Determination of metal speciation by reverse titrations

A new method is proposed to determine metal speciation by varying the concentration of a competing ligand at a constant metal concentration, with detection by cathodic stripping voltammetry. The free metal ion concentration is gradually lowered from its natural level while the method probes progressively deeper into the already complexed metal fraction: it is therefore a reverse titration rather than the forward titration which is used for conventional complexing ligand titrations. The sensitivity is greatest at the lowest free metal ion concentration, where it matters most, and the method can be carried out in a single sample aliquot in the voltammetric cell. The method is applied here to copper speciation, but in principle, it can also be used for other metals. Modeling shows that this method has good sensitivity at ligand concentrations near the metal concentration (lower as well as greater). Comparative measurements of copper speciation using reverse and forward titrations of representative water samples of oceanic and coastal origin show good agreement. The data showed that these samples did not contain low levels of strong ligands in addition to the ligands detected by the forward titrations.     

冲击载荷下泡沫铜-聚氨酯的缓冲性能

目的通过冲弯实验,测定泡沫铜-聚氨酯复合材料结构在动载荷作用下的缓冲吸能性能,对比研究该复合材料结构抗高冲击、高过载的性能差异。方法向泡沫铜试件中填充不同体积分数的聚氨酯,按照《金属常温冲击韧性实验法》在夏比冲击试验机上进行冲弯试验,测定试样的吸收功值,从而对比探究该种复合材料的力学性能。结果聚氨酯在试样中所占体积分数为50%时其能量均值相对最大,此时材料韧性较好,且材料抵抗冲击载荷能力较强。结论将聚氨酯填充到开孔泡沫铜材料中可构成一种性能优良的抗冲击吸能结构,其性能优于泡沫铜和聚氨酯单体,在抗高冲击、高过载的军工产业和民用产业中具有广阔的应用前景。     

Grating light reflection spectroscopy for determination of bulk refractive index and absorbance

An optical sensing technique is described and evaluated for sensitivity to changes in refractive index and absorbance of model sample matrices. A binary dielectric/metal transmission diffraction grating is placed in contact with a sample and utilized in reflection mode; thus, the light captured and analyzed does not pass through the sample. This particular condition creates thresholds at which a particular transmitted diffraction order is transformed from a traveling wave to an evanescent one. The positions of these thresholds depend upon the complex dielectric function of the sample, the period of the grating, and the wavelength and incident angle of light striking the grating. Experimental evidence directly supports the theoretical predictions regarding responses to both the real and imaginary portions of the refractive index: the reflection coefficient derivative wavelength peak position shifts linearly with changes in the real part of the refractive index, and the derivative peak amplitudes exhibit a square-root dependence on absorbance. Refractive index sensitivity to a series of ethanol/water solutions is demonstrated with detectable changes in index as small as 2 × 10(-)(6). Absorbance sensitivity is shown via the differentiation of methylene blue samples having equivalent 1 cm path length absorbances between 0.459 and 244 AU. In a single reflection measurement, GLRS offers a large dynamic range for absorbance detection, allows simultaneous determination of bulk refractive index in optically dense media, and provides a platform for performing continuous process analysis.     

Solid phase extraction method for the determination of lead, nickel, copper and manganese by flame atomic absorption spectrometry using sodium bispiperdine-1,1'-carbotetrathioate (Na-BPCTT) in water samples

A novel column solid phase extraction procedure was developed for the determination of lead, nickel, copper and manganese in various water samples by flame atomic absorption spectrometry (FAAS) after preconcentration on sodium bispiperdine-1,1'-carbotetrathioate (Na-BPCTT) supported by Amberlite XAD-7. The sorbed element was subsequently eluted with 1M nitric acid and the acid eluates are analysed by Flame atomic absorption spectrometry (FAAS). Various parameters such as pH, amount of adsorbent, eluent type and volume, flow-rate of the sample solution, volume of the sample solution and matrix interference effect on the retention of the metal ions have been studied. The optimum pH for the sorption of above mentioned metal ions was about 6.0+/-0.2. The loading capacity of adsorbent for Pb, Cu, Ni and Mn were found to 28, 26, 22 and 20x10(-6) g/mL, respectively. The recoveries of lead, copper, nickel and manganese under optimum conditions were found to be 96.7-99.2 at the 95% confident level. The limit of detection was 3.0, 3.2, 2.8 and 3.6x10(-6) g/mL for lead, copper, nickel and manganese, respectively by applying a preconcentration factor 50. The proposed enrichment method was applied for metal ions in various water samples. The results were obtained are good agreement with reported method.     

Copper(II)-rubeanic acid coprecipitation system for separation-preconcentration of trace metal ions in environmental samples for their flame atomic absorption spectrometric determinations

A simple and facile preconcentration procedure based on the coprecipitation of trace heavy metal ions with copper(II)-rubeanic acid complex has been developed. The analytical parameters including pH, amounts of rubeanic acid, sample volume, etc. was investigated for the quantitative recoveries of Pb(II), Fe(III), Cd(II), Au(III), Pd(II) and Ni(II). No interferic effects were observed from the concomitant ions. The detection limits for analyte ions by 3 sigma were in the range of 0.14 microg/l for iron-3.4 microg/l for lead. The proposed coprecipitation method was successfully applied to water samples from Palas Lake-Kayseri, soil and sediment samples from Kayseri and Yozgat-Turkey.     

pH-mediated field amplification on-column preconcentration of anions in physiological samples for capillary electrophoresis.

Two limitations of capillary electrophoresis (CE) are the low sample loadability of the capillary and an incompatibility with high ionic strength samples. Several strategies have been described to preconcentrate and lower the ionic strength of physiological samples prior to CE analysis. These have included both off-capillary and on-capillary approaches. We have previously described a version of on-column field-amplification stacking termed pH-mediated stacking. pH-mediated stacking was initially developed for the separation of cations. In this report, we describe the application of pH-mediated sample stacking to anions. In this method, an electrokinetic injection is used to introduce analyte anions into the CE system and simultaneously replace the sample matrix cations with ammonia from the background electrolyte. Base is then electrokinetically injected to neutralize the sample zone and create a low conductivity region across which the analyte anions will stack. Using this method, a sensitivity enhancement of more than 66-fold was achieved without loss in separation efficiency relative to normal electrokinetic injection. Detection limits of 0.3 microM for four phenolic acids in a physiological sample were achieved using simple UV absorbance detection. The limit to the amount of sample that could be loaded using this technique was the length of the separation capillary. To further increase the amount of sample that could be loaded, a double-capillary system was developed. Using the double-capillary system the sensitivity was increased more than 300-fold and detection limits of 0.06 microM were achieved.     

Enrichment of trace amounts of copper(II) ions in water samples using octadecyl silica disks modified by a Schiff base ionophore prior to flame atomic absorption spectrometric determination

Bis(5-bromo-2-hydroxybenzaldehyde)-1,2-propanediimine is synthesized by the reaction of 5-bromo-2-hydroxybenzaldehyde and 1,2-diaminopropane in ethanol. This ligand is used as a modifier of octadecyl silica disks for preconcentration of trace amounts of copper(II) ions, followed by nitric acid elution and flame atomic absorption spectrometric (FAAS) determination. The effect of parameters influencing the extraction efficiency, i.e. pH of the sample solutions, amount of the Schiff base, type and volume of stripping reagent, sample and eluent flow rates were evaluated. Under optimum experimental conditions, the capacity of the membrane disks modified by 4mg of the ligand was found to be 247.7 (+/-2.1)mug of copper. The detection limit and the concentration factor of the presented method are 2.4ng/l and greater than 400, respectively. The method was applied to the extraction, recovery and detection of copper in different synthetic and water samples.     

Solid-phase microextraction and headspace solid-phase microextraction for the determination of polychlorinated biphenyls in water samples

A solid-phase microextraction (SPME) method has been developed for the quantification of polychlorinated biphenyls (PCBs) in water samples. Parameters such as sampling time, volume of water, volume of headspace, temperature, addition of salts, and agitation of the sample were studied. Because the time for reaching equilibrium between phases takes several hours or days, depending on the experimental conditions, it was necessary to work in nonequilibrium conditions to keep the sample analysis to a reasonable time. The possibility of sampling the headspace over the water sample (HSSPME), instead of immersing the fiber into the water (SPME), was also investigated, and despite the low partition of PCB into the headspace, HSSPME offered higher sensitivity than SPME at 100 °C. The adsorption kinetics for SPME at room temperature, SPME at 100 °C, and HSSPME at 100 °C were investigated and compared. The proposed HSSPME method exhibits excellent linearity and sensitivity. The detection limit was in the sub-ng/L level. This method has been applied to a real industrial harbor water and compared with liquid-liquid extraction. Both techniques offered similar results, but HSSPME was much more sensitive and considerably faster, by eliminating all the manual process intensive sample workup, and reduces solvent consumption entirely. The only drawback was that matrix effects were observed, but with the addition of deuterated surrogates to the sample or the use of a standard addition calibration, accurate quantification can be achieved.     

Indirect fluorescence detection of amino acids on electrophoretic microchips

Microfabricated devices enable rapid separations of a variety of clinically significant analytes, including DNA, proteins, and amino acids. However, absorbance detection has been difficult to achieve on these devices, prohibiting analysis of nonfluorophore-bearing or nonfluorescently tagged analytes. An alternative detection technique exploiting indirect fluorescence has been adapted to the electrophoretic microchip to provide fast analysis of amino acids, bypassing the need for absorbance detection or fluorescence derivitization procedures. Nineteen of the standard amino acids could be detected with an average detection limit of 32.9 microM (approximately 1.6 amol). Despite the fact that the detection sensitivity was lower than that achievable by labeling the amino acids with fluorescein isothiocyanate (approximately 1 nM), circumventing sample preparation and the difficulties inherent with tagging complex samples make this technique attractive for a variety of assays where sensitivity is not critical. To demonstrate the applicability to real sample matrixes, the analysis of urine with elevated amino acid levels is used as a model system where the elevated levels are indicative of a variety of pathologies including amino acid metabolism disorders and kidney malfunction. The minimal sample handling and rapid separations achievable by employing indirect detection on microchips provides the potential for high-throughput applications for certain amino acid analyses.     

Direct electrochemical detection of purine- and pyrimidine-based nucleotides with sinusoidal voltammetry

Sinusoidal voltammetry was employed to detect both purine- and pyrimidine-based nucleic acids. Adenine and cytosine, representing these two classes of nucleic acids, could be measured with submicromolar detection limits at a copper electrode under these conditions, where the sensitivity for adenine was much higher than that for cytosine. Detection limits for purine-containing nucleotides [e.g., adenosine 5'-monophosphate (AMP), adenosine 5'-diphosphate (ADP), and adenosine 5'-triphosphate (ATP)] were on the order of 70-200 nM using this method. These detection limits are achieved for native nucleotides and are over 2 orders of magnitude lower than those found with UV absorbance detection. Submicromolar detection limits were also obtained for pyrimidine-based nucleotides, which could also be detected with high sensitivity due to the presence of a sugar backbone that is electroactive at the copper surface. This detector is not fouled by the nucleotides and may be used for the sensitive detection of analytes eluting continuously in a flowing stream, i.e., from a chromatography column or an electrophoresis capillary.     

Determination of Ca and Mg in aqueous solution by laser-induced breakdown spectroscopy using absorbent paper substrates

Laser-induced breakdown spectroscopy has been performed to detect trace metal elements (Ca and Mg) in aqueous solution. In order to overcome the sensitivity drawbacks in liquid sample analysis, an absorbent paper was used as the sample support in this experiment. Calibration curves were constructed by using the standard solution with variable concentration and the limit of detection was estimated for each element. Finally this system was used to analyze three types of water samples collected from different locations in Nanjing, China and the results were compared with inductively coupled plasma atomic emission spectroscopy and showed good correlation.     

Elemental analyses and determination of lead content in kohl (stone) by laser-induced breakdown spectroscopy

Elemental analyses of kohl (stone) samples collected from three different parts of the world were performed using laser-induced breakdown spectroscopy (LIBS). The analyses indicated that lead (Pb), copper (Cu), silver (Ag), iron (Fe), calcium (Ca), aluminum (Al), silicon (Si), and sodium (Na) were present in all the kohl samples. In addition to these elements, the sample from Madina, Kingdom of Saudi Arabia (KSA), contained the elements tin (Sn), zirconium (Zr), and antimony (Sb). The sample from Mount Toor, Egypt, also contained Sn. Also, quantitative analysis for lead was carried out by the standard addition method using the LIBS technique. The result showed the presence of 14.12 ± 0.28% by weight of Pb in the sample from Madina, which compares well with the measurement done using atomic absorption spectroscopy (AAS) (13.31 ± 0.46%). The standard addition method used three calibration curves drawn for three emission lines of the LIBS spectra of Pb. The limits of detection (LoD) for these calibration curves varied from 0.27% to 1.16% by weight. The lead contents of the samples from Mount Toor and the local market of Bangladesh were also measured by the AAS technique, and the results were 14.61 ± 0.48% and 8.98 ± 0.35% by weight, respectively. The reason for determining only the lead content in kohl, which may be used as an eye cosmetic, is the adverse effect that lead has on health.     

Experimental investigation on water drainage characteristics of open-cell metal foams with different wettabilities

For optimizing the metal foam heat exchangers used in dehumidification apparatus, the influence of surface wettability on drainage characteristics should be explicit. In the present study, the water drainage characteristics of metal foams with different wettabilities were experimentally investigated. The experimental results show that the stabilization time of the water drainage process for the hydrophobic sample is the shortest among the tested metal foam samples, and the water retention mass in the hydrophobic metal foam is much smaller than that in the other samples; the wettability impact factors for water retention are within 0.78–1.1 and 0.40–0.77 for the hydrophilic and hydrophobic samples, respectively. The water retention mass in the copper foam is 9.5%–52.6% smaller than that in the aluminum foam. For the hydrophobic copper foam, the water retention mass per unit volume in metal foams with PPI of 5–20 is 45%–66% smaller than that in fin–tube heat exchangers.     

Detection of toxic compounds in real water samples using a conductometric tyrosinase biosensor

A conductometric tyrosinase biosensor for the detection of some toxic compounds including diuron, atrazine, and copper ions was developed. The work of this biosensor is based on the principle of change of conductivity of the enzyme membrane when tyrosinase either interacts with 4-chlorophenol substrate or is inhibited by pollutants. The different samples tested were solutions containing diuron, atrazine, copper, lead and zinc ions, mixtures of copper/atrazine or copper/diuron and real water samples coming from a Vietnamese river. In the last case, classical techniques such as GC-MS or atomic absorption spectrometry were used in order to estimate exact concentration of these species in real water samples. Results have shown that such a biosensor could be used as an early warning system for the detection of these pollutants, as no matrix effect coming from the real sample was observed and no synergetic or antagonist effects were found for the mixture of toxic compounds. In addition, results were coherent with the content of the tyrosinase inhibitors.     

Dual photonic-electrochemical lab on a chip for online simultaneous absorbance and amperometric measurements

A dual lab on a chip (DLOC) approach that enables simultaneous optical and electrochemical detection working in a continuous flow regime is presented. Both detection modes are integrated for the first time into a single detection volume and operate simultaneously with no evidence of cross-talk. The electrochemical cell was characterized amperometrically by measuring the current in ferrocyanide solutions at +0.4 V vs gold pseudoreference electrode, at a flow rate of 200 μL min(-1). The experimental results for ferrocyanide concentrations ranging from 0.005 to 2 mM were in good agreement with the values predicted by the Levich equation for a microelectrode inside a rectangular channel, with a sensitivity of 2.059 ± 0.004 μA mM(-1) and a limit of detection (LoD) of (2.303 ± 0.004) × 10(-3) mM. Besides, optical detection was evaluated by measuring the absorbance of ferricyanide solutions at 420 nm. The results obtained therein coincide with those predicted by the Beer-Lambert law for a range of ferricyanide concentrations from 0.005 to 0.3 mM and showed an estimated LoD of (0.553 ± 0.001) × 10(-3) mM. The DLOC was finally applied to the analysis of L-lactate via a bienzymatic reaction involving lactate oxidase (LOX) and horseradish peroxidase (HRP). Here, the consumption of the reagent of the reaction (ferrocyanide) was continuously monitored by amperometry whereas the product of the reaction (ferricyanide) was recorded by absorbance. The DLOC presented good performance in terms of sensitivity and limit of detection, comparable to other fluidic systems found in the literature. Additionally, the ability to simultaneously quantify enzymatic reagent consumption and product generation confers the DLOC a self-verifying capability which in turn enhances its robustness and reliability.     

A flow injection on-line multiplexed sorption preconcentration procedure coupled with flame atomic absorption spectrometry for determination of trace lead in water, tea, and herb medicines

One of the limitations in previous flow injection (FI) sorption preconcentration procedures in a knotted reactor (KR), which have been carried out exclusively with a single continuous sample injection over a certain period, is the relatively low retention efficiency (typically 40-50%). Although the sensitivity of such systems could be improved by properly increasing sample preconcentration time, sample loading flow rate, or both, further improvement of the sensitivity has been limited by the narrow linearity of the relationship between signal intensity and preconcentration time or sample loading time. In this work, a novel on-line FI multiplexed sorption preconcentration procedure with repetitive sample injections was developed to overcome the above problems in the previous systems. In contrast to previous FI preconcentration systems, the proposed multiplexed preconcentration procedure evenly divides a single longer sample injection step into several shorter substeps while the total preconcentration time is still kept constant. To demonstrate its merits, the proposed FI on-line KR multiplexed sorption preconcentration system was combined with flame atomic absorption spectrometry (FAAS) for determination of trace lead in water, tea, and herb medicines. The lead in the sample solution on-line reacted with ammonium pyrrolidine dithiocarbamate, and the resultant analyte complex was sorbed on the inner walls of the KR. The residual sample solution was then removed from the KR with an air flow. The above two steps were repeated eight times with a total preconcentration time of 120 s. The sorbed analyte was eluted from the KR with 4.5 mol L(-1) HCl for on-line FAAS detection. The present multiplexed preconcentration procedure with eight repetitive sample injections for a total preconcentration time of 120 s gave a retention efficiency of 92%, twice that obtained by one single sample injection preconcentration (47%). In addition, the linear ranges of the diagrams of absorbance against sample loading flow rate and sample loading time were extended, offering more potential for achieving high sensitivity by increasing sample loading rates or sample loading time compared to the previous one single continuous sample injection preconcentration procedure. At a sample loading flow rate of 3.6 mL min(-1) for a total preconcentration period of 120 s, an enhancement factor of 57 and a detection limit (3sigma) of 8 microg L(-1) were obtained. The precision was 1.4% (RSD, n = 11) at the 200 microg L(-1) level. The developed method was successfully applied to the determination of trace lead in various water samples, herb medicines, and a certified tea reference material.     

A simple and selective spectrophotometric flow injection determination of trace amounts of ruthenium by catalytic oxidation of safranin-O

In this work, a simple, selective and rapid flow injection method has been developed for determination of ruthenium. The method is based on its catalytic effect on the oxidation of safranin-O by metaperiodate. The reaction was monitored spectrophotometrically by measuring safranin-O absorbance at lambdamax=521. The reagents and manifold variables, which have influences on the sensitivity, were investigated and the optimum conditions were established. The optimized conditions made it possible to determine ruthenium in the ranges of 0.4-20.0 ng/mL (DeltaA=0.2819CRu+1.1840) and 20.0-100.0 ng/mL (DeltaA=0.0984CRu+7.9391) with a detection limit of 0.095 ng/mL and a sample rate of 30+/-5 samples/h. Relative standard deviation for the five replicate measurements was less than 1.84%. The proposed method has been successfully applied for analysis of ultra trace amounts of ruthenium in real samples.     

Bi(III)4-methylpiperidinedithiocarbamate coprecipitation procedure for separation--pre-concentration of trace metal ions in water samples by flame atomic absorption spectrometric determination

A pre-concentration method was developed for determination of trace amounts of cadmium, copper and lead in water samples by FAAS after coprecipitation by using potassium 4-methylpiperidinedithiocarbamate (K4-MPDC) as a chelating agent and Bi(III) as a carrier element. This procedure is based on filtration of the solution containing precipitate on a cellulose nitrate membrane filter following Cd(II), Cu(II) and Pb(II) coprecipitation with Bi(III)4-MPDC and then the precipitates together with membrane filter were dissolved in concentrated nitric acid. The metal contents of the final solution were determined by FAAS. Several parameters including pH of sample solution, amount of carrier element and reagent, standing time, sample volume for precipitation and the effects of diverse ions were examined. The accuracy of the method was tested with standard reference material (MBH, C31XB20 and CRM BCR-32) and Cd, Cu and Pb added samples. Determination of Cd, Cu and Pb was carried out in sea water, river water and tap water samples. The recoveries were >95%. The relative standard deviations of determination were less than 10%.     

Determination of boron by flow injection analysis using a conductivity detector

A flow injection method for the determination of boron using a conductivity detector has been described. Boric acid injected into the flow system reacts with mannitol (0.3 M) in the mobile phase and an equivalent amount of H(+) is liberated in the stream. The increase in the conductance of the mobile phase due to the liberated H(+) has been equated to the boron concentration in the sample. A linear calibration for light- and heavy-water samples containing 0-20 μg/mL boron was obtained. Boron concentrations in the samples of light and heavy water and lithium pentaborate solution have been measured. The interferences due to various ions such as Na(+), Li(+), Cu(2+), Ni(2+), Co(2+), Fe(3+), Al(3+), SO(4)(2-), NO(3)(-), F(-), and Cl(-) could be eliminated by adopting a two-step sample pretreatment procedure. In the first step, all the anions were converted to Cl(-) by treating the sample solution with a strong anion-exchange resin. In the second step, the solution obtained from the first step was passed through a silver-guard cartridge to remove interfering cations and Cl(-). The relative standard deviation was ±0.25% for the determination of 1 μg of boron in light water, and the limit of detection was 0.01 μg present in an injection volume of 100 μL. The corresponding values for heavy water were ±0.38% and 0.1 μg, respectively.     

Coprecipitation of Ni(2+), Cd(2+) and Pb(2+) for preconcentration in environmental samples prior to flame atomic absorption spectrometric determinations

A coprecipitation procedure has been presented prior to flame atomic absorption spectrometric determination of nickel, cadmium and lead ions in environmental samples. Analyte ions were coprecipitated by using copper hydroxide precipitate. The influences of some analytical parameters like amounts of copper, sample volume, etc., on the recoveries of the analytes were investigated. The interference of other ions was negligible. Under the optimized conditions, the detection limits (3 sigma, n=15) of lead(II), nickel(II) and cadmium(II) were 7.0, 3.0 and 2.0 microg/L, respectively. The proposed method has been successfully applied for the determination of traces of Ni, Cd and Pb in environmental samples like tap water.