Thalassiosira weissflogii grown in various Zn levels shows different ecophysiological responses to seawater acidification.

The presence of zinc (Zn), a vital element for algal physiological functions, coupled with the silicification of diatoms implies that it plays an integral role in the carbon and silicon cycles of the sea. In this study, we examined the effects of different pCO2 and Zn levels on growth rate, elemental compositions and silicification by Thalassiosira weissflogii. The results showed that under normal pCO2 (400 µatm), cultures of T. weissflogii were depressed for growth rate and silica incorporation rate, but encouraged for cellular silicon content, Si/C, Si/N, and sinking rate when Zn deficient (0.3 pmol L-1). However, cellular silicon and sinking rate of Zn-deficient and Zn-replete (25 pmol L-1) T. weissflogii were decreased and increased at higher pCO2 (800 µatm), respectively. Thus, acidification may affect diatoms significantly differently depending on the Zn levels of the ocean and then alter the biochemical cycling of carbon and silica.

Responses of nickel bioavailability and toxicity of Prorocentrum Donghaienses to dissolved organic matter (DOM) fractions incubated in urea.

Urea, nickel (Ni) and dissolved organic matter (DOM) from land varied with different sources have a great impact on the offshore ecosystem. The heterogeneity of Ni bioavailability and toxicity of Prorocentrum donghaiense influenced by DOM fractions incubated in urea was investigated in this study. On the occasion, chlorophyll (Chl a) concentration, growth rate, and photosynthesis parameters were monitored to track changes occurring in the test organism. Chl a concentration and photosynthesis parameters in the treatment of hydrophilic DOM (HPI) with Ni-free was significantly higher than that in the control treatment, and similar data were shown in the treatment of hydrophobic DOM（HPO）with the low Ni environment (0.17µmol L-1). However, the opposite phenomena were observed in the treatments of HPO with the higher Ni environment (over 170µmol L-1). Moreover, the EC50 of Ni for P.donghaiense incubated in HPO was relatively lower than that in HPI and control treatment, which implied that HPO elevated the toxicity of Ni. Therefore, the varied DOM compositions because of different origins, as a chelating agent and potential nutrient source in coastal waters, shows the significantly different bioavailability and toxicity of Ni with the increasing inputs of urea, which in turn influences the dynamics of phytoplankton.

Low-toxic, fluorescent labeled and size-controlled graphene oxide quantum dots@polystyrene nanospheres as reference material for quantitative determination and in vivo tracing.

Polystyrene (PS) is selected as a representative nanoplastic and persistent pollutant for its difficult degradation and wide application. The environmental risk assessment of PS is obstructed by the toxic dye-based fluorescent PS, which false positives could be induced by the leakage of dye. For high biocompatibility, low toxicity, hydrophilicity, good water dispersibility, strong fluorescent stability, graphene oxide quantum dots (o-CQDs) are selected and embedded into PS microspheres, i.e., o-CQDs@PS, by microemulsion polymerization and denoted as CPS. Meanwhile, the sizes of CPS, e.g., 100, 150, and 200 nm, could be controlled by optimizing the type and number of water-soluble initiators. The anti-interference, low toxicity, and in vivo fluorescent tracing of CPS are proven by the coexistence of metals (including Fe2+, Fe3+, K+, Ba2+, Al3+, Zn2+, Mg2+, Ca2+, and Na+) on the fluorescence intensity of CPS, the growth of Chlorella pyrenoidosa and Artemia cysts as aquatic phytoplankton and zooplankton cultured with CPS, and the transfer of CPS from water into brine shrimp. In the concentration range of 0.1-100 mg/L, CPS can be quantitatively determined, which is suitable for coastal water and wastewater treatment plants. Therefore, CPS with standard size is suitable as reference material of PS.

Benefit-Risk Assessment of Dietary Patterns by Bioavailable Metals, Gut Microbes, and Their Interaction for Human Health.

The high-carbohydrate, low-fat, low-protein (HC-LFP) and low-carbohydrate, high-fat, high-protein (LC-HFP) diets are the main dietary patterns worldwide. The influence of dietary patterns on bioavailable metals, gut microbes, and their interaction is still unknown. A biomimetic digestive tract with full functions is constructed to transform the diets into chyme, and the gut microbes are cultured with the corresponding chyme. The diet species-specificity in bioavailable metal content and the positive and negative correlations between bioavailable metals and microbial reproductions are disclosed. The safe dosage and maximum consumption are 369.5 and 858.6 g/d and 268.6 and 3119.0 g/d for LC-HFP and HC-LFP, respectively. When replacing HC-LFP with LC-HFP for 21 days, the bioavailability of Fe and Cr is increased 83.2% and 268.4%, respectively; the reproductions of harmful and benefical microbes are significantly increased and decreased. The prevalences of obesity, inflammation, septicemia, and cancer are increased, and then the risk of dietary pattern shift is disclosed.

Long-term stable, high accuracy, and visual detection platform for In-field analysis of nitrite in food based on colorimetric test paper and deep convolutional neural networks.

Nitrite is one of the most common carcinogens in daily food. Its simple, rapid, inexpensive, and in-field measurement is important for food safety, based on the requirements of the standard from Codex Alimentarius Commission and China. Using polyacrylonitrile (PAN) and thin layer silica gel (SG), p-aminophenylcyclic acid (SA) and naphthalene ethylenediamine hydrochloride (NEH), as carriers and chromogenic agents, respectively, PAN-NSS as nitrite color sensor is proposed. After fixing and protecting of SA and NEH with layer-upon-layer PAN, the validity period of the test paper can be prolonged from 7 days to more than 30 days. The reproducibility of PAN-NSS preparation is ensured by electrospinning. Combined with PAN-NSS, deep convolutional neural network (DCNN) and APP as a visual monitoring platform, which has the functions of rapid sampling, data processing and transmission, intuitive feedback, etc., and provides a fully integrated detection system for field detection.

Benefit-risk assessment of metal bioavailability in edible fungi by biomimetic whole digestive tracts with digestion, metabolism, and absorption functions.

As worldwide edible fungi, Lentinula edodes and Agaricus bisporus accumulate both essential and harmful metals. Metal bioavailability is important for metal benefit-risk assessment. A full functional model of digestive tracts (including digestion, metabolism, and absorption) is established. Under the digestive tract functions, the bioaccessible and bioavailable metals are released from edible fungi and absorbed by intestinal tract, respectively. Based on bioavailable metal contents in the intestine, safe dosage and maximum consumption are 43.52 g/d and 248.7 g/d for Agaricus bisporu, 20.59/328.9 g/d (for males/ female) and 132.9 g/d for Lentinus edodes; V, Co, Ni, Cu, Zn, Se, Cr, Cd and Pb in Agaricus bisporus and Lentinula edodes are absorbed mainly in the large intestine; Fe is mainly absorbed in small intestine; edible fungi species-specificity in metal bioavailability is observed for As and Mn, which are mainly absorbed by small and large intestine for Agaricus bisporus and Lentinus edodes, respectively; and then metal toxicity on small and large intestine is disclosed. Metal benefit-risk is assessed by the content of monolayer liposome-extracted metal in the chyme from small and large intestine, which is controlled by the gastrointestinal functions, metal and edible fungi species.

[Anti-arthritic-related metal bioavailability for optimal compatibility ratio of Aconiti Radix Cocta and Paeoniae Radix Alba].

Trace metals deficiency or excess are associated with the etiology and pathogenesis of rheumatoid arthritis(RA). Aconiti Radix Cocta(A) and Paeoniae Radix Alba(B) are commonly used together for the treatment of RA. In this study, we aim to determine anti-arthritic-related metal bioavailability in the compatibility of herb A and B for avoiding metal deficiency or excess, and optimize the combination ratio of herb A and B, accordingly. Anti-arthritic-related metal bioaccessibility were evaluated by in vitro simulator of all gastrointestinal tract(including mouth, stomach, small and large intestines), and the roles of gastrointestinal digestive enzymes and intestinal microflora were investigated. Anti-arthritic-related metal bioavailability was assessed by the affinity adsorption with liposomes. The results indicated that compatibility proportion of corresponding herbal plants, gastrointestinal digestion and microbial metabolic, which could affect metal digestion and absorption. The optimal compatibility proportion of 1 A∶1 B is recommended, according to the dose of anti-arthritic-related metal bioavailability, which is often chosen for clinical practice of RA therapy. Thus, anti-arthritic-related metal bioavailability might be the key active substances for RA treatment.

Thermal discharge influences the bioaccumulation and bioavailability of metals in oysters: Implications of ocean warming.

Human-induced temperature changes influence coastal regions, both via thermal pollution and ocean warming, which exerts profound effects on the chemistry of metals and the physiology of organisms. However, it remains unknown whether the increased temperature of discharged water or ocean warming, as a result of climate change, lead to an increase of human health risks associated with the consumption of sea foods. In this study, the influence of temperature on metal accumulation by oysters was studied in individuals collected from a coastal area affected by the thermal water discharge of the Houshi Power Plant, China. The bioaccumulation factor (BAF) and oral bioavailability (OBA) of metals in oysters was determined. Elevated temperatures led to an increase in BAF for Cu, Zn, Hg, and Cd (p < 0.05), but no change was observed for As and Pb (p > 0.05). The OBA for Cd, As, and Pb correlated positively to elevated temperatures (p < 0.05). However, for Cu and Zn, OBA was negatively correlated with increasing temperature (p < 0.05). As, Pb, and Cd in the trophically available metal (defined as a sum of heat-stable proteins, heat-denaturable proteins, and organelles) was significantly elevated at the highest temperature seawater site (site A) compared to the lowest seawater site (site B). Thus, the irregular variation of OBA for each metal may be the result of variations in the subcellular distribution of metals and the protein quality influenced by the increased temperature. Moreover, the increased temperature and increased the hazard quotient values of As and Cd (p < 0.05 for As, n = 6, p < 0.05 for Cd, n = 6), which provided an indication of the potential risks of the consumption of oysters or other seafood to future warming under climate change scenarios.

Regulated effects of Prorocentrum donghaiense Lu exudate on nickel bioavailability when cultured with different nitrogen sources.

Exudates by marine phytoplankton and metals coexist in the seawater, but little is known about their interaction. In this study, cultures of Prorocentrum donghaiense Lu were grown in urea and ammonium, and then exposed to different Ni ion levels in order to study the effects of Ni ions on algal growth. The regulatory mechanisms of P. donghaiense Lu for coping with different Ni ion levels was investigating by characterizing dissolved organic carbon (DOC), carbohydrate and protein content released per cell, hydropathy properties (hydrophilic and hydrophobic fractions) and thiol compounds (cysteine-like or glutathione-like). Lower levels of Ni ions (pNi>10.0) significantly promoted the growth of P. donghaiense Lu when incubated in urea; however, the same was not true for P. donghaiense Lu cultivated in ammonium. An increased presence of hydrophobic fractions and thiol compounds (cysteine-like or glutathione-like compounds) induced by low Ni ions (pNi>10.0) in urea cultures suggest that the activation of cellular mechanisms in response to insufficient Ni ion stress enhances Ni bioavailability. Furthermore, the abundance of carbohydrates and proteins released by cells when exposed to higher Ni ions levels (from pNi = 10.0 to pNi = 8.0) both in urea and ammonium cultures suggests that algal cells may utilize exudate to complex Ni cations and reduce their toxicity. Therefore, it can be speculated that phytoplankton can produce large amounts of specific exudate, which may accelerate the metal bioavailability (insufficient levels) and reduce metal toxicity (excess levels) to maintain an equilibrium with metals in the environment.

The influence of urea and nitrate nutrients on the bioavailability and toxicity of nickel to Prorocentrum donghaiense (Dinophyta) and Skeletonema costatum (Bacillariophyta).

Nitrogen nutrients and nickel(Ni) are ubiquitous in aquatic environments, and they are important for primary production of ocean ecosystem. This study examined the interaction of nitrogen nutrients (specifically urea and nitrate) and Ni on chlorophyll (Chl a) concentration and photosynthesis parameters values of Prorocentrum donghaiense and Skeletonema costatum. The data presented here indicate that low concentration of Ni for P. donghaiense and S. costatum can enhance both Chl a concentration and photosynthesis parameters values when grown in urea containing environment. Despite this increase there was also an observed depression in both species tested when incubated in high concentration of Ni for P. donghaiense and S. costatum regardless of incubating in urea or nitrate. Additionally, EC50 values of Chl a and Fv/Fm for Ni at different time intervals were calculated in this study. These observations indicated that the Ni tolerance was higher in P. donghaiense as compared to S. costatum. The Ni tolerance of P. donghaiense incubated in urea was higher than that incubating in nitrate. The same phenomenon was not observed in S. costatum, which indicated that the influence of urea was dependent on the species investigated. Thus, urea input could impact Ni bioavailability and toxicity, and then affect the biodynamics thereafter.

Influence of acidification and eutrophication on physiological functions of Conticribra weissflogii and Prorocentrum donghaiense.

Eutrophication and acidification have been the most concerned environmental problems in coastal ecosystem. However, their combined effect on coastal ecosystem function was unknown. Both diatom (Conticribra weissflogii) and dinoflagellate (Prorocentrum donghaiense) are used as coastal algal model. Seven parameters were determined for physiological function assessment, including cell density, chlorophyll a (Chl a), protein, malonaldehyde (MDA), superoxide dismutase, carbonic anhydrase (CA), and nitrate reductase (NR). The influence of nitrate (N) and phosphate (P) on MDA and CA in C. weissflogii was significant, and that on Chl a and protein in P. donghaiense were also significant. However, the influence of acidification on physiological functions was not significant. The effect of acidification could be intensified by coastal eutrophication. More importantly, the coexist influence of acidification and eutrophication on CA, NR and protein in C. weissflogii and MDA in P. donghaiense was significant. Both NR activity and Chl a content in P. donghaiense were positively correlated to N and P concentration when pH were 7.9 and 7.8, respectively. With simultaneous worsening of acidification and eutrophication, the cell growth of P. Donghaiense was accelerated more obviously than C. weissflogii, i.e., dinoflagellate was more adaptable than diatom, thus algal species distribution and abundance could be changed.

Effect of excessive CO2 on physiological functions in coastal diatom.

Rising dissolution of anthropogenic CO2 in seawater may directly/indirectly cause ocean acidification and desalination. However, little is known about coastal physiological functions sensitivity to these processes. Here we show some links between ocean acidification/desalination and physiological functions in Thalassiosira weissflogii. Cell density (CD), protein, chlorophyll a (Chl a), malonaldehyde (MDA), superoxide dismutase (SOD), and carbonic anhydrase (CAs) were determined for the assessment of algal biomass, nutritional value, photosynthesis and respiration, lipid peroxidation, antioxidant capacity, and carbon sequestration ability. The influence of pH on the algal Chl a and MDA were extremely significant (P < 0.01). Salinity (S) on cell density and acidity (pH) on protein was significant (0.01 < P < 0.05). Additionally, a significant negative-correlation was observed between cell density and CAs. CAs and SOD had negatively correlations with CD, Chl a, protein, and MDA under pH or S influence, but positive correlation between themselves. Coastal physiological functions were affected by increasing order was acidification < acidification + desalination < desalination for Chl a and protein, desalination < acidification + desalination < acidification for SOD and CAs. Thus, the ongoing excessive CO2-driven ocean acidification and desalination should be of high attention when assessing the risks of climate change on coastal phytoplankton.

Effect of nitrate enrichment and diatoms on the bioavailability of Fe(III) oxyhydroxide colloids in seawater.

The photoconversion of colloidal iron oxyhydroxides was a significant source of bioavailable iron in coastal systems. Diatoms dominate phytoplankton communities in coastal and upwelling regions. Diatoms are often exposed to eutrophication. We investigated the effects of different species of diatom, cell density, illumination period, and nitrate additions on the bioavailability of Fe(III) oxy-hydroxide colloids in seawaters. With the increase of illumination period from 1 to 4 h, the ratios of concentrations of total dissolved Fe (DFe) to colloidal iron oxyhydroxides and Fe(II) to DFe increased up to 24.3% and 23.9% for seawater without coastal diatoms, 45.6% and 30.2% for Skeletonema costatum, 44.3% and 29.7% for Thalassiosira weissflogii, respectively. The photochemical activity of coastal diatoms themselves (excluding the dissolved organic matter secreted by algae) on the species transformation of iron in seawater (including the light-induced dissolution of Fe(III) oxyhydroxide colloids and the photo-reduction of Fe(III) into Fe(II)) was confirmed for the first time. There was no significant difference of the ability of S. costatum and Thalassiosira weissflogii on the photoconversion of colloidal iron oxyhydroxides. The photoproduction of dissolved Fe(II) and DFe in the seawater with or without diatoms could be depressed by the nitrate addition.

[Application of in vitro bionic digestion and biomembrane extraction for metal speciation analysis, bioavailability and risk assessment in lianhua qingwen capsule].

One of the causes of the high cost of pharmaceuticals and the major obstacles to rapidly assessing the bioavailability and risk of a chemical is the lack of experimental model systems. A new pre-treatment technology, in vitro bionic digestion was designed for metal analysis in Lianhua Qingwen capsule. The capsule was digested on 37 degrees C under the acidity of the stomach or intestine, and with the inorganic and organic compounds (including digestive enzymes) found in the stomach or intestine, and then the chyme was obtained. Being similar to the biomembrane between the gastrointestinal tract and blood vessels, monolayer liposome was used as biomembrane model Affinity-monolayer liposome metals (AMLMs) and water-soluble metals were used for metal speciation analysis in the capsule. Based on the concentration of AMLMs, the main absorption site of trace metals was proposed. The metal total contents or the concentration of AMLMs in the capsule were compared to the nutritional requirements, daily permissible dose and heavy metal total contents from the "import and export of medicinal plants and preparation of green industry state standards". The metal concentrations in the capsule were within the safety baseline levels for human consumption. After in vitro bionic digestion, most of trace metals were absorbed mainly in intestine. The concentration of As, Cd, Pb was 0.38, 0.07, 1.60 mg x kg(-1), respectively, far less than the permissible dose from the "import and export of medicinal plants and preparation of green industry state standards".

Influence of eutrophication on metal bioaccumulation and oral bioavailability in oysters, Crassostrea angulata.

Oysters (Crassostrea angulata) are often exposed to eutrophication. However, how these exposures influence metal bioaccumulation and oral bioavailability (OBA) in oysters is unknown. After a four month field experimental cultivation, bioaccumulation factors (BAF) of metals (Fe, Cu, As, Cd, and Pb) from seawater to oysters and metal oral bioavailability in oysters by bionic gastrointestinal tract were determined. A positive effect of macronutrient (nitrate N and total P) concentration in seawater on BAF of Cd in oysters was observed, but such an effect was not significant for Fe, Cu, Pb, and As. Only OBA of As was significantly positively correlated to N and P contents. For Fe, OBA was negatively correlated with N. The regular variation of the OBA of Fe and As may be due to the effect of eutrophication on the synthesis of metal granules and heat-stable protein in oysters, respectively.

Constituting fully integrated visual analysis system for Cu(II) on TiO2/cellulose paper.

As a cheap and abundant porous material, cellulose filter paper was used to immobilize nano-TiO2 and denoted as TiO2/cellulose paper (TCP). With high adsorption capacity for Cu(II) (more than 1.65 mg), TCP was used as an adsorbent, photocatalyst, and colorimetric sensor at the same time. Under the optimum adsorption conditions, i.e., pH 6.5 and 25 °C, the adsorption ratio of Cu(II) was higher than 96.1%. Humic substances from the matrix could be enriched onto TCP but the interference of their colors on colorimetric detection could be eliminated by the photodegradation. In the presence of hydroxylamine, neocuproine, as a selective indicator, was added onto TCP, and a visual color change from white to orange was generated. The concentration of Cu(II) was quantified by the color intensity images using image processing software. This fully integrated visual analysis system was successfully applied for the detection of Cu(II) in 10.0 L of drinking water and seawater with a preconcentration factor of 10(4). The log-linear calibration curve for Cu(II) was in the range of 0.5-50.0 µg L(-1) with a determination coefficient (R(2)) of 0.985 and its detection limit was 0.073 µg L(-1).

Influence of gastrointestinal digestion and edible plant combination on oral bioavailability of triterpene saponins, using a biomimetic digestion and absorption system and determination by HPLC.

Saponins have many biological activities, but their overload could cause toxicity to the human body. Bionic gastrointestinal digestion and monolayer liposome extraction were used for oral bioavailability assessment of triterpene saponins (notoginsenoside R1, ginsenosides Rb1 and Rd1) in an edible herb (San-Chi) and its compound herbal medicine (Pien Tze Huang, PZH). The concentrations of affinity-monolayer liposome saponins in the chyme were determined by HPLC and used for oral bioavailability assessment. With the digestion of San-Chi and PZH from the stomach to the intestine, the release of saponins in their chyme was increased. The intestinal absorption ratios of N-R1, G-Rb1, G-Rd1, and total saponins from San-Chi were 86.57, 18.56, 73.30, and 40.20%, respectively, which were more than those from PZH (i.e., 19.56, 10.11, 30.11, and 16.08%). The oral bioavailability of saponins was controlled by saponin species, gastrointestinal digestion, and edible plants combination.

Effects of nitrate addition and iron speciation on trace element transfer in coastal food webs under phosphate and iron enrichment.

Coastal organisms are often exposed to both iron enrichment and eutrophication. Trace elements transfer in coastal food webs are critical for marine life and therefore influence coastal ecosystem function and the global carbon cycle. However, how these exposures affect algal element uptake and the subsequent element transfer to marine copepods (Tigriopus japonicus) is unknown. Here we investigated the effects of nitrate addition and iron speciation (Fe (OH)3 or EDTA-Fe) on the biological uptake of Cu, Zn, and Se under phosphate and iron enrichment, using Thalassiosira weissflogii, Skeletonema costatum, and Chlorella vulgaris as model marine algae. Algal element adsorption/absorption generally increased with increasing macronutrient concentrations. Algal element assimilation efficiencies depended on iron speciation and marine algae species. Element assimilation efficiencies of copepods were significantly correlated to the intracellular element concentrations in algal cells. Element uptake and transfer were controlled by eutrophication, iron speciation, and algal species in coastal food webs.

Effect of the cp4-epsps gene on metal bioavailability in maize and soybean using bionic gastrointestinal tracts and ICP-MS determination.

The transformation and metabolism of dietary compounds are affected significantly by gut microbiota. Hence, gut microbiota are used to improve bionic gastrointestinal tracts. The effect of the cp4-epsps gene on metal bioavailability was proved by the comparison of the affinity-liposome metal content ratio (AMCR) in transgenic and conventional crops. The bioavailability of V, Mn, Co, Ga, Ag, Ba, and Pb in roundup ready soybean decreased significantly because the ratio of AMCR (R(AMCR)) in the transgenic crop and its corresponding conventional type ranged from 0.36 to 0.69. In roundup ready maize, metal bioavailability decreased for Li and Cr (i.e., R(AMCR) was 0.26 and 0.39, respectively) but increased for V, Co, and Pb (i.e., R(AMCR) was 1.48, 2.07, and 2.12, respectively). Compared with conventional crops, safe dosage and maximum consumption of roundup ready crops were 1.59 times for soybean and 0.78 times for maize.