Dynamics and scale variations of blooms of Phaeocystis globosa "giant colony" ecotype and key environmental factors in the Beibu Gulf, China.

The Beibu Gulf has experienced blooms of Phaeocystis globosa "giant colony" ecotype (PGGCE), with noticeable variations in bloom scale across years. However, driving environmental factors and their roles remain poorly understood. In this study, we quantified dynamics of PGGCE cells in 2016-2017 and 2018-2019, and analyzed their correlations with environment factors. The results revealed that PGGCE blooms primarily occurred in Guangxi coast and western waters of Leizhou Peninsula during winter months, exhibiting distinct developmental processes. Bloom intensity, duration, and distribution differed significantly between two bloom events. In 2016-2017, peak PGGCE density exceeded 2.0 × 105 cells L-1 nearly double that of 2018-2019. Furthermore, bloom sustained five months during 2016-2017, compared to three months during 2018-2019. Prolonged period of low temperatures and elevated nitrate concentrations favored PGGCE growth and colony formation, resulting in a larger scale bloom during winter 2016 as opposed to winter 2018.

High Pressure-Temperature Study of MgF2, CaF2, and BaF2 by Raman Spectroscopy: Phase Transitions and Vibrational Properties of AF2 Difluorides.

The phase transition of AF2 difluorides strongly depends on pressure, temperature, and cationic radius. Here, we have investigated the phase transition of three difluorides, including MgF2, CaF2, and BaF2, at simultaneously high pressures and temperatures using Raman spectroscopy and X-ray diffraction in externally heated diamond anvil cells up to 55 GPa at 300-700 K. Rutile-type difluoride MgF2 with a small cationic radius undergoes a transition to the CaCl2-type phase at 9.9(1) GPa and 300 K, to the HP-PdF2-type phase at 21.0(2) GPa, and to the cotunnite-type phase at 44.2(2) GPa. The phase transition pressure to the HP-PdF2 and cotunnite structure at 300 K for our single crystal was found to be higher than that in previous studies using polycrystalline samples. Elevating the temperature increases the transition pressure from rutile- to the CaCl2-type phase but has a negative influence on the transition pressure when MgF2 transforms from the HP-PdF2- to cotunnite-type phase. Meanwhile, the transition pressure from the CaCl2- to HP-PdF2-type phase for MgF2 was identified to be independent of the temperature. Raman peaks suspected to belong to the α-PbO2-type phase were observed at 14.6-21.0(1) GPa and 400-700 K. At 300 K, difluorides CaF2 and BaF2 in the fluorite structure with larger cationic radii transform to the cotunnite-type phase at 9.6(3) and 3.0(3) GPa at 300 K, respectively, and BaF2 further undergoes a transition to the Ni2In-type phase at 15.5(4) GPa. For both CaF2 and BaF2, elevating the temperature leads to a lower transition pressure from fluorite- to the cotunnite-type phase but has little influence on the transition to the Ni2In structure. Raman data provide valuable insights for mode Grüneisen parameters. We note that the mode Grüneisen parameters for both difluorides and dioxides vary linearly with the cation radius. Further calculations for the mode Grüneisen parameters at high pressures for MgF2, CaF2, and BaF2 yield a deeper understanding of the thermodynamic properties of the difluorides.

Influence of annealing pretreatment in different atmospheres on crystallization quality and UV photosensitivity of gallium oxide films.

Due to their high wavelength selectivity and strong anti-interference capability, solar-blind UV photodetectors hold broad and important application prospects in fields like flame detection, missile warnings, and secure communication. Research on solar-blind UV detectors for amorphous Ga2O3 is still in its early stages. The presence of intrinsic defects related to oxygen vacancies significantly affects the photodetection performance of amorphous Ga2O3 materials. This paper focuses on growing high quality amorphous Ga2O3 films on silicon substrates through atomic layer deposition. The study investigates the impact of annealing atmospheres on Ga2O3 films and designs a blind UV detector for Ga2O3. Characterization techniques including atomic force microscopy (AFM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) are used for Ga2O3 film analysis. Ga2O3 films exhibit a clear transition from amorphous to polycrystalline after annealing, accompanied by a decrease in oxygen vacancy concentration from 21.26% to 6.54%. As a result, the response time of the annealed detector reduces from 9.32 s to 0.47 s at an external bias of 10 V. This work demonstrates that an appropriate annealing process can yield high-quality Ga2O3 films, and holds potential for advancing high-performance solar blind photodetector (SBPD) development.

High-pressure microfluidization enhanced the stability of sodium caseinate-EGCG complex-stabilized fish oil emulsion.

Improving the emulsion-stabilizing effect of protein by chemical or physical modification has been paid much attention recently. Here, sodium caseinate (CS) was treated by high-pressure-microfluidization (HPM) under 0-100 MPa, and was further complexed with (-)-epigallocatechin-3-gallate (EGCG) to form an excellent emulsifier that stabilized fish oil emulsions. Results showed that HPM treatment (especially 80 MPa) significantly changed the secondary structure of CS, and 80 MPa-PCS-EGCG had the best emulsifying and antioxidant activities. In addition, after HPM treatment and EGCG bonding, CS formed a thicker interface layer on the surface of oil droplets, which could better protect the fish oil from the influence by oxygen, temperature and ion concentration. Moreover, the fish oil emulsion stabilized by PCS-EGCG complex significantly delayed the release of free fatty acids subjected to in vitro digestion. Conclusively, HPM-treated CS-EGCG complex could be a potential emulsifier to improve the stability of fish oil emulsions.

A dinoflagellate bloom caused by multiple species of Kareniaceae in the coastal waters of Fujian in June 2022 and its adverse impacts on Brachionus plicatilis and Artemia salina.

Recently, dinoflagellate blooms have frequently occurred in the coastal waters of Fujian, East China Sea. In June 2022, a fish-killing bloom of Kareniaceae species occurred in this region. In this study, four species of Kareniaceae, namely, Karenia longicanalis, K. papilionacea, Karlodinium veneficum, and Karl. digitatum were identified from this bloom event based on the results of single-cell PCR and clone libraries, and intraspecies genetic diversity was found in the Karl. veneficum population. The results of acute toxicity assays of the bloom water to two zooplankton species (Brachionus plicatilis and Artemia salina) demonstrated this bloom event strongly inhibited their swimming capacities and survival. The results of this study suggested that the bloom events caused by multiple species of Kareniaceae in the Fujian coastal waters had adverse impacts on the local fishery resources and zooplankton community.

Regulation of the surface activity of carbon anodes for rationalization of potassium storage.

The gradient temperature was manipulated to construct hollow irregular carbon spheres with regulated intrinsic defects and surface area targeting favorable potassium storage. An enlarged surface area, increased intrinsic defects, and superior conductivity induced more surface-active interfaces. These actions facilitated a high reversible capacity as well as excellent cycling stability.

Differentiation of Aspartic and Isoaspartic Acid Using 193 nm Ultraviolet Photodissociation Mass Spectrometry.

Spontaneous conversion of aspartic acid (Asp) to isoaspartic acid (isoAsp) is a ubiquitous modification that influences the structure and function of proteins. This modification of Asp impacts the stability of biotherapeutics and has been linked to the development of neurodegenerative diseases. We explored the use of 193 nm ultraviolet photodissociation (UVPD) to distinguish Asp and isoAsp in the protonated and deprotonated peptides. The differences in the relative abundances of several fragment ions uniquely generated by UVPD were used to differentiate isomeric peptide standards containing Asp or isoAsp. These fragment ions result from the cleavage of bonds N-terminal to Asp/isoAsp residues in addition to the side-chain losses from Asp/isoAsp or the losses of COOH, CO2, CO, or H2O from y-ions. Fragmentation of Asp-containing tryptic peptides using UVPD resulted in more enhanced w/w + 1/y - 1/x ions, while isoAsp-containing peptides yielded more enhanced y - 18/y - 45/y - 46 ions. UVPD was also used to identify an isomerized peptide from a tryptic digest of a monoclonal antibody. Moreover, UVPD of a protonated nontryptic peptide resulted in more enhanced y ions N- and C-terminal to isoAsp and differences in b/y ion ratios that were used to identify the isoAsp peptide.

Cloning, expression, and bioinformatics analysis of heavy metal resistance-related genes fd-I and fd-II from Acidithiobacillus ferrooxidans.

Five heavy metals were introduced into the bacterial heavy metal resistance tests. The results showed that apparent inhibition effects of Cd2+ and Cu2+ on the growth of Acidithiobacillus ferrooxidans BYSW1 occurred at high concentrations (>0.04 mol l-1). Significant differences (P < 0.001) were both noticed in the expression of two ferredoxin-encoding genes (fd-I and fd-II) related to heavy metal resistance in the presence of Cd2+ and Cu2+ . When exposed to 0.06 mol l-1 Cd2+, the relative expression levels of fd-I and fd-II were about 11 and 13 times as much as those of the control, respectively. Similarly, exposure to 0.04 mol l-1 Cu2+ caused approximate 8 and 4 times higher than those of the control, respectively. These two genes were cloned and expressed in Escherichia coli, and the structures, functions of two corresponding target proteins, i.e. Ferredoxin-I (Fd-I) and Ferredoxin-II (Fd-II), were predicted. The recombinant cells inserted by fd-I or fd-II were more resistant to Cd2+ and Cu2+ compared with wild-type cells. This study was the first investigation regarding the contribution of fd-I and fd-II to enhancing heavy metal resistance of this bioleaching bacterium, and laid a foundation for further elucidation of heavy metal resistance mechanisms caused by Fd.

Food protein glycation: A review focusing on stability and in vitro digestive characteristics of oil/water emulsions.

Recently, increasing studies have shown that the functional properties of proteins, including emulsifying properties, antioxidant properties, solubility, and thermal stability, can be improved through glycation reaction under controlled reaction conditions. The use of glycated proteins to stabilize hydrophobic active substances and to explore the gastrointestinal fate of the stabilized hydrophobic substances has also become the hot spot. Therefore, in this review, the effects of glycation on the structure and function of food proteins and the physical stability and oxidative stability of protein-stabilized oil/water emulsions were comprehensively summarized and discussed. Also, this review sheds lights on the in vitro digestion characteristics and edible safety of emulsion stabilized by glycated protein. It can further serve as a research basis for understanding the role of structural features in the emulsification and stabilization of glycated proteins, as well as their utilization as emulsifiers in the food industry.

Marked shifts of harmful algal blooms in the Bohai Sea linked with combined impacts of environmental changes.

The Bohai Sea, a semi-enclosed inland sea in China and an important mariculture region, has experienced extensive harmful algal blooms (HABs) and their negative impacts for several decades. To investigate the changes of HABs and their potential drivers over time and space, a dataset of 230 HAB events (1952-2017), along with corresponding environmental data (1990-2017) was compiled. The frequency of HAB events in the Bohai Sea has increased over time but plateaued in the last decade, and our analysis showed that history of HABs in the Bohai Sea could be categorized into three periods based on their frequency, scale, and HAB-forming species. The seasonal window of HAB events has started earlier and lasted longer, and the main hotspot has moved from Bohai Bay to coastal waters of Qinhuangdao over time. There were marked shifts in the representative HAB-forming microalgae, from dinoflagellates in the first period (before 2000) to haptophytes in the second period (2000-2009), and pelagophytes in the third period (2009 onwards). These community changes are accompanied by a trend toward diversification of HAB-forming microalgae, decrease in cell-size, and increase in negative impacts. Statistical analyses indicate that long-term changes in HABs in the Bohai Sea are linked with the combined effects of climate change, eutrophication and mariculture development. The results of the present study require to refine future monitoring programs, develop adaptive management strategies and predictive models for HABs in the Bohai Sea.

Brown tides linked to the unique nutrient profile in coastal waters of Qinhuangdao, China.

Brown tides caused by the pelagophyte Aureococcus anophagefferens have frequently occurred in the Bohai Sea since 2009 and have led to a dramatic collapse of the local scallop culture. To determine why brown tides occurred in the Bohai Sea rather than in other eutrophic coastal waters of China, phytoplankton communities and nutrients were evaluated and nutrient addition experiments were conducted in the Qinhuangdao coastal area. The concentration of dissolved organic nitrogen (DON) was nearly five times higher than that of dissolved inorganic nitrogen (DIN) during brown tides. High levels of phytoplankton biomass and nutrients were observed in the inshore waters, and the patterns of different nutrients were heterogeneous, which could be due to the uneven distribution of pelagophytes and non-brown tide phytoplankton populations (NBTP). The nutrient enrichment results indicated that the growth of the phytoplankton community was nitrogen-limited. Enrichment of DON, especially urea, could promote the growth of pelagophytes during the development stages of the brown tide. In brief, the results of this study imply that the unique nutrient profile (rich in DON but deficient in DIN) could support the outbreak of brown tides in the inshore waters of Qinhuangdao.

Atomic-Level Sn Doping Effect in Ga2O3 Films Using Plasma-Enhanced Atomic Layer Deposition.

In this work, the atomic level doping of Sn into Ga2O3 films was successfully deposited by using a plasma-enhanced atomic layer deposition method. Here, we systematically studied the changes in the chemical state, microstructure evolution, optical properties, energy band alignment, and electrical properties for various configurations of the Sn-doped Ga2O3 films. The results indicated that all the films have high transparency with an average transmittance of above 90% over ultraviolet and visible light wavelengths. X-ray reflectivity and spectroscopic ellipsometry measurement indicated that the Sn doping level affects the density, refractive index, and extinction coefficient. In particular, the chemical microstructure and energy band structure for the Sn-doped Ga2O3 films were analyzed and discussed in detail. With an increase in the Sn content, the ratio of Sn-O bonding increases, but by contrast, the proportion of the oxygen vacancies decreases. The reduction in the oxygen vacancy content leads to an increase in the valence band maximum, but the energy bandgap decreases from 4.73 to 4.31 eV. Moreover, with the increase in Sn content, the breakdown mode transformed the hard breakdown into the soft breakdown. The C-V characteristics proved that the Sn-doped Ga2O3 films have large permittivity. These studies offer a foundation and a systematical analysis for assisting the design and application of Ga2O3 film-based transparent devices.

An investigation on bloom dynamics of Alexandrium catenella and A. pacificum and toxin accumulation in shellfish along the coast of Qinhuangdao, China.

The dinoflagellate genus Alexandrium comprises most of the toxic bloom-forming species producing paralytic shellfish toxins (PSTs) in the sea. Recently, repeated paralytic shellfish poisoning episodes have been recorded in Qinhuangdao located at the west coast of the Bohai Sea. To elucidate the relationship between toxic Alexandrium blooms and the poisoning episodes, a year-round investigation was carried out in this region from July 2020 to July 2021. Two qPCR assays were used to detect A. catenella and A. pacificum, and LC-MS/MS was applied to analyze PSTs in phytoplankton and shellfish samples. The blooms of A. catenella and A. pacificum were found in April and July, respectively, and PST content in three bivalves exhibited notable increase following the bloom of A. catenella. The results revealed bloom dynamics of the two toxic Alexandrium species in the Bohai Sea for the first time, and further confirmed A. catenella as the causative agent of poisoning episodes.

Intense blooms of Phaeocystis globosa in the South China Sea are caused by a unique "giant-colony" ecotype.

The haptophyte Phaeocystis globosa, an important causative agent of harmful algal blooms globally, exhibits varying morphological and physiological features and high genetic diversity, yet the relationship among these has never been elucidated. In this study, colony sizes and pigment profiles of 19 P. globosa isolates from the Pacific and Atlantic Oceans were determined. Genetic divergence of these strains was analyzed using the chloroplast rbcS-rpl27 intergenic spacer, a novel high-resolution molecular marker. Strains could be divided into four genetic clades based on these sequences, or two groups based on colony size and the identity of diagnostic pigments (19'-hexanoyloxyfucoxanthin, hex-fuco, and 19'-butanoyloxyfucoxanthin, but-fuco). Three strains from the South China Sea (SCS), all belonging to the same genetic clade, have unique biological features in forming giant colonies and possessing but-fuco as their diagnostic pigment. Based on these findings, we propose that these SCS strains should be a unique "giant-colony" ecotype of P. globosa. During the period 2016-2021, more than 1000 rbcS-rpl27 sequences were obtained from 16 P. globosa colony samples and 18 phytoplankton samples containing solitary P. globosa cells in the SCS. Phylogenetic analysis indicated that >95% of the sequences from P. globosa colonies in the SCS were comprised of the "giant-colony" ecotype, whereas the genetic diversity of solitary cells was much higher. Results demonstrated that intense blooms of P. globosa featuring giant colonies in the SCS were mainly caused by this giant-colony P. globosa ecotype.

First record of a Takayama bloom in Haizhou Bay in response to dissolved organic nitrogen and phosphorus.

Since 1990s, harmful algal blooms (HABs) of Kareniaceae, primarily caused by species of Karenia and Karlodinium and rarely by Takayama species, have been substantially increasing in frequency and duration in the coastal waters of China. In this study, we recorded a bloom of high abundance of T. acrotrocha in the Haizhou Bay, the Yellow Sea in September 2020, which is the first record of a Takayama bloom in the temperate coastal waters of China. We found that high concentrations of DON and DOP accelerated the proliferation of T. acrotrocha in the Haizhou Bay. Intensive mariculture, and terrestrial nitrogen and phosphorus input may be responsible for the eutrophication in the Haizhou Bay featuring high concentrations of DON and DOP, and high DIN/DIP ratios. The results suggested that, under ocean warming, the HABs of Kareniaceae are becoming increasingly dominant in eutrophic temperate coasts with intensive mariculture activities.

Toxin production of dinoflagellate Gymnodinium catenatum isolated from the East China Sea.

Dinoflagellate Gymnodinium catenatum is an important producer of paralytic shellfish toxins (PSTs), including a novel group of hydroxybenzoate derivatives named GC toxins. In the East China Sea, G. catenatum has been considered as the causative agent for several paralytic shellfish poisoning (PSP) episodes, yet the knowledge on their toxin production was still quite limited. In this study, toxins produced by a strain of G. catenatum (MEL11) isolated from the East China Sea were determined, using high performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). Changes of toxin profile in the stain MEL11 in response to nutrient and temperature variations were also examined. A total of 11 PST components dominated by hydroxybenzoate analogs and N-sulfocarbamoyl toxins were detected, which was different from other G. catenatum strains previously established in the East China Sea in the presence of GC5 and the lack of dcGTX2&3. Cellular toxin composition and content of the strain had no apparent change within a range of temperature from 20°C to 26°C. In contrast, nutrient limitation and nitrogen source had notable impacts on toxin production. The molar percentage of GC toxins decreased remarkably at the stationary growth phase under nutrient-deprived conditions of both nitrogen (N) and phosphorus (P). The replacement of nitrate with ammonium as the source of N significantly promoted PST production by G. catenatum. The study revealed the potential diversity of toxin profiles of G. catenatum in the East China Sea, and highlighted the effects of nutrients on production of GC toxins by G. catenatum.

Green Tides in the Yellow Sea Promoted the Proliferation of Pelagophyte Aureococcus anophagefferens.

Harmful algal blooms formed by fast-growing, ephemeral macroalgae have expanded worldwide, yet there is limited knowledge of their potential ecological consequences. Here, we select intense green tides formed by Ulva prolifera in the Yellow Sea, China, to examine the ecological consequences of these blooms. Using 28-isofucosterol in the surface sediment as a biomarker of green algae, we identified the settlement region of massive floating green algae in the area southeast of the Shandong Peninsula in the southern Yellow Sea. The responses of the phytoplankton assemblage from the deep chlorophyll-a maximum layer were then resolved using high-throughput sequencing. We found striking changes in the phytoplankton community in the settlement region after an intensive green tide in 2016, characterized by a remarkable increase in the abundance of the pelagophyte Aureococcus anophagefferens, the causative species of ecosystem disruptive brown tides. Our study strongly suggests that the occurrence of massive macroalgal blooms may promote blooms of specific groups of microalgae through alteration of the marine environment.

Pigment Characterization of the Giant-Colony-Forming Haptophyte Phaeocystis globosa in the Beibu Gulf Reveals Blooms of Different Origins.

The giant-colony-forming haptophyte Phaeocystis globosa has caused several large-scale blooms in the Beibu Gulf since 2011, but the distribution and dynamics of the blooms remained largely unknown. In this study, colonies of P. globosa, as well as membrane-concentrated phytoplankton samples, were collected during eight cruises in the Beibu Gulf from September 2016 to August 2017. Pigments were analyzed by high-performance liquid chromatography coupled with a diode array detector (HPLC-DAD). The pigment 19'-hexanoyloxyfucoxanthin (hex-fuco), generally considered a diagnostic pigment for Phaeocystis, was not detected in P. globosa colonies in the Beibu Gulf, whereas 19'-butanoyloxyfucoxanthin (but-fuco) was found in all colony samples. Moreover, but-fuco in membrane-concentrated phytoplankton samples exhibited a similar distribution pattern to that of P. globosa colonies, suggesting that but-fuco provided the diagnostic pigment for bloom-forming P. globosa in the Beibu Gulf. Based on the distribution of but-fuco in different water masses in the region prior to the formation of intensive blooms, it is suggested that P. globosa blooms in the Beibu Gulf could originate from two different sources. IMPORTANCE Phaeocystis globosa has formed intensive blooms in the South China Sea and even around the world, causing huge social economic losses and environmental damage. However, little is known about the formation mechanism and dynamics of P. globosa blooms. 19'-Hexanoyloxyfucoxanthin (hex-fuco) is often used as the pigment proxy to estimate Phaeocystis biomass, while this is challenged by the giant-colony-forming P. globosa in the Beibu Gulf, which contains only 19'-butanoyloxyfucoxanthin (but-fuco) but not hex-fuco. Using but-fuco as a diagnostic pigment, we traced two different origins of P. globosa blooms in the Beibu Gulf. This study clarifies the development process of P. globosa blooms in the Beibu Gulf, which provides a basis for the early monitoring and prevention of the blooms.

Distribution of Aureococcus anophagefferens in relation to environmental factors and implications for brown tide seed sources in Qinhuangdao coastal waters, China.

Brown tides caused by Aureococcus anophagefferens have occurred along the Qinhuangdao coastline in the Bohai Sea (BS) in recent years. Little is known about the spatio-temporal distribution of A. anophagefferens, particularly its profile distribution and the effects of environmental controls. In this study, four surveys were conducted in Qinhuangdao coastal waters during the brown tide from June to July 2013; another survey was conducted to cover a larger region in the BS in May 2016. Temperature, salinity, nutrients, and chlorophyll a were analyzed; and the density of A. anophagefferens was detected by a sensitive qPCR method. The intensive brown tide only occurred in Qinhuangdao inshore waters at temperatures ranging from 21.5 to 23.2 °C and relatively high salinity (> 29). Redundancy analysis indicated that the low dissolved inorganic nitrogen limited the growth of other pico- and nano-algal species; high dissolved organic nitrogen and low inorganic nutrients were suitable for the development of brown tides in Qinhuangdao coastal waters, which also contained a thermocline during the brown tide. At the early stage of the brown tide, a high abundance of A. anophagefferens appeared at the bottom of offshore waters characterized by low temperature and high salinity. The A. anophagefferens cells were speculated to originate from water mass located in a depression between the central ridge and the Qinhuangdao coastal area. In brief, this study reported the spatio-temporal variation of brown tides based on the abundance of A. anophagefferens and environmental forces and implied that A. anophagefferens could be transported from the bottom of offshore waters to promote brown tides in inshore waters of Qinhuangdao.

Zeolite Imidazolate Frameworks-67 Precursor to Fabricate a Highly Active Cobalt-Embedded N-Doped Porous Graphitized Carbon Catalyst for the Thermal Decomposition of Ammonium Perchlorate.

The more apparent specific heat release at a lower high-temperature decomposition (HTD) temperature of ammonium perchlorate (AP) poses a challenge for the development of highly active catalysts. In this work, a well-designed cobalt-embedded N-doped porous graphitized carbon (Co@NC) catalyst is obtained by high-temperature calcination of a zeolite imidazolate frameworks-67 precursor, in which the cobalt catalytic active center realizes effective nanoscale dispersion; meanwhile, the cobalt and N-doped porous graphitized carbon can release considerable heat after oxidation, and the cobalt oxides have an excellent catalytic effect on reducing the HTD temperature of AP. The catalytic activity of Co@NC was tested by a differential thermal analytical method. The results indicated that the HTD peak of AP was significantly decreased by 100.5 °C, the apparent activation energy of the HTD reaction of AP was reduced by 82.0 kJ mol-1, and the heat release compared with pure AP increased 2.9 times. On teh basis of these findings, Co@NC is expected to be one of the best candidate materials for AP thermal decomposition.