Differential pulse adsorptive stripping voltammetric determination of simeton in its formulations and vegetables

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.     

Development of a harmonised phosphorus extraction procedure and certification of a sediment reference material

A harmonised procedure for the determination of the forms of phosphorus in freshwater sediments, developed in the frame of the European Programme, Standards, Measurements and Testing (SMT) has been used for a certification campaign for a reference material. This operationally defined scheme is a good compromise between method performance and reproducibility. Furthermore, the method is rather simple to implement and could be used by water managers on a routine basis. A homogeneous and stable sediment reference material has been prepared and will be available before mid 2001. The so-called SMT protocol, together with the reference material, are useful tools in the field of water management, especially at a time when quality assurance is of paramount importance in laboratory analyses. Knowledge of the bioavailable forms of phosphorus is important not only for analysis of sediments but also for sludge and soils. Therefore, the SMT protocol could be extended to these materials.     

Evaluation of the temporal scaling variability in forecasting ground-level ozone concentrations obtained from multiple linear regressions

Ozone is a highly unpredictable pollutant which severely affects living conditions in urban and surrounding areas in the Mediterranean basin. This secondary pollutant periodically reaches extremely high concentrations, damaging human health. Multiple linear regression has been widely used in previous works due to the fact that it is a simple and versatile method for forecasting ozone concentrations. However, these models usually prove their validity using fulfillment of statistical constraints, ignoring other intrinsic characteristics existing in the time series, such as the temporal scaling behavior and the data distribution over different time scales. In previous works, it has been demonstrated that observed ozone time series are of a multifractal nature, meaning that the data distribution can be described by using the multifractal spectrum. This work focuses on the capacity of a forecasting model to reproduce the scaling features existing in an observed time series when several chemical and meteorological explanatory variables are introduced following the stepwise procedure. A comparison between the observed spectrum and the simulated ones for each step is used to check which explanatory variables better reproduce the multifractal nature in real ozone time series. It has been confirmed that a model with few explanatory variables allows reproducing the multifractal nature in the simulated time series with an acceptable accuracy without compromising the values of the coefficient of determination and root-mean-squared error, which were used as performance indicators.     

Antifouling strategies for marine and riverine sensors

Traditionally, water quality has been monitored by sampling and lab based analysis. However, there are disadvantages associated with this method, for example, deterioration of samples with time, limited sampling points, limited temporal monitoring. This has provided impetus for the development of sensors which can be deployed from remote locations over extended deployment periods. However, a major limitation of these systems is their vulnerability to biofouling. This review outlines the research that has been carried out on strategies for the protection of marine and riverine sensors against fouling.     

Higher Pollution Episode Detection Using Image Classification Techniques

Image classification techniques have been applied to detect higher pollution episodes in modelled air pollution data. These techniques are widely used in video processing to find patterns in videos. An attempt for the first time has been made to apply these techniques by considering air pollution as continuous video frames as the spatio-temporal changes in the pollution are linked to its previous state of the atmosphere. The applicability of these techniques has been tested over Northern Italy to detect ozone pollution episodes in year 2004 using model simulated concentrations. The methods tested in this paper are pixel, block-based, histogram, pertinent pixel and twin-comparison method. While these techniques have some kind of merits and demerits, a modified pertinent pixel comparison algorithm has been proposed to detect pollution episodes. The proposed method has been validated to detect PM10 episodes over Milan metropolitan area during 2 months in 2008 and is able to detect PM10 episodic events as well as non-events. This method provides a single binary index that can be applied by the air quality modellers and decision makers to determine the pollution episode over a given domain.     

顶空固相微萃取-气相色谱法测定水中四乙基铅

建立了水中四乙基铅的测定方法——顶空固相微萃取-气相色谱法,探讨了影响水中四乙基铅萃取效率的温度、转速和萃取时间等因素。实验结果表明,在0.08～10μg/L范围内线性关系良好,方法检出限为0.02μg/L,实际水样加标回收率为96.2%～98.3%。     

An Analysis of the Annual and Seasonal Trends of Air Quality Index of Delhi

The Air Quality Index (AQI) is an index for reporting daily air quality. A study on the annual and seasonal variations of Air Quality Index over a period of 9 years (1996-2004) based on daily averaged concentration data of criteria air pollutants has been conducted for Delhi. An attempt has been made to quantify the changes in the AQI on annual and seasonal (winter, summer, monsoon and post monsoon) basis for 9 years. Measurements for the seven monitoring sites (Nizamuddin, Ashok Vihar, Shahzada Baug, Shahadara, Janakpuri, Sirifort and ITO) in Delhi were analysed and trends were also compared amongst these sites. Maximum Operator Function method was used to compute the Air Quality Index of the above areas and percentage variations in different severity class is discussed which provides in depth analysis of the trends. The best air quality was depicted by Shahzada Baug followed by Shahdara, both of these were classified as industrial areas indicating that policy measures relating to the industries in the city during past years have helped in improving the air quality. The air quality in other areas have improved slightly in the span of nine years but still remains critical indicating continued rigorous efforts in this direction. Increased traffic density seems to have resulted into the worst air quality at ITO in the city amongst all the monitoring stations. There is a shift for the worst AQI in the city from winter to summer season in a time span of these nine years. Change of season for worst AQI from Winter to Summer may also be likely due to increased photochemical reactions playing major role with change in the nature of emissions imposed due to different control measures such as CNG implementation, significant shift to LPG in domestic sector etc. calling for a detailed study, those which started after the year 2000. After the year 2000, there is a significant increase in the Nitrogen-dioxide (NO(2)) concentration at all stations. ITO which has shown continuous exponential increase in pollution levels has first time showed a declining AQI trend in the year 2004 and one of the contributing factors could have been the Delhi metro (initiated in 2002) passing through congested neighbouring areas causing traffic decongestion here. In general, the areas which are farthest from metro route viz., Siri-fort, Nizamuddin, Janakpuri etc. did not record declining AQI in 2003 onwards as happened with stations closer to Metro route such as Ashok Vihar and ITO. An attempt has been made to quantify the reasons that lead to the changes in the values of the AQI.     

Evaluation of a simultaneous sampling method of PAHs, PCDD/Fs and dl-PCBs in ambient air

The Stockholm Convention on Persistent Organic Pollutants (POPs) was signed in May 2001 by 127 countries. Currently, 12 substances are regulated by the convention, and the work on finding new candidate chemicals to the convention has started. Among these 12 substances, dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are the objects of this study. There are no European standard methods for the simultaneous determination of these microorganic compounds, together with polycyclic aromatic hydrocarbons (PAHs) in ambient air--they must be referred to three different methods developed by the U.S. Environmental Protection Agency (EPA). The quali-quantitative analysis of these microorganic pollutants is an important challenge due to the low concentrations at which they may be present. In this study, the development of a simplified, alternative, fast and affordable sampling method for the determination of PAHs, PCDDs, PCDFs and PCBs in ambient air was performed. The sampling time was extended from 24 h to 7 d in order to enrich the sample, to fall within the instrumental limits of detection and to reduce the number of samples to be processed and, therefore, errors that may arise. First of all, experiments with labelled standards were conducted in the research area of Montelibretti (rural station, which is sited about 20 km northeast of Rome), with the purpose of optimizing sampling efficiency. Finally, the method was applied to the analysis of these compounds in the air of a suburban area with small industrial plants in order to evaluate the feasibility of the proposed sampling method system, by comparing concentrations of native compounds acquired during simultaneous daily and weekly sampling.     

顶空便携式气相色谱—质谱仪现场测定地表水中苯系物

对顶空便携式气相色谱—质谱仪分析水中的苯、甲苯、乙苯、邻-二甲苯、间-二甲苯、对-二甲苯、异丙苯的方法进行了研究,并讨论了平衡时间、平衡温度、水中含盐量等因素对测定的影响。结果表明,方法的回收率为94.15%~98.67%,相对标准偏差为2.32%~4.88%,最低检出限为0.031~0.094μg/L。该方法快速、准确、重复性好。     

New procedures for simultaneous determination of mesotrione and atrazine in water and soil. Comparison of the degradation processes of mesotrione and atrazine

A method for the determination of residues of mesotrione, atrazine and its degradation products: deethylatrazine, hydroxyatrazine, deisopropylatrazine, desethyldesisopropylatrazine in a variety of water and soil matrices has been developed. Mesotrione is a new selective herbicide for use in corn, which has been substituted for atrazine, which has been banned in European Union countries since 2007. Although atrazine has not been used for three vegetative periods, it is still detected in the environment. The analysis was conducted by means of ultra-high-pressure liquid chromatography with ultraviolet detection and liquid chromatography with diode array detection. The procedures for analyte separation from water and soil matrices were also established. The optimal conditions for solid-phase extraction (SPE) were determined. The recoveries were compared with that obtained by means of SPE. Method fortification recoveries from water samples averaged 78–97% and for soil 80–97% depending on the analyte and type of sample. The limits of detection were 0.04–0.61 μg/L for water samples and for soil samples 0.02–0.88 μg/g. The soil samples were collected in spring 2009 from three different fields with water samples being made from effluents from these fields. Samples collection was conducted in the day of mesotrione (Callisto 100SC) application and then done weekly, until the mesotrione concentration was below the limit of quantification. The results enabled the monitoring of mesotrione degradation in soil and its permeability into surface waters; simultaneously, the same studies were conducted for atrazine.     

吹扫捕集-气相色谱质谱法分析土壤和沉积物中挥发性有机物

采用吹扫捕集-气相色谱质谱法对土壤和沉积物中挥发性有机物进行分析,优化了实验条件,所有物质的相对标准偏差小于5.0％,土壤样回收率在78.2％ ～99.8％之间,沉积物样的回收率在55.2％～95.2％之间.     

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.     

The extraction of aged polycyclic aromatic hydrocarbon (PAH) residues from a clay soil using sonication and a Soxhlet procedure: a comparative study

A sonication method was compared with Soxhlet extraction for recovering polycyclic aromatic hydrocarbons (PAH) from a clay soil that had been contaminated with tar materials for several decades. Using sonication over an 8 h extraction period, maximum extraction of the 16 US EPA priority PAH was obtained with dichloromethane (DCM)-acetone (1 + 1). The same procedure using hexane-acetone (1 + 1) recovered 86% of that obtained using DCM-acetone (1 + 1). PAH recovery was dependent on time of extraction up to a period of 8 h. The sonication procedure showed that individual PAH are extracted at differing rates depending on the number of fused rings in the molecule. Soxhlet extraction [with DCM-acetone (1 + 1)] over an 8 h period recovered 95% of the PAH removed by the sonication procedure using DCM-acetone (1 + 1), indicating that rigorous sonication can achieve PAH recoveries similar to those obtained by Soxhlet extraction. The lower recovery with the Soxhlet extraction was explained by the observed losses of the volatile PAH components after 1-4 h of extraction. The type of solvent used, the length of time of extraction and extraction method influenced the quantification of PAH in the soil. Therefore, the study has implications for PAH analyses in soils and sediments, and particularly for contaminated site assessments where the data from commercial laboratories are being used. The study emphasizes the importance of establishing (and being consistent in the application of) a vigorous extraction, particularly for commercial laboratories that handle samples of soil in batches (at different times) from a single site investigation or remediation process. The strong binding of PAH to soil, forming aged residues, has significant implications for extraction efficiency. This paper illustrates the problem of the underestimation of PAH using the US EPA method 3550, specifically where a surrogate spike is routinely employed and the efficiency of the extraction procedure for aged residues is unknown. The implications of this study for environmental monitoring, particularly where numerous batches of samples from a single site assessment or remediation program are submitted to commercial laboratories, is that it would be advisable for these laboratories to check their existing method's extraction efficiencies by conducting a time course sonication extraction on their particular soil to determine the optimum extraction time.     

Determination of acrylic acid in air by using diffusion denuder tubes combined with HPLC technique

A procedure for the determination of atmospheric acrylic acid in air at the microgram m-3 to mg m-3 level is described. Diffusion-based sampling, designed to discriminate gaseous analytes from their particulate counterparts, has been used. Acrylic acid is collected with an efficiency of > 98% in tubular denuders coated with sodium hydroxide-barium hydroxide-hydroquinone monomethyl ether, and analyzed by high performance liquid chromatography with UV absorbance detection. The detection limit is 2.9 micrograms m-3 at a flow rate of 0.5 L min-1 and 30 min sampling time. A precision (p = 0.95, n = 10) of 7.5% of the overall procedure was achieved at the 100 micrograms m-3 level. Results of laboratory studies concerning the effect of the coating reagent and the relative humidity on the sampling efficiency as well as possible interferences, in particular by ozone, and the elimination of these interferences are discussed. This method was developed to monitor workplace atmospheres as well as ambient air in industrial environments.     

Determination of Pb and Cd in road dusts over the period in which Pb was removed from petrol in the UK

It is commonly agreed that automobile exhaust has been the most important source of Pb pollution in urban areas, and that Cd may come from wear and tear of tyres. This study evaluates the fall in Pb concentrations in road dusts in Manchester as a consequence of the removal of Pb from petrol in January 2000. In the work presented here a slurry graphite furnace atomic absorption methodology for the determination of Pb and Cd in road dusts has been developed and is compared with an acid digestion method in terms of efficiency. The reproducibility and accuracy of the results obtained by acid digestion and the slurry method have been studied and a certified reference material CRM 038 was analysed to confirm the reliability of the proposed methods. Different factors were evaluated throughout this work including: (i) the effect of traffic density on Pb and Cd levels in road dust samples collected weekly during the period of May 1999 until September 2000; (ii) comparison between the Pb and Cd levels in a busy road and a residential street; (iii) the effect of distance from the source on Pb and Cd levels; The results of these experiments show a reduction in Pb levels over the sampling period. The relationship between road dust particle size and Pb and Cd concentration was also investigated in the 4-250 microns size range using the slurry method, showing that there is a relationship between metal concentration and particle size; the highest concentrations being for the smallest particle size.     

An ultrasound accelerated sequential extraction method and its application for element partitioning studies in compost from mixed waste streams

A rapid ultrasound accelerated sequential extraction procedure is presented which is modified from the standard BCR protocol and validated using the BCR 601 reference material. The method is accelerated at the extraction steps: for example, in the standard method each extraction step takes 16 h whereas with the ultrasonic extraction method developed in this work each step took 15 min. This means a further step can be included in the protocol without greatly increasing the experimental time. An extraction with pyrophosphate solution was therefore included to provide more information about the interaction between the elements and humic substances during the composting process. The new method has been applied to monitoring the metal partitioning behaviours in a composting process involving mixed waste streams. The metal partitioning profiles obtained from this new method show that in many cases composting tends to redistribute the metals from more labile forms to combined forms, especially to forms combined with humic substances.     

Speciation/fractionation of nickel in airborne particulate matter: improvements in the Zatka sequential leaching procedure

Modifications are reported to the sequential leaching analytical method for nickel speciation/fractionation specified by Zatka so that larger sample masses can be analyzed. Improvements have been made in the completeness of the sulfide/metallic separation during the peroxide-citrate leach step by use of a larger volume of leachant, a longer leach duration and an orbital shaker. Minimal extraction of metallic nickel in this prolonged sulfidic nickel extraction has been confirmed. An increase in the number of samples analyzed simultaneously using these modifications has resulted in substantial productivity improvements and concomitant lower costs. It is critical for practitioners of sequential leaching techniques to recognize potential limitations and to use professional judgment when interpreting results. For example, results obtained may not be biologically relevant in assessing health risks; the acts of sampling and storage may result in changes in fractionation with time; surface coatings/films may alter the ability of a leachant to react with the target compound; and leaching behaviours may be different for samples differing only in particle size distributions.     

The effect of humic acids on the sequential extraction of metals in soils and sediments using ICP-AES and chemometric analysis

The effect of humic acids on the sequential extraction of metals from various soils and sediments has been studied. A new multi-element extraction method optimised via experimental design has been employed. The method uses centrifugation to pass the extractant solution, at varying pH, through the sediment sample. The sequential leaches were collected and analysed by ICP-AES. Chemometric data processing was utilised to identify the composition of the physico-chemical components in order to characterise the sample. A sediment sample collected from Carnon River (Cornwall, UK) and a reference material (NIST 2711 agricultural soil) were spiked with humic acids and the sequential extraction scheme was used to monitor the changes in metal distribution. The method has proved a quick and reliable way to evaluate different sediment samples, and has potential as a new tool for environmental geochemistry analysis.     

凝胶渗透色谱-硅胶柱-气相色谱-负化学离子源质谱测定生物介质中49种BFRs类化合物

建立了生物介质内22种多溴联苯(PBBs)和27种多溴联苯醚(PBDEs)的净化和分析方法。通过分析不同时间段凝胶渗透色谱(GPC)洗脱液中49种化合物含量,得出不同化合物凝胶色谱洗脱曲线。样品经过凝胶渗透色谱-混合硅胶柱净化后,再使用GC-(NCI)/MS对样品进行检测。实验结果表明,PBBs和PBDEs检出限分别为0.02~0.88 pg/g和0.01~74.00 pg/g。对实验过程进行验证发现,样品不同浓度加标回收率为80%~120%,相对标准偏差小于20%。该方法具有良好的净化效果、准确度和精密度,拥有良好的线性范围及检出限,满足生物介质中溴代阻燃剂的检测分析实际要求。     

The sensitive and selective determination of aluminium by spectrofluorimetric detection after complexation with N-o-vanillidine-2-amino-p-cresol

A simple, easy to use and selective spectrofluorimetric method for the determination of trace levels of aluminium has been developed. A new Schiff base, N-o-vanillidine-2-amino-p-cresol (OVAC), has been synthesized and its fluorescence activity with aluminium investigated. Based on this chelation reaction, a spectrofluorimetric method has been developed for the determination of aluminium in samples buffered at pH 4.0 using acetic acid-sodium acetate. The chelation reaction between Al(iii) and N-o-vanillidine-2-amino-p-cresol was very fast, requiring only 20 min at room temperature to complex completely. The excitation and emission wavelengths were 423.0 and 553.0 nm, respectively, at which the OVAC-Al complex gave the maximum fluorescence intensity at pH 4.0 in a 50% ethanol-50% water medium. The interference from fluoride ions was minimized by the addition of Be(2+). Other ions were found not to interfere at the concentrations likely to be found in natural waters. Under these conditions, the calibration plot was linear up to 1000 microg L(-1) (r = 0.999). The limit of detection (3sigma) for the determination of Al(iii) was 0.19 microg L(-1) and the precision for multiple determinations of 3 ng mL(-1) Al(iii) prepared in ultra-pure water was found to be 0.29% (n = 16). The Schiff base ligand could be used to determine ultra-trace aluminium from natural waters. Analysis of environmental certified reference materials showed good agreement with the certified values. The procedure was found to be equally applicable to both fresh water and saline solutions (including sea water) using either normal external calibration or the standard additions method.