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.

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.

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).

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 role of copper in enhancing the performance of heteronuclear diatomic catalysts for the electrochemical CO_(2)conversion to C_(1) chemicals

Diatomic catalysts(DACs)with two adjacent metal atoms supported on graphene can offer diverse functionalities,overcoming the inherent limitations of single atom catalysts(SACs).In this study,density functional theory calculations were conducted to investigate the reactivity of the carbon dioxide(CO_(2))reduction reaction(CO_(2)RR)on metal sites of both DACs and SACs,as well as their synergistic effects on activity and selectivity.Calculation of the Gibbs free energies of CO_(2)RR and associated values of the limiting potentials to generate C_(1) products showed that Cu acts as a promoter rather than an active catalytic centre in the catalytic CO_(2)conversion on heteronuclear DACs(CuN_(4)-MN_(4)),improving the catalytic activity on the other metal compared to the related SAC MN_(4).Cu enhances the initial reduction of CO_(2)by promoting orbital hybridization between the key intermediate*COOH 2p-orbitals and the metals 3d-orbitals around the Fermi level.This degree of hybridization in the DACs CuN_(4)-MN_(4) decreases from Fe to Co,Ni,and Zn.Our work demonstrates how Cu regulates the CO_(2)RR performance of heteronuclear DACs,offering an effective approach to designing practical,stable,and high-performing diatomic catalysts for CO_(2)electroreduction.

Paclobutrazol induces the concurrent accumulation of chrysolaminarin and lipids in the diatom Phaeodactylum tricornutum

Paclobutrazol is a plant growth regulator and inhibitor of endogenous gibberellin synthesis.It is a powerful inhibitor of vegetative growth by changing the photosynthetic rate and plant hormone levels,thereby affecting plant growth and development.In this study,the effects of paclobutrazol on the model diatom Phaeodactylum tricornutum were investigated.Results show that 2.5-mg/L and 10-mg/L paclobutrazol significantly inhibited the algal growth by inhibiting chlorophyll synthesis,which affects photosynthesis.The antioxidant system,including catalase(CAT)and glutathione peroxidase(GPx)was severely damaged.Chrysolaminarin content was significantly elevated and doubled up to 127 mg/g dry cell weight(DCW)by 10-mg/L paclobutrazol treatment.In combination with transcriptomic analysis,paclobutrazol was demonstrated to play a regulatory role in the accumulation of chrysolaminarin and neutral lipids.

Environmental heterogeneity and productivity drive the assemblage of benthic diatom:a case study of the Three Gorges Reservoir

Dam construction has a critical effect on river ecosystems in the world,resulting in a rapid decline in biodiversity and ecosystem health.However,the effect of dam construction on the assemblage pattern of benthic diatoms remains unclear.The benthic diatoms assemblages in the tributary backwater area of the Three Gorges Reservoir(TGR)were investigated under low water level(LWL)and high water level(HWL)conditions.Results show that Discostella stelligera,Nitzschia palea,and Craticula subminuscula were dominant species in LWL,while Achnanthidium minutissimum and Nitzschia dissipata were dominant in HWL.Furthermore,environmental variables,productivity parameters,diversity indices,and community similarity were found significantly different between LWL and HWL periods.The Mantel test indicated that both environmental and spatial factors had significant effects on diatom communities in backwater area,while productivity was also a key driving force in LWL.The variation partitioning analysis(VPA)further demonstrated that environment factors could explain the largest variance of diatom assemblages in HWL(9%)and LWL(11%),followed by spatial factors.The relative importance of productivity to diatom community was significantly enhanced in LWL,but only a slight effect was found in HWL.These results indicate that the diatom assemblages were shaped by both environmental filtering and spatial factors.The relative importance of spatial factors depended on the degree of productivity.Therefore,the homogenization of diatom communities due to environmental disturbance,e.g.eutrophication and dam building,is the underlying mechanism in assembling the benthic diatoms.

Rational design of Fe/Co-based diatomic catalysts for Li–S batteries by first-principles calculations

Fe/Co-based diatomic catalysts decorated on an N-doped graphene substrate are investigated by first-principles calculations to improve the electrochemical properties of Li–S batteries.Our results demonstrate that Fe CoN8@Gra not only possesses moderate adsorption energies towards Li2Snspecies,but also exhibits superior catalytic activity for both reduction and oxidation reactions of the sulfur cathode.Moreover,the metallic property of the diatomic catalysts can be well maintained after Li2Snadsorption,which could help the sulfur cathode to maintain high conductivity during the whole charge–discharge process.Given these exceptional properties,it is expected that Fe CoN8@Gra could be a promising diatomic catalyst for Li–S batteries and afford insights for further development of advanced Li–S batteries.

Mechanistic Insights into Electrocatalytic Nitrogen Reduction Reaction on the Pd-W Heteronuclear Diatom Supported on C_(2)N Monolayer:Role of H Pre-Adsorption

The electrocatalytic N_(2) reduction reaction(eNRR)is a potential alternative to the Haber-Bosch process for ammonia(NH3)production.Tremendous efforts have been made in eNRR catalyst research to promote the practical application of eNRR.In this work,by means of density functional theory calculations and the computational hydrogen electrode model,we evaluated the eNRR performance of 30 single metal atoms supported on a C_(2)N monolayer(M@C_(2)N),and we designed a new thermodynamically stable Pd-W hetero-metal diatomic catalyst supported on the C_(2)N monolayer(PdW@C_(2)N).We found that PdW@C_(2)N prefers to adsorb H over N_(2),and then,the pre-generated hydrogen-terminated PdW@C_(2)N selectively adsorbing N_(2) behaves as the actual functioning“catalyst”to catalyze the eNRR process,exhibiting excellent performance with a low overpotential(0.31 V),an ultralow NH3 desorption free energy(0.05 eV),and a high selectivity toward eNRR over hydrogen evolution reaction(HER).Moreover,PdW@C_(2)N shows a superior eNRR performance to its monomer(W@C_(2)N)and homonuclear diatom(W_(2)@C_(2)N)counterparts.The revealed mechanism indicates that the preferential H adsorption over N_(2) on the active site may not always hamper the eNRR process,especially for heteronuclear diatom catalysts.This work encourages deeper exploration on the competition of eNRR and HER on catalyst surfaces.

Diatom-based dissolved inorganic nitrogen reconstruction in the Changjiang River estuary and its adjacent areas

A five-component weighted average partial least squares(WA-PLS)calibration model was developed by analysing diatom assemblages in 34 surface sediment samples(collected in 2015)from the Changjiang River estuary(CRE)and its adjacent areas to infer dissolved inorganic nitrogen(DIN)concentrations.Eighteen additional sets of surface sediment diatoms and corresponding upper water DIN data(collected in 2012)were used to evaluate the accuracy of the model,and the relationship between observed and diatom-inferred DIN(DI-DIN)values(R2=0.85)illustrated the strong performance of the transfer function,indicating that precise reconstructions of former DIN are possible.The diatom-DIN transfer function was applied to the diatom record from a sediment core DH8-2(1962‒2012)collected in the Fujian-Zhejiang area south of the CRE.The reconstruction based on the DI-DIN model showed a significant DIN increase from 1962-2012,reflecting the influence of human activities on the very large increase in eutrophication.Three distinct periods can be seen from the changes in DIN and diatom taxa.In the 1962-1972 period,the DIN content was relatively low,with an average of 5.94μmol/L,and more than 80%of the diatom species identified were benthic taxa.In the 1972-2004 period,as the impact of human activities intensified,large nutrient inputs caused the DIN content to increase,with an average of 8.25μmol/L.The nutrient inputs also caused a significant change in the nutrient components and a distinct increase in small planktonic taxa.In the 2004-2012 period,the DIN content continued to rise,fluctuating at approximately 10μmol/L.A continuous increase in the frequency of planktonic taxa(up to 65.48%)indicated that eutrophication was further intensified,which was confirmed by the transformation from diatom-induced red tide to dinoflagellate-induced red tide during this period.

Quantitative relationship between surface sedimentary diatoms and water depth in North-Central Bohai Bay,China

To study the quantitative relationship between surface sedimentary diatoms and water depth,67 surface samples were collected for diatom analysis on eight profiles with water depth variation from the muddy intertidal zone to the shallow sea area in North-Central Bohai Bay,China.The results showed that the distribution of diatoms changed significantly in response to the change in water depth.Furthermore,the quantitative relationship between the distribution of dominant diatom species,their assemblages,and the water depth was established.The water depth optima for seven dominant species such as Cyclotella striata/stylorum,Paralia sulcata,and Coscinodiscus perforatus and the water depth indication range of seven diatom assemblages were obtained in the study area above the water depth(elevation)of-10 m.The quantitative relationship between surface sedimentary diatoms and water depth provides a proxy index for diatom-paleo-water depth reconstruction in the strata in Bohai Bay,China.

Novel Proposal of Bio-based Sewing Timber Joint:Learning from Diatoms

The twenty-first century is one of the most complex in the history of humanity,mainly due to the ecological crisis it is going through.The construction sector generates about 40%of CO2 emissions into the environment;the foregoing should motivate this sector to seek new alternatives to develop new building practices.Taking these current needs into account,this document classifies and presents a multidisciplinary solution that integrates biology,engineering and architecture to develop a new and innovative lightweight timber structure;it divides with a main structure made of timber and an innovative joint system made of bio-polymers connecting all the panels.Through the study of diatoms,it was able to analyze the bio-morphology of the structure,joints and in particular the geometry since they were the inspiration for the design of this structure that presents an innovative and novel design of structural optimization.Through parametric design and digital fabrication,it was able to create a complex geometry that obtains excellent structural behavior.This research discusses and explores how materials,geometry led to the optimization of a structure and how new structures can arise,thanks to biology new solutions can be obtained that are completely sustainable,being a clear example of how to combat the effects of the climate change and in a precise way it highlights the advantages of the bio-design in the architectural design.

Toxic marine diatoms of Hong Kong:A paleoecological study

To determine whether toxic diatoms in Hong Kong's Victoria Harbour have become more common during the last four decades,a gravity core was taken from the anaerobic sediments of Kowloon Bay in the harbour. Analysis of these sediments from a depth of 0-1cm,4-5cm and 9-10cm indicated that 6.4%,2.4% and 1.5% of the diatoms observed at each of these three respective depths belonged to the genus Pseudonitzschia. The abundance of Pseudonitzschia frustules in the surface sediments of Victoria Harbour was significantly higher(p<0.05)than it was in the harbour's deeper and older(ca.1965)sediments. The increase in potentially toxic diatom species over the last 30 years was attributed to a variety of factors including the addition of large amounts of nutrients to Hong Kong's coastal waters as a re- sult of man's activities.

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.

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.

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...

Photoinduced toxicity single and binary mixtures of four polycyclic aromatic hydrocarbons to the marine diatom Skeletonema costatum

Diatom Skeletonema costatum Cleve is one of the main predominant phytoplankton species in the Changjiang Estuary in China. In order to provide some basic information for future assessment of the potential risk on phytoplankton communities in this estuary caused by polycyclic aromatic hydrocarbons（ PAHs）, this alga was selected as a representative to investigate the photoinduced toxicity of PAHs, in single and mixture. Four PAHs including three-ring phenanthrene and anthracene, four-ring fluoranthene and pyrene were tested in the laboratory. The single toxicity of each PAH on this microalga was compared with and without the simulated solar UV radiation. The results showed that this microalga was sensitive to PAH＇ s photoinduced toxicity. Ratios of the 72 h median effect concentration obtained for fluorescent and UV light tests were about 8.4 for phenanthrene, 13.0 for anthracene, 6. 5 for fluoranthene, and 5.7 for pyrene, indicating that UV light enhanced the PAH toxicity to this alga significantly. Under the fluorescent radiation （lacking UV ）, the dose-response curves based on chemical concentrations revealed that the order of toxic strength was fluoranthene greater than pyrene greater than anthracene greater than phenanthrene; while under the UV radiation （476 μW/cm^2 for UVA, 6.5 μW/cm^2 for UVB） it became fluoranthene approximately equaling anthracene greater than pyrene greater than phenanthrene, indicating that the UV light also changed its relative toxicity to this alga. The photoinduced toxicity of PAHs to the marine diatom S. costatum might be a synergistic effect of photosensitization reactions （ e. g. , generation of singlestate oxygen） and photomodification （photooxidation and/or photolysis）. The combined effects of six binary mixtures on the marine diatom S. costatum were investigated using the additive-index method. Four binary-mixtures （ phenanthrene plus anthracene ; phenanthrene plus pyrene ; anthracene plus fluoranthene ; anthracene plus pyrene） were found to be synergistic joint action mode, while two binary-mixtures （phenanthrene plus fluoranthene; fluoranthene plus pyrene） displayed antagonist, revealing a complex pattern of possible interactions. The combined action mode of PAHs might be related to various factors such as the mixture compounds, mixture ratios and test conditions, etc.

The environmental implication of diatom fossils in the surface sediment of the Changjiang River estuary(CRE) and its adjacent area

In order to depict the distribution of diatom fossils in surface sediments and to establish a reliable reference data for further paleoenvironmental study in the Changjiang (Yangtze) River estuary and its adjacent waters, the diatom fossils from 34 surface sediment samples and their relationship with environmental variables were analyzed by principal component analysis and redundancy correspondence analysis. The diversity and abundance of diatom fossils were analyzed. Some annual average parameters of the overlying water (salinity, temperature, turbidity, dissolved oxygen, depth, dissolved inorganic nitrogen, dissolved inorganic phosphate and dissolved inorganic silicate) were measured at each sampling site. A total of 113 diatom taxa and one silicoflagellate species were identified in the investigation area. Diatom fossils were better preserved in fine sediments. The absolute abundance of diatom fossils did not significantly diff er between inshore and off shore areas, the species diversity decreased from inshore to off shore. This may be because high nutrients and low salinity promoted the growth of more brackish species in coastal waters. The diatom taxa were divided into three groups, on the basis of their response and indication to environmental changes. For example, Actinocyclus ehrenbergii and Cyclotella stylorum were dominant in coastal waters (Group 1 and Group 3) with high nutrients and low salinity;the relative abundances of Paralia sulcata and Podosira stelliger were significantly higher in off shore sites (Group 2, average 39.5%), which were characterized by high salinity and deep water. Four environmental variables (salinity, dissolved inorganic nitrogen, temperature and water depth) explained the composition and distribution of diatom taxa independently ( P< 0.05), this finding can be applied in further paleoenvironmental reconstruction research in this area.

Late Quaternary diatom and sea level changes in estuarine plain of the Jiulong River

Four units and twenty-four zones of diatom have been discerned in the Borehole ZK5 in the estuarine plain of the Jiulong River, Fujian Province. Comprehensive analysis of these, together with microbiological assemblages and age determinations in some other boreholes, shows that during the Late Wurm Glacial, sea level of the study area rose and fell frequently, but had principally been in the environments of estuary-bay. This mainly resulted from the tectonic subouction. In this period 3 low sea levels occurred. at 18, 16 and 12 kaBP respectively. During Holocene, sea weter intruded massively and the sea level over the transgnaion maximum had been 5-10 m higher than that of the present.