EFFECT OF ORGANICS (AMINO ACIDS AND FULVIC ACID) ON THE INTERACTION BETWEEN Cu(II) AND CLAYS IN SEA WATER I. EFFECT OF pH

By the study of the effects of pH on the exchange ratio ( %) of Cu (II) with clay (illite) in the presence of different concentrations of amino acids and fulvic acid, a new model of the mechanism of the effect of organics has been presented in this paper.     

NATURE OF COPPER IN PARENT PRAWN HEPATOPANCREAS

Copper content in the hepatopancreas of wild parent Panaeus orientals was more than 500 ug/g(wet wt), among which over 90% distributed in the cytosol. 99% of the Cu in the subcellular fraction distributed in a very low molecular weight (VLMW )pool.DE-11 anion exchange chromatography of the VLMW material indicated that about 83% of the Cu in the pool could not be absorbed in the exchanger. Some main compounds containing copper (accounting for 77% of the Cu in the cytosol )were isolated from the cytosol fraction using a CM-32 cation exchange column. Amino acid analysis of the compounds showed that histidine was a major component, accounting for 58.2% of the total amino acids in the compounds, and that the contents of lysine and serine were also higher (9.6% and 7.6%, respectively), indicating that Cu in the material isolated by CM-32 perhaps mainly existed as a histidine-Cu complex, and that some of it could have complexed with serine, glysine and/or their peptides.     

THE INTRINSIC ACIDITY CONSTANTS AND SPECIFIC SURFACE AREA OF MARINE SOLID PARTICLESII. THE RELATIONSHIP BETWEEN THE INTRINSIC ACIDITY CONSTANT AND THE TERNARY SURFACE COMPLEX

This paper deals with the infrared spectra of " amino acid- clay , calcium carbonate and y-AlOOH" and " Cu (II )-clay-amino acid" model systems, and shows that the model of the ternary surface complex is M-OHLCu (L = amino acid) for marine solid particle-Cu (II)-amino acid. Study of the formation mechanism of the ternary surface complex shows that the specific surface area , and especially the intrinsic acidity constant, determine whether the ternary surface complex is easily formed, and that factor, FTSC,quantifies the relationship between the promoting effect of organics on Mt-marine solid particle ion exchange and the intrinsic acidity constant and specific surface area.     

THE EFFECT OF AMINO ACIDS ON COPPER (Ⅱ)-GOETHITE ION EXCHANGE IN SEAWATER

In seawater, aside from metal elements and suspended particles, organic substances amount to about 500-2,000 ug carbon/1[8], which is not neglegible in comparison with that of minor metal elements. But in the study of the interaction of the three constituents (metal elements, organics, and suspended particles), theeffect of organics in seawater on the surface reaction of metal element--suspended particles has usuallybeen neglected. Recent theoretical research[1,11] confirmed the importance of the effect of organics inseawater on the surface reaction of metal element--suspended particles. Generally, the effect of organicson the reaction of metal ions, especially Cu(II), on a solid surface is either promotive[2] or inhibitive[7,9]. So far the fact that organics cannot affect the surface reaction of Cu(II) ions on solids has not been reported in literature. Our experimental results showed that none of the amino acids in seawater affect Cu(II)-goethite ion exchange under certain experimental condition (such     

Comparison in nutritional quality between wild and cultured cuttlefish Sepia pharaonis

In this study, the proximate composition and the amino and fatty acid profi les of shrimp Litopenaeus vannamei(prey) and wild and cultured cuttlefi sh Sepia pharaonis(the latter fed the prey) were determined and compared with FAO/WHO recommendations. The resulting scores for isoleucine, phenylalanine+tyrosine, histidine, lysine, threonine, and tryptophan in cultured cuttlefi sh were ≥150. The ratio of EAA(essential amino acids)/nonessential amino acids in cultured cuttlefi sh(0.82) was higher than in the wild form(0.80). All EAA amino acid scores for cultured cuttlefi sh were higher than their wild counterparts, except for histidine and tryptophan. Both groups of cuttlefi sh possessed similar saturated fatty acid content, with the cultured containing much more total(Σ) monounsaturated fatty acids, Σ n-6 polyunsaturated fatty acids(PUFA), and eicosapentaenoic acid(C20:5 n-3) but less Σ n-3 PUFA, arachidonic acid(C20:4 n-6), and docosahexaenoic acid(C22:6 n-3) than their wild counterparts. Therefore, the present results suggest that these cultured cuttlefi sh were better than the wild form for human health. Notably, these results also indicate that the nutritional composition of these cuttlefi sh might have been signifi cantly affected by diet.     

A NEW TYPE OF ISOTHERM FOR ZINC LIQUID-SOLID PARTITIONING ON δ-MnO_2,γ-MnOOH AND MANGANIIE IN SEAWATER

This article deals with the interaction of zinc with δ-MnO2,γ-MnOOH and manganite existing in natural water systems. The mechanism of the reaction has been studied in detail. From the fact that the "ratio of ion exchange (%)-pH" graph is an "S shaped" curve, it is possible to deduce that the chemical reaction is of the nature of cation exchange. And since the pH range of ion exchange = 4, it is possible to further deduce that the reaction can be explained by the mechanism of monovalence cation exchange.The main result of this article is the discovery of a new type of isotherm which has not been mentioned in previous literature here and abroad. This isotherm cannot be represented by any presently available adsorption isotherm equations in marine chemistry. The characteristics of this new type of isotherm are as follows: the isotherm has two "knees" and three "plateaus", the heights of these three "plateaus" are in the ratio 1:2:3. In order to explain theoretically our new isotherm, this article suggest     

Effect of growth phase on the fatty acid compositions of four species of marine diatoms

The fatty acid compositions of four species of marine diatoms (Chaetoceros gracilis MACC/B13, Cylindrotheca fusiformis MACC/B211, Phaeodactylum tricornutum MACC/B221 and Nitzschia closterium MACC/B222), cultivated at 22 ℃±1 ℃ with the salinity of 28 in f/2 medium and harvested in the exponential growth phase, the early stationary phase and the late stationary phase, were determined. The results showed that growth phase has significant effect on most fatty acid contents in the four species of marine diatoms. The proportions of 16:0 and 16: 1n-7 fatty acids increased while those of 16 :3n-4 and eicosapentaenoic acid (EPA) decreased with increasing culture age in all species studied. The subtotal of saturated fatty acids (SFA) increased with the increasing culture age in all species with the exception of B13. The subtotal of monounsaturated fatty acids (MUFA) increased while that of polyunsaturated fatty acids (PUFA) decreased with culture age in the four species of marine diatoms. MUFA reached their lowest value in the exponential growth phase, whereas PUFA reached their highest value in the same phase.     

FOURIER-TRANSFORM INFRARED SPECTROSCOPIC STUDIES ON THE INTERACTION AMONG MARINE TRACE METAL IONS , SOLID PARTICLES AND ORGANICS Ⅱ. THE STEP WISE CHANGE IN THE SURFACE HYDROXYL GROUPS

IR spectra of Cu (Ⅱ)-marine solid particle systems show that Cu (Ⅱ)-marine solid particle ion exchange causes a stepwise change in the surface H-bonding hydroxyl groups on illite . montmorillonite, CaCO3,r. AlOOH and goethite, but that this does not affect the surface free hydroxyl groups on illite. montmorillonite and CaCO3. and framework hydroxyl group on goethite and on γ- AlOOH . Over the range of Cu(Ⅱ) exchange amounts in the present experiment, four stepwise changes were discovered for the surface H- bonding hydroxyl group on illite. while two stepwise changes were observed on the other marine solids. The interfacial stepwise ion exchange theory was first demonstrated by the above experimental evidence .     

PLATEAU TYPE E(%)-pH CURVES OF INTERFACIAL EXCHANGE BETWEEN LIQUID AND SOLID IN SEAWATER

A study on the curves of the exchange ratio E(%)-pH on the liquid-solid interface of the systems Zn(II) with clay minerals (Kaolinite , illite and montmorillonite), Zn(II) with hydrous ferric oxides (amorphous ferric oxide, goethite and hematite). Zn(II) with hydrous manganese oxide (y-MnOOH, manganite and 5-MnO2) etc . in seawater resulted in the discovery of new plateau type exchange ratio ?%)-pH curves not yet reported in literature. The two factors that decide the growth , decline and the change of the " plateau type " curve are : (1) the inherent characteristics of systems , which can be explained by the exchange constants i(i=1 ,2 , 3 . etc .) of interfacial stepwise ion / coordination particle exchange between liquid and solid ; and (2)The theory of interfacial stepwise ion/coordination(the amount of solid exchange reagent)particle exchange in seawater was applied to explain the experimental results of the above study and a general formula was derived for the plateau type exchange ratio E(%)-pH c     

DETERMINATION OF AMINO ACIDS IN TWO POLYSIPHONIA SPECIES AND STUDY OF ENZYMATIC HYDROLYSIS METHOD

The total content ot the nch amino acids in two common red algae, Potystpnoma urceolata and Polysiphonia japonica growing in the Qingdao seashore were determined. The algae powder was hydrolyzed by 6 mol/L HC1 at 110℃ for 48 h and determined by amino acid analyzer. The content was 25.35% and 24.16% , respectively, much higher than that of some other species. In addition, a nutritive liquid with abundant amino acids was prepared (by the enzymatic hydrolysis method using Polysiphonia urceolata ) as raw material for a kind of health beverage. The dried seaweed was decolored by 0.25% KMnO4 and 0.5% active carbon, then enzymalized. In the selection of enzymalizing condition, the orthogonal experimental design was used. Four factors including kinds of enzyme, quantity of enzyme, temperature and time were studied at 3 levels. According to the orthogonal design results, we can choose an optimal condition: hydrolyzing at 45℃ by neutral proteinase (0.25% , w/w) for 2 h, adjusting pH to 8.5, then adding trypsin (0.25% , w/w) and hydrolyzing for 2 h. Finally the above solution was alkalized by NaOH and neutralized by casein. After the hydrolyzed liquid was filtered and concentrated, suitable additives were added. The final products contain rich amino acids.     

SYNTHESIS AND PROPERTIES OF SULFHYDRYL CHITOSAN

A new adsorbent for heavy metal ions, sulfhydryl chitosan (S-chitosan), was produced by treatment of chitosan with sulhydryl acetic acid in the presence of sulfuric acid as a catalyst. Its structure was confrrmed by elemental analysis and FI‘-IR spectra analysis. The adsorption properties of sulthydryl chitosan for Cu(Ⅱ ), Cd(Ⅱ ), Pb(Ⅱ), Cr(Ⅲ) and Ni(Ⅱ) were investigated, and the effect of pH value on adsorption, adsorption kinetics, and selective adsorption was examined. It was shown that S-chitosan has good adsorption for Pb(Ⅱ), Cu(Ⅱ) and Cd(Ⅱ) like chitosan, is also insoluble in acid solution; has good adsorption kinetic properties for heavy metal ions; and can be used in acid solution. The adsorption capacities of S-chitosan can be affected by media acidity. The adsorbed Cu(Ⅱ) Cd(Ⅱ) and Pb(Ⅱ) could be eluted by diluted chlorhydric acid.     

Biochemical Composition and Nutritional Value of Different Shell Color Strains of Pacific Oyster Crassostrea gigas

The shell color of Pacific oyster(Crassostrea gigas) is a desirable trait; but the nutritional studies on C. gigas with different shell colors have not been conducted. Through successive selective breeding, five shell color strains of black(B), purple(P), orange(O), golden(G) and white(W) C. gigas have been developed. The aim of this study was to evaluate the chemical composition and nutritional value of five shell color strains and one commercial population with a common color. The biochemical composition including moisture, total protein, glycogen, ash, total fat, fatty acids(FA), amino acids and minerals was detected. The results indicated that the protein(50.76%–56.57%) was the major component. The content of glycogen showed a significant difference between orange shell and golden shell strains, as well as between commercial population and golden shell strain. In addition, all shell color strains contained a large amount of essential amino acids(12.20–14.15 g(100 g)~(-1)), of them leucine(2.81–3.29 g(100 g)~(-1)) and lysine(2.79–3.28 g(100 g)~(-1)) were predominant. The oysters were rich in polyunsaturated fatty acids(42.26%–45.24% of total fatty acid) with high levels of DHA(18.53%–21.16% of total fatty acid) and EPA(17.23%–18.68% of total fatty acid). Significant differences of mineral contents(Mg, Zn, Fe and Cu) were identified among the six populations. These results indicated that C. gigas with different shell colors presented rich nutritional value with high protein, glycogen, essential amino acids and polyunsaturated fatty acids. The biochemical composition obtained in this study is useful for selective breeding of C. gigas with different shell colors.     

Comparison of Nutritional Quality in Fish Maw Product of Croaker Protonibea diacanthus and Perch Lates niloticus

Fish maw(the dried swimbladders of fish) is ranked in the list of the four sea treasures in Chinese cuisine. Fish maw is mainly produced from croaker, which is the most highly priced. However, some of the fish maw being sold as croaker maw are in fact not from croaker, but from the Nile perch Lates niloticus. The present work determined and compared the proximate composition, amino acid and fatty acid composition of croaker Protonibea diacanthus maw and perch L. niloticus maw. The results indicated that both maws were high protein sources and low in fat content. The dominant amino acids in both maws were glycine, proline, glutamic acid, alanine and arginine. These amino acids constituted 66.2% and 66.4% of the total amino acids in P. diacanthus and L. niloticus, respectively. The ratio of FAA: TAA(functional amino acids: total amino acids) in both maws were 0.69. This is a good explanation for why fish maws have been widely utilized as a traditional tonic and remedy in Asia. Except valine and histidine, all the essential amino acid contents in P. diacanthus were higher than in L. niloticus. Moreover, croaker P. diacanthus maw contained more AA and DHA than perch L. niloticus maw, showing a higher ratio of n-3 / n-6, which is more desirable.     

Identification of a Long-Chain Fatty Acid Elongase from Nannochloropsis sp. Involved in the Biosynthesis of Fatty Acids by Heterologous Expression in Saccharomyces cerevisiae

The marine microalga Nannochloropsis sp. contains various elongases and desaturases that are critical for biosynthesis of polyunsaturated fatty acids. A full-length cDNA encoding a long-chain fatty acid elongase, named Ns FAE, was cloned from Nannochloropsis sp.. The open reading frame of Ns FAE(GenBank accession no. MF680548) consisted of 1068 bp and encoded a predicted protein of 355 amino acids with molecular mass 38.8 k Da. The deduced polypeptide showed 43%–44% identity to fatty acyl elongases from other algae. RT-PCR experiments indicated that the Ns FAE gene exhibited the highest expression in Nannochloropsis sp. at 72 h(i.e., during the third growth stage) and the expression was significantly lower in the other four growth stages. Plasmid p Ns FAE-CRISPR and a recombinant DNA fragment(ADH1p-Ns FAE-CYCt) were transformed into Saccharomyces cerevisiae strain BY4742 using the CRISPR-Cas system. Yeast transformants containing Ns FAE produced three fatty acids not normally present in wild-type BY4742-linoleic acid, linolenic acid and eicosadienoic acid-indicating that Ns FAE encodes a functional elongase enzyme.     

Biochemical composition of the alligator pipefish,Syngnathoides biaculeatus(Bloch, 1785)

Considering the economic importance in traditional Chinese medicine(TCM) and lack of baseline information, we evaluated the proximate composition, fatty acid and amino acid profiles, trace element content and C:N ratio in the alligator pipefish, Syngnathoides biaculeatus. Amongst proximate principals, a crude protein formed the major biochemical component((58.9±2.2)% dry weight). Mean percent concentrations(dry weight) of other components such as a total lipid(TL), ash and nitrogen-free extract measured were,(1.8±0.2)%,(19.2±2.2)% and(20.1±0.45)%, respectively. The fatty acid profile revealed the presence of 27 saturated fatty acids(SFA) with 13 straight-chained and 14 branched-chained, 28 unsaturated fatty acids(UFA) with 14 monounsaturated and 14 polyunsaturated and nine other minor fatty acids. Mean percent contributions of total SFAs and UFAs to TL were found to be(55.41±0.24)% and(44.05±0.25)%, respectively. Altogether, 16 dif ferent amino acids with an equal number of essential(EAA) and non-essential(NAA) ones were identified. Percent contributions by EAA and NAA to the total amino acid content were 38.11% and 61.89%, respectively. Trace metal concentrations in S. biaculeatus were generally low and their distribution followed the order, MgFeZnMnCuCrNiHgCo. The C:N ratio was(4.37±0.04)%. The profile of major biochemical constituents in alligator pipefish, S. biaculeatus revealed its potential use in TCM as well as a nutritional diet for human consumption. The results of the study would also form the basis for formulation and optimization of diets for the culture of S. biaculeatus.     

Metabolomic Fingerprint of the Model Ciliate,Tetrahymena thermophila Determined by Untargeted Profiling Using Gas Chromatography-Mass Spectrometry

The ciliate Tetrahymena is a valuable model organism in the studies of ecotoxicology. Changes in intracellular metabolism are caused by exogenous chemicals in the environment. Intracellular metabolite changes signify toxic effects and can be monitored by metabolomics analysis. In this work, a protocol for the GC-MS-based metabolomic analysis of Tetrahymena was established. Different extraction solvents showed divergent effects on the metabolomic analysis of Tetrahymena thermophila. The peak intensity of metabolites detected in the samples of extraction solvent Formula 1(F1) was the strongest and stable, while 61 metabolites were identified. Formula 1 showed an excellent extraction performance for carbohydrates. In the samples of extraction solvent Formula 2(F2), 66 metabolites were characterized, and fatty acid metabolites were extracted. Meanwhile, 57 and 58 metabolites were characterized in the extraction with Formula 3(F3) and Formula 4(F4), respectively. However, the peak intensity of the metabolites was low, and the metabolites were unstable. These results indicated that different extraction solvents substantially affected the detected coverage and peak intensity of intracellular metabolites. A total of 74 metabolites(19 amino acids, 11 organic acids, 2 inorganic acids, 11 fatty acids, 11 carbohydrates, 3 glycosides, 4 alcohols, 6 amines, and 7 other compounds) were identified in all experimental groups. Among these metabolites, amino acids, glycerol, myoinositol, and unsaturated fatty acids may become potential biomarkers of metabolite set enrichment analysis for detecting the ability of T. thermophila against environmental stresses.     

Effect of Long-Term Low-Salinity Culture on the Survival,Growth, and Nutrient Composition of Mud Crab Scylla paramamosain

This study investigated the effects of long-term low-salinity on the growth performance,proximate composition,amino acid and fatty acid profiles of Scylla paramamosain.The salinity of the low-salinity-culture group(LC)and maintained-salinity-cul-ture group(MC)were set at 5 and 25 respectively.After rearing for 30 d,the survival rate(SR)of the LC group was significantly lower,whereas the average daily molting frequency(ADMF)was significantly higher than those in MC group(P<0.05).There were no significant difference for weight gain rate(WGR)and specific growth rate(SGR)between the two groups.The moisture content of the LC group was slightly higher than the MC group without significant difference.The contents of ash,crude lipid and crude pro-tein in the LC group were lower than those in the MC group,but no significant differences were found except for ash content.A total of 17 free amino acids and 23 fatty acids were identified from the muscle of S.paramamosain.The total amino acids(TAA),essen-tial amino acids(EAA)and essential amino acid index(EAAI)had no significant difference between the two groups.The crabs from LC group had a significantly higher HUFA,including EPA,DHA,ARA.The percentage of n-3 PUFA and the ratio of n-3/n-6 PUFA were significantly higher in the LC group.These results indicated that S.paramamosain rearing at low salinity had significantly de-creased SR;however,the low-salinity environment significantly promoted the accumulation of unsaturated fatty acids(UFAs),espe-cially the n-3 PUFA,which might be related to the osmoregulation mechanism.     

Construction and characterization of a normalized cDNA library of Nannochloropsis oculata(Eustigmatophyceae)

We constructed and characterized a normalized cDNA library of Nannochloropsis oculata CS-179,and obtained 905 nonredundant sequences(NRSs) ranging from 431-1 756 bp in length.Among them,496 were very similar to nonredundant ones in the GenBank(E ≤1.0e-05),and 349 ESTs had significant hits with the clusters of eukaryotic orthologous groups(KOG).Bases G and/or C at the third position of codons of 14 amino acid residues suggested a strong bias in the conserved domain of 362 NRSs(60%).We also identified the unigenes encoding phosphorus and nitrogen transporters,suggesting that N.oculata could efficiently transport and metabolize phosphorus and nitrogen,and recognized the unigenes that involved in biosynthesis and storage of both fatty acids and polyunsaturated fatty acids(PUFAs),which will facilitate the demonstration of eicosapentaenoic acid(EPA) biosynthesis pathway of N.oculata.In comparison with the original cDNA library,the normalized library significantly increased the efficiencies of random sequencing and rarely expressed genes discovering,and decreased the frequency of abundant gene sequences.     

Role of organic acids in desorption of mercury from contaminated soils in eastern Shandong Province, China

Batch experiments were conducted to study the effects of low-molecular-weight organic acids(LMWOAs) on desorption of Hg from two kinds of soils in the eastern Shandong Province,China.Of all LMWOAs,oxalic and citric acids were chosen as the representatives in this experiment because they are most common in soils.Desorption of Hg increases with the increase of extracting time,until the highest desorption amount at 6-8 h,and then declines.It indicates that timeliness is very important when organic acids are used for phytoremediation in contaminated soils.When the concentrations of organic acids increase from 1.0 mmol/L to 10.0 mmol/L,Hg desorption increases significantly regardless of oxalic or citric acid.Compared with oxalic acid,citric acid is more effective to enhance the desorption of Hg,especially from fluvo-aquic soil.With the increase of initial pH value from 3 to 8,Hg desorption decreases directly in the presence of oxalic acid.However,Hg desorption first decreases,then increases,and eventually decreases again in the presence of citric acid due to the variation of competitive ability between chelating of citric acid and adsorption of soil in different pH values.Citric acid showed greater ability to release Hg from soils than oxalic acid.According to the results of the present study,it is found that the bioavailabilities of heavy metal can be improved with selecting suitable types and concentrations of organic acid amendment and reasonable soil condition.