A self-cleaning micro-fluidic chip biospired by the filtering system of manta rays.

Size-based particle filtration has become indispensable in numerous biomedical and environmental applications. In this study, bioinspired by the filter-feeding mechanism (lobe filtration) of manta rays, we designed a U-shaped biomimetic gill rake filter that combined lobe filtration and Dean flow to filter monodisperse suspensions, bi-disperse suspensions and yeast cells. Compared with other equipment using the inertial focusing technology, our equipment can perform high-throughput (up to 8 mL min-1) and high-efficiency filtration of particles (maximum filtration efficiencies of 96.08% and 97.14% for 10 and 15 µm monodisperse suspensions at the optimum flow rate of 6 mL min-1). The complex velocity field of the micro-fluidic flow within the filter is numerically simulated, and in combination with experiments, a threshold for the flow rate is identified. When the inlet flow rate exceeds the threshold value, the efficiency of particle filtration is increased rapidly. Afterwards, by analysing the filtration mechanism, we develop three novel filtration processes. The equilibrium positions of the particles and yeast cells in the main channel are close to the outer wall at high flow rate, which diminishes the likelihood of particles and yeast cells entering the side channel. This configuration establishes a self-cleaning mechanism, ensuring prolonged and efficient operation of the filter with high-throughput processing. Furthermore, the influence of the filter lobe angle and channel width on the filtration efficiency and outlet flow rate ratio are explored, and an optimisation plan is prepared.

Unraveling the drivers for interannual variabilities of N2O fluxes from forests soils across climatic zones.

Forest soils are an important source of nitrous oxide (N2O), however, field observations of N2O emission have often exhibited large variabilities when compared with managed agricultural lands. In the last decade, the number of forest N2O studies has increased more than tenfold, but only a few of them have looked into the interannual flux variabilities from the regional scale. Here, we have collected 30 long-term N2O monitoring studies (≥ 2 years) based on a global database, and extracted variabilities (VARFlux) as well as relative variabilities (VAR%, in proportions) of annual N2O fluxes. The relationship of mean annual precipitation (MAP), mean annual temperature (MAT), and nitrogen (N) deposition with flux variabilities was examined to explore the underlying mechanisms for N2O emission on a long-term scale. Our results show that mean VARFlux is 0.43 kg N ha-1 yr-1 and VAR% is 28.68%. Across climatic zones, the subtropical forests have the largest annual N2O fluxes, as well as the largest fluctuations among annual budgets, while the tropics were the smallest. We found that the regulating factors for VARFlux and VAR% are fundamentally different, i.e., MAT and N input determine the annual fluxes as well as VARFlux while MAP and other limiting soil parameters determine VAR%. The relative contributions of different seasons to flux variabilities were also explored, indicating that N2O fluxes of warm and cool seasons are more responsible for the fluctuations in annual fluxes of the (sub)tropical and temperate forests, respectively. Overall, despite the limitation in interpretations due to few long-term studies from literature, this work highlights that significant interannual variabilities are common phenomena for N2O emission from different climatic zones forest soils; by unraveling the divergent drivers for VARFlux and VAR%, we have provided the possibility of improving N2O simulation models for constraining the heterogeneity of N2O emission processes from climatic zones forest soils.

Mussel-Inspired Antimicrobial and Antifouling Coating Constructed by the Combination of Zwitterionic Copolymers and Silver Nanoparticles.

Biofouling and bacterial infections are significant challenges in biomedical devices. In this study, a biocompatible dual-functional coating with antimicrobial and antifouling properties is developed by co-depositing the zwitterionic copolymer and silver nanoparticles via a dopamine-assisted strategy. Inspired by mussel adhesion, the coating exhibits substrate-independent adhesion as a result of the formation of irreversible covalent bonds. The zwitterionic copolymer in the dual coating plays a crucial role in improving surface wettability and reducing protein adsorption and platelet and bacterial adhesion, thereby improving its antifouling property significantly. The silver nanoparticles reduced by self-polymerized polydopamine without the addition of any chemical reductants can effectively improve the antimicrobial activity. Furthermore, as the zwitterion content in the zwitterion polymer increases, the antibacterial and antifouling properties of the coating can be further advanced. The simple and effective approach presented here provides a promising pathway for constructing potent antibacterial and antifouling surfaces, demonstrating great potential for clinical applications in implanted materials.

Curcumin Supplementation Improves Growth Performance and Anticoccidial Index by Improving the Antioxidant Capacity, Inhibiting Inflammatory Responses, and Maintaining Intestinal Barrier Function in Eimeria tenella-Infected Broilers.

This study was conducted to investigate the effects of dietary curcumin supplementation on growth performance, anticoccidial index, antioxidant capacity, intestinal inflammation, and cecum microbiota in broilers infected with Eimeria tenella. A total of 234 one-day-old broilers were categorized into three treatments, with six replicates per treatment containing 13 broilers each. The three treatments included the control group, Eimeria tenella group, and Eimeria tenella + curcumin (200 mg/kg) group. The feeding trial lasted for 42 days, during which the broilers were orally administered with 0.9% saline or 5 × 104Eimeria tenella oocysts on day 14 of the study. On day 17 and day 21, one bird per replicate was selected for slaughtering. Results indicated an increased survival rate and anticoccidial index and improved productive performance in coccidia-infected broilers with curcumin supplementation. Furthermore, curcumin enhanced the serum antioxidant capacity in Eimeria tenella-infected broilers, evidenced by increased serum catalase activity (3d, 7d), as well as decreased malondialdehyde level (3d, 7d) and nitric oxide synthase activity (7d) (p < 0.05). Curcumin also improved intestinal inflammation and barrier function, evidenced by the downregulation of interleukin (IL)-1ß (3d, 7d), TNF-alpha (TNF-α) (3d, 7d), and IL-2 (7d) and the up-regulated mRNA levels of claudin-1 (7d), zonula occludens (ZO-1; 3d, 7d), and occludin (3d, 7d) in the ceca of infected broilers (p < 0.05). Eimeria tenella infection significantly disrupted cecum microbial balance, but curcumin did not alleviate cecum microbial disorder in broilers infected with Eimeria tenella. Collectively, curcumin supplementation enhanced growth performance and anticoccidial index in Eimeria tenella-infected broilers via improving antioxidant ability and cecum inflammation without affecting cecum microbiota.

Modeling denitrification nitrogen losses in China's rice fields based on multiscale field-experiment constraints.

Denitrification plays a critical role in soil nitrogen (N) cycling, affecting N availability in agroecosystems. However, the challenges in direct measurement of denitrification products (NO, N2 O, and N2 ) hinder our understanding of denitrification N losses patterns across the spatial scale. To address this gap, we constructed a data-model fusion method to map the county-scale denitrification N losses from China's rice fields over the past decade. The estimated denitrification N losses as a percentage of N application from 2009 to 2018 were 11.8 ± 4.0% for single rice, 12.4 ± 3.7% for early rice, and 11.6 ± 3.1% for late rice. The model results showed that the spatial heterogeneity of denitrification N losses is primarily driven by edaphic and climatic factors rather than by management practices. In particular, diffusion and production rates emerged as key contributors to the variation of denitrification N losses. These findings humanize a 38.9 ± 4.8 kg N ha-1 N loss by denitrification and challenge the common hypothesis that substrate availability drives the pattern of N losses by denitrification in rice fields.

Identification of a new allele of BraA09g066480.3C controlling the wax-less phenotype of Chinese cabbage.

BACKGROUND: Epidermal wax covers the surfaces of terrestrial plants to resist biotic and abiotic stresses. Wax-less flowering Chinese cabbage (Brassica campestris L. ssp. chinesis var. utilis tsen et lee) has the charateristics of lustrous green leaves and flower stalks, which are of high commercial value. RESULTS: To clarify the mechanism of the wax deficiency, the wax-less flowering Chinese cabbage doubled-haploid (DH) line 'CX001' and Chinese cabbage DH line 'FT', obtained from isolated microspore culture, were used in the experiments. Genetic analysis showed that the wax-less phenotype of 'CX001' was controlled by a recessive nuclear gene, named wlm1 (wax-less mutation 1), which was fine-mapped on chromosome A09 by bulked segregant analysis sequencing (BSA-seq) of B.rapa genome V3.0. There was only one gene (BraA09g066480.3C) present in the mapping region. The homologous gene in Arabidopsis thaliana is AT1G02205 (CER1) that encodes an aldehyde decarboxylase in the epidermal wax metabolism pathway. Semi-quantitative reverse transcription PCR and transcriptome analysis indicated that BraA09g066480.3C was expressed in 'FT' but not in 'CX001'. BraA09g066480.3C was lost in the CXA genome to which 'CX001' belonged. CONCLUSION: The work presented herein demonstrated that BraA09g066480.3C was the causal gene for wax-less flowering Chinese cabbage 'CX001'. This study will lay a foundation for further research on the molecular mechanism of epidermal wax synthesis in flowering Chinese cabbage.

Water status and macronutrient concentrations, but not carbon status, of Viscum album ssp. album are determined by its hosts: a study across nine mistletoe-host pairs in central Switzerland.

Introduction: European mistletoe, Viscum album L., is a hemiparasite that can infect various tree species, yet our understanding of its physiological interactions with host species is limited. Methods: Nine mistletoe-host pairs (i.e. V. album ssp. album growing on nine different broadleaf tree species) under different growth conditions in central Switzerland were selected to examine the carbon, water and nutrient relationships between mistletoe and its hosts. We measured leaf morphological traits, isotopic compositions (δ13C and δ15N), concentrations of non-structural carbohydrates (NSC) and specific compounds (i.e. mobile sugars and starch), and macronutrients (i.e. N, P, K, Ca, Mg, S) in leaf and xylem tissues of both mistletoe and its hosts. Results and Discussion: There were only non-significant relationships between NSC concentrations in mistletoe and in its host species across the nine mistletoe-host pairs, suggesting the carbon condition of V. album ssp. album is determined by both the heterotrophic carbon transfer and self-photosynthetic capacity among different mistletoe-host pairs. However, mistletoe leaf morphological traits (single leaf area and mass, and leaf mass per unit leaf area) did not change across the nine mistletoe-host pairs, and mistletoe leaf δ13C, water content and macronutrient concentrations were linearly correlated with those in the host leaves. Macronutrients showed accumulations in mistletoe across the nine pairs. Further, tissue N concentrations were significantly higher in mistletoe grown on N-fixing hosts than on non-N-fixing hosts. Finally, leaf N:P in mistletoe was significantly correlated with the ratio in the host across the nine mistletoe-host pairs. Overall, our results indicate strong relationships between mistletoe and its hosts for water- and nutrient-related traits, but not for carbon-related traits, which demonstrates that V. album ssp. album can adjust its physiology to survive on different deciduous tree species hosts and under different site conditions.

Controlling high-speed droplet splashing and superspreading behavior on anisotropic superhydrophobic leaf surfaces by ecofriendly Pseudogemini surfactants.

BACKGROUND: Efficient deposition of high-speed droplets on superhydrophobic leaf surfaces remains an important challenge. For anisotropic wired superhydrophobic leaf surfaces, the splashing phenomenon is especially serious because it leads to the low effective utilization of pesticides by biological targets. The lost pesticides cause serious ecological environment pollution, therefore there is an urgent need to develop a green and sustainable cost-effective strategy to achieve efficient deposition of high-speed droplets on anisotropic superhydrophobic leaf surfaces at low dosage. RESULTS: One type of green pseudogemini surfactant is constructed based on fatty acids and hexamethylenediamine by electrostatic interaction to control the splashing and spreading of high-speed droplets on superhydrophobic surfaces. The formed surfactant can not only achieve complete inhibition of the bouncing of droplets, but also promote rapid spreading on superhydrophobic leaf surfaces at very low usage. The efficient deposition and superspreading phenomenon are attributed to the rapid migration and adsorption of the surfactant from the dynamic spherical micelles at the newly formed solid-liquid interface, the network-like aggregated spherical micelles, and the Marangoni effect caused by the surface tension gradient. Moreover, the surfactant shows an excellent synergistic effect with herbicides to control weeds by inhibiting droplet splashing. CONCLUSION: This work provides a simpler, more effective and sustainable approach to utilize aggregated spherical micelles rather than conventional vesicles or wormlike micelles to improve the droplet deposition on superhydrophobic leaf surfaces and reduce the impact of surfactants and pesticides on the ecological environment. © 2023 Society of Chemical Industry.

Recent Advances of Organ-on-a-Chip in Cancer Modeling Research.

Although many studies have focused on oncology and therapeutics in cancer, cancer remains one of the leading causes of death worldwide. Due to the unclear molecular mechanism and complex in vivo microenvironment of tumors, it is challenging to reveal the nature of cancer and develop effective therapeutics. Therefore, the development of new methods to explore the role of heterogeneous TME in individual patients' cancer drug response is urgently needed and critical for the effective therapeutic management of cancer. The organ-on-chip (OoC) platform, which integrates the technology of 3D cell culture, tissue engineering, and microfluidics, is emerging as a new method to simulate the critical structures of the in vivo tumor microenvironment and functional characteristics. It overcomes the failure of traditional 2D/3D cell culture models and preclinical animal models to completely replicate the complex TME of human tumors. As a brand-new technology, OoC is of great significance for the realization of personalized treatment and the development of new drugs. This review discusses the recent advances of OoC in cancer biology studies. It focuses on the design principles of OoC devices and associated applications in cancer modeling. The challenges for the future development of this field are also summarized in this review. This review displays the broad applications of OoC technique and has reference value for oncology development.

Chaos-Based Lightweight Cryptographic Algorithm Design and FPGA Implementation.

With the massive application of IoT and sensor technologies, the study of lightweight ciphers has become an important research topic. In this paper, an effective lightweight LZUC (lightweight Zu Chongzhi) cipher based on chaotic system is proposed to improve the traditional ZUC algorithm. In this method, a further algorithm is designed for the process of integrating chaos into the lightweighting of ZUC. For the first time, this design introduces the logistic chaotic system into both the LFSR (linear feedback shift register) and nonlinear F-function of the cryptographic algorithm. The improved LZUC algorithm not only achieves a certain effect in lightweighting, but also has good statistical properties and security of the output sequence. To verify the performance of the LZUC cipher, we performed NIST statistical tests and information entropy analysis on its output key streams and discussed the typical attacks on the algorithm's resistance to weak key analysis, guess-determination analysis, time-stored data trade-off analysis, and algebraic analysis. In addition, we completed the design of an image security system using the LZUC cipher. Histogram analysis and correlation analysis are used to analyze both plaintext and ciphertext data. At the end of the article, the plaintext and ciphertext images displayed by LCD can be further visualized to verify the encryption effectiveness of the LZUC cipher.

Challenges in measuring nitrogen isotope signatures in inorganic nitrogen forms: An interlaboratory comparison of three common measurement approaches.

RATIONALE: Stable isotope approaches are increasingly applied to better understand the cycling of inorganic nitrogen (Ni ) forms, key limiting nutrients in terrestrial and aquatic ecosystems. A systematic comparison of the accuracy and precision of the most commonly used methods to analyze δ15 N in NO3 - and NH4 + and interlaboratory comparison tests to evaluate the comparability of isotope results between laboratories are, however, still lacking. METHODS: Here, we conducted an interlaboratory comparison involving 10 European laboratories to compare different methods and laboratory performance to measure δ15 N in NO3 - and NH4 + . The approaches tested were (a) microdiffusion (MD), (b) chemical conversion (CM), which transforms Ni to either N2 O (CM-N2 O) or N2 (CM-N2 ), and (c) the denitrifier (DN) methods. RESULTS: The study showed that standards in their single forms were reasonably replicated by the different methods and laboratories, with laboratories applying CM-N2 O performing superior for both NO3 - and NH4 + , followed by DN. Laboratories using MD significantly underestimated the "true" values due to incomplete recovery and also those using CM-N2 showed issues with isotope fractionation. Most methods and laboratories underestimated the at%15 N of Ni of labeled standards in their single forms, but relative errors were within maximal 6% deviation from the real value and therefore acceptable. The results showed further that MD is strongly biased by nonspecificity. The results of the environmental samples were generally highly variable, with standard deviations (SD) of up to ± 8.4‰ for NO3 - and ± 32.9‰ for NH4 + ; SDs within laboratories were found to be considerably lower (on average 3.1‰). The variability could not be connected to any single factor but next to errors due to blank contamination, isotope normalization, and fractionation, and also matrix effects and analytical errors have to be considered. CONCLUSIONS: The inconsistency among all methods and laboratories raises concern about reported δ15 N values particularly from environmental samples.

Isotopically characterised N2 O reference materials for use as community standards.

RATIONALE: Information on the isotopic composition of nitrous oxide (N2 O) at natural abundance supports the identification of its source and sink processes. In recent years, a number of mass spectrometric and laser spectroscopic techniques have been developed and are increasingly used by the research community. Advances in this active research area, however, critically depend on the availability of suitable N2 O isotope Reference Materials (RMs). METHODS: Within the project Metrology for Stable Isotope Reference Standards (SIRS), seven pure N2 O isotope RMs have been developed and their 15 N/14 N, 18 O/16 O, 17 O/16 O ratios and 15 N site preference (SP) have been analysed by specialised laboratories against isotope reference materials. A particular focus was on the 15 N site-specific isotopic composition, as this measurand is both highly diagnostic for source appointment and challenging to analyse and link to existing scales. RESULTS: The established N2 O isotope RMs offer a wide spread in delta (δ) values: δ15 N: 0 to +104‰, δ18 O: +39 to +155‰, and δ15 NSP : -4 to +20‰. Conversion and uncertainty propagation of δ15 N and δ18 O to the Air-N2 and VSMOW scales, respectively, provides robust estimates for δ15 N(N2 O) and δ18 O(N2 O), with overall uncertainties of about 0.05‰ and 0.15‰, respectively. For δ15 NSP , an offset of >1.5‰ compared with earlier calibration approaches was detected, which should be revisited in the future. CONCLUSIONS: A set of seven N2 O isotope RMs anchored to the international isotope-ratio scales was developed that will promote the implementation of the recommended two-point calibration approach. Particularly, the availability of δ17 O data for N2 O RMs is expected to improve data quality/correction algorithms with respect to δ15 NSP and δ15 N analysis by mass spectrometry. We anticipate that the N2 O isotope RMs will enhance compatibility between laboratories and accelerate research progress in this emerging field.

Industry 4.0 Engineering Product Life Cycle Management Based on Multigranularity Access Control Model.

In order to improve the management efficiency of the safety status of Industry 4.0 engineering products, the multigranularity access control model (MGACM) Industry 4.0 engineering product life cycle management (PLM) is adopted to optimize the safety management mode of Industry 4.0 engineering products in this paper. The multigranularity access control model is constructed in this paper, which has strong nonlinearity and better fault tolerance. In addition, the parameters of PLM are optimized through the multiparticle access control model, and PLM search is enabled. Taking into account the slow and easy convergence of the multigranular access control model, a niche technology with full life cycle heterogeneity and elimination mechanism is proposed to solve the premature convergence problem of the multigranular access control model. The final simulation results of this paper show that, compared with traditional algorithms, the proposed multigranularity access control model is more reliable and effective and has faster convergence speed and higher management efficiency.

Oral Administration of Cryptotanshinone-Encapsulated Nanoparticles for the Amelioration of Ulcerative Colitis.

BACKGROUND: Inappropriate macrophages phenotype transition contributes to the development of ulcerative colitis, and the poly (ethylene glycol)-block-poly (d, l-lactic acid) (PEG-PLA) nanoparticles delivery system can be utilized to improve the cryptotanshinone (CTS)-based therapy. METHODS: We used a single emulsification method to prepare CTS-encapsulated nanoparticles (NPCTS). The therapeutic efficacy of NPCTS was evaluated in dextran sulfate sodium (DSS)-induced colitis mice. Then the proportion of total macrophages and M2-like macrophages were assayed with flow cytometry, and the relative content of pro-inflammatory cytokines in the colon was detected with Western blot. Bone-marrow-derived macrophages (BMDMs) were induced into M1-like macrophages, which were further incubated with NPCTS to repolarize into M2 subtype. RESULTS: Cryptotanshinone could induce the transition of M1 subtype to M2 subtype as indicated by up-regulated expression of arginase 1 (ARG1), interleukin (IL)-10, and CD206. In vivo, orally administrated NPCTS accumulated in the colon-infiltrated macrophages in colitis mice. It further revealed that NPCTS significantly alleviated colitis symptoms as indicated by increased body weight and colon length, decreased tumor necrosis factor (TNF)-α, IL-1ß, and IL-6 content in the colon, and diminished total macrophage proportion (CD45+CD11b+F4/80+) and up-regulated M2 proportion (CD45+CD11b+F4/80+CD206hi). CONCLUSION: Oral administration of NPCTS could ameliorate ulcerative colitis with the conversion of M1-like macrophages to M2-like macrophages.

Relative Bioavailability of Broiler Chickens Fed with Zinc Hydroxychloride and Sulfate Sources for Corn-Soybean Meal.

This study was conducted to determine relative bioavailability (RBV) of basic zinc chloride (BZC) compared to zinc sulfate monohydrate (ZSM) for broilers. A randomized design involving a 2 × 3 factorial arrangement of the different treatment regimens plus one negative control was set up for this study. A total of 630 newly hatched male AA broiler chicks were randomly allocated to 42 different pens (15 chickens/pen) and assigned to 7 dietary treatments in a completely randomized design. The diet was supplemented with 0, 20, 40, or 80 mg of Zn mg/kg of feed in the form of ZSM or BZC. The results showed that zinc supplementation altered average daily gain (ADG) and feed conversion ratio (FCR) (P < 0.05) for both zinc sources. It was observed that the weight gain increased linearly (P < 0.01) and FCR decreased linearly as dietary BZC and ZSM concentration increased. Moreover, compared with chickens fed with ZSM, chickens fed with BZC had higher ADG and lower FCR from days 0 to 14 (P < 0.05), and higher activity of plasma alkaline phosphatase (ALP) (P < 0.05), total superoxide dismutase (T-SOD), and CuZn superoxide dismutase (CuZn-SOD) (P < 0.01) in the plasma of chickens fed with BZC at zinc level 80 mg/kg at day 14. The pancreas divalent metal-ion transporter-1 (DMT1) mRNA expression of chickens fed with BZC was found to be significantly enhanced at day 28, and the pancreas metallothionein (MT) mRNA expression for BZC fed group was also markedly increased at Zn levels of 20 and 40 mg/kg respectively. The relative bioavailability (RBV) of BZC (Zn sulfate 100%) based on ADG in the starter phase was 110.82%, whereas the tibia zinc content, as well as the activities of plasma ALP and CuZn-SOD, and the pancreas MT mRNA level were in the range between 108 and 119%. It was thus concluded that BZC was more efficacious than Zn sulfate and could serve as a potentially novel zinc source in the broilers.

Electroinduced Reconfiguration of Complex Emulsions for Fabrication of Polymer Particles with Tunable Morphology.

Continuous morphological control of anisotropic particles is always an important challenge in the field of materials. In this study, a new strategy for continuous fabrication of polymer particles with various morphologies induced by electricity is reported using complex emulsions as template. A synthetic electro-responsive surfactant containing ferrocene group is used to prepare complex emulsions, which contain a polymerizable monomer as inner phase. With the increasing time of electrical stimulation on the complex emulsions, hollow, hemispherical, mushroom-like, and spherical particles are constructed successively after photopolymerization. The Marangoni effect caused by the heterogeneity in the interfacial tension at the droplet surface is the reason for the reconfigurable morphology of the complex emulsion. The controllable complex emulsions by electricity present a versatile platform for constructing fine control of the microstructure and shape anisotropy of particles having customized shapes and functionalities, opening a new possibility for designing sophisticated architectures.

pH-Responsive Pickering emulsions stabilized solely by surface-inactive nanoparticles via an unconventional stabilization mechanism.

Using solely highly hydrophilic particles to stabilize emulsions, especially high internal phase emulsions, has always been an important challenge. Here pH-responsive Pickering emulsions stabilized by a low concentration of bare highly hydrophilic Ludox CL nanoparticles without surface modification or addition of surfactants are developed at neutral pH. The dispersed nanoparticles can be transformed into an aggregate state with a network-like structure near the isoelectric point, which contributes to the stabilization of the emulsions. Moreover, the vdW attraction between particles and droplets also plays a key role in the formation of emulsions, which can make the aggregated nanoparticles adsorb tightly around the droplets rather than penetrate the oil-water interface. The formed protective armor and network-like aggregates separate droplets from each other to prevent coalescence. At a low nanoparticle concentration (0.5 wt%), a high internal phase emulsion can be formed and can last up to half a year. This system can emulsify not only the hydrocarbon oil but also the fluoroalkane oil phase. Finally, organic-inorganic composite particles are fabricated using the template action of the Pickering emulsions. The method of preparing composite particles is more convenient than the traditional Pickering emulsion polymerization which often requires the modification of the surface of the hydrophilic particles or the addition of auxiliary monomers. This study provides a simple green strategy for the preparation of a more stable Pickering emulsion stabilized by surface-inactive nanoparticles and will broaden the scope of applications.

Topography-related controls on N2O emission and CH4 uptake in a tropical rainforest catchment.

Forest soils in the warm-humid tropics significantly contribute to the regional greenhouse gas (GHG) budgets. However, spatial heterogeneity of GHG fluxes is often overlooked. Here, we present a study of N2O and CH4 fluxes over 1.5 years, along a topographic gradient in a rainforest catchment in Xishuangbanna, SW China. From the upper hillslope to the foot of the hillslope, and further to the flat groundwater discharge zone, we observed a decrease of N2O emission associated with an increase of soil water-filled-pore-space (WFPS), which we tentatively attribute to more complete denitrification to N2 at larger WFPS. In the well-drained soils on the hillslope, denitrification at anaerobic microsites or under transient water-saturation was the potential N2O source. Negative CH4 fluxes across the catchment indicated a net soil CH4 sink. As the oxidation of atmospheric CH4 is diffusion-limited, soil CH4 consumption rates were negatively related to WFPS, reflecting the topographic control. Our observations also suggest that during dry seasons N2O emission was significantly dampened (<10 µg N2O-N m-2 h-1) and CH4 uptake was strongly enhanced (83 µg CH4-C m-2 h-1) relative to wet seasons (17 µg N2O-N m-2 h-1 and 56 µg CH4-C m-2 h-1). In a post-drought period, several rain episodes induced exceptionally high N2O emissions (450 µg N2O-N m-2 h-1) in the groundwater discharge zone, likely driven by flushing of labile organic carbon accumulated during drought. Considering the global warming potential associated with both GHGs, we found that N2O emissions largely offset the C sink contributed by CH4 uptake in soils (more significant in the groundwater discharge zone). Our study illustrates important topographic controls on N2O and CH4 fluxes in forest soils. With projected climate change in the tropics, weather extremes may interact with these controls in regulating forest GHG fluxes, which should be accounted for in future studies.

What can we learn from N2 O isotope data? - Analytics, processes and modelling.

The isotopic composition of nitrous oxide (N2 O) provides useful information for evaluating N2 O sources and budgets. Due to the co-occurrence of multiple N2 O transformation pathways, it is, however, challenging to use isotopic information to quantify the contribution of distinct processes across variable spatiotemporal scales. Here, we present an overview of recent progress in N2 O isotopic studies and provide suggestions for future research, mainly focusing on: analytical techniques; production and consumption processes; and interpretation and modelling approaches. Comparing isotope-ratio mass spectrometry (IRMS) with laser absorption spectroscopy (LAS), we conclude that IRMS is a precise technique for laboratory analysis of N2 O isotopes, while LAS is more suitable for in situ/inline studies and offers advantages for site-specific analyses. When reviewing the link between the N2 O isotopic composition and underlying mechanisms/processes, we find that, at the molecular scale, the specific enzymes and mechanisms involved determine isotopic fractionation effects. In contrast, at plot-to-global scales, mixing of N2 O derived from different processes and their isotopic variability must be considered. We also find that dual isotope plots are effective for semi-quantitative attribution of co-occurring N2 O production and reduction processes. More recently, process-based N2 O isotopic models have been developed for natural abundance and 15 N-tracing studies, and have been shown to be effective, particularly for data with adequate temporal resolution. Despite the significant progress made over the last decade, there is still great need and potential for future work, including development of analytical techniques, reference materials and inter-laboratory comparisons, further exploration of N2 O formation and destruction mechanisms, more observations across scales, and design and validation of interpretation and modelling approaches. Synthesizing all these efforts, we are confident that the N2 O isotope community will continue to advance our understanding of N2 O transformation processes in all spheres of the Earth, and in turn to gain improved constraints on regional and global budgets.

First investigation and absolute calibration of clumped isotopes in N2 O by mid-infrared laser spectroscopy.

RATIONALE: Unravelling the biogeochemical cycle of the potent greenhouse gas nitrous oxide (N2 O) is an underdetermined problem in environmental sciences due to the multiple source and sink processes involved, which complicate mitigation of its emissions. Measuring the doubly isotopically substituted molecules (isotopocules) of N2 O can add new opportunities to fingerprint and constrain its cycle. METHODS: We present a laser spectroscopic technique to selectively and simultaneously measure the eight most abundant isotopocules of N2 O, including three doubly substituted species - so called "clumped isotopes". For the absolute quantification of individual isotopocule abundances, we propose a new calibration scheme that combines thermal equilibration of a working standard gas with a direct mole fraction-based approach. RESULTS: The method is validated for a large range of isotopic composition values by comparison with other established methods (laser spectroscopy using conventional isotopic scale and isotope ratio mass spectrometry). Direct intercomparison with recently developed ultrahigh-resolution mass spectrometry shows clearly the advantages of the new laser technique, especially with respect to site specificity of isotopic substitution in the N2 O molecule. CONCLUSIONS: Our study represents a new methodological basis for the measurements of both singly substituted and clumped N2 O isotopes. It has a high potential to stimulate future research in the N2 O community by establishing a new class of reservoir-insensitive tracers and molecular-scale insights.