A diffusive sampling device for the determination of formaldehyde in air using N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) as reagent

A new method utilizing the diffusive sampling of formaldehyde in air has been developed. Formaldehyde is sampled with the use of a glass fiber filter impregnated with N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) and phosphoric acid. The formaldehyde hydrazone formed is desorbed from the filter with acetonitrile and determined by high-performance liquid chromatography (HPLC) with UV/visible detection at 474 nm. The sampling rate was determined to be 24.7 mL min-1 with a relative standard deviation of 7% for 48 experiments. The measured sampling rates were not dependent on the formaldehyde concentration (0.1-1.0 mg m-3), sampling time (15-482 min) or relative humidity (20-85%). The detection limit was 70 micrograms m-3 for a 15 min sampling period and 2 micrograms m-3 for an 8 h sampling period.     

Indoor air sampling of organophosphate triesters using solid phase extraction (SPE) adsorbents

In this paper we demonstrate the use of SPE cartridges for sampling of organophosphate triesters in indoor air by adsorptive enrichment. The method has been optimised for the sampling and analysis of organophosphate triesters using a 25 mg aminopropyl silica SPE cartridge. The same cartridge is used for the active air sampling as well as for the subsequent extraction and clean-up of the sample. This makes the method fast and eliminates some tedious and time-consuming manual sample handling steps. Sampling and extraction efficiency was high for the investigated organophosphates, and limit of detection was in the range 0.1-0.3 ng m(-3). The method was applied to measurements of organophosphate triesters in two lecture halls and an electronics dismantling facility, and was compared with results from common filter/adsorbent sampling at each site. Analysis was made by GC with selective detection by NPD set in phosphorus mode, and by GC-MS. Thirteen organophosphate triesters (not counting isomers) were detected in the electronic dismantling facility. Chlorinated organophosphate triesters were detected in all locations with concentrations over 1 microg m(-3) in the lecture halls. This kind of adsorptive enrichment using an SPE cartridge could be adjusted to other types of analytes as well.     

Analysis of volatile organic compounds (VOCs) in sediments using in situ SPME sampling

A new method of determining the composition of sediment/soil gases and their volatile organic compound (VOC) content is described. VOCs were collected in situ from intertidal sediments in the Menai Strait and surrounding areas. The sampling was performed using a portable sampler comprising a funnel coupled to a SPME fibre. Gases were extracted from the sediments using a small vacuum pump pulling 100 mL min(-1) at atmospheric pressure. Sixty one different compounds were detected in the samples, and their fluxes and concentrations were determined. The compounds were classified into groups: halogenated, sulfur containing compounds, aldehydes, BTEXs (benzene, toluene, ethyl benzene and xylene) and aliphatic hydrocarbons. Results of principal component analysis (PCA) showed that the chemical composition of extracted gas was influenced primarily by sediment type. Muddy anoxic sediments were dominated by halogenated and sulfur containing compounds and sandy sediments had more aldehydes and BTEXs.     

Study on determination of iron,cobalt, nickel,copper, zinc and manganese in drinking water by solid-phase extraction and RP-HPLC with 2-(2-quinolinylazo)-5-diethylaminophenol as precolumn derivatizing reagent

A new method for the determination of iron, cobalt, nickel, copper, zinc and manganese in drinking water by the reversed-phase high-performance liquid chromatography (RP-HPLC) with 2-(2-quinolinylazo)-5-diethylaminophenol (QADEAP) as precolumn derivatizing reagent was studied in this paper. The iron, cobalt, nickel, copper, zinc, and manganese ions react with QADEAP to form color chelates in the presence of cetyl trimethylammonium bromide (CTMAB) and acetic acid-sodium acetic buffer solution medium of pH 4.0. These chelates were enriched by solid-phase extraction with a Waters Nova-Pak C18 cartridge and eluted the retained chelates from the cartridge with tetrahydrofuran (THF). The enrichment factor of 100 was achieved. Then the chelates were separated on a Waters Nova-Pak C18 column (3.9 x 150 mm, 5 microm) by gradient elution with methanol (containing 0.2% of acetic acid and 0.1% of CTMAB) and 0.05 mol L(-1) acetic acid-sodium acetic buffer solution (containing 0.1% of CTMAB) (pH 4.0) as mobile phase at a flow rate of 0.5 ml min(-1), and monitored with a photodiode array detector from 450 approximately 700 nm. The detection limits (S/N = 3) of iron, cobalt, nickel, copper, zinc and manganese are 0.8, 1.1, 0.9, 1.1, 1.5 and 2.0 ng L(-1), respectively, in the original sample. This method can be applied to determination at the microg L(-1) level of iron, cobalt, nickel, copper, zinc and manganese in drinking water with good results.     

Passive sampling of herbicides combined with effect analysis in algae using a novel high-throughput phytotoxicity assay (Maxi-Imaging-PAM)

We propose to combine a passive sampler for polar organic compounds (POS) with a specific bioassay for phytotoxicity to assess the hazard of herbicidal compounds in surface waters. The POS consisted of an Empore disk coated with styrenedivinylbenzene deployed in a Teflon housing, which has relatively high sampling rates (e.g., approximately 1 L d(-1) for diuron). POS were deployed for 5 days in a small-scale field study in South East Queensland, Australia, in a relatively pristine environment and an urban environment to explore sensitivity towards herbicides and potential influences of non-herbicidal pollutants. Besides chemical analysis of 8 herbicides, a novel bioassay (Maxi-Imaging-PAM, IPAM) was employed to assess the phytotoxic effects of water samples and POS extracts. The IPAM allows rapid assessment of photosynthetic quantum yields of a large number of samples via chlorophyll-fluorescence imaging and the saturation pulse method. Sampling rates for several herbicides from laboratory calibrations were found to be applicable under field conditions. Toxic equivalent concentrations (with reference to the herbicide diuron) were computed from the concentrations determined by chemical analysis and the relative potency (also termed toxic equivalence factor) of the detected herbicides. There was good agreement between diuron equivalent concentrations from chemical analysis and diuron equivalent concentrations determined with the IPAM.     

5-氯-2-(吡啶偶氮)-1,3-二氨基苯分光光度法测定水质钴

采用5-氯-2-(吡啶偶氮)-1,3-二氨基苯分光光度法测定水质钴。对分析方法的样品前处理、样品保存、样品分析条件、干扰消除、检出限及测定范围、实际样品测定进行了深入研究和技术改进。水样经消解后测定的方法检出限为0.009 mg/L,经富集后测定的方法检出限为4×10-4mg/L,干扰消除实验的回收率为96%~101%,地表水、地下水、生活污水及工业废水等4种类型水样的加标回收率为92%~103%。     

Dissipation and residue of MCPA (4-chloro-2-ethylphenoxyacetate) in wheat and soil

A rapid and simple HPLC method has been developed for the quantitation of 4-chloro-2-methylphenoxyacetic acid (MCPA) in both wheat and soil samples. Samples were extracted in acidic media and cleaned up by solid-phase extraction with C(18) cartridges before HPLC-DAD detection. The limits of detection and quantification of MCPA were 0.02 ng and 0.01 mg/kg for both wheat and soil. The mean recoveries ranged from 87.1% to 98.2%, and the RSDs ranged from 0.604% to 3.44% for the three spiked levels (0.01, 0.1, 0.5 mg/kg). The proposed method was successfully applied to the analysis of MCPA residues in wheat and soil samples from an experimental field. The dissipation half-lives in soil were calculated to be 3.22 days (Beijing) and 3.10 days (Tianjin), respectively. Direct confirmation of the analytes in real samples was achieved by gas chromatography-mass spectrometry. The results indicated that at harvest time, the residues of MCPA in wheat were well below the maximum residue levels and were safe to apply in wheat.     

Transfer of CO2, N2O and CH4 to butyl rubber (polyisobutylene) septa during storage

Greenhouse gases are more sampled than ever because of environmental interests. Gas samples are often inserted into vials with gas tight butyl rubber septa before concentration analysis. Little is known on the global transfer property of butyl rubber septa for CO2, N2O and CH4. Sorption kinetics were measured by injecting CO2, N2O or CH4 into glass vials with either one of four butyl rubber septa types and stored during 90 days. CO2 and N2O concentrations decreased during storage depending upon septa type and initial concentration, with the highest linear rate being 0.023 for CO2 and 0.0015 mg L(-3) day(-1) for N2O. When a low concentration was injected, CH4 concentration changes over time were small and did not differ between septa types. Sorption isotherms were measured using nine concentrations and stored during 45 days. CO2 sorption isotherms ranged from 0 to 3.7 x 10(-3) m(3) m(-2) and N2O from 0.3 to 1.4 x 10(-3) m(3) m(-2). Examples of errors associated with the use of these butyl rubber septa are given.     

The condition of coral reefs in South Florida (2000) using coral disease and bleaching as indicators

The destruction of coral reef habitats has occurred at unprecedented levels during the last three decades. Coral disease and bleaching in the Caribbean and South Florida have caused extensive coral mortality with limited recovery, often coral reefs are being replaced with turf algae. Acroporids were once dominant corals and have diminished to the state where they are being considered as endangered species. Our survey assessed the condition of reef corals throughout South Florida. A probability-based design produced unbiased estimates of the spatial extent of ecological condition, measured as the absence or presence and frequency or prevalence of coral diseases and bleaching intensity over large geographic regions. This approach allowed us to calculate a quantifiable level of uncertainty. Coral condition was estimated for 4100 hectares (ha) (or 41.0 km²) of coral reefs in South Florida, including reefs in the Florida Keys National Marine Sanctuary (FKNMS), New Grounds, Dry Tortugas National Park (DTNP), and Biscayne National Park (BNP). The absence or presence of coral disease, causal coral bleaching, partial bleaching and coral paling were not good indicators of overall coral condition. It was more useful to report the prevalence of anomalies that indicated a compromised condition at both the population and community levels. For example, 79% of the area in South Florida had less than 6% of the coral colonies diseased, whereas only 2.2% (97.15 ha) of the sampled area had a maximum prevalence of 13% diseased coral colonies at any single location. The usefulness of causal bleaching might be more important when considering the prevalence of each of the three different states at a single location. For example, paling was observed over the entire area, whereas bleaching and partial bleaching occurred at 19 and 41% of the area, respectively. An index for coral reef condition might integrate the prevalence and species affected by each bleaching state at individual locations. By establishing these baselines, future surveys can examine changes and trends in the spatial distribution of coral conditions in South Florida and able to score the reefs as to their health status.     

分光光度比浊法测定氢氟酸中SO_4~(2-)

在混合稳定剂的存在下,利用BaSO4的比浊法测定氢氟酸中的SO42-。SO42-浓度在0—50mg/L保持线性,2 5　工作曲线和灵敏度SO42-形成稳定的相应盐类。最低检出量为1mg/L。该方法已用于实际样品的测定。按实验方法测定其吸光度,SO42-的质量浓2 2　酸度的控制     

A novel wet-scrubbing process using Fe(VI) for simultaneous removal of SO2 and NO

The objective of this work was to develop a novel wet-scrubbing process using Fe(VI) for the simultaneous removal of gaseous NO and SO(2). The oxidation of SO(2) and NO with Fe(VI) was studied in aqueous solution at alkaline pH (9.0-11.0). A stoichiometric molar ratio for NO and SO(2) oxidation with Fe(VI) was determined to be nearly 3.0. Sulfate and nitrate was identified as final products by ion chromatography from the reaction at pH 9.0-11.0. The feasibility of simultaneous removal of multiple gas pollutants with the continuous feeding of ferrate in lab-scale was investigated from the view of industrial application. It was found that the removal efficiency of NO and SO(2) was enhanced with the increase of Fe(VI) concentration, more than 90% NO removal efficiency and 100% SO(2) removal efficiency were achieved by wet-scrubbing process using Fe(VI) at room temperature and ambient atmosphere. The results demonstrate that Fe(VI) could be an effective wet-scrubbing agent for the simultaneous removal of NO and SO(2).     

Temporal trend of mercury in polar bears (Ursus maritimus) from Svalbard using teeth as a biomonitoring tissue

We examined the use of mercury (Hg) and nitrogen and carbon stable isotopes in teeth of polar bear (Ursus maritimus) from Svalbard as biotracers of temporal changes in Hg pollution exposure between 1964 and 2003. Teeth were regarded as a good matrix of the Hg exposure, and in total 87 teeth of polar bears were analysed. Dental Hg levels ranged from 0.6 to 72.3 ng g(-1) dry weight and increased with age during the first 10 years of life. A decreasing time trend in Hg concentrations was observed over the recent four decades while no temporal changes were found in the stable isotope ratios of nitrogen (δ(15)N) and carbon (δ(13)C). This suggests that the decrease of Hg concentrations over time was more likely due to a lower environmental Hg exposure in this region rather than a shift in the feeding habits of Svalbard polar bears.     

Chemistry of Dissolved Organic Carbon at Bear Brook Watershed, Maine: Stream Water Response to (NH4)2SO4 Additions

This study was conducted to determine the response of stream water DOC and organic acidity to increased inputs of ammonium sulfate to a whole catchment. Precipitation, throughfall, soil solutions (from Spodosols) and stream waters were characterized for DOC concentrations and fractions (hydrophobic acids and neutrals, hydrophilic acids, bases, and neutrals) in both the control (East Bear) and the treatment (West Bear) catchments of Bear Brook Watershed, Maine (BBWM), a northern hardwood forest. In all solutions except precipitation, DOC was composed primarily of organic acids, with hydrophobic acids dominating (> 60% of DOC) in forest floor leachates (5000 mol C L-1), and a balance of hydrophobic and hydrophilic acids in deep B horizons and stream waters ( 150 mol C L-1). Stream waters had higher concentrations of DOC during storm or snowmelt events (high discharge), often reaching 300 to 400 mol C L-1. Forest floor leachate C was rapidly attenuated by the mineral soils under all flow conditions, indicating how important mineral soil sorption of DOC was in reducing the loss of C via surface water from BBWM. No differences occurred between control and treatment streams for concentration or composition of DOC due to treatment from 1989 through 1994. In 1995, West Bear Brook had much lower concentrations of DOC than East Bear for the first time. However, this occurred during a year of record low runoff, suggesting that hydrology may have affected export of C. Average annual export of DOC from the catchments was similar (1000 to 2000 mol C ha-1 yr-1). Organic anions in streamwaters increased slightly during high flow events (e.g., East Bear had means of 15 and 19 eq L-1 organic anions during base flow and high discharge in 1995). Treatment of West Bear caused a decrease in organic anions, both in concentration and contribution to overall anion composition (organic anions during high discharge as a percentage of total anions decreased from about 8 to 4% for 1987-89 and 1993-95 samples, respectively). This was probably due to decreased solution pH (greater protonation of organics) and higher concentrations of inorganic anions. Overall, there were no clear, detectable changes in stream water DOC, with only minor changes in organic anions, as a result of treatment with ammonium sulfate.     

Solid phase extraction and determination of Cr(III) by spectrophotometry using cefaclor as a complexing reagent and FAAS

The present study reports on the application of modified groundnut shell as a new, easily prepared, and stable sorbent for the extraction of trace amount of Cr(III) in aqueous solution. 2-Hydroxybenzaldiminoglycine was immobilized on groundnut shells in alkaline medium and then used as a solid phase for the column preconcentration of Cr(III). The elution was carried out with 3 mL of 2 mol?L^?1 HCl. The amount of eluted Cr(III) was determined by spectrophotometry using cefaclor as a complexing reagent and by flame atomic absorption spectrometry (FAAS). Different experimental variables such as pH, amount of solid sorbent, volume and concentration of eluent, sample and eluent flow rate, and interference of other metal ions on the retention of Cr(III) were studied. Under the optimized conditions, the calibration curves were found to be linear over the concentration range of 13–104 and 10–75 μg?L^?1 with a detection limit of 3.64 and 1.24 μg?L^?1 for spectrophotometric method and FAAS, respectively. An enrichment factor of 200 and RSD of ±1.19–1.49 % for five successive determinations of 25 μg?L^?1 were achieved. The column preconcentration was successfully applied to the analysis of tap water and underground water samples.     

Spectrophotometric determination of platinum(IV) in alloys, complexes, environmental, and pharmaceutical samples using 4-[N,N-(diethyl)amino] benzaldehyde thiosemicarbazone

4-[N,N-(Diethyl)amino] benzaldehyde thiosemicarbazone (DEABT) is proposed as an analytical reagent for the spectrophotometric determination of platinum(IV). The DEABT forms 1:2 yellow complex with Pt(IV), which is sparingly soluble in water and completely soluble in water–ethanol–DMF medium. The Pt(IV)–DEABT complex shows maximum absorbance at 405 nm. Beer’s law is valid up to 7.80 μg cm^???3, and optimum concentration range for the determination of platinum(IV) is 0.48–7.02 μg cm^???3. The molar absorptivity and Sandell’s sensitivity of the method are found to be 1.755 × 10⁴ dm³ mol^???1 cm^???1 and 0.0012 μg cm^???2, respectively. The relative error and coefficient of variation (n?=?6) for the method does not exceed ±0.43% and 0.35%, respectively. Since the method tolerates a number of metal ions commonly associated with platinum, it can be employed for the determination of platinum in environmental samples, pharmaceutical samples, alloys, catalysts, and complexes. The method is rapid as the Pt(IV)–DEABT complex is soluble in water–ethanol–DMF medium and not requiring any time consuming extraction method for the complex.     

Influences of metal cations on the determination of the alpha-oxocarboxylates as the methyl esters of the O-(2,3,4,5,6-pentafluorobenzyl)oximes by gas chromatography: the importance of accounting for matrix effects

The alpha-oxocarboxylates alpha-ketocarboxylates) and the corresponding alpha-oxoacids (alpha-ketoacids) have been reported as disinfection byproducts of ozonation of potable water supplies. In this analytical method, the oxo moiety is derivatized with O-(2,3,4,5,6-pentafluorobenzyl)oxylamine (PFBOA) to form an oxime which is then extracted into tert-butyl methyl ether. The carboxylic acid moiety is esterified (methylated) with diazomethane. In this study, five analytes were investigated: oxoethanoate (glyoxylate), 2-oxopropanoate (pyruvate), 2-oxobutanoate (2-ketobutyrate), 2-oxopentanoate (2-ketovalerate), and oxopropanedioate (ketomalonate, mesoxalate). The influence of Lewis acid metal cations in the water matrix was evaluated for the gas chromatographic method commonly used for the quantitation of these analytes at concentrations < or = 150 ng mL(-1). Tested metals included Ca(II), Mg(II), Fe(III), Cu(II) and Zn(II). At typical concentrations, calcium, in particular, can have profound impact, especially on oxoethanoate quantitation. Oxopropanoate experiences an increase in recovery in the presence of metal cations. 2-Oxobutanoate and 2-oxopentanoate are the most resistant to these effects, but 2-oxopentanoate shows increased recoveries at higher concentrations when assayed in the presence of calcium ion. Oxopropanedioate generally shows poorer precision and recovery when determined in solutions containing metal ions. This investigation demonstrates the significance of metal effects in the quantitative determination of these analytes and further emphasizes the importance of thorough matrix characterization and careful recovery studies with fortified (spiked) samples and blanks.     

NH4NO3-Pd(NO3)2联合基体改进剂石墨炉法测海水中痕量镉

用NH4NO3-Pd(NO3)联合基体改进剂,石墨炉法直接测海水中痕量镉.通过不同条件的实验,确定了最佳的分析条件;并通过对实际样品平行性和加标回收率的测定,验证了方法的精密度和准确度.建立了空白实验,在0.19～5.0μg/L线性范围内,镉的最低检出限为0.19μg/L.实验结果表明,该方法快速方便,提高了分析效率,准确度高,精密度好.     

Surfactant-mediated complex formation for determination of traces amounts of zinc, cadmium, and lead with 4-(2-thiazolylazo) resorcinol and chemometric methods

The partial least squares modeling is a powerful multivariate statistical tool applied to the spectrophotometric simultaneous determination of the divalent ions of zinc, cadmium, and lead based on the formation of their complexes with 4-(2-thiazolylazo) resorcinol in surfactant media. The linear concentration range for zinc, cadmium, and lead were 0.10-1.31, 0.148-1.92, and 0.148-3.70 mg L(?-1), respectively. The experimental calibration set was composed of 36 sample solutions using a mixture design for three component mixtures. The absorption spectra were recorded from 380 through 650 nm. The effect of pH on the sensitivity in determination of zinc, cadmium, and lead was studied in order to choose the optimum pH (pH = 8) for determination. The root-mean-square errors of predictions for zinc, cadmium, and lead were 0.0466, 0.0282, and 0.050, respectively. The proposed method was successfully applied for the determination of zinc, cadmium, and lead in water samples.     

The efficiency of Amberlite XAD-4 resin loaded with 1-(2-pyridylazo)-2-naphthol in preconcentration and separation of some toxic metal ions by flame atomic absorption spectrometry

A selective method has been developed for the determination of trace amount of metal ions after preconcentration on 1-(2-pyridylazo)-2-naphthol loaded Amberlite XAD-4 resin. The chelating resin was characterized on the basis of infra red spectra, thermal and chemical stability, and hydrogen ion capacity. High preconcentration factor of 160?C400 up to a low preconcentration limit of 10 ??g L^???1 has been achieved for almost all the metals. The chelating resin was highly selective even in the presence of large concentrations of alkali and alkaline earth metals and various matrix components. Chromatographic separation of metal ions in binary mixtures has been accomplished. The analytical utility of the resin for metal ions was explored by analyzing natural water and standard reference materials.