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1.
Cadmium and lead were determined simultaneously in seawater by differential pulse stripping voltammetry (DPSV) preceded by adsoptive collection of complexes with 8-hydroxyquinoline (oxine) on to a hanging mercury drop electrode (HMDE). In preliminary experiments the optimal analytical condition for oxine concentration was found to be 2.10−5 M, at pH 7.7, the accumulation potential was −1.1 V, and the initial scannig potential was −0.8 V. The peak potentials were found −0.652 V for Cd and −0.463 V for Pb At the 60 s accumalation time. The limit of detection (LOD) and limit of quantitatification (LOQ) were found to be by voltammetry as 0.588 and 1.959 μg l−1 (RSD, 5.50%) for Cd and 0.931 and 3.104 μg l−1 (RSD, 4.10%) for Pb at 60 s stirred accumulation time respectively. In these conditions the most of the seawater samples are amenable for direct voltammetric determination of cadmium and lead using a HMDE. An adsorptive stripping mechanism of the electrode reaction was proposed. For the comparison, seawater samples were also analysed by ICP-atomic emission spectrometry method (ICP-AES). The applied voltammetric technique was validated and good recoveries were obtained.  相似文献   

2.
The reaction of 2-[3-(triethoxysilyl)propylamino]ethanethiol (LH, a) and 1-methyl-2-[3-(triethoxysilyl)propylamino]ethanethiol (LH, b) with ZnX2 and CdX2 (X = Cl, Br, I, NO3) in tetrahydrofuran (THF) or CH2Cl2 gives several complexes depending on the experimental conditions. Elemental analyses, IR, Raman, 13C[1H], 1H NMR and mass spectroscopies indicated the formation of mononuclear and dinuclear complexes. In the absence of NEt3 as proton quencher, the protonated ligands react in their zwitterionic form giving dinuclear [M(LH)X2]2 [M = Zn (1), Cd (2); LH = a, b; X = Cl, Br, I] or mononuclear M(NO3)2(LH)2 [M = Zn (5), Cd (6); LH = a] complexes. In both cases, coordination occurs through the S atoms, the ligands acting as terminal and bridging species. With NEt3, the deprotonated ligands are chelated through their N and S atoms and bridging occurs through the S atoms in [MLX]2 [M = Zn (3), Cd (4); LH = a; X = Cl, Br] complexes. The LH ligand is chemically grafted onto silica, the procedure optimized and the resulting material characterized by 13C and 29Si cross-polarization, magic-angle spinning (CP-MAS) NMR and DRIFT. This material is evaluated as a supported molecular trap for binding heavy metals (Cd2+, Hg2+, Pb2+) in aqueous solution. In both batch and column processes, it appears that Hg2+ and Pb2+ are trapped more than Cd2+, but in all cases values lower than those allowed were obtained.  相似文献   

3.
The successful determination of mutagenic/carcinogenic heterocyclic amines (HCAs) in trace amounts (ng/g, ppb levels) in commercial foods depends largely on the detection sensitivity and selectivity, as well as the quality of clean-up of complex food matrices. In the present study, UV and fluorescence detection in series with gradient elution HPLC was used for the separation and determination of eight HCAs present in a local delicacy, satay. The identification of peaks was carried out by UV diode-array spectrophotometry. The most common HCA found in all types of satay (chicken, mutton, pork) cooked under Chinese and Malay styles was 2-amino-9H-pyrido[2,3-b]indole (AC) (1.3-12 ppb) while 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2) was found at comparatively high levels (78 ppb) in both Chinese-style pork and Malay-style chicken satay. Other major HCAs included 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole (Trp-P-1) (non-detectable (ND) to 31 ppb), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) (ND-12 ppb) and 2-aminodipyrido[1,2-a:3,2-d]-imidazole (Glu-P-2) (ND-25 ppb). Comutagen norharman (NH) was also detected at levels up to 84 ppb, while harman (H) was only detected in one sample (Chinese-style pork satay), at a level of 25 ppb. The differences in the type and level of HCAs in satay samples may be attributed to the variation in raw foodstuffs cooked under different styles by Chinese or Malay vendors, and the ingredients added during cooking.  相似文献   

4.
Episodic events may be critical with respect to aluminium (Al) toxicity in moderately acidified salmon rivers. The present work demonstrates that sea salt episodes enhance the toxicity of Al in acidic rivers. The documented sea salt episode (300 [micro sign]M Cl) mobilized positively charged Al species (0.4 to 1.1 [micro sign]M Al(i)), enhanced the Al accumulation on fish gills (0.9 to 10 [micro sign]mol g(-1) dw) and caused increased stress responses (6 to15 mM blood glucose) in fish. Accumulated Al on gills remained high several days after the episode. The presented results are based on a six-week field study in two tributary rivers on the west coast of Norway. Changes in the river water qualities and Al speciation were followed using in situ fractionation techniques. Al accumulation on gills and stress responses were followed for Atlantic salmon (Salmo salar) kept in tanks continually exposed to the changing water quality. The potential mobilization of Al from the two catchments was studied by extracting soils with diluted seawater (salinity of 3). To counteract Al toxicity, one of the tributary catchments has been limed. The potential mobility of Al by sea salt was lower in limed soils compared to acid soils, and the Al deposition on fish gills (<3.5 [micro sign]mol g(-1) dw) and associated stress responses stayed low during the sea salt episode in the river draining the limed catchment. Thus, for acid river systems in coastal areas, catchment liming should be considered as a useful countermeasure for Al toxicity.  相似文献   

5.
A sensitive adsorptive stripping voltammetric method for the determination of simeton with universal buffer solution has been described. The method was based on the adsorption accumulation of simeton at a hanging mercury drop electrode. The overall reduction process is under controlled diffusion. The adsorptive peak was observed at ?0.8 V vs SCE in acidic solution 2 < pH < 6. The peak response was characterized with respect to pH, accumulation potential, time, and scan rate. The calibration plot was found to be linear from 1.13 × 10???5 to 3.5 × 10???8 M with a limit of detection of 2.0 × 10???8 M. Finally, the method has been applied for the determination of simeton in its formulations and vegetable samples.  相似文献   

6.
The pesticide diazinon was determined in its insecticidal formulations by square wave adsorptive stripping voltammetry. The method of its determination is based on the irreversible reduction reaction at the hanging mercury drop electrode. The optimal signal was detected at -1.05?V vs. Ag/AgCl in Britton-Robinson buffer at pH?4.4. Various parameters such as pH, buffer concentration, frequency, amplitude, step potential, accumulation time, and potential were investigated to enhance the sensitivity of the determination. The highest response was recorded at an accumulation potential -0.4?V, accumulation time 60?s, amplitude 75?mV, frequency 100?Hz, and step potential 5?mV. The pesticide electrochemical behavior was considered under experimental conditions. The electroanalytical procedure enabled diazinon determination in the concentration range 4.0?×?10(-8)-3.9?×?10(-7)?mol?L(-1) in supporting electrolyte. The detection and quantification limit were found to be 1.1?×?10(-8) and 3.7?×?10(-8)?mol?L(-1), respectively. The method was applied successfully in the determination of the active ingredients in the insecticidal formulations Diazinon 10GR and Beaphar 275.  相似文献   

7.
The analytical techniques used for the determination of butyltin compounds in biological tissues are generally based on a succession of steps (e.g., extraction, derivatization, separation, detection) which are all prone to systematic errors. An interlaboratory programme performed at the EU level and based on a stepwise approach has enabled one to identify and remove most of these errors and to improve considerably the state of the art so that certification of a mussel reference material has been made possible. This paper describes the preparation of this mussel reference material containing monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT), the homogeneity and stability studies and the analytical work performed for the certification of the contents of MBT [Sn(C4H9)3+], DBT [Sn(C4H9)2(2+)] and TBT [Sn(C4H9)3+]. The results obtained by a group of expert EU laboratories are discussed along with the methods used to certify the mass fractions (based on dry mass) of monobutyltin (1.50 +/- 0.28 mg kg-1 as MBT cations), dibutyltin (1.54 +/- 0.12 mg kg-1 as DBT cations) and tributyltin (2.20 +/- 0.19 mg kg-1 as TBT cations). The paper also describes an attempt to certify the content of triphenyltin in this material which, although reasonable agreement was found among the participants' results, failed owing to the instability of this compound. This new material will be of great support to ensure the quality control of butyltin determination in shellfish, as carried out in environmental monitoring programmes.  相似文献   

8.
Mass concentrations and chemical components (18 elements, 9 ions, organic carbon [OC] and elemental carbon [EC]) in atmospheric PM(10) were measured at five sites in Fushun during heating, non-heating and sand periods in 2006-2007. PM(10) mass concentrations varied from 62.0 to 226.3 μg m(-3), with 21% of the total samples' mass concentrations exceeding the Chinese national secondary standard value of 150 μg m(-3), mainly concentrated in heating and sand periods. Crustal elements, trace elements, water-soluble ions, OC and EC represented 20-47%, 2-9%, 13-34%, 15-34% and 13-25% of the particulate matter mass concentrations, respectively. OC and crustal elements exhibited the highest mass percentages, at 27-34% and 30-47% during heating and sand period. Local agricultural residuals burning may contribute to EC and ion concentrations, as shown by ion temporal variation and OC and EC correlation analysis. Heavy metals (Cr, Ni, Zn, Cu and Mn) from coal combustion and industrial processes should be paid attention to in heating and sand periods. The anion/cation ratios exhibited their highest values for the background site with the influence of stationary sources on its upper wind direction during the sand period. Secondary organic carbon were 1.6-21.7, 1.5-23.0, 0.4-17.0, 0.2-33.0 and 0.2-21.1 μg m(-3), accounting for 20-77%, 44-88%, 4-77%, 8-69% and 4-73% of OC for the five sampling sites ZQ, DZ, XH, WH and SK, respectively. From the temporal and spatial variation analysis of major species, coal combustion, agricultural residual burning and industrial emission including dust re-suspended from raw material storage piles were important sources for atmospheric PM(10) in Fushun at heating, non-heating and sand periods, respectively. It was confirmed by principal component analysis that coal combustion, vehicle emission, industrial activities, soil dust, cement and construction dust and biomass burning were the main sources for PM(10) in this coal-based city.  相似文献   

9.
利用鲁米诺-铁氰化钾-尿酸化学发光体系,在酸性介质中,NO-2将亚铁氰化钾氧化为铁氰化钾,建立了一种间接测定痕量亚硝酸盐的新方法。  相似文献   

10.
We developed a method to analyze atmospheric SO(x) (particulate SO(4)(2-)+ gaseous SO(2)) and NO(x) (NO + NO(2)) simultaneously using a battery-operated portable filter pack sampler. NO(x) determination using a filter pack method is new. SO(x) and NO(x) were collected on a Na(2)CO(3) filter and PTIO (2-phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl) + TEA (triethanolamine) filters (6 piled sheets), respectively. Aqueous solutions were then used to extract pollutants trapped by the filters and the resulting extracts were pre-cleaned (e.g. elimination of PTIO) and analyzed for sulfate and nitrite by ion chromatography. Recoveries of SO(2) and NO(x) from standard pollutant gases and consistency of the field data with those from other instrumental methods were examined to evaluate our method. SO(x) and NO(x) could be analyzed accurately with determination limits of 0.2 ppbv and 1.0 ppbv (as daily average concentrations), respectively. The sampler can determine SO(x) and NO(x) concentrations at mountainous or remote sites without needing an electric power supply.  相似文献   

11.
Industrial wastewater typically contains various metal ions. Traditional metal ion treatment processes such as chemical precipitation generate large volumes of toxic sludge which needs to be further solidified or disposed of. The ferrite process (FP), which is another effective approach of treating metal ion-containing wastewater, can crystallize metal ions into ferrites; the sludge easily precipitates, is stable and can be recycling. This investigation explores the feasibility of the Fenton process and the FP (FFP) for treating wastewater that contains metal ions. It considers one factor that adds noise to the FP, ethylenediaminetetraacetic acid, and establishes the optimum parameters of each procedure. The analytical results demonstrate that the proper conditions for Fenton process were pH = 2, [Fe(2+)] = 10(-2) M, H(2)O(2) dosing rate = 5 x 10(-4) mol min(-1), reaction time = 12 min. For the proposed multi-stage FP, the preferred Fe(2+) dosage was 0.098 mol in each stage and the sludge met the toxicity characteristic leaching procedure standards. Following the FFP, the effluent water or the sludge easily met Taiwan's standards. Finally, the SEM test demonstrated that size of the sludge particles was 50-110 nm.  相似文献   

12.
A liquid chromatographic method for the determination of aldehydes and ketones based on mass spectrometric detection is described. Recently developed modular derivatizing agents are employed for analysis. These hydrazine reagents, e.g. 4-dimethylamino-6-(4-methoxy-1-naphthyl)-1,3,5-triazine-2-hydrazine (DMNTH), react with the carbonyl compounds with the formation of the respective hydrazones, which are separated by HPLC-MS with atmospheric pressure chemical ionization in the positive mode. Electrospray ionization may also be used for analysis. Particular focus is directed on various calibration approaches, including external calibration with standard solutions and internal calibration with a hydrazone standard of cyclobutanone, an aldehyde not likely to occur in real samples. A second approach for internal calibration is based on the 13C2-labelled acetaldehyde hydrazone standard. Different calibration approaches may then be used for the analysis of real samples. Limits of detection range from 2 x 10(-8) to 5 x 10(-8) mol L-1 for a series of hydrazones, including hydrazones of saturated aldehydes with alkyl chain lengths from 1 to 7 carbon atoms, and hydrazones of selected unsaturated and aromatic aldehydes as well as ketone hydrazones.  相似文献   

13.
3, 4-Dihydroxybenzaldehydeisonicotinoylhydrazone was prepared, characterized with spectral analyses and used for developing a new method for the simple, sensitive and rapid spectrophotometric determination of vanadium(V) which gives maximum absorbance at wave length 360 nm. The metal ion gives a yellow colored complex with 3, 4-DHBINH in acetate buffer of pH 5.5 with 1:1 (metal:ligand) composition. The method obeys Beer's law in the range 0.5-5.3 mug mL(-1) of vanadium(V). The molar absorptivity and Sandell's sensitivity were found to be 1.29 x 10(4) L mol(-1) cm(-1) and 0.003949 mug cm(-2) respectively. The correlation co-efficient of the V(V)-3, 4-DHBINH complex was 0.992 which indicated an excellent linearity between the two variables. The repeatability of the method was checked by finding the relative standard deviation (RSD) as 0.424% (n = 5), and its detection limit 0.01677 mug mL(-1) of vanadium(V). The instability constant of the method was calculated by Asmus' method as 4.1666 x 10(-3). The interfering effect of various cations and anions were also studied. The proposed method was successfully applied to the determination of vanadium(V) in environmental samples (water and soil) tobacco leaves and alloy samples. The validity of the method was tested by comparing the results with those obtained using an atomic absorption spectrophotometer.  相似文献   

14.
Chemical (polycyclic aromatic hydrocarbon - PAH and heavy metal) levels in stormwater and sediment samples collected from the London Orbital (M25) motorway drainage dry detention pond at Oxted, Surrey, UK were determined. Such chemicals are derived from vehicular combustion products and the wear and tear materials deposited onto the motorway surface. Gas chromatography-mass spectrometry (GC-MS) was used for the qualitative and quantitative determination of 16 USEPA priority PAHs in motorway drainage sediments. The GC-MS method, incorporating a solid phase extraction step, provides detection limits ranging from 0.17 to 0.41 mg kg(-1)(dry weight). Almost all of the 16 USEPA listed PAHs were detected. Phenanthrene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(a)pyrene and benzo(g,h,i)perylene (PAH numbers 5, 7, 8, 9, 10, 11, 13 and 16) were among the PAHs found at "higher" levels (ranging from 0.3-10.2 mg kg(-1), dry weight) in the sediment samples. PAH levels show little change along the motorway drainage silt trap (facility for reducing the levels of suspended particulate matter in the stormwater). PAH concentrations are considerably higher in the dry detention pond outflow interceptor. Statistical analysis showed that significant correlation coefficients (based on a t-test at the 95% confidence interval) were obtained between those PAHs found at high concentrations over all of the sampling sites. Several PAHs were dispersed beyond the treatment facility and accumulation in the sediment of the deer park resulted in levels ranging from 0.3-1.6 mg kg(-1), dry weight. These PAHs found beyond the treatment facility (in the local farm deer park) may contribute a serious health threat to farm animals or even fish in the aquatic environment. Heavy metal levels (V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Cd, Sb and Pb) of the drainage stormwater and sediments were determined by inductively coupled plasma mass spectrometry (ICP-MS), with quality control evaluation using two certified reference materials. Typical detection limits were found to be below 0.1 [micro sign]g l(-1) for stormwater and 0.005 mg kg(-1) for acid digested sediments. Raised heavy metal levels were found throughout the dry detention pond facility and only decrease when the stormwater is diluted following discharge into the river Eden. Statistical analysis also confirms that some significant correlations exist between various heavy metals and PAHs. However, no overall conclusive trend is found indicating that a particular PAH is deposited in sediment relative to a specific heavy metal/s. These results raise some serious concerns about the dispersion and accumulation of chemicals in the sediments of motorway stormwater drainage systems and the need for maintenance and clean-up of contaminated material from such systems.  相似文献   

15.
A novel analytical method has been established for on-line simultaneous determination of fluorene and acenaphthene,chrysene and benzo[a]anthracene (B[a]A) by polarization synchronous fluoromet.y (PSF) coupled to high performance liquid chromatography (HPLC). The detection limits were: 0.039, 0.046, 0.016 and 0.042 mgL-1 for fluorene, acenaphthene, chrysene and B[a]A, respectively. The proposed method has been successfisily applied to simultaneous determination of these PAHs in environmental air and marine sediment samples.  相似文献   

16.
We present in this paper fifteen years' measurements, from March 1991 to September 2005, of stratospheric NO2 vertical columns measured by a SAOZ zenith-sky visible spectrometer. The instrument spent most of its time at Aberystwyth, Wales, with occasional excursions to other locations. The data have been analysed with the WinDOAS analysis program with low-temperature high-resolution NO2 cross-sections and fitting a slit function to each spectrum. Because of a change in detector in May 1998 there is some uncertainty about the relative changes before and after this date, which are partially constrained by the results of an intercomparison exercise. However, the effect of the Mt Pinatubo aerosol cloud is very evident in the data from 1991-94, with a decrease of 10% in NO2 in the summer of 1992 (the SAOZ was located in Lerwick, Scotland during the winter of 1991-92 and observed very low NO2 values but these cannot be directly compared to the Aberystwyth data). To focus more on interannual and long-term variations in NO2, a seasonal variation comprising an annual and semi-annual component was fitted to the morning and evening twilight separately from 1995 to the present. This fit yielded average NO2 columns of 4.08 x 10(15) cm(-2) and 2.68 x 10(15) cm(-2) for the evening and morning twilight, respectively, with a corresponding annual amplitude of +/-2.08 x 10(15) cm(-2) and +/-1.50 x 10(15) cm(-2). Departures from the fitted curve show a trend of 6% per decade, consistent with that reported elsewhere, for the period 1998-2003, but in the past two years a distinct interannual variation of amplitude of approximately 8% has emerged.  相似文献   

17.
To date, no ligand binding assay has been described for the carbamate herbicide asulam, although a variety of physical methods, dependent on pre-concentration of water samples, have been documented for its assessment. However, asulam is increasingly used in sensitive agricultural areas, and statutory regulations concerning its monitoring will undoubtedly become more stringent. Antibodies are optimal partners in ligand binding assays, but it is commonly understood by immunological researchers that where no antibody reactive with a particular antigen has yet been described, the immunogenicity of the antigen may be particularly restricted. By the expedient of employing a specialised approach to final immunisation with an asulam-protein conjugate, prior to the immortalisation of a specific anti-asulam antibody-producing cell, we have succeeded in generating a monoclonal antibody reactive specifically with asulam that can be configured in a convenient immunoassay. This antibody may be used flexibly in a number of ways: small sample volumes of 10 microl can be assessed to sensitivities of 4.35 x 10(-7) M (10 microg L(-1)) while avoiding discrepancies contributed by the assay matrix; this antibody-based assay can also be formatted to deliver sensitivities at levels stipulated by regulatory authorities (e.g., 4.35 x 10(-9) M or 0.1 microg L(-1)) directly from a water sample, without prior pre-concentration.  相似文献   

18.
PM(2.5) nitrate [Formula: see text] and sulfate ([Formula: see text]) were measured continuously with R&P8400N and R&P8400S instruments, respectively, and compared with filter-based measurements at the Fresno Supersite from October, 2000 through December, 2005. [Formula: see text] concentrations were higher in winter than summer with a long-term decreasing trend. Correlations between 24-h average continuous and filter-based [Formula: see text] were greater than 0.96 in 4 out of 5 years. Continuous [Formula: see text] was generally lower than filter-based [Formula: see text] although the difference decreased over time, from -52% in 2001 to +13% in 2005. These differences were similar in winter (-23%) and summer (-19%) while the corresponding differences between ambient and instrument temperature were -12 and 0.7 degrees C, respectively. Neither seasonal nor long-term trends in [Formula: see text] can be explained by variations in ambient temperature, the difference between ambient and instrument temperature, or changes in aerosol chemical composition. There were no seasonal or long-term trends in [Formula: see text] concentrations, partially due to low concentrations observed in Fresno. Long-term variability in the performance of R&P8400 [Formula: see text] and [Formula: see text] instruments suggest that collocation with filter measurements is needed for long-term measurements.  相似文献   

19.
A new complexing agent, 2-((2-((1H-benzo[d]imidazole-2yl)methoxy)phenoxy)methyl)-1H-benzo[d]imidazole (BIMPI), was used in cloud point extraction and applied for selective pre-concentration of trace amounts of cadmium in cigarette samples. Cadmium was complexed with BIMPI in a buffer solution (pH?=?10) using Triton X-114 as surfactant and quantitatively extracted into a small volume of the surfactant-rich phase after centrifugation. Under optimized conditions (pH?=?10.0, 0.8?×?10?4?mol?L?1 BIMPI and 0.08 % (w/v) Triton X-114), calibration graph was linear in the range of 34.0–1,670.0 μg?L?1. The proposed method was applied to the determination of Cd in various cigarette (tobacco) samples which gave satisfactory results.  相似文献   

20.
Characteristics of the monsoonal bloom of phytoplankton at Orissa Coast in the Bay of Bengal were studied through bimonthly observation from April 2001 to December 2002. Three photosynthetic pigments chlorophyll-a (Chl a), chlorophyll-b (Chl b) and carotenoid (Car) were analyzed by absorption spectroscopic method. The seasonal variation of Chl a included phytoplankton bloom in the coastal area during monsoon period. The water column integrated Chl a reached to 68 mg m(-2) at the station-1(St1), and amounted to 20 mg m(-2) at 30 km off the river mouth during August 2001. In contrast the same amount was found at 15 km off the Mahanadi river mouth during August 2002. Salinity during this period varied from 5 psu at the St1 to 27 psu at the edge of the bloom area. The total amount of river discharge in the monsoon period calculated from daily river discharge data reported by Water Resources Department in India was 84 x 10(9) m(3) during 2001 and 20 x 10(9) m(3) during 2002. Both nitrate and phosphate concentrations showed negative quadratic relationship with salinity throughout the observation period. Extrapolated nitrate and phosphate concentration discharge from the Mahanadi river were 10.8 and 4 microg-at l(-1), respectively. Microscopic identification revealed dominance of fluvial Chlorophyceae and diatoms during the monsoon period showing influence of the freshwater discharge.  相似文献   

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