Composition Engineering Opens an Avenue Toward Efficient and Sustainable Nitrogen Fixation

In this work,we open an avenue toward rational design of potential efficient catalysts for sustainable ammonia synthesis through composition engineering strategy by exploiting the synergistic effects among the active sites as exemplified by diatomic metals anchored graphdiyne via the combination of hierarchical high-throughput screening,first-principles calculations,and molecular dynamics simulations.Totally 43 highly efficient catalysts feature ultralow onset potentials(|U_(onset)|≤0.40 V)with Rh-Hf and Rh-Ta showing negligible onset potentials of 0 and-0.04 V,respectively.Extremely high catalytic activities of Rh-Hf and Rh-Ta can be ascribed to the synergistic effects.When forming heteronuclears,the combinations of relatively weak(such as Rh)and relatively strong(such as Hf or Ta)components usually lead to the optimal strengths of adsorption Gibbs free energies of reaction intermediates.The origin can be ascribed to the mediate d-band centers of Rh-Hf and Rh-Ta,which lead to the optimal adsorption strengths of intermediates,thereby bringing the high catalytic activities.Our work provides a new and general strategy toward the architecture of highly efficient catalysts not only for electrocatalytic nitrogen reduction reaction(eNRR)but also for other important reactions.We expect that our work will boost both experimental and theoretical efforts in this direction.

Two new Stephanodiscaceae species(Bacillariophyta)from SW China

Two new freshwater centric diatom species were described from the southwest of China based on light and scanning electron microscopy.Pliocaenicus weixiense sp.nov.has a transversely undulate valve face,marginal fultoportulae situated at the end of the hyaline strips,central fultoportulae forming a ring positioned in a circular pattern,each with 3-4(usually 3)satellite pores,and a single rimoportula located at the base of the inner distal end of the costa.Tertiarius aspera sp.nov.has an uneven valve face with small granules that may be present on the marginal area and valve mantle,marginal fultoportulae situated on each costa close to the margin of the valve,6-7 central fultoportulae forming a ring near the valve center each with two satellite pores,and one rimoportula located on the valve face/mantle junction in the middle of costa on the internal valve.T.aspera sp.nov.is the first reported extant species in the genus.This study played an important role in studying the taxonomic status and ecological information of the genus,and the establishment of the two new taxa will help demonstrate the unique nature of freshwater diatom flora in the southwest of China.

Lineaperpetua gen.nov.:a new diatom genus in the Thalassiosirales supported by morphology and molecular data

Based on a combination of morphology and molecular data of ribosomal DNA genes,a new diatom genus Lineaperpetua gen.nov.Yu,You,Kociolek&Wang is described.The features that help define Lineaperpetua at the level of genus include:a tangentially undulated valve face;continuous cribra areolae on the valve interior consisting of pores arranged as strips;single rimoportula located inside the ring of marginal fultoportulae.Additionally,phylogenetic analysis based on nuclear small subunit(SSU)rDNA sequences and nuclear large subunit(LSU)rDNA gene placed the three strains of L.lacustris in a single,monophyletic clade at a considerable sequence distance from the other genera(Thalassiosira,Conticribra,Planktoniella,Shinodiscus,and other genera)belonging to Thalassiosirales.Despite the similarities with some species of Thalassiosira,Conticribra,and Spicaticribra,the suite of features found in Lineaperpetua differentiate it from these other genera.These molecular data and morphological characters suggest an affinity of the new genus to the Thalassiosiraceae.

Response of phytoplankton functional group to spring drought in a large subtropical reservoir

Global warming has caused an increase in the frequency and duration of droughts worldwide.Droughts could trigger large changes in physico-chemical conditions and phytoplankton community in waterbodies,resulting in a shift in the phytoplankton community.Spring diatom blooms in reservoirs have been increasingly observed in the past decade in the Taihu Lake basin.The aim of the present study is to elucidate the impacts of droughts on aquatic environment and to determine the driving factors for the succession of the phytoplankton functional groups based on the analysis of data collected during spring from 2009 to 2020 in the Daxi Reservoir.The unimodal relationship between 1-month aggregated precipitation index and phytoplankton species richness indicated the competitive exclusion occurred in extremely drought period.The structural equation modeling indicated that drought-related low water level conditions intensified sediment resuspension,and increased the phosphorus-enriched nonalgal turbidity in the Daxi Reservoir.Concurrently,a steady shift in the Reynolds phytoplankton functional groups from L 0,TD,J,X 2,and A(phytoplankton taxa preferring low turbidity and nutrient conditions)to TB(pennate diatoms being adapt to turbid and nutrient-rich conditions)was observed.The increased TP and non-algal turbidity in addition to the lowered disturbance contribute to the prevalence of Group TB.Considering the difficulties in nutrient control,timely water replenishment is often a feasible method of controlling the dominance of harmful algae for reservoir management.Finally,alternative water sources are in high demand for ensuring ecological safety and water availability when dealing with drought.

Yuzaoea gen. nov., a new biraphid diatom(Bacillariophyceae)genus and its phylogenetic significance

The flexed frustules in pennate diatoms are usually associated with monoraphid diatoms. Interestingly, we found a biraphid diatom species with flexed frustules in an offshore intertidal beach environment on Weizhou Island,Beihai City, Guangxi Zhuang Autonomous Region, China. Therefore, based on morphological characteristics, we described a new genus of diatoms Yuzaoea sinensis gen. et sp. nov. CH Li, HH Liu, YH Gao & CP Chen. The frustule of this genus is characterized by heterogeneous frustule with one concave valve and one convex valve,complete raphe on both valves, straight and moderately eccentric raphe, uniseriate striae and girdle bands with a single row of areolae. The most identifying feature of this genus was the flexed frustule, which is rare in biraphid diatoms and common in monoraphid diatoms. We compared the morphometric characteristics of genus Yuzaoea with genus Rhoikoneis and several genera within the family Rhoicospheniaceae, including Rhoicosphenia,Campylopyxis, and Cuneolus. Phylogenetic analyses based on SSU rRNA and rbc L showed that the genus Yuzaoea was the sister group to the clade of Rhoicosphenia with a high support value(bootstrap values = 100%), and the clade “Yuzaoea+Rhoicosphenia” was sister to the clade of monoraphid diatoms, in which the genera Achnanthidium, Planothidium and some Cocconeis with high support values(bootstrap = 100%).Morphologically, the genus Yuzaoea shares many morphological features with monoraphid diatoms like genera Achnanthidium and Planothidium and the members within the Rhoicospheniaceae. Therefore, based on a combined morphological studies and phylogenetic results we suggested that this branch may represented the evolution of one kind monoraphid diatoms, from biraphid diatoms(e.g. genus Yuzaoea), to incompleted biraphid diatoms(e.g. genera Rhoicosphenia, Campylopyxis), to monoraphid diatoms(e.g. genera Achnanthidium and Planothidium).

The Middle and Late Holocene climate change in Bohai Bay revealed by diatom proxy

A total of 98 samples from two boreholes in shallow sea area and two oyster reefs in adjacent coastal plain in the northwestern coast of Bohai Bay were collected for diatom analyses and species identification.The ratio of the marine species Thalassionema nitzschioides to the intertidal-coastal species complex Cyclotella striata/stylorum serves as a novel proxy for assessing the strength of marine influence.Chronological data,corrected for the local residence time effect,facilitated the construction of a diatom proxy-based marine influence curve for the study area.This curve delineates the dynamics of marine influence and their correlations with paleo-climate fluctuations and the East Asian monsoon variability,as well as their role in chenier formation.Results include:(1)eight periods of intensified marine influence have been documented since 7000 a BP in the study area.The peak of each period,as determined by the diatom proxy,corresponds closely to the warm climatic phases and stronger East Asian summer monsoons,suggesting that the peaks marine influence indicate typically the periods of climatic warmth and monsoon activity intensification in the region;(2)a strong correlation exists between the development of cheniers and marine influence,and chenier formation began with the increasing marine influence and terminated at the end of warm periods as marine influence weakens.The climatic changes in the coastal area,as indicated by the diatom proxy,hold significant potential for future related research endeavors.

Effects of Different Culture Conditions and Growth States on the Structure and Hemostatic Properties of Coscinodiscus sp.

As a renewable marine inorganic material,Coscinodiscus sp.has significant potential in the field of rapid hemostasis.However,the low yield of Coscinodiscus sp.seriously limits the application.In this study,two new culture modes were adopted to increase the production of Coscinodiscus sp.,the effect of changes in culture conditions and growth status on the hemostatic activity of diatoms was detected.To prevent Coscinodiscus sp.from sinking in culture,the suspension culture mode was realized by adding0.5%agar.The semi-continuous high nutrient concentration culture mode increased the cell density of Coscinodiscus sp.to 11000cells mL^(-1)and shorten the culture cycle to 5 d.In terms of coagulation activity,the addition of frustules reduced the in vitro coagulation time by half and the activation time of coagulation by 70%.The hemolysis rate and cytotoxicity of frustules harvested in the two culture modes did not change significantly.The results showed that suspension culture mode and high nutrient concentration culture mode only changed the growth state of Coscinodiscus sp.,while the hemostatic performance remained stable.

Diatoms as indicators of environmental change in coastal areas:a case study in Lianjiang coast of East China Sea

Owing to the significant differences in environmental characteristics and explanatory factors among estuarine and coastal regions,research on diatom transfer functions and database establishment remains incomplete.This study analysed diatoms in surface sediment samples and a sediment core from the Lianjiang coast of the East China Sea,together with environmental variables.Principal component analysis of the environmental variables showed that sea surface salinity(SSS)and sea surface temperature were the most important factors controlling hydrological conditions in the Lianjiang coastal area,whereas canonical correspondence analysis indicated that SSS and pH were the main environmental factors affecting diatom distribution.Based on the modern diatom species–environmental variable database,we developed a diatom-based SSS transfer function to quantitatively reconstruct the variability in SSS between 1984 and 2021 for sediment core HK3 from the Lianjiang coastal area.The agreement between the reconstructed SSS and instrument SSS data from 1984 to 2021 suggests that diatombased SSS reconstruction is reliable for studying past SSS variability in the Lianjiang coastal area.Three low SSS events in AD 2019,2013,and 1999,together with an increased relative concentration of freshwater diatom species and coarser sediment grain sizes,corresponded to two super-typhoon events and a catastrophic flooding event in Lianjiang County.Thus,a diatom-based SSS transfer function for reconstructing past SSS variability in the estuarine and coastal areas of the East China Sea can be further used to reflect the paleoenvironmental events in this region.

Theoretical investigation of excited dipole bound states of alkali-containing diatomic anions

Information about electronic excited states of molecular anions plays an important role in investigating electron attachment and detachment processes.Here we present a high-level theoretical study of the electronic structures of 12 alkali-metal-containing diatomic anions MX-(MX = LiH,LiF,LiCl,NaF,NaCl,NaBr,RbCl,KCl,KBr,RbI,KI and CsI).The equation-of-motion electron-attachment coupled-cluster singles and doubles(EOM-EA-CCSD) method is used to calculate the electron binding energies(EBEs) of 10 electronic excited states of each of the 12 molecule anions.With addition of different s-/p-/d-type diffusion functions in the basis set,we have identified possible excited dipole bound states(DBSs) of each anion.With the investigation of EBEs on the 12 MXs with dipole moment(DM) up to 12.1 D,we evaluate the dependence of the number of anionic excited DBSs on molecular DM.The results indicate that there are at least two or three DBSs of anions with a molecular DM larger than 7 D and a molecule with DM > 10 D can sustain a π-DBS of the anion.Our study has some implications for the excited DBS electronic states of alkali-metal-containing diatomic molecules.

The Expression Characteristics and Potential Functions of Heat Shock Factors in Diatom Phaeodactylum tricornutum

Heat shock transcription factor(HSF)are essential regulators of heat shock protein(HSP)gene expression in plants and algae,contributing to their resilience against biotic and abiotic stresses.However,the localization,structure,phylogenetic relationship,and characteristics of PtHSF genes in microalgae,especially in diatom Phaeodactylum tricornutum,remain largely unexplored.This study presents a comprehensive analysis of the PtHSF gene family in P.tricornutum.A genome-wide analysis identified 68 PtHSF genes,which were classified into two distinct subfamilies:traditional and untraditional.Motif and structure analyses revealed evidence of multiple duplication events within the PtHSF gene family.Expression profiling revealed diurnal patterns,with 34 genes being downregulated during the light period and upregulated during the dark period,while 19 genes exhibited the opposite pattern.These findings suggest that PtHSF genes may have specialized functions during the diurnal cycle and play a crucial role in maintaining cellular homeostasis in response to various stresses.Notably,PtHSF16,30,and 43 genes exhibited higher expression levels,suggesting their potential importance.This study provides a valuable foundation for future investigations into the specific functions of HSFs under different stress conditions and their regulatory mechanisms in P.tricornutum and other microalgae.

Diatom and Diatomite: Different Focus on Natural Media to Material Science Path

Bio-silica issued from diatom, a microalgae, is attracted increasing attention in material science thanks to its peculiar nanoarchitecture and related properties with versatile applications. The present work is a deep analysis on morphological and chemical properties of bio-silica issued from fossil origin (diatomaceous earth) and living one (algal paste). An optimization in purification protocol was performed to obtain multiparous bio-silica from its raw media with keeping its original shape entirely. Multiple characterization methods as scanning electronic microscopy (SEM), infrared spectroscopy, x-ray diffraction (DRX), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), nitrogen adsorption and inverse gas chromatography (IGC), were used to check the purification protocol efficiency as well as to gather accurate information on morphology and chemical composition of diatom material obtained in large amount.

Dynamics of Dimethylsulfide and Dimethylsulfoniopropionate Produced by Phytoplankton in the Chinese Seas - Distribution Patterns and Affecting Factors

Distribution of dimethylsulfide (DMS) and/or particulate dimethylsulfoniopropionate (DMSPp) concentrations in the Jiaozhou Bay, Zhifu Bay and East China Sea were investigated during the period of 1994 - 1998. Both DMS and DMSPp levels showed remarkable temporal and spatial variations. High values occurred in the coastal or shelf waters and low values in the offshore waters. The highest levels were observed in spring or summer and lowest in autumn. DMS or DMSPp distribution patterns were associated with water mass on a large geographical scale, while biological and chemical factors were more likely influential on smaller-scale variations. Diatoms could play an important role in total DMS or DMSPp abundance in coastal waters. Nitrate was found to have a two-phase relationship with DMSPp concentrations: positive when nitrate concentration was lower than 1 mumol/L, and negative when it was above. Anthropogenic factors such as sewage input and aquaculture also showed influences on DMS or DMSPp concentration.

Development of Sedimentary Environment in the Northeastern South China Sea Since the Last Glacial Stage

Core D （21°23′02″N, 116°47′13″E, water depth 405 m） was sampled from the upper slope from the northeastern South China Sea （SCS） and applied to analyze the sedimentary environmental change in this sea area since the last glacial stage. The results of grain size analysis, diatom analysis and detrital mineral analysis were well matched. We divided the core D into two layers. The surface sand layer （0 - 2 cm） consisted of residual sediments, which might be originally the sediment in the late Pleistocene and later suffered from being transformed in the post glacial transgression. The lower layer （2 - 130 cm） was quite different from the surface one, which might mainly result from a neritic sedimentary environment in the last glacial stage. Two sedimentary cycles could be detected in the core D： regression during Marine isotope stage （MIS） 4 to transgression during MIS 3 and regression during MIS 2 to transgression during the post glacial.

阿什河流域底栖硅藻群落特征及水环境健康评价

为探索黑龙江省阿什河流域底栖硅藻群落特征及环境相关性,并对阿什河流域进行水环境健康评价,本研究于2018年7月(丰水期)和2018年10月(枯水期)对阿什河流域8个典型采样点进行调查。基于相似性分析检验(analysisofsimilarities,ANOSIM)和相似百分比分析(similarity percentages,SIMPER)分析探索枯水期与丰水期之间底栖硅藻的群落差异,通过冗余分析(redundancyanalysis,RDA)对驱动底栖硅藻的关键环境因子进行筛选;使用硅藻生物指数(biological diatom index,IBD)、硅藻属指数(generic index of diatom,GI)和水体营养指数(trophic state index,TSI)对研究区域水体营养状态进行初步评价。结果表明,研究期间共鉴定底栖硅藻89种,其中丰水期80种、枯水期57种。独立样本T检验(T-test)表明阿什河流域物种丰富度丰水期显著高于枯水期(P<0.05),Shannon-wiener指数变化不显著(P>0.05)。ANOSIM结合SIMPER分析结果显示阿什河流域硅藻群落格局存在一定的时空异质性。RDA分析表明水的电导率是驱动阿什河流域底栖硅藻空间分布的环境因子,枯水期与丰水期之间高锰酸盐指数(CODMn)含量的变化是影响硅藻群落演替的因素之一。IBD、GI和TSI指数结果显示阿什河流域受人为活动干扰区域营养状态较差,IBD指数较GI指数能更有效的反映阿什河流域水体营养状况。

Pigment signatures of some diatoms isolated from China seas

The photosynthetic pigments of 12 species （14 strains） of cultured diatoms from six genera under specific conditions were examined by the HPLC. The diatom genera were Skeletonema, Thalassiosira, Chaetoceros, Nitzschla, Phaeodactylum and Meuniera. All strains were isolated from China seas and most of them were from the Jiaozhou Bay, China. Fifteen pigments were identified and eight of them were various chlorophyll a derivatives. Chlorophyll a, c2 and c1 and the carotenoids fucoxanthin, diadinoxanthin, diatoxanthin and β, β-carotene existed in all species. The ratios of each pigment to chlorophyll a were compared with the results in literatures. The pigment ratios of this study generally fall within the ranges reported by the literatures although the maximum ratio of fucoxanthin to chlorophyll a was higher and the ratios of chlorophyll c and diatoxanthin to chlorophyll a were low. The pigment ratios are useful to understanding the pigment signatures of diatoms in the Jiaozhou Bay, China, and to setting up the chemotaxonomic method of phytoplankton in these sea areas.

Preparation and hygrothermal performance of composite phase change material wallboard with humidity control based on expanded perlite/diatomite/paraffin

Phase change material(PCM)can reduce the indoor temperature fluctuation and humidity control material can adjust relative humidity used in buildings.In this study,a kind of composite phase change material particles(CPCMPs)were prepared by vacuum impregnation method with expanded perlite(EP)as supporting material and paraffin as phase change material.Thus,a PCM plate was fabricated by mould pressing method with CPCMPs and then composite phase change humidity control wallboard(CPCHCW)was prepared by spraying the diatom mud on the surface of PCM plate.The composition,thermophysical properties and microstructure were characterized using X-ray diffraction instrument(XRD),differential scanning calorimeter(DSC)and scanning electron microscope(SEM).Additionally,the hygrothermal performance of CPCHCW was characterized by temperature and humidity collaborative test.The results can be summarized as follows:(1)CPCMPs have suitable phase change parameters with melting/freezing point of 18.23°C/29.42°C and higher latent heat of 54.66 J/g/55.63 J/g;(2)the diatom mud can control the humidity of confined space with a certain volume;(3)the combination of diatom mud and PCM plate in CPCHCW can effectively adjust the indoor temperature and humidity.The above conclusions indicate the potential of CPCHCW in the application of building energy efficiency.

Biomass,species composition and diversity of benthic diatoms in mangroves of the Houyu Bay,China

The biomass, species composition and diversity of benthic diatom assemblages in mud-flat soils in Kandelia candel (L.) Druce communities with and without vegetation were studied seasonally at the Houyu Bay in Fuding City, Fujian Province, China. A total of 103 taxa were identified (including varieties). Eighty-four taxa were found in the mud-flat with vegetation and 74 taxa in the mud-flat without vegetation, while the biomass was large in January and April and decreased from July to October. The most abundant species in the mud-flat with vegetation are Nitzschia cocconeiformis, Gyrosigma scalproides and N. fasciculata, compared with G. scalproides and N. obtusa var. scalpelliformis in the mud-flat without vegetation. High H' values at 2 sites during all seasons suggest that diatom assemblages in the sediments of the Houyu Bay represent an original environment. Multi-dimensional scaling of diatom assemblages from mud-flats with and without vegetation shows that a slight seasonal change and only a single association occur in the mangroves.

STUDIES ON CULTURE CONDITIONS OF BENTHIC DIATOMS FOR FEEDING ABALONE Ⅲ. EFFECTS OF IRON AND SILICON NUTRIENTS AND OF ORTHOGONAL COMBINATIONS OF NITROGEN,PHOSPHORUS,IRON AND SILICON ON GROWTH RATE

Effects of iron and silicon nutrients and of orthogonal combinations of nitrogen, phosphorus, iron and silicon on the growth rate of three benthic diatoms were studied by using an in situ OD measurement method. The results of monofactor tests of ironand silicon shawed that Fe-EDTA was bettef than ferric citrate in the culture of these diatoms;that the favourable concentration of Fe-EDTA was about 0.5 mg/L of Fe and that of silicate was 2.5 mg/L of Si or more.The orthogonal test showed that the optimal concentration ratios(mg/L)of nitrogen, phosphorus, iron and silicon were: 5. 0: 0. 25: 0.5: 2. 0 for Cocconeis scutellum var. parva; 2.5: 1.0: 1.0: 2.0 for Amphora coffeaeformis; and 5.0: 0. 15: 0.5: 2.0 for N. mollis.

Long-term nutrient variation trends and their potential impact on phytoplankton in the southern Yellow Sea,China

The concentration and composition of nutrients,such as N,P,and Si,respond to biogeochemical processes and in turn,impact the phytoplanktons'community structure and primary production.In this study,historical data was systematically analyzed to identify long-term variations in nutrient trends,red tide frequency,phytoplankton community abundance,and dominant species succession in the southern Yellow Sea(SYS).Results showed that N/P concentration ratios dramatically increased as a function of increasing dissolved inorganic nitrogen concentrations,and Si/N concentration ratios were generally larger than 1,indicating that N limitation morphed to P limitation and potentially to Si limitation,which impacted the phytoplankton community.Furthermore,inter-annual trends over the past 50 years show that phytoplankton community abundance has been higher in spring and summer,relative to autumn and winter.Moreover,with respect to red tide frequency,diatom abundance gradually decreased,while that of dinoflagellates gradually increased.Dominant species succession showed that the phytoplankton community exhibited an evident tendency to transform from diatoms to dinoflagellates.These research results clearly depict the presence of an important correlation between the phytoplankton community and nutrient structure in the SYS.

Toxic effects of fluoranthene and copper on marine diatom Phaeodactylum tricornutum

To investigate the effects of polycyclic aromatic hydrocarbons (PAHs) and metals on the population reproduction,antioxidative defense system and cell ultrastructure of the marine diatom,fluoranthene and Cu2+ were selected to test their toxicity to Phaeodactylum tricorntum,in the laboratory.The results indicated that both fluoranthene and Cu2+ inhibited population reproduction of P.tricorntum.When the algal cells were exposed to fluoranthene or Cu2+ for 72 h,ultrastructure damage in the cells was observed un...