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Net nitrogen mineralization (Nmin) and nitrification regulate soil N availability and loss after severe wildfires in boreal forests experiencing slow vegetation recovery. Yet, how microorganisms respond to postfire phosphorus (P) enrichment to alter soil N transformations remains unclear in N-limited boreal forests. Here, we investigated postfire N-P interactions using an intensive regional-scale sampling of 17 boreal forests in the Greater Khingan Mountains (Inner Mongolia-China), a laboratory P-addition incubation, and a continental-scale meta-analysis. We found that postfire soils had an increased risk of N loss by accelerated Nmin and nitrification along with low plant N demand, especially during the early vegetation recovery period. The postfire N/P imbalance created by P enrichment acts as a "N retention" strategy by inhibiting Nmin but not nitrification in boreal forests. This strategy is attributed to enhanced microbial N-use efficiency and N immobilization. Importantly, our meta-analysis found that there was a greater risk of N loss in boreal forest soils after fires than in other climatic zones, which was consistent with our results from the 17 soils in the Greater Khingan Mountains. These findings demonstrate that postfire N-P interactions play an essential role in mitigating N limitation and maintaining nutrient balance in boreal forests.

The co-occurrence of cadmium (Cd) pollution and selenium (Se) deficiency commonly exists in global soils, especially in China. As a result, there is great interest in developing practical agronomic strategies to simultaneously achieve Cd remediation and Se mobilization in paddy soils, thereby enhancing food quality/safety. To this end, we conducted a field-plot trial on soils having high geological background levels of Cd (0.67 mg kg-1) and Se (0.50 mg kg-1). We explored 12 contrasting fertilizers (urea, potassium sulfate (K2SO4), calcium-magnesium-phosphate (CMP)), amendments (manure and biochar) and their combinations on Cd/Se bioavailability. Soil pH, total organic carbon (TOC), soil available Cd/Se, Cd/Se fractions and Cd/Se accumulation in different rice components were determined. No significant differences existed in mean grain yield among treatments. Results showed that application of urea and K2SO4 decreased soil pH, whereas the CMP fertilizer and biochar treatments increased soil pH. There were no significant changes in TOC concentrations. Three treatments (CMP, manure, biochar) significantly decreased soil available Cd, whereas no treatment affected soil available Se at the maturity stage. Four treatments (CMP, manure, biochar and manure＋urea＋CMP＋K2SO4) achieved our dual goal of Cd reduction and Se enrichment in rice grain. Structural equation modeling (SEM) demonstrated that soil available Cd and root Cd were negatively affected by pH and organic matter (OM), whereas soil available Se was positively affected by pH. Moreover, redundancy analysis (RDA) showed strong positive correlations between soil available Cd, exchangeable Cd and reducible Cd with grain Cd concentration, as well as between pH and soil available Se with grain Se concentration. Further, there was a strong negative correlation between residual Cd/Se (non-available fraction) and grain Cd/Se concentrations. Overall, this study identified the primary factors affecting Cd/Se bioavailability, thereby providing new guidance for achieving safe production of Se-enriched rice through fertilizer/amendment management of Cd-enriched soils.

Recent studies suggest that hypolimnetic respiration may be responsible for greenhouse gas (GHG) emissions from deep reservoirs. Currently, quantitative evaluation of aerobic vs. anaerobic processes and priming (enhanced processing of organic matter due to the addition of labile carbon) in regulating GHG production and emissions across the reservoir-downstream continuum remains largely unknown. High-resolution, annual time-series observations in a large, subtropical reservoir (Shuikou) experiencing seasonal hypoxia in southeast China indicate that aerobic hypolimnetic CO2 production dominated in most periods of the stratified spring/summer with higher rates at higher temperatures. In addition, anaerobic production of hypolimnetic CO2 occurred in the late stratified spring/summer period, which stimulated hypolimnetic production of CH4 and N2O. Incubation experiments showed that priming in spring enhanced both aerobic and anaerobic production of excess GHGs. A late spring flood event generated the highest daily efflux of CO2 through the flushing of GHG-enriched hypolimnion waters. Turbine degassing contributed 59%, 93%, and 63% of annual CO2, CH4, and N2O effluxes, respectively. Moreover, annual downstream GHG emissions were similar to those in the transition/lacustrine zone of the Shuikou reservoir. Diurnal variation observations revealed net CO2 emissions even during algal bloom seasons. The reservoir-downstream river continuum was a year-round source of GHGs (218.5 ± 18.9 Gg CO2-equivalent yr−1; CO2 contributed 91%). However, the loss of oxygen also leads to increased production and storage of recalcitrant dissolved organic carbon (RDOC). Thus, identifying mechanisms controlling both GHG emissions and RDOC production is crucial to constrain the carbon neutrality issue of hydroelectric reservoirs in the context of climate change mitigation strategies.

Riverine nitrogen pollution is ubiquitous and attracts considerable global attention. Nitrate is commonly the dominant total nitrogen (TN) constituent in surface and ground waters; thus, stable isotopes of nitrate (δ15N/δ18O-NO3-) are widely used to differentiate nitrate sources. However, δ15N/δ18O-NO3- approach fails to present a holistic perspective of nitrogen pollution for many coastal-plain river networks because diverse nitrogen species contribute to high TN loads. In this study, multiple isotopes, namely, δ15N/δ18O-NO3-, δ18O-H2O, δ15N-NH4+, δ15N-PN, and δ15Nbulk/δ18O/SP-N2O in the Wen-Rui Tang River, a typical coastal-plain river network of Eastern China, were investigated to identify transformation processes and sources of nitrogen. Then, a stable isotope analysis in R (SIAR) model-TN source apportionment method was developed to quantify the contributions of different nitrogen sources to riverine TN loads. Results showed that nitrogen pollution in the river network was serious with TN concentrations ranging from 1.71 to 8.09 mg/L (mean ± SD: 3.77 ± 1.39 mg/L). Ammonium, nitrate, and suspended particulate nitrogen were the most prominent nitrogen components during the study period, constituting 45.4 %, 28.9 %, and 19.9 % of TN, respectively. Multiple hydrochemical and isotopic analysis identified nitrification as the dominant N cycling process. Biological assimilation and denitrification were minor N cycling processes, whereas ammonia volatilization was deemed negligible. Isotopic evidence and SIAR modeling revealed municipal sewage was the dominant contributor to nitrogen pollution. Based on quantitative estimates from the SIAR model, nitrogen source contributions to the Wen-Rui Tang River watershed followed: municipal sewage (40.6 %) ≈ soil nitrogen (39.5 %) > nitrogen fertilizer (9.7 %) > atmospheric deposition (2.8 %) during wet season; and municipal sewage (59.1 %) > soil nitrogen (30.4 %) > nitrogen fertilizer (4.1 %) > atmospheric deposition (1.0 %) during dry season. This study provides a deeper understanding of nitrogen dynamics in eutrophic coastal-plain river networks, which informs strategies for efficient control and remediation of riverine nitrogen pollution.

Viruses are crucial in shaping soil microbial functions and ecosystems. However, studies on soil viromes have been limited in both spatial scale and biome coverage. Here we present a comprehensive synthesis of soil virome biogeographic patterns using the Global Soil Virome dataset (GSV) wherein we analysed 1,824 soil metagenomes worldwide, uncovering 80,750 partial genomes of DNA viruses, 96.7% of which are taxonomically unassigned. The biogeography of soil viral diversity and community structure varies across different biomes. Interestingly, the diversity of viruses does not align with microbial diversity and contrasts with it by showing low diversity in forest and shrubland soils. Soil texture and moisture conditions are further corroborated as key factors affecting diversity by our predicted soil viral diversity atlas, revealing higher diversity in humid and subhumid regions. In addition, the binomial degree distribution pattern suggests a random co-occurrence pattern of soil viruses. These findings are essential for elucidating soil viral ecology and for the comprehensive incorporation of viruses into soil ecosystem models.

Aquatic ecosystems world-wide are being irreversibly altered, suggesting that new and innovative management strategies are necessary to improve ecosystem function and sustainability. In river ecosystems degraded by dams environmental flows and selective withdrawal (SWD) infrastructure have been used to improve habitat for native species. Yet, few studies have quantified nutrient and food web export subsidies from upstream reservoirs, despite their potential to subsidize downstream riverine food webs. We sampled nutrient, phytoplankton, and zooplankton concentrations in outflows from the Shasta-Keswick reservoir complex in Northern California over a 12-month period to understand how SWD operation and internal reservoir conditions interact to influence subsidies to the Sacramento River. We found that nutrients, phytoplankton, and zooplankton were continuously exported from Shasta Reservoir to the Sacramento River and that gate operations at Shasta Dam were important in controlling exports. Further, our results indicate that gate operations and water-export depth strongly correlated with zooplankton community exports, whereas internal reservoir conditions (mixing and residence time) controlled concentrations of exported zooplankton biomass and chlorophyll a. These results demonstrate that reservoirs can be an important source of nutrient and food web subsidies and that selective withdrawal infrastructure may provide a valuable management tool to control ecosystem-level productivity downstream of dams.

Bacteria are an important component of the aquatic ecosystem playing a key role in the transformation and mineralisation of allochthonous organic matter, nutrients and pollutants. However, there is no clear understanding of spatio-temporal patterns of particle-attached versus free-living bacterial abundances, diversities and communities, which limits our in-depth understanding of hypereutrophic urban river ecosystems and the mechanisms regulating nutrient cycling and biogeochemical transformations. In order to investigate spatio-temporal patterns and associated factors for aquatic particle-attached versus free-living bacterial communities, we conducted a 2-year study of four contrasting habitats in a hypereutrophic urban river network of eastern China. Bacterial abundance and community structure in relation to various environmental variables were assessed by epifluorescence microscopy and high-throughput sequencing techniques. Results revealed that particle-attached bacterial abundance depended mainly on suspended particle concentrations, whereas free-living bacterial abundance was correlated with nutrient availability and water temperature. Organic carbon was related to a decrease of free-living and particle-attached bacterial richness, and particulate matter input increased free-living bacterial diversity. Seasonal changes of water temperature were linked to the temporal dynamics of bacterial community composition, and the differences in total organic carbon concentrations contributed to spatial differences in bacterial community composition. There were significant differences in bacterial community composition between particle-attached and free-living assemblages in low-turbidity/low-nutrient rivers found in land areas comprising mainly natural vegetation. These differences were especially prominent for the relative abundances of Cyanobacteria and Actinobacteria, which were higher in the particle-attached and free-living fractions, respectively. However, no significant differences were found in turbid/nutrient-rich rivers. Total organic carbon was the most significant factor shaping the composition similarity between particle-attached and free-living bacterial communities. Our findings indicate that spatio-temporal variations in water temperature, suspended particle and resource availability, especially for organic carbon, appreciably contribute to changes in the abundance, diversity and composition of aquatic particle-attached versus free-living bacterial communities in the hypereutrophic urban river network. Considering that biodiversity is important for supporting ecosystem functioning, this study informs spatio-temporal patterns of particle-attached and free-living bacterial abundance, diversity and composition of communities, and their underlying control mechanisms, thereby providing fundamental knowledge of microbial ecological functions for remediation and sustainable management of hypereutrophic urban river ecosystems.

Microplastics are an emerging and persistent pollutant due to their threat to global ecological systems and human health. Recent studies showed that microplastics have infiltrated the remote Third Pole - the Tibetan Plateau. Here, we summarize the current evidence for microplastic pollution in the different environments (rivers/lakes, sediment, soil, ice/snow and atmosphere) of the Tibetan Plateau. We assess the spatial distribution, source, fate, and potential ecological effects of microplastics in this broad plateau. The integrated results show that microplastics were pervasive in biotic and abiotic components of the Tibetan Plateau, even at the global highest-altitude, Mt. Everest. Although the concentration of microplastics in the Tibetan Plateau was far below that found in the densely populated lowlands, it showed a higher concentration than that in the ocean system. Tourist populations are identified as a substantial source of anthropogenic plastic input rather than local residents due to the rapid development of the tourism industry. In the sparsely inhabited remote area of the Tibetan Plateau, long-range atmospheric transport facilitates allochthonous microplastic diffusion. Robust solar radiation in the Tibetan Plateau might enhanced production of secondary microplastics by weathering (UV-photooxidation) of abandoned plastic waste. A rough estimation showed that the microplastic export flux from melting glaciers was higher than that measured in most of the world's largest rivers, which affects local and downstream areas. Since the Tibetan Plateau is vital for Asian water supply and numerous endangered wildlife, the potential human and ecological risk of microplastics to these fragile ecosystems needs to be fully evaluated within the context of climate-change impacts.

The soil microbial food web plays a vital role in soil health, nutrient cycling and agricultural productivity. Notably, there is a distinct paucity of information regarding the effects of heavy metal contamination on trophic-level interactions within the microbial food web of agricultural soils, which experience appreciably metal contamination worldwide. Herein, we investigated trophic interactions among predators (protists), their preys (bacteria and fungi) and competitors (nematodes) under four metal contamination levels using high-throughput sequencing and a laboratory verification experiment. Metal contamination decreased growth of protist-preferential prey (e.g., small-sized and gram-negative bacteria), increased the growth of protist-nonpreferential prey (e.g., pathogenic fungi and Actinobacteria), and had a limited effect on the soil protist-competitor (i.e., nematodes). This resulted in a considerable decrease in the diversity and abundance of protistan consumers and a re-arrangement of their interactions with other organisms. From a systemic view, the direct link was weaker between heavy metal contamination and the protist community than the indirect linkage, i.e., metal-induced changes in the prey community. We further validated these results with laboratory incubation trials that documented growth inhibition of protist (Colpoda) and protist-preferential prey (Spingomonas) versus growth stimulation of protist-nonpreferential prey (Arthrobacter) under metal contamination. These findings indicate that metal contamination collapses trophic-level interactions within the soil microbial food web via bottom-up regulation, providing important implications for managing trophic interactions to maintain agricultural ecosystem services under the challenge of worldwide metal contamination.

• Peak standing crop (PSC) and residual dry matter (RDM) are the primary measures of production and grazing intensity on California's annual rangelands. • One of the most common methods of monitoring forage metrics is to clip 1-ft2 quadrats. The USDA Forest Service, Bureau of Land Management, universities, and other land managers have been using this methodology since the 1930s. • We used best linear unbiased predictors (BLUEs) to determine 95% confidence intervals for PSC and RDM. For both PSC and RDM, as the number of samples taken increased from 1 to 10, the predictive ability also significantly increased. We found no evidence of increased predictive power past 10 samples.

Viruses are critical for regulating microbial communities and biogeochemical processes affecting carbon/nutrient cycling. However, the role of soil phages in controlling microbial physiological traits and intrinsic dissolved organic matter (DOM) properties remains largely unknown. Herein, microcosm experiments with different soil phage concentrates (including no-added phages, inactive phages, and three dilutions of active phages) at two temperatures (15 °C and 25 °C) were conducted to disclose the nutrient and DOM dynamics associated with viral lysing. Results demonstrated three different phases of viral impacts on CO2 emission at both temperatures, and phages played a role in maintaining Q10 within bounds. At both temperatures, microbial nutrient limitations (especially P limitation) were alleviated by viral lysing as determined by extracellular enzyme activity (decreased Vangle with active phages). Additionally, the re-utilization of lysate-derived DOM by surviving microbes stimulated an increase of microbial metabolic efficiency and recalcitrant DOM components (e.g., SUV254, SUV260 and HIX). This research provides direct experimental evidence that the "viral shuttle" exists in soils, whereby soil phages increase recalcitrant DOM components. Our findings advance the understanding of viral controls on soil biogeochemical processes, and provide a new perspective for assessing whether soil phages provide a net "carbon sink" vs. "carbon source" in soils.

The response of soil microbes to heavy metal pollution provides a metric to evaluate the soil health and ecological risks associated with heavy metal contamination. However, a multitrophic level perspective of how soil microbial communities and their functions respond to long-term exposure of multiple heavy metals remains unclear. Herein, we examined variations in soil microbial (including protists and bacteria) diversity, functional guilds and interactions along a pronounced metal pollution gradient in a field surrounding an abandoned electroplating factory. Given the stressful soil environment resulting from extremely high heavy metal concentrations and low nutrients, beta diversity of protist increased, but that of bacteria decreased, at high versus low pollution sites. Additionally, the bacteria community showed low functional diversity and redundancy at the highly polluted sites. We further identified indicative genus and "generalists" in response to heavy metal pollution. Predatory protists in Cercozoa were the most sensitive protist taxa with respect to heavy metal pollution, whereas photosynthetic protists showed a tolerance for metal pollution and nutrient deficiency. The complexity of ecological networks increased, but the communication among the modules disappeared with increasing metal pollution levels. Subnetworks of tolerant bacteria displaying functional versatility (Blastococcus, Agromyces and Opitutus) and photosynthetic protists (microalgae) became more complex with increasing metal pollution levels, indicating their potential for use in bioremediation and restoration of abandoned industrial sites contaminated by heavy metals.

Drivers of phytoplankton and zooplankton dynamics vary spatially and temporally in estuaries due to variation in hydrodynamic exchange and residence time, complicating efforts to understand controls on food web productivity. We conducted approximately monthly (2012–2019; n = 74) longitudinal sampling at 10 fixed stations along a freshwater tidal terminal channel in the San Francisco Estuary, California, characterized by seaward to landward gradients in water residence time, turbidity, nutrient concentrations, and plankton community composition. We used multivariate autoregressive state space (MARSS) models to quantify environmental (abiotic) and biotic controls on phytoplankton and mesozooplankton biomass. The importance of specific abiotic drivers (e.g., water temperature, turbidity, nutrients) and trophic interactions differed significantly among hydrodynamic exchange zones with different mean residence times. Abiotic drivers explained more variation in phytoplankton and zooplankton dynamics than a model including only trophic interactions, but individual phytoplankton–zooplankton interactions explained more variation than individual abiotic drivers. Interactions between zooplankton and phytoplankton were strongest in landward reaches with the longest residence times and the highest zooplankton biomass. Interactions between cryptophytes and both copepods and cladocerans were stronger than interactions between bacillariophytes (diatoms) and zooplankton taxa, despite contributing less biovolume in all but the most landward reaches. Our results demonstrate that trophic interactions and their relative strengths vary in a hydrodynamic context, contributing to food web heterogeneity within estuaries at spatial scales smaller than the freshwater to marine transition.

Early-stage pedogenic processes and formation rates on completely obliterated volcanic landscapes, such as the super explosive 1815 Mount Tambora eruption, have not previously been robustly explored. The objectives of this study were to determine (i) the mineralogical composition of the sand fraction, selected physical and chemical soil properties and potential nutrient reserves after 200 years of pedogenesis, and (ii) chemical weathering indices, rate of soil formation, and rates of C and N accretion. Soil formation was examined for five soil profiles on stable plain/foot slope positions representing the diversity of soils in these landscape positions, which are important for agricultural production. Results showed that the soil mineralogical composition of the sand fraction was dominated by easily weatherable minerals (e.g., labradorite and augite volcanic glass) indicating high potential nutrient reserves (e.g., Ca2+, Mg2+, K+, P) as confirmed by X-ray fluorescence (XRF) analyses. Allophanic material formation was minimal ( B horizons (45.4 ± 2.4) > C horizons (43.8 ± 4.2) ≈ tephra/lava (43.1), indicating accumulation of Al oxides and depletion of base cations in the upper horizons. Similarly, the base depletion index (BDI) showed a trend of A horizons (1.13 ± 0.18) < B horizons (1.25 ± 0.09) < C horizons (1.34 ± 0.20) ≈ tephra/lava (1.35), indicating depletion of base cations (Ca2+, Mg2+, K+, Na+) from the soil surface to C horizons. Based on solum depths (A + B horizons) and 200 years of post-eruption soil development, the solum formation rate ranged from 1.2 to 5.3 mm yr−1. Appreciable stocks of SOC (2.3–12.8 kg C m−2) and SON (0.21–0.77 kg m−2) accumulated over the 200 year period. Eruption materials from the Mt. Tambora eruption with a precisely known timescale contributed new pedological insights documenting rapid soil formation rates from pyroclastic materials leading to a rapid recovery of soil functions to support agricultural production.

Dissolved organic matter (DOM) in soils drives biogeochemical cycling and soil functions in different directions depending on its molecular signature. Notably, there is a distinct paucity of information concerning how the molecular signatures of soil DOM vary with different degrees of weathering across wide geographic scales. Herein, we resolved the DOM molecular signatures from 22 diverse Chinese reference soils and linked them with soil organic matter and weathering-related mineralogical properties. The mixed-effects models revealed that the yields of DOM were determined by soil organic carbon content, whereas the molecular signature of DOM was primarily constrained by the weathering-related dimension. The soil weathering index showed a positive effect on the lability and a negative effect on the aromaticity of DOM. Specifically, DOM in highly weathered acidic soils featured more amino sugars, carbohydrates, and aliphatics, as well as less O-rich polyphenols and condensed aromatics, thereby conferring a higher DOM biolability and lower DOM aromaticity. This study highlights the dominance of the weathering-related dimension in constraining the molecular signatures and potential functions of DOM in soils across a wide geographic scale.

Total antioxidant capacity (TAC) can be evaluated by detecting the content of antioxidants, such as ascorbic acid, based on the enzyme-mimetic activity of nanomaterials. Herein, we fabricated a 3D-V2O5/NC nanocomposite using a self-templating strategy, which achieved ultrafine particles (∼2.5 nm), a porous carbon layer, large specific surface area (152.4 m2/g), N-doping and heterogeneous structure. The strong catalytic activity of 3D-V2O5/NC resulted from the integrated effect between the ultrafine structure of V2O5 nanoparticles and the 3D porous nitrogen-doped carbon framework, effectively increasing the number of active sites. This nanozyme presented a higher catalytic activity than its components or precursors in the nanocomposite (e.g., VN/NC, NC, V2O5, and VO2/g-C3N4). ROS scavenging experiments confirmed that the dual enzyme-like activity of 3D-V2O5/NC (catalase-like and oxidase-like) resulted from their co-participation of ‧O2-, h+ and ‧OH, among which ‧O2- played a crucial role in the catalytic color reaction. By virtue of the 3D-V2O5/NC nanoenzyme activity and TMB as a chromogenic substrate, the mixed system of 3D-V2O5/NC + TMB + H2O2 provided a low detection limit (0.03 μM) and suitable recovery (93.0-109.5%) for AA. Additionally, a smartphone-based colorimetric application was developed employing "Thing Identify" software to evaluate TAC in beverages. The colorimetric sensor and smartphone-detection platform provide a better or comparable analytical performance for TAC assessment in comparison to commercial ABTS test kits. The newly developed smartphone-based colorimetric platform presents several prominent advantageous, such as low cost, simple/rapid operation, and feasibility for outdoor use.

Active Al, Fe and Si (i.e., oxalate extractable fraction: Alo, Feo, Sio) strongly affect soil physical, chemical and biological properties. This study examined the pedogenic factors affecting Alo, Feo and Sio contents across a soil weathering sequence in the Cameroon volcanic line. We investigated the B horizon (∼50-cm depth) from 26 soils formed in basaltic materials at different elevations (110–2570 m) incorporating a wide range of temperature (14–27 °C) and precipitation (1520–3130 mm). The weathering sequence ranged from weakly weathered Andisols in the southwest region grading to strongly weathered Oxisols on the central highlands. We assumed pyrophosphate extractable Al/Fe (Alp/Fep) as organo-Al/Fe complexes, and Sio, (Alo − Alp) and (Feo − Fep) as short-range-order (SRO) minerals. Factor analysis of climatic (e.g., temperature and precipitation/leaching metrics) and soil geochemical properties (e.g., weathering indices) identified three independent factors representing temperature/dry season intensity, weathering degree and precipitation/leaching as the primary determinants of Alo, Feo and Sio concentrations. Organo-metal complexes (Alp and Fep) were negatively correlated with the temperature/dry season intensity factor, whereas the SRO mineral phases (Sio, Alo − Alp and Feo − Fep) were negatively correlated with weathering degree. The precipitation/leaching factor positively correlated with Alo, Feo and Sio. Our analysis infers that low temperature promotes the formation and preservation of organo-Al/Fe complexes, whereas weathering degree is more critical for SRO minerals. Further, increased weathering and a drier climate enhance the formation of crystalline clay minerals at the expense of SRO minerals. Allophanic materials (Sio) were evident (Sio: 9–43 g kg−1) only in weakly weathered soils. However, low allophanic contents were found in more highly weathered soils (Sio: 2–7 g kg−1) accompanied by high Alp and Fep, suggesting the importance of volcanic parent materials as a direct source of Al and Fe via weathering for the formation of organo-metal complexes. In sum, we clarified the discriminatory effects of climatic factors and degree of weathering in regulating the composition of the active Al, Fe and Si fractions along the Cameroon volcanic line.

Rangelands support many important ecosystem services and are highly sensitive to climate change. Understanding temporal dynamics in rangeland gross primary production (GPP) and how it may change under projected future climate, including more frequent and severe droughts, is critical for ranching communities to cope with future changes. Herein, we examined how climate regulates the interannual variability of GPP in California’s diverse annual rangeland, based on the contemporary records of satellite derived GPP at 500 m resolution since 2001. We built Gradient Boosted Regression Tree models for 23 ecoregion subsections, relating annual GPP with 30 climatic variables, to disentangle the partial dependence of GPP on each climate variable. The machine learning results showed that GPP was most sensitive to growing season (GS) precipitation, with a reduction in GPP up to 200 g cm−2 yr−1 when GS precipitation decreased from 400 to 100 mm yr−1 in one of the driest subsections. We also found that years with more evenly distributed GS precipitation had higher GPP. Warmer winter minimum air temperature enhanced GPP in approximately two-thirds of the subsections. In contrast, average GS air temperatures showed a negative relationship with annual GPP. When the pre-trained models were forced by downscaled future climate projections, changes in the predicted rangeland productivity by mid- and end of century were more remarkable at the ecoregion subsection scale than at the state level. Our machine learning-based analysis highlights key regional differences in GPP vulnerability to climate and provides insights on the intertwining and potentially counteracting effects of seasonal temperature and precipitation regimes. This work demonstrates the potential of using remote sensing to enhance field-based rangeland monitoring and, combined with machine learning, to inform adaptive management and conservation within the context of weather extremes and climate change.

Water pollution is a great risk to aquatic ecosystems and human health. Among water pollution remediation strategies, adsorption mechanisms provide strong efficacy for a wide variety of pollutants. Several recent efforts examined the development of low cost adsorbents utilizing commonly available agricultural wastes. However, raw (i.e., unaltered) agricultural wastes typically exhibit low sorption capacity for pollutants due to their non-reactive structural/composition properties. Hence, modifications of raw agricultural wastes to enhance their sorption capacities for various aquatic pollutants are necessary to optimize their performance for pollutant removal. Numerous modification techniques are effective in altering agricultural wastes for improved sorption performance. This paper reviews the development of modified agricultural waste materials for pollutant removal from water. We compiled an extensive inventory of modification techniques applied to agricultural wastes to enhance their adsorption capacities for removal of a wide range of pollutants. Modification strategies and their effects on sorption properties were rigorously examined to highlight key advancements in the preparation of adsorbents from agricultural wastes. Finally, the costs of these materials were examined, along with the benefits and drawbacks concerning their use. This review provides a thorough assessment for advancing the utilization of agricultural wastes for preparing adsorbents for water treatment. Graphical Abstract: [Figure not available: see fulltext.]

Estuaries are among the most productive of aquatic ecosystems. Yet the collective understanding of patterns and drivers of primary production in estuaries is incomplete, in part due to complex hydrodynamics and multiple controlling factors that vary at a range of temporal and spatial scales. A whole-ecosystem experiment was conducted in a deep, pelagically dominated terminal channel of the Sacramento-San Joaquin Delta (California, USA) that seasonally appears to become nitrogen limited, to test whether adding calcium nitrate would stimulate primary productivity or increase phytoplankton density. Production did not respond consistently to fertilization, in part because nitrate and phytoplankton were dispersed away from the manipulated area within 1–3 days. Temporal and spatial patterns of gross primary production were more strongly related to stratification and light availability (i.e., turbidity) than nitrogen, highlighting the role of hydrodynamics in regulating system production. Similarly, chlorophyll was positively related not only to stratification but also to nitrogen—with a positive interaction—suggesting stratification may trigger nutrient limitation. The average rate of primary production (4.3 g O2 m−2 d−1), metabolic N demand (0.023 mg N L−1 d−1), and ambient dissolved inorganic nitrogen concentration (0.03 mg N L−1) indicate that nitrogen can become limiting in time and space, especially during episodic stratification events when phytoplankton are isolated within the photic zone, or farther upstream where water clarity increases, dispersive flux decreases, and stratification is stronger and more frequent. The role of hydrodynamics in organizing habitat connectivity and regulating physical and chemical processes at multiple temporal and spatial scales is critical for determining resource availability and evaluating biogeochemical processes in estuaries.

Climate and parent material are considered the primary factors determining the distributions of soil clay (secondary) minerals, but their influence has not been rigorously elucidated for tropical volcanic soils. Herein, we investigated soil secondary mineral distributions in volcanic regions of Java and Sumatra islands representing large variations in climatic (mean annual temperature (MAT): 13 to 27°C; precipitation: 1910 to 3950 mm) and parent material conditions (rhyolitic-to-basaltic tephra). Soil secondary minerals were assessed by selective extractions, X-ray diffraction analysis, and differential thermal analysis. Moreover, the thermodynamic stabilities of minerals were evaluated based on the ion activities of equilibrated soil–water suspensions. Factor analysis of climate and soil geochemical (e.g., total Si, Fe and K) properties identified temperature, dry season intensity, and parent material as the primary factors regulating secondary mineral distributions. A negative correlation between oxalate extractable Al and Fe (Alo and Feo) and the temperature factor indicates low temperature promoted the formation and preservation of short-range-order (SRO) minerals and organo-Al/Fe complexes, which resulted in Alo + 1/2Feo ≥ 20 g kg−1 (andic property criterion) at MAT

Herein, we fabricated a magnetic 3D nanocomposite based on Co,Ni-codoped and N-modified carbon nanotubes and reduced graphene (CoNi-N-CNTs/rGO). This nanomaterial possessed strong magnetism due to the presence of Co-Ni alloy, abundant defect sites owing to N doping, and a 3D multi-porous structure resulting from CNT in-situ growth on the graphene surface. Based on DFT calculations, H-bonding, hydrophobic and π-π conjugation were inferred to facilitate bisphenol adsorption by nanocomposites, among which π-π interactions provided the greatest adsorption contribution within a given N-doping type. By employing BPM as model compound, the adsorption energies (ΔEa) for π-π conjugation were −1.80, −1.59 and −2.08 eV for graphitic-N, pyridinic-N, and pyrrolic-N, respectively. This infers that pyrrolic-N sites form the strongest BP sorption bonds with the nanocomposite. The nanocomposites were utilized as an extractant in an effervescence tablet-assisted magnetic solid-phase microextraction (ET-MSPE) procedure that was optimized using Plackett-Burman design (PBD) and central composite design (CCD). Under optimized conditions, the ET-MSPE/HPLC-FLD method provided strong analytical performance for quantification of six BPs in juice with limits of detection of 0.06–0.20 μg/L, recoveries of 82.4–103.7 % and RSDs of 1.2–5.3 %. The particular novelty of this study lies in demonstrating the enhancement of adsorption/extraction efficiencies for BPs by nanocomposites resulting from N doping to generate the superior adsorption properties associated with the pyrrolic-N structure. These findings provide a theoretical foundation to inform the rational design of N-doped adsorbents/extractants based on a rigorus understanding of the molecular interactions occurring between carbon-based nanocomposites and BP analogues.

A novel photosensitized living biohybrid was fabricated by inward-to-outward assembly of amine-functionalized carbon dots (NCDs) and polydopamine (PDA) to Shewanella oneidensis MR-1 and applied for high-efficiency, microbial-photoreduction of Cr(VI). Within a 72 h test period, biohybrids achieved a pronounced catalytic reduction capacity (100%) for 100 mg/L Cr(VI) under visible illumination, greatly surpassing the poor capacity (only 2.5%) displayed by the wild strain under dark conditions. Modular configurations of NCDs and PDA afforded biohybrids with a large electron flux by harvesting extracellular photoelectrons generated from illuminated NCDs and increasing reducing equivalents released from an enlarged intracellular NADH/NAD+ pool. Further, increased production of intracellular c-type cytochromes and extracellular flavins resulting from the modular configuration enhanced the biohybrid electron transport ability. The enhancement of electron transport was also attributed to more conductive conduits at NCDs-PDA junction interfaces. Moreover, because NCDs are highly reductive, the enhanced Cr(VI) reduction was also attributed to direct reduction by the NCDs and the direct Cr(VI) reduction by sterile NCDs-assembled biohybrid was up to 20% in the dark. Overall, a highly efficient strategy for removal/transformation of Cr(VI) by using NCD-assembled photosensitized biohybrids was proposed in this work, which greatly exceeded the performance of Cr(VI)-remediation strategies based on conventional microbial technologies.

Nitrate pollution is of considerable global concern as a threat to human health and aquatic ecosystems. Nowadays, δ15N/δ18O-NO3- combined with a Bayesian-based SIAR model are widely used to identify riverine nitrate sources. However, little is known regarding the effect of variations in pollution source isotopic composition on nitrate source contributions. Herein, we used δ15N/δ18O-NO3-, SIAR modeling, probability statistical analysis and a perturbing method to quantify the contributions and uncertainties of riverine nitrate sources in the Wen-Rui Tang River of China and to further investigate the model sensitivity of each nitrate source. The SIAR model confirmed municipal sewage (MS) as the major nitrate source (58.5-75.7%). Nitrogen fertilizer (NF, 8.6-20.9%) and soil nitrogen (SN, 7.8-20.1%) were also identified as secondary nitrate sources, while atmospheric deposition (AD,

The fate of phosphorus (P) during pedogenesis has been historically conceptualized (Walker-Syers model) with time as the primary controlling state factor. Herein, we demonstrate that both climate and lithology exert a strong and interacting influence on the fate of P by examining coupled bioclimatic and parent material effects on soil P fractions. Three transects were investigated spanning a 2150-m elevation gradient (MAT = 17 → 3 °C/MAP = 330 → 1400 mm) across three separate bedrock lithologies (lithosequence: granite, andesite and basalt) within the Sierra Nevada and southern Cascades of California. The elevation gradient entails four bioclimatic zones (bioclimosequence: blue oak, ponderosa pine, white fir and red fir). Soil P fractions were determined by sequential fractionation and interpreted in the context of associated soil characterization data. The bioclimatic sequences demonstrate a weathering gradient with maximum intensity at mid-elevation sites, and corresponding changes in Fe/Al-(hydr)oxide content and aluminosilicate crystallinity. Phosphorus content of parent material varied by an order of magnitude (mean; mg P kg−1): andesite (1500) > basalt (1000) > granite (131). Differences in P content of parent material influenced Pt in soils. However, amounts and proportions of P in fractions were influenced by subtle to significant interactions between climate and lithology, owing to differences in chemical weathering and the abundance and crystallinity of Fe/Al-(hydr)oxides and aluminosilicates. This interactive effect of pedogenesis on clay mineralogy led to differences in P fractions dependent upon lithology and bioclimatic zone. Labile inorganic P (Pi) was uniformly higher in soils derived from granite, despite granite having significantly lower P content, a result of lower Fe/Al-(hydr)oxide generation in granitic soils. With descending elevation and increased weathering intensity, HCl-Pi (primary mineral bound P-apatite) declined in basalt and andesite but remained unchanged in granite owing to its greater resistance to chemical weathering. As weathering intensity increased, occluded P increased in basalt, decreased in andesite and was unchanged in granite, contradicting the paradigm of progressive P occlusion with increased weathering. This incongruity for andesite results from a dominance of poorly crystalline materials (e.g., ferrihydrite, allophane/imogolite) at less weathered sites versus more crystalline minerals at more weathered sites. This study highlights several caveats to the paradigm that time (i.e., degree of weathering) is universally the dominant pedogenic control of P fractionation. We identify the importance of interactions between lithology and climate in regulating the amount and types of weathering products that in turn control P fractionation and ecosystem P availability.

Mercury (Hg) is a ubiquitous contaminant in the environment and its methylated form, methylmercury (MeHg), poses a worldwide health concern for humans and wildlife, primarily through fish consumption. Global production of forest fire ash, derived from wildfires and prescribed burns, is rapidly increasing due to a warming climate, but their interactions with aqueous and sedimentary Hg are poorly understood. Herein, we compared the differences of wildfire ash with activated carbon and biochar on the sorption of aqueous inorganic Hg and sedimentary Hg methylation. Sorption of aqueous inorganic Hg was greatest for wildfire ash materials (up to 0.21 μg g-1 or 2.2 μg g-1 C) among all of the solid sorbents evaluated. A similar Hg adsorption mechanism for activated carbon, biochar made of walnut, and wildfire ash was found that involves the formation of complexes between Hg and oxygen-containing functional groups, especially the -COO group. Notably, increasing dissolved organic matter from 2.4 to 70 mg C L-1 remarkably reduced Hg sorption (up to 40% reduction) and increased the time required to reach Hg-sorbent pseudo-equilibrium. Surprisingly, biochar and wildfire ash, but not activated carbon, stimulated MeHg production during anoxic sediment incubation, possibly due to the release of labile organic matter. Overall, our study indicates that while wildfire ash can sequester aqueous Hg, the leaching of its labile organic matter may promote production of toxic MeHg in anoxic sediments, which has an important implication for potential MeHg contamination in downstream aquatic ecosystems after wildfires.

Aquaculture sediments are a purported sizable pool of antibiotic resistance genes (ARGs). However, the pathways for transmission of ARGs from sediments to animals and humans remain unclear. We conducted an ARG survey in sediments from a bullfrog production facility located in Guangdong, China, and simulated zebrafish breeding systems were constructed, with or without biochar addition in sediments, to explore the effects of biochar on ARGs and their precursors of the sediment and zebrafish gut. After 60 days, 6 subtypes of ARGs and intI1 were detected, with sediments harboring more ARGs than zebrafish gut. The addition of biochar reduced the abundance of ARGs in the sediment and zebrafish gut, as well as suppressed the horizontal transmission of ARGs from sediment to zebrafish gut. Network analysis and partial least squares path modeling revealed that ARG enrichment was mainly affected by bacterial groups dominated by Nitrospirae, Gemmatimonades, Chloroflexi, and Cyanobacteria and intI1. Our findings provide insights into the transmission of ARGs from sediment to animals and highlight the efficacy of biochar amendments to aquaculture sediments to reduce the transmission of ARGs.

High-intensity wildfires alter the chemical composition of organic matter, which is expected to be distinctly different from low-intensity prescribed fires. Herein, we used pyrolysis gas chromatography/mass spectrometry (Py-GC/MS), in conjunction with solid-state 13C nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectroscopy, to assess chemical alterations from three wildfires and a long-term frequent prescribed fire site. Our results showed that black ash formed under moderate intensity burns contained less aromatic (ArH), polyaromatic hydrocarbon (PAH), and nitrogen-containing compounds (Ntg) but more lignin (LgC) and phenol compounds (PhC), compared to white ash formed under high intensity burns. Both 13C NMR and FT-IR confirmed a higher relative percentage of carboxyl carbon in white ash, indicating the potential for higher water solubility and more mobile carbon, relative to black ash. Compared to wildfires, ash from low-intensity prescribed fire contained less ArH, PAH, and Ntg and more LgC and PhC. Controlled laboratory burning trials indicated that organic matter alteration was sensitive to the burn temperature, but not related to the fuel type (pine vs fir) nor oxygen absence/presence at high burn temperatures. This study concludes that higher burn temperatures resulted in higher (poly)aromatic carbon/nitrogen and lower lignin/phenol compounds.

Identifying the sources and transformations of riverine nitrate plays a critical role in mitigating nitrogen enrichment of river networks. Several previous studies have used δ18O-NO3− to quantitatively assess riverine nitrate contributed by atmospheric nitrate and terrestrial sources, but their results have great uncertainty due to the wide range of δ18O-NO3− values and isotopic fractionation during nitrogen-cycling processes in terrestrial environment. The nitrate 17O anomaly (△17O-NO3−), as an unambiguous tracer of atmospheric nitrate, is a promising tool to effectively separate atmospheric nitrate from microbially produced nitrate. However, to our knowledge, △17O-NO3− approach has not been previously applied to identify nitrate pollution sources in plain river networks of eastern China. In this study, we used a multiple isotope approach (δD/δ18O-H2O and δ15N/δ18O/△17O-NO3−) for the first time to quantitatively identify sources and transformations of riverine nitrate in a hypereutrophic coastal plain river network namely Wen-Rui Tang River located in eastern China, which is a region receiving high inputs of atmospheric nitrogen deposition. The △17O-NO3− values in precipitation and river water during the study period (April–June of 2021) varied from 14.83‰ to 31.39‰ and from − 2.82‰ to 9.66‰, respectively. The δD/δ18O-H2O values revealed that river water mainly originated from recent precipitation with little evaporation. Moreover, the δ15N/δ18O-NO3− values indicated that microbial nitrification, not denitrification, was the predominant nitrogen-cycling process in the watershed. Based on a Bayesian mixing model (Stable Isotope Analysis in R, SIAR) using δ15N/△17O-NO3−, municipal sewage was identified as the dominant nitrate source (50.5 ± 11.7%), followed by soil nitrogen (23.8 ± 13.7%), atmospheric nitrate deposition (14.3 ± 2.9%), and nitrogen fertilizer (11.4 ± 8.7%). Finally, an uncertainty analysis for nitrate source apportionment demonstrated that the greatest uncertainty was associated with soil nitrogen, followed by municipal sewage, nitrogen fertilizer, and atmospheric nitrate deposition. This study provides important scientific information on riverine nitrate source apportionment to guide pollution control/remediation strategies and highlights the benefits of utilizing △17O-NO3− to enhance nitrate source apportionment.

Global impoundment of river systems represents a major anthropogenic forcing to carbon cycling in reservoirs with seasonal thermal stratification. Currently, a quantitative and mechanistic understanding of how hypolimnetic deoxygenation in stratified reservoirs alters dissolved organic matter (DOM) cycling and lateral transport along the river continuum remains unresolved. Herein, we used optical and high-resolution mass spectrometric analyses to track seasonal and spatial compositional changes of DOM from a large, subtropical impounded river in southeast China. Aliphatic compounds were contributed by algal blooms to epilimnetic DOM during the spring/summer and by baseflow to the overall DOM pool during low-discharge periods. Deoxygenation-driven hypolimnetic mineralization enhanced in situ production of bio-refractory molecules and humic-like fluorescent DOM (FDOMH) by utilizing bio-labile DOM and settling biogenic particles during periods of stratification. Production efficiency of hypolimnetic FDOMH was 159-444% higher than that of the global dark ocean, and was strongly regulated by temperature and possibly substrate supply. The in situ production rate of hypolimnetic FDOMH was four to five orders-of-magnitude higher than the dark ocean, with much faster turnover rates in dark inland waters versus the dark ocean. Collectively, these findings indicate that the hypolimnion is a hotspot for microbial carbon transformations, and hence an important source and pool of refractory DOM in aquatic systems. The lateral FDOMH flux increased 10.8-32.1% due to hypolimnetic reservoir release during periods of stratification, highlighting the importance of incorporating hypolimnetic carbon transformations into models for carbon cycling of inland waters and the land-sea interface.

A two-chamber slurry microbial fuel cell (SMFC) was constructed using black-odorous river sediments as substrate for the anode. We tested addition of potassium ferricyanide (K3[Fe(CN)6]) or sodium chloride (NaCl) to the cathode chamber (0, 50, 100, 150, and 200 mM) and aeration of the cathode chamber (0, 2, 4, 6, and 8 h per day) to assess their response on electrical generation, internal resistance, and methane emission over a 600-h period. When the aeration time in the cathode chamber was 6 h and K3[Fe(CN)6] or NaCl concentrations were 200 mM, the highest power densities were 6.00, 6.45, and 6.64 mW·m-2, respectively. With increasing K3[Fe(CN)6] or NaCl concentration in the cathode chamber, methane emission progressively decreased (mean ± SD: 181.6 ± 10.9 → 75.5 ± 9.8 mg/m3·h and 428.0 ± 28.5 → 157.0 ± 35.7 mg/m3·h), respectively, but was higher than the reference having no cathode/anode electrodes (~ 30 mg/m3·h). Cathode aeration (0 → 8 h/day) demonstrated a reduction in methane emission from the anode chamber for only the 6-h treatment (mean: 349.6 ± 37.4 versus 299.4 ± 34.7 mg/m3·h for 6 h/day treatment); methane emission from the reference was much lower (85.3 ± 26.1 mg/m3·h). Our results demonstrate that adding an electron acceptor (K3[Fe(CN)6]), electrolyte solution (NaCl), and aeration to the cathode chamber can appreciably improve electrical generation efficiency from the MFC. Notably, electrical generation stimulates methane emission, but methane emission decreases at higher power densities.

Sinking of microplastics (MPs) after biofouling is considered an important mechanisms responsible for the downward transport/sedimentation of MPs in the ocean and freshwaters. Previous studies demonstrated MP sinking caused by an increase in the composite density of MPs after biofouling, while MPs with smaller size or shapes with higher surface area to volume ratios (SA:V), such as films, are speculated to sink faster. In this study, we designed an in situ microcosm to simulate the ambient environmental conditions experienced by floating MPs to elucidate the biofouling and sinking of polyethylene (PE), polypropylene (PP), and expanded-polystyrene (EPS) MPs of various sizes and shapes. Our results showed smaller PE and PP MP granules sank faster than large ones. Even EPS granules of 100 μm diameter, having a much lower density (0.02 mg/mm3) than water, started to sink after 2 weeks of biofouling. Moreover, PE film and fiber MPs with higher SA:V did not sink faster than PE MP granules of the same mass, implying that mechanisms other than SA:V, such as fouling contact area and drag coefficient, play a role in the regulation of biofouling and sinking of MPs.

Currently, the industrial application of bioelectrochemical systems (BESs) that are incubated with natural electrochemically active microbes (EABs) is limited due to inefficient extracellular electron transfer (EET) by natural EABs. Notably, recent studies have identified several novel living biomaterials comprising highly efficient electron transfer systems allowing unparalleled proficiency of energy conversion. Introduction of these biomaterials into BESs could fundamentally increase their utilization for a wide range of applications. This review provides a comprehensive assessment of recent advancements in the design of living biomaterials that can be exploited to enhance bioelectrocatalytic performance. Further, modular configurations of abiotic and biotic components promise a powerful enhancement through integration of nano-based artificial mediators and synthetic biology. Herein, recent advancements in BESs are synthesized and assessed, including heterojunctions between conductive nanomaterials and EABs, in-situ hybrid self-assembly of EABs and nano-sized semiconductors, cytoprotection in biohybrids, synthetic biological modifications of EABs and electroactive biofilms. Since living biomaterials comprise a broad range of disciplines, such as molecular biology, electrochemistry and material sciences, full integration of technological advances applied in an interdisciplinary framework will greatly enhance/advance the utility and novelty of BESs. Overall, emerging fundamental knowledge concerning living biomaterials provides a powerful opportunity to markedly boost EET efficiency and facilitate the industrial application of BESs to meet global sustainability challenges/goals.

Human-health risks from microplastics have attracted considerable attention, but little is known about human-exposure pathways and intensities. Recent studies posited that inhalation of atmospheric microplastics was the dominant human-exposure pathway. Herein, our study identified that atmospheric microplastics ingested from deposition during routine dining/drinking activities represent another important exposure pathway. We measured abundances of atmospheric-deposited microplastics of up to 105 items m-2 d-1 in dining/drinking venues, with 90% smaller than 100 µm and a dominance of amorphous fragments rather than fibers. Typical work-life scenarios projected an annual ingestion of 1.9 × 105 to 1.3 × 106 microplastics through atmospheric deposition on diet, with higher exposure rates for indoor versus outdoor dining/drinking settings. Ingestion of atmospheric-deposited microplastics through diet was similar in magnitude to presumed inhalation exposure, but 2-3 orders of magnitude greater than direct ingestion from food sources. Simple mitigation strategies (e.g., covering and rinsing dishware) can substantially reduce the exposure of atmospheric deposition microplastics through diet.

Although the previous research confirmed that triclosan (TCS) induced an estrogen effect by acting on a novel G-protein coupled estrogen-membrane receptor (GPER), the underlying mechanisms by which downstream pathways induce neurotoxicity remain unclear after TCS activation of GPER. By employing a series of techniques (Illumina miRNA-seq, RT-qPCR, and artificial intervention of miRNA expression), we screened out four important miRNAs, whose target genes were directly/indirectly involved in neurodevelopment and neurobehavior. Especially, the miR-144 up-regulation caused vascular malformation and severely affected hair-cell development and lateral-line-neuromast formation, thereby causing abnormal motor behavior. After microinjecting 1-2-cell embryos, the similar phenotypic malformations as those induced by TCS were observed, including aberrant neuromast, cuticular-plate development and motor behavior. By KEGG pathway enrichment analysis, these target genes were demonstrated to be mainly related to the PKC/MAPK signaling pathway. When a PKC inhibitor was used to suppress the PKC/MAPK pathway, a substantial alleviation of TCS-induced neurotoxicity was observed. Therefore, TCS acts on GPER to activate the downstream PKC/MAPK signaling pathway, further up-regulating miR-144 expression and causing abnormal modulation of these nerve-related genes to trigger neurodevelopmental toxicity. These findings unravel the molecular mechanisms of TCS-induced neurodegenerative diseases, and offer theoretical guidance for TCS-pollution early warning and management.

We fabricated a novel N,S-co-doped carbon/Co1-xS nanocomposite (NSC/Co1-xS) using a facile sol-gel approach, which featured a multiporous structure, abundant S vacancies and Co-S nanoparticles filling the carbon-layer pores. When the Co1-xS nanoparticles were anchored onto the surface of N,S-co-doped carbon, a synergistic catalysis action occurred. The NSC/Co1-xS nanocomposites possessed both peroxidase-like and oxidase-mimetic dual-enzyme activities, in which the oxidase-mimetic activity dominated. By scavenger capture tests, the nanozyme was demonstrated to catalyze H2O2 to produce h+, •OH and •O2-, among which the strongest and weakest signals were h+ and •OH, respectively. The multi-valence states of Co atoms in the NSC/Co1-xS structure facilitated electronic transfer that enhanced redox reactions, thereby improving the resultant color reaction. Based on the NSC/Co1-xS's enzyme-mimetic catalytic reaction, a visual colorimetric assay and Android "Thing Identify" application (app), installed on a smartphone, offered detection limits of 1.93 and 2.51 mg/dl, respectively, in human serum samples. The selectivity/interference experiments, using fortified macromolecules and metal ions, demonstrated that this sensor had high selectivity and low interference potential for cholesterol analysis. Compared to standard assay kits and previously reported visual detection, the Android smartphone-based assays provided higher accuracy (recoveries up to 93.6-104.1%), feasibility for trace-level detection, and more convenient on-site application for cholesterol assay due to the superior enzymatic activity of NSC/Co1-xS. These compelling performance metrics lead us to posit that the NSC/Co1-xS-based nanozymic sensor offers a promising methodology for several practical applications, such as point-of-care diagnosis and workplace health evaluations.

Ammonia-oxidizing bacteria (AOB) attached to aquatic particles are important participants in ammonia oxidation within hypereutrophic urban river systems. To explore the effects of aquatic nitrogen pollution on particle-attached AOB in urban river, we utilized laboratory mesocosms to investigate the responses of abundances and community structure of particle-attached AOB to ammonium (NH4+) and glycine (C2H5NO2) amendments. The abundance and community structure of particle-attached AOB were determined with quantitative real-time polymerase chain reaction (qRT-PCR) analysis and high-throughput sequencing based on the AOB amoA gene, respectively. Most of the bacterial amoA sequences from different treatments were affiliated with uncultured Nitrosomonadaceae bacterium, uncultured Nitrosomonadales bacterium, and uncultured Nitrosomonas sp., which are closely associated with organic pollution. The species richness and diversity of particle-attached AOB communities increased with increasing NH4+ and glycine concentrations. Treatment effects contributed significantly to the variance in particle-attached AOB communities. Although, glycine was completely transformed to ammonium within a few days and ammonium amendments would change the community structure of particle-attached AOB, the effect of glycine on the particle-attached AOB community was regulated by both the resulting ammonium concentration, as well as organic matter availability to the heterotrophic bacteria. Results suggested that high anthropogenic nitrogen loadings appeared to promote higher particle-attached AOB richness and diversity in the hypereutrophic urban river, but the effect of organic nitrogen on the particle-attached AOB community was different from the effect of inorganic nitrogen. This study informs ammonia oxidization mechanisms in the hypereutrophic urban rivers, which contributes to remediation/restoration strategies.

Condition indices are key predictors of health and fitness in wild fish populations. Variation in body condition, therefore, can be used to identify stressful conditions that may impact endangered species, such as California’s endemic Delta Smelt (Hypomesus transpacificus McAllister, 1963). Here, we examined spatiotemporal variation in the condition indices of > 1600 Delta Smelt collected over nine years (2011–2019), a period characterized by tremendous variability in hydrodynamic and water quality conditions. The population exhibited low hepatosomatic index (HSI) and condition factor (CF) during September/October/November (fall), and both condition indices declined over the nine-year study during fall. HSI was positively correlated with indicators of pelagic productivity (e.g., Chlorophyll a, zooplankton biomass, and proximity to tidal wetlands), whereas CF was negatively correlated with temperature, peaking at a relatively cool 10–13 °C. In sum, seasonal and interannual variation in body condition corresponded most strongly with pelagic productivity and water temperature, with little correlation to freshwater outflow. Management actions that increase pelagic productivity, restore and freshen productive wetlands during late summer-fall, and reduce water temperatures overall are likely to benefit condition indices and, therefore, fitness of the Delta Smelt population.

Ammonia oxidation by ammonia-oxidising archaea (AOA) and bacteria (AOB) is the first and rate-limiting step of nitrification. By providing substrate to the nitrogen–removing denitrification processes, nitrification is an important process for attenuation of allochthonous nitrogen loads in urban rivers, thereby mitigating eutrophication of downstream ecosystems. However, the relative importance of AOA and AOB communities in ammonia oxidation, the distribution and varied patterns of these groups and the underlying mechanisms have received limited study in hypereutrophic urban river networks. To investigate spatial and temporal patterns of particle-attached and free-living ammonia-oxidising microbial communities, we conducted a 2-year study of four different water quality/habitat conditions within a hypereutrophic urban river network of eastern China. The structure and dynamics of ammonia-oxidising microbial communities were determined by high-throughput sequencing based on the AOA and AOB amoA gene. We found significant spatial and temporal heterogeneity of ammonia-oxidising microbial communities, but no significant differences between particle-attached and free-living fractions. Analysis revealed that changes in the diversity and composition of ammonia-oxidising microbial communities were mainly related to substrate availability (e.g., ammonia, nitrite, dissolved oxygen). AOB communities were more complex and had a higher species richness and diversity compared with AOA communities. Our findings indicate that high anthropogenic nitrogen loadings appear to promote higher ammonia-oxidising microbial richness and diversity, and AOB are more adaptable to the hypereutrophic conditions, thereby playing a more important role than AOA in nitrogen transformations in hypereutrophic urban river networks. This study highlights the importance of ammonia-oxidising microorganisms in nutrient-rich river systems and provides valuable insights into ammonia transport and transformations in urban river networks.

Herein, we systematically investigated the mechanisms of OH production and arsenic (As(III)) oxidation induced by sulfur vacancy greigite (Fe3S4) under anoxic and oxic conditions. Reactive oxygen species analyses revealed that sulfur vacancy-rich Fe3S4 (SV-rich Fe3S4) activated molecular oxygen to produce hydrogen peroxide (H2O2) via a two-electron reduction pathway under oxic conditions. Subsequently, H2O2 was decomposed to OH via the Fenton reaction. Additionally, H2O was directly oxidized to OH by surface high-valent iron (Fe(IV)) resulting from the abundance of sulfur vacancies in Fe3S4 under anoxic/oxic conditions. These differential OH-generating mechanisms of Fe3S4 resulted in higher OH production of SV-rich Fe3S4 compared to sulfur vacancy-poor Fe3S4 (SV-poor Fe3S4). Moreover, the OH production rate of SV-rich Fe3S4 under oxic conditions (19.3 ± 1.0 μM•h-1) was 1.6 times greater than under anoxic conditions (11.8 ± 0.4 μM•h-1). As(III) removal experiments and X-ray photoelectron spectra (XPS) showed that both OH production pathways were favorable for As(III) oxidation, and a higher concentration of As(V) was immobilized on the surface of SV-rich Fe3S4 under oxic conditions. This study provides new insights concerning OH production and environmental pollutants removal mechanisms on surface defects of Fe3S4 under anoxic and oxic conditions.