regions, whereas As, Cd, and Hg were the main pollutants in the downstream industrial regions. Different types of industry caused different types of contamination. Mining industries caused the most serious soil contamination, the main pollutants of which were Hg and Cd, followed by Cu, Pb, and Zn. Furthermore, metal processing industries mainly caused Cd and Pb contamination. The surrounding soils of chemical industries were contamination-free or only slightly polluted by the eight heavy metals, whereas petroleum processing industries mainly caused Cd contamination. Our study provides important theoretical basis for the future prevention and control of soil heavy metal contamination in industrial regions of the Yangtze River Economic Belt.

Near-Infrared Light-Emitting Diodes utilizing a Europium-Activated Calcium Oxide Phosphor with External Quantum Efficiency of up to 54.7.

Near-infrared (NIR) luminescence materials with broadband emissions are necessary for the development of light-emitting diodes (LEDs) based light sources. However, most known NIR-emitting materials are limited by their low external quantum efficiency. This work demonstrates how the photoluminescence quantum efficiency of europium-activated calcium oxide (CaO:Eu) NIR phosphor can be significantly improved and stabilized at operating temperatures of LEDs. A carbon paper wrapping technology is innovatively developed and used during the solid-state sintering to promote the reduction of Eu3+ into Eu2+ . In parallel, the oxygen vacancies in the CaO lattice are repaired utilizing GeO2 decomposition. Through this process, a record-high external quantum efficiency of 54.7% at 740 nm is obtained with a thermal stability greatly improved from 57% to 90% at 125 °C. The as-fabricated NIR-LEDs reach record photoelectric efficiency (100 mA@23.4%) and output power (100 mA @ 319.5 mW). This discovery of high-performance phosphors will open new research avenues for broadband NIR LED light sources in a variety of photonics applications.

Effects of foreign metal doping on the step-by-step oxidation process in M-OMS-2 catalyzed activation of PMS.

Various metal cations M (M = Mg2+, Ca2+, Zn2+, Cu2+, Fe3+) were doped into the tunnel of manganese octahedral molecular sieve (OMS-2). Redox-inactive metal (Ca, Mg and Zn) doped OMS-2 exhibited better peroxymonosulfate (PMS) catalytic activity than redox metal-doped Cu-OMS-2 and Fe-OMS-2. Redox-inactive metals doping improves the conductivity and reducibility of the catalyst, while transition metal doping reduces the dispersion of manganese. More importantly, the degradation of ACE can be divided into two stages. In the first stage, ACE was oxidized dominantly through mediated electron transfer process. Subsequently, singlet oxygen (1O2) gradually dominated oxidative degradation in the second stage, which was derived from the reaction between superoxide radical (O2•-) and metastable manganese intermediates. The long half-life of O2•- on the surface of OMS-2 ensured the delay generation of 1O2. This study not only provides a new idea for improving the efficiency of heterogeneous catalysts activation of PMS, but also meaningful for the in-depth study of multiple reaction mechanisms in PMS activation processes.