Stoichiometric Imbalance Research Articles

Effects of moss biocrusts on soil-microbe-ectoenzyme stoichiometric characteristics in a subtropical area

The formation and development of biological soil crusts (biocrusts) potentially affect the cycles and stoichiometric characteristics of soil carbon (C), nitrogen (N), and phosphorus (P). However, it is still unclear how soil microbes adapt to such changes. In this study, we examined the effects of moss-dominated biocrusts coverage (0, 1%-20%, 20%-40%, 40%-60%, 60%-80%, and 80%-100%) on soil physicochemical properties, soil microbial biomass, and ectoenzyme activities [β-1, 4-glucosidase (BG), β-1, 4-N-acetyl glucosidase (NAG), acid phosphatase (AP)] in two soil layers (0-5 and 5-10 cm) in the Three Gorges Reservoir area, as well as the covariations of soil-microbe-ectoenzyme C:N:P stoichiometry. The results showed that biocrust development significantly increased soil clay content, water stable aggregates, soil C, N, P contents, and significantly decreased soil bulk density and sand content. Microbial biomass C, N, P and ectoenzyme activities were significantly increased with increasing biocrust coverage. Soil depth did not affect soil physicochemical properties and C:N:P, but significantly affected microbial biomass, ectoenzyme activities, BG:AP and NAG:AP. Soil C, N and P contents were significantly positively correlated with microbial biomass and ectoenzyme activities, negatively correlated with BG:NAG, while positively correlated with NAG:AP, but had no significant correlation with microbial biomass C:N:P. There was no significant correlation between soil-microbe and microbial-ectoenzyme C:N:P. BG:NAG:AP decreased gradually with the increase of C:N:P stoichiometric imbalance between microbe and soil. This study indicated that the microbial metabolism was co-limited by N and P and with stronger P limitation. Microbes could maintain homeostasis by adjusting their own biomass and ectoenzyme C:N:P to adapt to changes in soil ecological stoichiometry driven by biocrust development.

Dynamic Phycobilin Pigment Variations in Diazotrophic and Non-diazotrophic Cyanobacteria Batch Cultures Under Different Initial Nitrogen Concentrations.

Increased anthropogenic nutrient loading has led to eutrophication of aquatic ecosystems, which is the major cause of harmful cyanobacteria blooms. Element stoichiometry of cyanobacteria bloom is subject to nutrient availabilities and may significantly contribute to primary production and biogeochemical cycling. Phycobilisome is the antenna of the photosynthetic pigment apparatus in cyanobacteria, which contains phycobilin pigments (PBPs) and linker proteins. This nitrogen (N)-rich protein complex has the potential to support growth as a N-storage site and may play a major role in the variability of cyanobacteria N stoichiometry. However, the regulation of PBPs during bloom formation remains unclear. We investigated the temporal variation of N allocation into PBPs and element stoichiometry for two ubiquitous cyanobacteria species, Microcystis aeruginosa and Dolichospermum flos-aquae, in a batch culture experiment with different initial N availabilities. Our results indicated that the N allocation into PBPs is species-dependent and tightly regulated by the availability of nutrients fueling population expansion. During the batch culture experiment, different nutrient uptake rates led to distinct stoichiometric imbalances of N and phosphorus (P), which substantially altered cyanobacteria C: N and C: P stoichiometry. Microcystis invested cellular N into PBPs and exhibited greater flexibility in C: N and C: P stoichiometry than D. flos-aquae. The dynamics of such N-rich macromolecules may help explain the N stoichiometry variation during a bloom and the interspecific difference between M. aeruginosa and D. flos-aquae. Our study provides a quantitative understanding of the elemental stoichiometry and the regulation of PBPs for non-diazotrophic and diazotrophic cyanobacteria blooms.

Nitrogen input enhances microbial carbon use efficiency by altering plant–microbe–mineral interactions

Microbial growth and respiration are at the core of the soil carbon (C) cycle, as these microbial physiological performances ultimately determine the fate of soil C. Microbial C use efficiency (CUE), a critical metric to characterize the partitioning of C between microbial growth and respiration, thus controls the sign and magnitude of soil C-climate feedback. Despite its importance, the response of CUE to nitrogen (N) input and the relevant regulatory mechanisms remain poorly understood, leading to large uncertainties in predicting soil C dynamics under continuous N input. By combining a multi-level field N addition experiment with a substrate-independent 18 O-H2 O labelling approach as well as high-throughput sequencing and mineral analysis, here we elucidated how N-induced changes in plant-microbial-mineral interactions drove the responses of microbial CUE to N input. We found that microbial CUE increased significantly as a consequence of enhanced microbial growth after 6-year N addition. In contrast to the prevailing view, the elevated microbial growth and CUE were not mainly driven by the reduced stoichiometric imbalance, but strongly associated with the increased soil C accessibility from weakened mineral protection. Such attenuated organo-mineral association was further linked to the N-induced changes in the plant community and the increased oxalic acid in the soil. These findings provide empirical evidence for the tight linkage between mineral-associated C dynamics and microbial physiology, highlighting the need to disentangle the complex plant-microbe-mineral interactions to improve soil C prediction under anthropogenic N input.

Regulation of protein complex partners as a compensatory mechanism in aneuploid tumors.

Aneuploidy, a state of chromosome imbalance, is a hallmark of human tumors, but its role in cancer still remains to be fully elucidated. To understand the consequences of whole-chromosome-level aneuploidies on the proteome, we integrated aneuploidy, transcriptomic, and proteomic data from hundreds of The Cancer Genome Atlas/Clinical Proteomic Tumor Analysis Consortium tumor samples. We found a surprisingly large number of expression changes happened on other, non-aneuploid chromosomes. Moreover, we identified an association between those changes and co-complex members of proteins from aneuploid chromosomes. This co-abundance association is tightly regulated for aggregation-prone aneuploid proteins and those involved in a smaller number of complexes. On the other hand, we observed that complexes of the cellular core machinery are under functional selection to maintain their stoichiometric balance in aneuploid tumors. Ultimately, we provide evidence that those compensatory and functional maintenance mechanisms are established through post-translational control, and that the degree of success of a tumor to deal with aneuploidy-induced stoichiometric imbalance impacts the activation of cellular protein degradation programs and patient survival.

Adaptation of soil micro-food web to elemental limitation: evidence from the forest-steppe ecotone

Stoichiometric imbalance between resources and their decomposers can alter the activity and structure of soil microbial communities and play an important role in regulating nutrient and carbon cycling in terrestrial ecosystems. However, whether and how ecological networks of soil micro-food web change to cope with the stoichiometric imbalance has never been assessed so far. In this study, we tested how the soil micro-food web responded to elemental limitations along a forest-steppe ecotone. We measured several adaptation mechanisms including soil microbial stoichiometry, enzyme activities and the composition of soil microbial and nematode communities. The microbial investment in resource acquisition shifted from nutrient-to C-acquiring enzymes with decreasing soil C:N:P ratios along the forest-steppe ecotone. The shifts in element use efficiencies could be a compensatory way besides enzyme allocation, implemented by microbial communities to cope with stoichiometric imbalance in their substrates. The community structure of soil micro-food web also changed with a decrease in saprotrophic fungi and fungivorous nematodes from the steppe plots towards the forest plots. The co-occurrence networks were less complex and stable with decreasing soil C:N:P ratios, suggesting that trophic interactions were less diverse and C-limitation plays an important role in structuring ecological interactions in soil food webs. Our findings provide insights into how stoichiometric constraints may induce shifts in ecological networks and have important implications for integrating shifts in individual physiological metabolism as well as changes in community composition of soil biota and to better understand and predict soil biogeochemical cycling in terrestrial ecosystems.

Substoichiometric action of long noncoding RNAs

Low expression levels and stoichiometric imbalances of long noncoding RNAs (lncRNAs) are often used as evidence for their probable lack of function or for limiting the scope of their potential influence. Recent advances in our understanding of the substoichiometric functions of lncRNAs challenge these notions and suggest routes through which unabundant lncRNAs can affect cellular functions and gene regulatory networks.

Adaptive Pathways of Microorganisms to Cope With the Shift From P- to N-Limitation in Subtropical Plantations.

Ecological stoichiometry is increasingly acknowledged as one of the main control factors for microbial activity and diversity. Soil carbon/nitrogen (C/N) and carbon/phosphorus (C/P) ratios are usually much higher than microbial nutrient requirements and vary with planting density and stand age in forestlands. However, how microorganisms cope with such stoichiometric imbalances and how they regulate nutrient cycling remain unclear. Here, 5- and 35-year-old experimental Cunninghamia lanceolata [Lamb.] Hook plantations with five planting densities (1,667, 3,333, 5,000, 6,667, and 10,000 stems ha−1) were used to explore the underlying mechanism of the response of microorganisms to stoichiometric imbalances. We found that (i) enzyme activity and microbial biomass and diversity increased with planting density at age 5 but decreased at age 35; (ii) soil microorganisms were P-limited at age 5, but gradually shifted from P- to N-limitation during the development of plantations from 5 to 35 years; and (iii) significantly negative relationships between microbial biomass stoichiometry and enzymatic stoichiometry were observed. The adaptive pathways of soil microorganisms to cope with stoichiometric imbalances include (i) adjusting the stoichiometry of microorganisms and enzymes; (ii) changing the relative abundance of the dominant microbial phyla; and (iii) increasing the ratio of fungal to bacterial diversity. These results highlight how to use the ecological stoichiometry method to identify soil microbial nutrient limitations with planting density during the development of plantations. By underlining the important role of stoichiometry on microbial growth and activity, these findings furthermore emphasize the dependency of organic matter transformation and nutrient cycling on the microbial community.

Growth of soil microbes is not limited by the availability of nitrogen and phosphorus in a Mediterranean oak-savanna

The environmental conditions under which the availability of inorganic nutrients such as nitrogen (N) and phosphorus (P) influence soil microbial growth are poorly understood, especially with regards to how fertilization changes specific aspects of microbial growth such as carbon-use efficiency (CUE). Microbial CUE is the fraction of C converted into biomass out of all C taken in and plays a critical role in global C budgets. Using the 18O labeled water method we tested short vs. long-term effects of N and/or P fertilization on microbial growth, CUE, and C, N, and P-acquiring enzyme activities in two soils from an oak-savanna, which differ in their soil organic matter (SOM) content. We hypothesized that soils with more SOM (from under tree canopies) would have higher microbial growth rates than soils with less SOM (from open grassland), and that microbial growth and CUE would increase with fertilization. We further hypothesized that these increases would be associated with a decrease in enzyme activity and a shift towards older SOM substrates in the short-term, in contrast to substrates from recently fixed C resulting from increased plant productivity in the long-term. We found that nutrient additions did not affect microbial growth or CUE in the relatively high SOM habitat on either time scale. In contrast, the low SOM habitat had lower growth and CUE when single nutrients were added, with significantly reduced growth when P alone was added, but was unchanged when N and P were added together. Our results show that short-term, stoichiometric imbalances can reduce microbial growth and that microbial growth at this site is limited not by nutrients but by the amount of C available to soil microbes.

Low acclimation potential compromises the performance of water-stressed pine saplings under Mediterranean xeric conditions

Predicted hotter and drier climatic conditions in the Mediterranean Basin will probably hamper current afforestations and reforestations by negatively influencing tree performance. Understanding how saplings can adjust their physiology to shortages in water availability is essential to predict early-stage success of forest ecological restoration. Pines are common target species used in afforestations and reforestations; however, the capacity of their saplings for physiological plasticity to promote drought tolerance remains largely unexplored. In this study, we evaluated the demographical and resource-use consequences of short-term irrigation among four pine species (Pinus halepensis, Pinus pinea, Pinus nigra and Pinus sylvestris) growing under water-limiting conditions in a common garden experiment. Summer irrigation increased the survival rate of those pines that were suffering from hydric stress under the xeric conditions of the common garden (i.e. P. pinea, P. nigra and P. sylvestris). Moreover, short-term water supplementation slightly enhanced aboveground biomass production across species. However, leaf isotopic composition and nutrient concentrations did not change after summer irrigation. Independently of water supplementation, P. halepensis was the best adapted species to water scarcity and showed the best physiological and growth performance. By contrast, P. pinea, P. nigra and P. sylvestris saplings exhibited drought-induced reductions in stomatal conductance and low water-use efficiency, nutrient deficiency, and severe N:P and N:K stoichiometric imbalances, leading to impaired growth. We conclude that the lack of physiological plasticity of water-stressed pine saplings to withstand the impacts of climate aridification will likely cause severe impairment of their nutrient status, growth and survival, with dire implications for the successful establishment of Mediterranean afforestation and reforestation programs.

Bioenergetic and Metabolic Adaptation in Tumor Progression and Metastasis.

The ability of cancer cells to adjust their metabolism in response to environmental changes is a well-recognized hallmark of cancer. Diverse cancer and non-cancer cells within tumors compete for metabolic resources. Metabolic demands change frequently during tumor initiation, progression and metastasis, challenging our quest to better understand tumor biology and develop novel therapeutics. Vascularization, physical constraints, immune responses and genetic instability promote tumor evolution resulting in immune evasion, opportunities to breach basement membrane barriers and spread through the circulation and lymphatics. In addition, the unfolded protein response linked to the ubiquitin proteasome system is a key player in addressing stoichiometric imbalances between nuclear and mitochondrially-encoded protein subunits of respiratory complexes, and nuclear-encoded mitochondrial ribosomal protein subunits. While progressive genetic changes, some of which affect metabolic adaptability, contribute to tumorigenesis and metastasis through clonal expansion, epigenetic changes are also important and more dynamic in nature. Understanding the role of stromal and immune cells in the tumor microenvironment in remodeling cancer cell energy metabolism has become an increasingly important area of research. In this perspective, we discuss the adaptations made by cancer cells to balance mitochondrial and glycolytic energy metabolism. We discuss how hypoxia and nutrient limitations affect reductive and oxidative stress through changes in mitochondrial electron transport activity. We propose that integrated responses to cellular stress in cancer cells are central to metabolic flexibility in general and bioenergetic adaptability in particular and are paramount in tumor progression and metastasis.

C:P stoichiometric imbalance between soil and microorganisms drives microbial phosphorus turnover in the rhizosphere

C:P stoichiometric imbalance between soil and microorganisms drives microbial phosphorus turnover in the rhizosphere

From webs, loops, shunts, and pumps to microbial multitasking: Evolving concepts of marine microbial ecology, the mixoplankton paradigm, and implications for a future ocean

AbstractEmerging knowledge of mixoplankton—ubiquitous microbes that employ phototrophy and phagotrophy synergistically in one cell—reshapes our knowledge of the flow of materials and energy, with wide‐reaching impacts on marine productivity, biodiversity, and sustainability. Conceptual models of microbial interactions have evolved from food‐chains, where carbon‐fixing phytoplankton are conceived as being grazed solely by zooplankton that, in turn, support fisheries and higher trophic levels, to microbial webs, loops, and shunts, as knowledge about abundance, activity, and roles of marine microbial organisms—as well as the complexity of their interactions—has increased. In a future world, plankton that depend on a single strategy for acquiring nutrition (photo‐autotrophy or phago‐heterotrophy) may be disadvantaged with increasing temperatures and ocean acidification impacting vital rates, thermal stratification decreasing water column nutrient exchange, and anthropogenic pollution shifting amounts, forms, and proportions of nutrients. These conditions can lead to stoichiometric imbalances that may promote mixoplanktonic species with an increasing likelihood of harmful blooms. Such changes in plankton species composition alters the interconnectivity of oceanic microbes with direct consequences on biogeochemical cycling, trophic dynamics, and ecosystem services. Here, the implications of the mixoplankton paradigm relative to traditional concepts of microbial oceanography in a globally‐changing, anthropogenically‐impacted world are explored.

Stoichiometric imbalances and the dynamics of phosphatase activity and the abundance of phoC and phoD genes with the development of Cunninghamia lanceolata (Lamb.) Hook plantations

Soil phosphatase and P-cycling functional genes, such as phoC and phoD, are crucial factors in regulating terrestrial P cycling, especially in highly weathered subtropical and tropical soils. Soil element stoichiometry (especially available C:N:P by measuring dissolved organic C (DOC):available N (AN):Olsen P plays an essential role in biogeochemical P cycling, but how it affects phosphatase activity and the abundance of phoC and phoD genes following afforestation is unclear. Here, we investigated how soil C:N:P stoichiometry affected the dynamics of soil phosphatase activity and the abundance of phoC and phoD genes in an age sequence of 6-, 12-, 18-, 25-, 32-, and 49-year-old Chinese fir plantations. The results showed that the phosphatase activity and the abundance of phoC gene were overall higher in 18- and 25-year-old plantations than in the other four plantations. The abundance of phoD gene gradually increased with stand age. Phosphatase activity significantly and positively correlated with DOC:Olsen P and AN:Olsen P ratios, but not with DOC:AN ratio. Soil phosphatase activity significantly positively correlated with phoC gene abundance, but not with phoD gene abundance, indicating that the phoC gene abundance is the dominant predictor of the microbial functional potential for secreting phosphatase. Further analysis suggested that the ratios of DOC:Olsen P and AN:Olsen P, total N, DOC, AN, Olsen P, and microbial biomass C were the main predictors of phoC gene abundance and that DOC:AN, total P, AN, Olsen P, and microbial biomass C were the main predictors of phoD gene abundance. These findings together highlight the importance of soil available element stoichiometry regulating microbial functional genes, with potential implications for subtropical and tropical biogeochemical processes and for understanding how soil available C:N:P stoichiometry regulates P biotransformation.

Seasonal drought in Mediterranean soils mainly changes microbial C and N contents whereas chronic drought mainly impairs the capacity of microbes to retain P

Intensification of droughts may aggravate the generally low capacity of Mediterranean soils to store C and nutrients and induce soil C:N:P stoichiometric imbalances through its impact on soil microbial biomass and activity. Soil microbes may nonetheless have different responses to seasonal and chronic drought, but very few studies investigate long-term drought periods under field conditions. This study compares the effects of seasonal drought versus the impacts of 16 years of chronic experimental drought on microbial biomass and nutrients and assess the implications for soil nutrient availability and biogeochemical functioning in a Mediterranean forest. The chronic drought treatment reduced substantially and persistently microbial biomass C, N and particularly P, probably due to P-sparing community shifts or microbial adaptations. The smaller microbial N pool and lower mineralization activity contributed to the accumulation of C- and N-rich organic compounds in the soil and to a lower availability of mineralized forms of N during the vegetation growing season. As a result, chronic drought conditions may increase the risks of N losses from the plant-soil system in Mediterranean ecosystems. Microbial C:N ratios remained unaltered under chronic drought compared to control, likely associated with the equivalent accumulation of C- and N-rich osmolytes by microbial communities. In contrast, microbial biomass increased its C content relative to N content in response to seasonal drought, but also reduced considerably its N and P pool. Therefore, while microbial P was more sensitive to chronic water stress, microbial N and C were more closely coupled to the seasonal fluctuations of water availability.

Highest primary production achieved at high nitrogen levels despite strong stoichiometric imbalances with phosphorus in hypereutrophic experimental systems

AbstractLakes in human‐dominated landscapes often face high loads of nutrients that may alter ecosystem function. High N loads relative to P are especially common in agricultural watersheds, where nitrate (NO3) in particular is elevated due to fertilizer application and runoff. While past research has focused extensively on the impact of nutrient loads on reductions in water quality, we still lack assessment of the impact of high N loading and extreme stoichiometric imbalance on ecosystem process rates, specifically measurements of gross primary production (GPP), ecosystem respiration (ER), and net ecosystem productivity (NEP). We used open‐bottomed experimental mesocosms (limnocorrals) to establish four treatments of increasing N : P by increasing N loads while leaving P loads consistent, and measured chlorophyll concentration and metabolic rates. We observed significant differences in productivity among treatments, with higher biomass and GPP in the highest two N : P treatments and a unimodal pattern between GPP and N concentrations. Declines in GPP at high N may have been due to limitation by P or light. In contrast to other studies, we did not observe any significant differences in ER with fertilization, potentially from a lack of dissolved organic carbon loading often associated with higher nutrient concentrations in those lakes. Maximum GPP and NEP observed here was far above commonly cited thresholds for likely P limitation at a molar N : P of approximately 330. Our results highlight the potential for high productivity despite stoichiometric imbalance that is common in agricultural systems, suggesting N management may be important in reducing primary production in hypereutrophic lakes.

Divergent Responses of Dominant Forest Tree Species to Manipulated Canopy and Understory N Additions in Terms of Foliage Stoichiometric, Photosynthetic, and Hydraulic Traits

AbstractNitrogen (N) deposition effects on the stoichiometric balance and photosynthetic and hydraulic couplings in subtropical forests has drawn wide attentions. The previously adopted understory application of N fertilization is criticized because it might ignore foliar N retention for different species. This paper reports a fertilizing application from the canopy (CAN) and under the canopy (UAN) in a phosphorus (P) limited ecosystem. Foliage stoichiometric, photosynthetic, and hydraulic traits of six dominant species were measured and analyzed. Both treatments equally enhanced foliage N and N/P, but not foliage P, who was highly species‐specific depending on tree height, which implied enhanced P limitation. Decreased isotope abundance of 15N (δ15N) that approaching to the level in the urea fertilizer under CAN suggested the existence of canopy retention of N. Besides, N response sensitivity of N, P and δ15N that positively related to tree height (H) under CAN indicated different exposure to the added N, which promoted stoichiometric imbalance among species. The photosynthetic traits represented by net photosynthesis (An) increased under both treatments. A divergent foliar photosynthetic and hydraulic traits variation was identified by significant decreased stomatal conductance (gs) and An/gs for CAN treatments, which induced the elevated isotope abundance of 13C (δ13C). Correspondingly, foliage hydraulic traits that shifted to water use efficiency axis were identified only under CAN in principal component analysis. Overall, our results proved that the canopy absorption and species heterogeneity should be considered regarding foliar safety versus efficiency trade‐off in response to nitrogen additions in the future.

Microbial storage and its implications for soil ecology.

Organisms throughout the tree of life accumulate chemical resources, in particular forms or compartments, to secure their availability for future use. Here we review microbial storage and its ecological significance by assembling several rich but disconnected lines of research in microbiology, biogeochemistry, and the ecology of macroscopic organisms. Evidence is drawn from various systems, but we pay particular attention to soils, where microorganisms play crucial roles in global element cycles. An assembly of genus-level data demonstrates the likely prevalence of storage traits in soil. We provide a theoretical basis for microbial storage ecology by distinguishing a spectrum of storage strategies ranging from surplus storage (storage of abundant resources that are not immediately required) to reserve storage (storage of limited resources at the cost of other metabolic functions). This distinction highlights that microorganisms can invest in storage at times of surplus and under conditions of scarcity. We then align storage with trait-based microbial life-history strategies, leading to the hypothesis that ruderal species, which are adapted to disturbance, rely less on storage than microorganisms adapted to stress or high competition. We explore the implications of storage for soil biogeochemistry, microbial biomass, and element transformations and present a process-based model of intracellular carbon storage. Our model indicates that storage can mitigate against stoichiometric imbalances, thereby enhancing biomass growth and resource-use efficiency in the face of unbalanced resources. Given the central roles of microbes in biogeochemical cycles, we propose that microbial storage may be influential on macroscopic scales, from carbon cycling to ecosystem stability.

Intracellular Storage Reduces Stoichiometric Imbalances in Soil Microbial Biomass – A Theoretical Exploration

Microbial intracellular storage is key to defining microbial resource use strategies and could contribute to carbon (C) and nutrient cycling. However, little attention has been devoted to the role of intracellular storage in soil processes, in particular from a theoretical perspective. Here we fill this gap by integrating intracellular storage dynamics into a microbially explicit soil C and nutrient cycling model. Two ecologically relevant modes of storage are considered: reserve storage, in which elements are routed to a storage compartment in proportion to their uptake rate, and surplus storage, in which elements in excess of microbial stoichiometric requirements are stored and limiting elements are remobilized from storage to fuel growth and microbial maintenance. Our aim is to explore with this model how these different storage modes affect the retention of C and nutrients in active microbial biomass under idealized conditions mimicking a substrate pulse experiment. As a case study, we describe C and phosphorus (P) dynamics using literature data to estimate model parameters. Both storage modes enhance the retention of elements in microbial biomass, but the surplus storage mode is more effective to selectively store or remobilize C and nutrients according to microbial needs. Enhancement of microbial growth by both storage modes is largest when the substrate C:nutrient ratio is high (causing nutrient limitation after substrate addition) and the amount of added substrate is large. Moreover, storage increases biomass nutrient retention and growth more effectively when resources are supplied in a few large pulses compared to several smaller pulses (mimicking a nearly constant supply), which suggests storage to be particularly relevant in highly dynamic soil microhabitats. Overall, our results indicate that storage dynamics are most important under conditions of strong stoichiometric imbalance and may be of high ecological relevance in soil environments experiencing large variations in C and nutrient supply.

Effects of long-term nitrogen addition on dissolved organic matter characteristics in a temperate wetland of Northeast China

Dissolved organic matter (DOM) plays an indispensable role in ecosystem services and functions in wetlands. While most wetlands have undergone increased nitrogen (N) loading due to intensive human activities, the response of DOM characteristics to long-term N addition remains unexplored. In this study, we assessed the changes in dissolved organic carbon (DOC), NH4+, NO3-, dissolved organic N (DON), dissolved total N (DTN), and dissolved total phosphorus (DTP) in surface water and soil pore water at 15 cm depth after 10 years of N addition at four levels (0, 60, 120, and 240 kg N hm−2 year−1) in a freshwater marsh of Northeast China. We also examined the effect of N addition on DOM aromaticity and humification by measuring the specific UV absorbance at 254 nm (SUVA254), the color per C unit (C/C ratio), and the fulvic acid/humic acid ratio (E4/E6 ratio). Our results showed that N addition significantly altered DOM properties, but the direction and magnitude of these changes generally did not vary with the N addition level. During the growing season, DOC, NH4+, NO3-, DON, and DTN concentrations in both surface water and soil pore water were increased by N addition. Accordingly, N addition increased the DOC/DTP and DTN/DTP ratios but decreased the DOC/DTN ratio in surface water and soil pore water. In addition, the SUVA254 value and C/C ratio increased, while the E4/E6 ratio reduced after N addition in surface water and soil pore water, indicating increases in DOM aromaticity and humification. These observations suggest that long-term N addition changes DOM characteristics by causing stoichiometric imbalances and increasing recalcitrant compounds in temperate freshwater wetlands, which may then deteriorate water quality, alter microbial-mediated ecological processes, and impact downstream aquatic ecosystem structures.

On nanocomposite fabrication: using rheology to characterize filler/polymer interactions in epoxy-based nanocomposites

The interactions that occur between an amorphous silicon nitride (Si3N4) nanofiller and an epoxy matrix are examined, as revealed by rheological changes in a diglycidyl ether of bisphenol-A (DGEBA)-based epoxy resin prior to curing and thermal analysis, scanning electron microscopy, and dielectric spectroscopy of the resulting amine-cured systems. The results show that isothermally heating the as-received Si3N4 in DGEBA at 100 °C leads to increases in the viscosity of the mixture. Analysis of rheological data obtained from unfilled, as-received Si3N4-filled, and calcined Si3N4-filled epoxy systems leads us to interpret this increase in viscosity as arising from reactions between epoxide groups of the DGEBA and nanoparticle surface groups, notably involving surface amines, which are stimulated by the elevated temperature. The extent of this filler/resin reaction depends on the material processing protocol used, particularly prior calcination of the Si3N4 and the temperature and duration of nanoparticle/DGEBA mixing. Glass transition temperature data show that cured samples prepared using different methods have significantly different glass transition temperatures, which is a consequence of the epoxide/amine stoichiometric imbalances that result from prior reactions between the Si3N4 and the DGEBA. Consistent behavior was observed in the dielectric response. These results demonstrate that ultimate macroscopic properties of Si3N4/epoxy nanocomposites are critically affected by details of the processing protocol. Furthermore, we infer that, by using controlled prior calcination of the Si3N4, it is may be possible to vary the initial surface chemistry of the nanoparticles so as to adjust their reactivity with epoxy-containing moieties. Here, this is exemplified using only two somewhat extreme thermal treatments and a bifunctional DGEBA-type compound but, we suggest, that the concept may be extended to many other mono- and polyfunctional epoxy-containing compounds in order to generate a wide range of different grafted nanoparticle systems. This strategy may provide a versatile means of adjusting the surface chemistry of inorganic nitride nanoparticles, in order to tailor their surface chemistry and thereby modify resulting nanocomposite properties.