A Kinetic Spectrophotometric Method for the Determination of Iron (Ⅲ) in Water Samples

A new kinetic spectrophotometric method has been developed for the determination of iron (Ⅲ). The method is based on the catalytic effect of iron (Ⅲ) on the oxidation of weak acid brilliant blue dye (RAWL) by KIO4 in acid medium. The advantages of the proposed method are that it is sensitive, accurate, rapid, inexpensive, can be operated under room temperature and has a large determination concentration range compared to other techniques. The obtained optimum conditions are: pH 3.15, RAWL (200 mgL-1) 5.00mL, Potassium periodate solution (0.01 molL-1) 0.30mL, phenanthroline (0.02molL-1) 1.00mL, reaction temperature 25℃ and reaction time 7 miu. With this method iron could quantitively be determined in the range 0.00-0.02 mgL-1, the detection limit being 4.10×10-10mL-1. The relative standard deviations (RSD) in five replicate determinations for 3 μgL-1 and 5μgL-1 iron (Ⅲ) are 3.1% and 1.9%, respectively. The method has been applied to the determination of iron (Ⅲ) in tap water samples and seawater samples (from the South China Sea), the recovery rates being 98.0% and 100.5%, respectively.     

Determination of Trace Vanadium (Ⅴ) in Seawater and Fresh Water by the Catalytic Kinetic Spectrophotometric Method

A new kinetic spectrophotometric method has been developed for the determination of vanadium (Ⅴ).The method is based on the catalytic effect of vanadium (Ⅴ) on the oxidation of weak acid brilliant blue dye (RAWL) by KBrO3 using the citric acid as activation reagent.The obtained optimum conditions are:c (RAWL)=1×10-4 molL-1, c (KBrO3)=3×10-2 molL-1, c (citric acid)= 9×10-3 molL-1, pH=2.50, the reaction time being 7.0 min and the temperature being 25.0℃.Under the optimum conditions, the pro-posed method allows the determination of vanadium (Ⅴ) in the range of 0?70.0 ng mL-1 and the detection limit is down to 0.407 ng mL-1.For standard vanadium (Ⅴ) solution determination, the recovery efficiency is in the range of 98.5%?102% and the RSD ranges from 0.76%?1.25%.Moreover, it is demonstrated that most cations and anions do not interfere with the determination of vanadium (Ⅴ) under the analytical condition.The new method was successfully applied in the determination of vanadium (Ⅴ) in fresh water and seawater samples with satisfactory results.Vanadium (Ⅴ) in the seawater samples from Qingdao offshore was determined using the method and the distribution of vanadium (Ⅴ) was mapped.Compared with other instrumental analytical methods, the proposed method shows good selectivity, sensitivity, simplicity, lower cost and rapidity.It can be employed on shipboard easily.     

Determination of Trace Copper （Ⅱ） in Water Samples by Kinetic-spectrophotometry

A new kinetic-spectrophotometric method is proposed for the determination of copper （ Ⅱ ）. The method is based on the catalytic effect of copper （ Ⅱ ） on the oxidation of weak acid brilliant blue dye （RAWL） by hydrogen peroxide. The copper （ Ⅱ ） can be determined spectrophotometrically by measuring the decrease of absorbance of RAWL at λ = 626 nm using the fix-time method. The optimum reaction conditions are as follows： pH 7.20, buffer solution NaOH-KH2PO4, RAWL （200 mgL-1） 5.00 mL, H2O2 （30%） 0.50 mL, reaction temperature 80 ？？ and reaction time 20 min. The linear range of this method is between 0 μg L^-1 and 12 μg L^-1 and the limit of detection is 0.011 μg L-1, the relative standard deviation （RSD） in five replicate determinations for 2 and 8 μg L-1 copper （ Ⅱ ） are 3.2% and 2.3%, respectively. Twenty ions do not interfere in the determination of copper （ Ⅱ ）. The method has been applied satisfactorily to the determination of copper （ Ⅱ ） in freshwater samples （tap water and Yellow River water from Lijin, Shandong, China） and seawater samples （from the South China Sea）, the recovery rates are 98.0%, 102.5% and 96.0%, respectively.     

Measurement of Trace Manganese(Ⅱ) by the Catalytic Kinetic Spectrophotometric Method

A new kinetic spectrophotometric method is developed for the measurement of manganese (Ⅱ) in water. The method is based on the catalytic effect of manganese (Ⅱ) with the oxidation of weak acid brilliant blue dye (RAWL) by KIO4 using the Nitrilo triacetic acid (NTA) as an activation reagent. The optimum conditions obtained are 40mgL-1 RAWL, 1×10-4molL-1 KIO4, 2×10-4molL-1 Nitrilo triacetic acid (NTA), pH = 5.8, the reaction time of 3.00 min and the temperature of 20.0 ℃. Under the optimum con-ditions, the proposed method allows the measurement of manganese (Ⅱ) in a range of 0-50.0ngmL-1 and with a detection limit of down to 0.158 ng mL-1. The recovery efficiency in measuring the standard manganese (Ⅱ) solution is in a range of 98.5%-102%, and the RSD is in a range of 0.76%-1.25%. The new method has been successfully applied to the measurement of manganese (Ⅱ) in both fresh water and seawater samples with satisfying results. Moreover, few cations and anions interfere with the measurement of man-ganese (Ⅱ). Compared with other kinetic catalytic methods and instrumental methods, the proposed method shows fairly good selec-tivity and sensitivity, low cost, cheapness, low detection limit and rapidity. It can be applied on boats easily.     

Study on the Determination of Trace Ni（Ⅱ） by the Catalytic Kinetic Spectrophotometric Method

A new kinetic spectrophotometric method has been developed for the determination of trace Ni (II) in natural water.The method is based on the catalytic effect of Ni (II) on the oxidation of weak acid brilliant blue dye (RAWL) by KIO4 in acid medium.The concentration of nickel (II) can be determined spectrophotometrically by measuring the decrease of absorbance of RAWL at λ= 626 nm using the fix-time method.The influencing factors are investigated by the orthogonal experimental design.The obtained optimum analytical conditions are:pH=2.00,c RAWL=5.00×10-5 mol L-1,cKIO 4= 2.00×10-5 mol L-1,the reaction time t=10 min and the temperature T=25℃..Under the optimum conditions,the developed method allows the measurement of Ni (II) in a range of 0-40.0 ng mL-1.The standard deviation of eleven independent measurements of blank reaction is S=3.08×10-3 and the limit of detection is 2.20 ng mL-1.The relative standard deviations (RSDs) in six replicate determinations of 5 ng mL-1 and 8 ng mL-1 Ni (II) are 2.87% and 1.11%,respectively.Moreover,the experiments show few cations and anions can interfere with the measurement of Ni (II).The recovery efficiencies of this method are in a range of 97.0%-102.5% in freshwater samples.But there is a decreasing effect,which is about 0.2 times the added Ni (II) in seawater medium.After reasonable calibration this processing method is used for the determination of Ni (II) in seawater samples successfully.The results show this developed method has high accuracy and precision,high sensitivity,large range of linearity and high speed.The method can,therefore,be employed at room temperature.     

Mechanistic Study and Kinetic Determination of Cu(Ⅱ) by the Catalytic Kinetic Spectrophotometric Method

A highly sensitive and selective catalytic kinetic spectrophotometric method for the determination of Cu(Ⅱ) is proposed. It is based on the catalytic effect of Cu(Ⅱ) on the oxidation of glutathione(GSH) by potassium hexacyanoferrate(Ⅲ) in acidic medium at 25.0℃. The reaction is monitored spectrophotometrically by measuring the decrease in absorbance of oxidant at 420 nm using the fix-time method. Under the optimum conditions, the proposed method allows the determination of Cu(Ⅱ) in a range of 0-35.0 ng m L~(-1) with good precision and accuracy and the limit of detection is down to 0.04 ng m L~(-1). The relative standard deviation(RSD) is 1.02%. The reaction orders with respect to each reagent are found to be 1, 1/2, and 1/2 for potassium hexacyanoferrate(Ⅲ), glutathione and Cu(Ⅱ) respectively. On the basis of these values, the rate equation is obtained and the possible mechanism is established. Moreover, few anions and cations can interfere with the determination of Cu(Ⅱ). The new proposed method can be successfully used to the determination of Cu(Ⅱ) in fresh water samples and seawater samples. It is found that the proposed method has fairly good selectivity, high sensitivity, good repeatability, simplicity and rapidity.     

Membrane preconcentration of iron in seawater samples and on-site determination in spectrophotometry

A novel method for on-site determination of trace iron was developed using membrane preconcentration and spectrophotometric detection. Fe(Ⅱ)-ferrozine complex was reacted with cetyltrimethylammonium bromide (CTAB) to form a Fe(Ⅱ)-ferrozine-CTAB paired compound, which was collected on a membrane by filtration under vacuum. The membrane was immersed in 2 mL of ethanol-nitric acid and the absorbance of the solution measured for quantitative analysis. Various factors affecting the iron collection and determination were investigated. With different sample preconcentration volumes, the range of determination was broadened to 0.5-120 g/L. The detection limit of this method reached 0.19 g/L and the recoveries were between 97.2 and 109% when the concentration enrichment was about 45. The relative standard deviation (n = 7) was 1.9% for samples containing 10 g/L Fe. Twelve seawater samples were analyzed on-site using the proposed method, and two were also analyzed in inductively coupled plasma mass spectrometry. No significant difference was shown between the two methods by the Student’s t-test. The method has also been used on-site for iron enrichment experiments with phytoplankton and concluded to be simple, accurate and inexpensive.     

Simultaneous determination of iron and manganese in water using artificial neural network catalytic spectrophotometric method

A new analytical method using Back-Propagation (BP) artificial neural network and kinetic spectrophotometry for simultaneous determination of iron and magnesium in tap water, the Yellow River water and seawater is established. By conditional experiments, the optimum analytical conditions and parameters are obtained. Levenberg-Marquart (L-M) algorithm is used for calculation in BP neural network. The topological structure of three-layer BP ANN network architecture is chosen as 15-16-2 (nodes). The initial value of gradient coefficient μ is fixed at 0.001 and the increase factor and reduction factor of μ take the default values of the system. The data are processed by computers with our own programs written in MATLAB 7.0. The relative standard deviation of the calculated results for iron and manganese is 2.30% and 2.67% respectively. The results of standard addition method show that for the tap water, the recoveries of iron and manganese are in the ranges of 98.0%-104.3% and 96.5%-104.5%, and the RSD is in the range of 0.23%-0.98%; for the Yellow River water (Lijin district of Shandong Province), the recoveries of iron and manganese are in the ranges of 96.0%-101.0% and 98.7%-104.2%, and the RSD is in the range of 0.13%-2.52%; for the seawater in Qingdao offshore, the recoveries of iron and manganese are in the ranges of 95.3%-104.8% and 95.3%-104.7%, and the RSD is in the range of 0.14%-2.66%. It is found that 21 common cations and anions do not interfere with the determination of iron and manganese under the optimum experimental conditions. This method exhibits good reproducibility and high accuracy in the determination of iron and manganese and can be used for the simultaneous determination of iron and manganese in tap water and natural water. By using the established ANN- catalytic spectrophotometric method, the iron and manganese concentrations of the surface seawater at 11 sites in Qingdao offshore are determined and the level distribution maps of iron and manganese are drawn.     

Chemical oxygen demand of seawater determined with a microwave heating method

This paper investigates a microwave heating method for the determination of chemical oxygen demand (COD) in seawater. The influences of microwave-power, heating time and standard substances on the results are studied. Using the proposed method, we analyzed the glucose standard solution, the coefficient of variation being less than 2%. Compared with the traditional electric stove heating method, the results of F-test and T-test showed that there was no significant difference between the two methods, but the microwave method had slightly higher precision and reproducibility than the electric stove method. With the microwave heating method, several seawater samples from Jiaozhou Bay and the South Yellow Sea were also analyzed. The recovery was between 97.5% and 104.3%. This new method has the advantages of shortening the heating time, improving the working efficiency and having simple operation and therefore can be used to analyze the COD in seawater.     

Speciation analysis of arsenic compounds in seafood by ion chromatography-atomic fluorescence spectrometry

Ion chromatography-ultra violet-hydride generation-Atomic Florescence Spectrometry was applied to detect 5 arsenic species in seafoods. The arsenic species studied include arsenobetaine(As B), arsenite(As(III)), dimethylarsinic acid(DMA), monomethylarsonic acid(MMA), and arsenate(As(V)), which were extracted from samples using 2% formic acid. Gradient elution using 33 mmol L~(-1) CH_3COONH_4 and 15 mmol L~(-1) Na_2CO_3 with 10 mL CH_3CH_2OH at pH 8.4 allowed the chromatographic separation of all the species on a Hamilton PRP-X100 anion-exchange column in less than 8 min. In this study, an ultrasound extraction method was used to extract arsenic species from seafood. The extraction efficiency was good and the recoveries from spiked samples were in the range of 72.6%–109%; the precision between sample replicates was higher than 3.6% for all determinations. The detection limits were 3.543 μg L~(-1) for As B, 0.4261 μg L~(-1) for As(III), 0.216 μg L~(-1) for DMA, 0.211 μg L~(-1) for MMA, and 0.709 μg L~(-1) for As(V), and the linear coefficients were greater than 0.999. We also developed an application of this method for the determination of arsenic species in bonito, Euphausia superba, and Enteromorpha with satisfactory results. Therefore, it was confirmed that this method was appropriate for the detection of arsenic species in seafood.     

Measurement of trace manganese (II) by the catalytic kinetic spectrophotometric method

A new kinetic spectrophotometric method is developed for the measurement of manganese (II) in water. The method is based on the catalytic effect of manganese (II) with the oxidation of weak acid brilliant blue dye (RAWL) by KIO₄ using the Nitrilo triacetic acid (NTA) as an activation reagent. The optimum conditions obtained are 40 mgL⁻¹ RAWL, 1×10⁻⁴molL⁻¹ KIO₄, 2×10⁻⁴ molL⁻¹ Nitrilo triacetic acid (NTA), pH = 5.8, the reaction time of 3.00 min and the temperature of 20.0 °C. Under the optimum conditions, the proposed method allows the measurement of manganese (II) in a range of 0–50.0 ng mL⁻¹ and with a detection limit of down to 0.158 ng mL⁻¹. The recovery efficiency in measuring the standard manganese (II) solution is in a range of 98.5%–102%, and the RSD is in a range of 0.76%–1.25%. The new method has been successfully applied to the measurement of manganese (II) in both fresh water and seawater samples with satisfying results. Moreover, few cations and anions interfere with the measurement of manganese (II). Compared with other kinetic catalytic methods and instrumental methods, the proposed method shows fairly good selectivity and sensitivity, low cost, cheapness, low detection limit and rapidity. It can be applied on boats easily.     

Determination of trace vanadium (V) in seawater and fresh water by the catalytic kinetic spectrophotometric method

A new kinetic spectrophotometric method has been developed for the determination of vanadium (V). The method is based on the catalytic effect of vanadium (V) on the oxidation of weak acid brilliant blue dye (RAWL) by KBrO₃ using the citric acid as activation reagent. The obtained optimum conditions are: c (RAWL) = 1×10⁻⁴ molL⁻¹, c (KBrO₃) = 3×10⁻² molL⁻¹, c (citric acid) = 9×10⁻³ molL⁻¹, pH = 2.50, the reaction time being 7.0 min and the temperature being 25.0°C. Under the optimum conditions, the proposed method allows the determination of vanadium (V) in the range of 0–70.0 ng mL⁻¹ and the detection limit is down to 0.407 ng mL⁻¹. For standard vanadium (V) solution determination, the recovery efficiency is in the range of 98.5%–102% and the RSD ranges from 0.76%–1.25%. Moreover, it is demonstrated that most cations and anions do not interfere with the determination of vanadium (V) under the analytical condition. The new method was successfully applied in the determination of vanadium (V) in fresh water and seawater samples with satisfactory results. Vanadium (V) in the seawater samples from Qingdao offshore was determined using the method and the distribution of vanadium (V) was mapped. Compared with other instrumental analytical methods, the proposed method shows good selectivity, sensitivity, simplicity, lower cost and rapidity. It can be employed on shipboard easily.     

Effects of nutritional factors on the growth and heterotrophic eicosapentaenoic acid production of diatom <Emphasis Type="Italic">Nitzschia laevis</Emphasis>

The effects of several nutritional factors on the growth and eicosapentaenoic acid (EPA) production of diatom Nitzschia laevis were studied. 4 LDM (quadrupled concentration of the nutrient salt) was the optimal concentration of nutrient salt for the growth and EPA production of N. laevis. The growth of N. laevis was inhibited when the glucose concentration was either lower than 10 gL⁻¹ or higher than 15 gL⁻¹. Both sodium nitrate and urea were good nitrogen sources for the growth and EPA production, while ammonium chloride seriously decreased the dry cell weight (DW) and the EPA content. Silicate seriously influenced the growth of N. laevis. The maximum DW of 2.34 gL⁻¹ was obtained in the presence of 150 mgL⁻¹ Na₂SiO₃·9H₂O. The EPA content remained almost the same when the silicate concentration was lower than 150 mgL⁻¹; however, higher silicate concentrations resulted in a steady decrease of EPA content. Low medium salinity (⩽29) did not seem to influence the DW of N. laevis, and high salinity resulted in a decrease of DW. The highest EPA content (4.08%) and yield (110 mgL⁻¹) were observed at the salinity of 36 and 29, respectively.     

Bioflocculant Produced by Klebsiella sp. MYC and Its Application in the li＇eatment of Oil-field Produced Water

Seventy-nine strains of bioflocculant-producing bacteria were isolated from 3 activated sludge samples. Among them, strain MYC was found to have the highest and stable flocculating rate for both kaolin clay suspension and oil-field produced water. The bacterial strain was identified as Klebsiella sp. MYC according to its morphological and biochemical characteristics and 16SrDNA sequence. The optimal medium for bioflocculant production by this bacterial strain was composed of cane sugar 20 g L^-1, KH2PO4 2 g L^-1, K2HPO4 5 g L^- 1, （ NH4）2SO4 0.2 g L^-1, urea 0.5 g L^- 1 and yeast extract 0.5 g L^- 1, the initial pH being 5.5. When the suspension of kaolin clay was treated with0.5% of Klebsiella sp. MYC culture broth, the flocculating rate reached more than 90.0% in the presence of 500mg L^-1 CaCI2, while the flocculating rate for oil-field produced water was near 80.0% in a pH range of 7.0 - 9.0 with the separation of oil and suspended particles from the oil-field produced water under similar conditions. The environment-friendly nature of the bioflocculant and high flocculating rate of the strain make the bioflocculant produced by Klebsiella sp. MYC an attractive bioflocculant in oil-field produced water treatment.     

The inhibitory degree between Skeletonema costatum and dinoflagllate Prorocentrum donghaiense at different concentrations of phosphate and nitrate/phosphate ratios

Interactions between Skeletonema costatum (S. costatum) and Prorocentrum donghaiense (P. donghaiiense) were inves-tigated using bi-algal cultures at different concentrations of phosphate (PO4-P) and nitrate/phosphate (N/P) ratios. Experiments were conducted under P-limited conditions and the Lotka-Volterra mathematical model was used to simulate the growth of S. costatum and P. donghaiense in the bi-algal cultures. Both of these two species were inhibited significantly in bi-algal culture. The results of the simulation showed that the inhibitory degree of S. costaum by P. donghaiense was high when the concentration of PO4-P was low (0.1μmolL-1/2 d), but that of P. donghaiense by S. costaum was high with increased PO4-P supply (0.6μmolL-1/2 d). At low concen-tration of PO4-P (0.1μmolL-1/2 d), or high concentration of PO4-P (0.6μmolL-1/2 d) with high N/P ratio (160), the interactions be-tween S. costatum and P. donghaiense were dependent on the initial cell densities of both species. At high concentration of PO4-P (0.6μmolL-1/2 d) with low N/P ratio (25 or 80), S. costatum exhibited a survival strategy superior to that of P. donghaiense. The de-gree of inhibition of P. donghaiense by S. costaum increased with elevated N/P ratio when the medium was supplemented with con-centration 0.1μmolL-1/2 d of PO4-P. The degree of inhibition to P. donghaiense by S. costaum increased with elevated N/P ratio at low concentration of PO4-P (0.1 μmolL-1/2 d). This trend was conversed at high concentration of PO4-P (0.6μmolL-1/2 d). However, the degree of inhibition of S. costaum by P. donghaiense increased with the increased N/P ratio at different PO4-P concentrations (0.1μmolL-1/2 d and 0.6μmolL-1/2 d). These results suggested that both phosphate concentration and N/P ratio affected the competition between S. costaum and P. donghaiense: P. donghaiense is more competitive in environments with low phosphate or high N/P ratio and the influence of N/P ratio on the competition was more significant with lower phosphate concentration.     

Determination of Selenium in Marine Aquatic Products by Hydride Generation-atomic Fluorescence Spectrometry （HG-AFS）

A method for the analysis of selenium in marine aquatic products by HG-AFS has been investigated. The method is based on the reduction of inorganic selenium to volatile SeH2 which is bubbled out by carrier gas of pure argon, and then swept to Ar-H2 flame quarts atomizer to measure its fluorescence intensity. The hydride generation, transportation, atomization and some instrumental parameters were studied by a kind of orthogonal design. The optimum conditions selected are as follows： reactive acidity, 20% HC1; the amount of NaBH4, 4.9mL; gas flow of argon, 600mLmin^-1; atomizing temperature, 200 ℃ ; negative high voltage, - 300V; light current, 100 mA; integral time, 7s. The detection limit of the presented method is 0.072μgL^-1 for selenium. The calibration curve shows a satisfactory line inthe concentration range from 0.000 to 1.000μgL^-1 Se. The recovery is 95.8%-102.2%.     

Exopolysaccharide Production by Four Cyanobacterial Isolates and Preliminary Identification of These Isolates

Four marine cyanobacterial isolates, named 104, 109, 113 and 115, from marine water off China＇s coast can release a large amount of exopolysaccharide （EPS） to medium. The effects of different components in medium on EPS production by the four isolates were investigated. Under the optimal condition, the EPS released by isolates 104,109, 113 and 115 reached 7.48 g L^-1, 8.33 g L^-1, 18.26 g L^-1, and 6.78 g L^-1 within 14 d,respectively. Based on the conventional identification methods for cyanobacteria,these isolates were assigned to genus Cyanothece.     

Cryopreservation of Gametophytes of Laminaria japonica （Phaeophyta） Using Encapsulation-Dehydration with Two-Step Cooling Method

Gametophytes of Laminaria japonica were cryopreserved in liquid nitrogen using encapsulation-dehydration with two-step cooling method. Gametophytes cultured at 10℃ and under continuous irradiance of 30 μmol m-2 s-1 for 3 weeks were encapsulated in calcium alginate beads. The beads were dehydrated in 0.4 molL-1 sucrose prepared with seawater for 6 h, desiccated in an incubator set at 10℃ and 70% relative humidity for 4 h, pre-frozen at either -40℃ or -60℃ for 30 min, and stored in liquid nitrogen for ＞24 h. As high as 43% of survival rate was observed when gametophytes were thawed by placing the beads in 40℃seawater and re-hydrated in 0.05 molL-1 citrate sodium prepared using 30‰ NaC1 7 d later. More cells of male gametophytes survived the whole procedure in comparison with female gametophytes. The cells of gametophytes surviving the preservation were able to grow asexually and produce morphologically normal sporophytes.