Dibenzazepin hydrochloride as a new spectrophotometric reagent for determination of hydrogen peroxide in plant extracts

A rapid, simple, accurate, and sensitive visible spectrophotometric method for the determination of trace amounts of hydrogen peroxide in acidic buffer medium is reported. The proposed method is based on the oxidative coupling of Ampyrone with dibenzazepin hydrochloride by hydrogen peroxide in the buffer medium of pH?4.0 which is catalyzed by ferrous iron. The blue-colored product formed with maximum absorption at 620?nm was found to be stable for 2?h. Beer's law is obeyed for hydrogen peroxide concentration in the range of 0.03-0.42?μg?ml(-1). The optimum reaction conditions and other important optical parameters are reported. The molar absorptive and Sandell's sensitivity are found to be 5.89?×?10(4)?mol(-1)?cm(-1) and 0.57?g/cm(2), respectively. The interference due to diverse ions and complexing agents was studied. The method is successfully applied to the determination of hydrogen peroxide in green plants satisfactorily.     

Assessment of pumped mercury vapour adsorption tubes as passive samplers using a micro-exposure chamber

Mercury vapour adsorption tubes manufactured for pumped sampling and analysis have been evaluated for their performance as passive samplers. This has been done by exposing these tubes in a novel micro-exposure chamber. The uptake rates of these tubes have been found to be low (approximately 0.215 ml min(-1)) as compared to bespoke passive samplers for mercury vapour (typically in excess of 50 ml min(-1)). The measured uptake rates were shown to vary significantly between tubes and this was attributed to the variability in the air-sorbent interface and the proportion of the cross sectional area removed by the crimp in the quartz tubes used to secure the sorbent material. As a result of this variability the uptake rate of each tube must be determined using the micro-exposure chamber prior to deployment. Results have shown that the uptake rate determined in the micro-exposure chamber is invariant of concentration, and therefore these uptakes rates may be determined at a high mercury vapour concentration for many tubes at once in less than one hour. The uptake rate of the adsorption tubes under these conditions may be determined with a precision of 5%. Measurements made on a limited field trial in indoor and outdoor ambient air have shown that these tubes give results in acceptable agreement with more traditional pumped sampling methods, although longer sampling periods are required in order to reduce the uncertainty of the measurement, which is currently approximately 30%.     

Workplace monitoring for volatile organic compounds using thermal desorption-gas chromatography-mass spectrometry

The interest in the identification of volatile organic compounds in the workplace has been a major focus of many National Institute for Occupational Safety and Health (NIOSH) field studies. A primary technique for sampling and analysis of these compounds is summarized by NIOSH Manual of Analytical Methods (NMAM) 2549. This is a screening method that uses a multi-bed sorbent to trap a wide variety of compounds and compound classes. Thermal desorption techniques are used as a first attempt to characterize potential contaminants in a workplace and to determine what future sampling and analyses must be performed. Field examples are provided to show the versatility of thermal desorption methods and techniques. Due to their sensitivity, thermal desorption tube methods are sometimes required in order to measure the workplace concentrations of unusual compounds. In other situations, the exposures are too high or varied to make thermal desorption tubes practical. In these cases, the identification of contaminants with thermal desorption tubes leads to new method developments for the quantification of specific compounds using more conventional solid sorbent-solvent desorption based methods.     

离子色谱法测定空气中氟化氢氯化氢和硫酸

以多孔玻板吸收管采样,采用离子色谱法同时测定作业场所空气中的氟化氢、氯化氢和硫酸,采样效率>92%。氟化氢在0 mg/L～2.00 mg/L、氯化氢在0 mg/L～2.50 mg/L、硫酸在0 mg/L～4.00 mg/L范围内线性良好,检出限分别为0.003 mg/m3、0.02 mg/m3、0.023 mg/m3(按采样体积60 L计),标准溶液平行测定的RSD≤8.0%,两个质量浓度水平加标的平均回收率为92.6%～106%。     

Performance of methods for measurement of exposure to inorganic acids in workplace air

BGIA has organised round robins for the analysis of samples of inorganic acids in workplace air for a number of years. Test samples of the volatile acids HCl and HNO(3) are collected from a standard atmosphere and samples of the non-volatile acids H(3)PO(4) and H(2)SO(4) are prepared by spiking filters with acid solution. The last two round robins have also covered the sampling of volatile acids, with up to 15 "active" participants able to visit the test facility in Dresden and take samples themselves. For other "passive" participants, BGIA takes samples from the same atmosphere. The acid concentrations generated lie between 0,1 and 1 times the German limit values for HCl and HNO(3). The results for the last round robin showed no significant difference between the performance of the "active" and "passive" participants. The participant means were in good agreement with the theoretical concentrations and the quality control measurements. For "active" participants RSDs were between 7% and 14% and for all participants between 8% and 16%. The round robin for the non-volatile acids showed similar results. The participant means were again in excellent agreement with the quality control measurements and RSDs were between 12% and 15%. The BGIA round robins have demonstrated the proficiency of laboratories measuring exposure to inorganic acids in air. However, concerns remain about the performance of published methods. It has shown that the sampling efficiency of sorbent tubes falls off with increasing particle size and hence silica gel tube methods may give low results for acid mists. Another issue with silica gel tubes is that a substantial proportion of the sample can be collected on the glass wool plugs that retain the sorbent. This can be up to 50% for HCl and 100% for HNO(3). Hence, low results may be obtained if the glass wool plugs are discarded. Similarly, methods for volatile inorganic acids that use a pre-filter to remove particulates usually overlook the fact that the acids can react with co-particulate matter on the pre-filter. Low recoveries in the range 30%-50% have been found when sampling HCl through filters loaded with potential interferents. Finally, particulate salts interfere with filter sampling methods for non-volatile inorganic acids. A two-part International Standard is in preparation for inorganic acids by ion chromatography and the issues discussed above are being taken into consideration during its development.     

On-site Comparison of Canister and Solid-Sorbent Trap Collection of Highly Volatile Hydrocarbons in Ambient Atmospheres

A field experiment for the comparison of the efficiency of canisters and adsorption multibed tubes for sampling atmospheric highly volatile hydrocarbons at ppbv levels is described. The canister was passivated by the Summa process and the adsorption tubes were filled with Carbotrap C, Carbotrap B and Carbosieve S-III. The sampling with the adsorption tubes was performed at ambient temperature and at -10°C. The highest concentrations were generally obtained with canisters but these results are very similar to those obtained with refrigerated multibed adsorption tubes. Both methods appear to be equivalent for most of the highly volatile hydrocarbons encountered in moderately polluted urban areas. In contrast, sampling with ambient temperature tubes provides lower concentrations. This study has also shown that K2CO3 drying efficiently removes humidity from air samples allowing the obtention of reliable concentration data on highly volatile hydrocarbons at ppbv levels. These drying tubes can easily be re-conditioned and tested for blanks and memory effects, which greatly facilitates the control of external contamination and sample cross-contamination.     

Exposure to airborne allergens: a review of sampling methods

A number of methods are used to assess exposure to high-molecular weight allergens. In the occupational setting, airborne dust is often collected on filters using pumps, the filters are eluted and allergen content in the eluate analysed using immunoassays. Collecting inhalable dust using person-carried pumps may be considered the gold standard. Other allergen sampling methods are available. Recently, a method that collects nasally inhaled dust on adhesive surfaces within nasal samplers has been developed. Allergen content can be analysed in eluates using sensitive enzyme immunoassays, or allergen-bearing particles can be immunostained using antibodies, and studied under the microscope. Settling airborne dust can be collected in petri dishes, a cheap and simple method that has been utilised in large-scale exposure studies. Collection of reservoir dust from surfaces using vacuum cleaners with a dust collector is commonly used to measure pet or mite allergens in homes. The sampling methods differ in properties and relevance to personal allergen exposure. Since methods for all steps from sampling to analysis differ between laboratories, determining occupational exposure limits for protein allergens is today unfeasible. A general standardisation of methods is needed.     

固定源硫酸雾国内外采样方法优劣分析

固定污染源硫酸雾的国标采样方法为滤筒法,但对其采样效率研究较少。在调研国内外标准方法及相关文献的基础上,通过大量实样测定,对国标采样法进行改进：在内装滤筒的烟尘采样管后串联一个冲击式吸收瓶,此改进方法弥补了国标漏测气态硫酸雾的缺陷,采样效率达到99％以上,国标法仅为改进法的47％～68％。将国标改进法与USEPA采样法进行比对,结果表明,由于中国环境本底颗粒物浓度较高,硫酸雾易吸附于颗粒物上,致使USEPA采样效率仅为国标改进法的2?4％～12％。     

Diffusive Sampling of VOCs as an Aid to Monitoring Urban Air Quality

Diffusive sampling of Volatile Organic Compounds (VOCs) onto thermal desorption tubes, followed by gas chromatography, is an established technique for area or personal monitoring of typical workplace concentrations and there has been increasing interest in extending the application to environmental levels, particularly for benzene, toluene and xylene (BTX). Diffusive sampling rates for BTX on Chromosorb 106 and Carbograph-1 (a graphitised carbon) were measured over periods of 1-4 weeks in field validation experiments using ambient air and parallel pumped sampling (the reference method) at the HSL site in central Sheffield. The reference method was also used to investigate the possible bias of an open-path spectrophotometer (OPSIS) used by Sheffield City Council. A bias for BTX was suspected from results of a two-week initial exercise in which several diffusive samplers were placed close to the light path. In the full field validation of the diffusive samplers carried out subsequently, the significant bias of BTX concentrations reported by OPSIS were confirmed when compared with concurrent results from the reference method. OPSIS gave benzene and toluene values up to eight times higher than expected from the GC measurements. Xylene discrepancies were smaller, but in one 3-day peak episode, OPSIS demonstrated a negative correlation with GC.     

Determination of hydrogen peroxide in workplace air: interferences and method validation

A dynamic system for the generation of stable hydrogen peroxide test atmospheres was applied to the evaluation of samplers used for the determination of hydrogen peroxide in workplace air. The system is able to generate gas mixtures of between 0.1 and 10 ppm at different combinations of relative humidity (20-80%) and temperature (10-30 degrees C). Gaseous hydrogen peroxide is sampled on glass filters impregnated with Ti(IV) chloride and sulfuric acid and analyzed by UV spectroscopy. An interference was observed due to the acid catalyzed decomposition of peroxyacetic acid to hydrogen peroxide. This was significantly reduced by applying high sample flow rates and by lowering the concentration of sulfuric acid. The performance of the sampler and sources of uncertainties were tested according to the European Standard EN 1076.     

A two-stage cyclone using microcentrifuge tubes for personal bioaerosol sampling

Personal aerosol samplers are widely used to monitor human exposure to airborne materials. For bioaerosols, interest is growing in analyzing samples using molecular and immunological techniques. This paper presents a personal sampler that uses a two-stage cyclone to collect bioaerosols into disposable 1.5 ml Eppendorf-type microcentrifuge tubes. Samples can be processed in the tubes for polymerase chain reaction (PCR) or immunoassays, and the use of multiple stages fractionates aerosol particles by aerodynamic diameter. The sampler was tested using fluorescent microspheres and aerosolized fungal spores. The sampler had first and second stage cut-off diameters of 2.6 microm and 1.6 microm at 2 l min(-1)(geometric standard deviation, GSD = 1.45 and 1.75), and 1.8 microm and 1 microm at 3.5 l min(-1)(GSD = 1.42 and 1.55). The sampler aspiration efficiency was >or=98% at both flow rates for particles with aerodynamic diameters of 3.1 microm or less. For 6.2 microm particles, the aspiration efficiency was 89% at 2 l min(-1) and 96% at 3.5 l min(-1). At 3.5 l min(-1), the sampler collected 92% of aerosolized Aspergillus versicolor and Penicillium chrysogenum spores inside the two microcentrifuge tubes, with less than 0.4% of the spores collecting on the back-up filter. The design and techniques given here are suitable for personal bioaerosol sampling, and could also be adapted to design larger aerosol samplers for longer-term atmospheric and indoor air quality sampling.     

Extending wipe sampling methodologies to elements other than lead

Wipe sampling is the USA regulatory protocol for determination of "dust lead loadings" in residential environments. Few studies have applied the wipe sampling method to metals other than lead (Pb) for the purpose of residential exposure assessments. This study was undertaken to develop and expand the wipe method for quantifying additional metal(loid)s including arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), and antimony (Sb); and to provide information on typical background loadings for these metals in urban Canadian homes. A total of 932 wipe samples, 220 field blanks, and 220 duplicate wipes were collected from 222 homes located in three cities in Ontario, Canada using the ASTM 1728 standard. The wipes were digested using a modified version of the ASTM 1644 standard for Pb, which prescribes a hot nitric acid/hydrogen peroxide digestion. The key modification was the addition of hydrofluoric acid to improve recoveries of the target elements, and determination using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Generally, a large proportion of the results fell below the limits of detection (LOD) and quantification (LOQ). To distinguish "elevated" metal loadings from loadings characterized as "urban background", an upper background threshold for each element was derived using a normality (Q-Q) plot. LOQ was determined to be the appropriate minimum threshold based on quality assurance criteria. It is concluded that wipes are a useful sampling option to investigate multi-element loadings in residential environments.     

Development and validation of methods for environmental monitoring of cyclophosphamide in workplaces

Methods to monitor contamination of workplaces with antineoplastic drugs have been developed and validated. Cyclophosphamide (CP) was used as a model compound as it is one of the most commonly used antineoplastic drugs. A wipe sampling method to detect contamination with CP at surfaces was developed. A personal air sampling method to sample gas and vapour on solid sorbent tubes and particles with filters was also developed. Wipe and filter samples were extracted and sorbent samples were eluted, all with ethyl acetate. The samples were analysed with liquid chromatography tandem mass spectrometry. (2)H(6)-labelled cyclophosphamide was used as an internal standard. The between-day precision was 2-5% for wipe samples, 4-6% for sorbent samples and 3-8% for filter samples. The limit of detection was 0.02 ng CP per sample for the wipe and filter methods and 0.03 ng CP per sample for the solid sorbent method. Wipe sampling on surfaces made of different materials resulted in mean recoveries between 78-106%. The desorption recovery was between 97-102% for the wipe samples, 97% for the sorbent samples and 101% for the filter samples. Samples were stable for up to 2 months at 5 degrees C and -20 degrees C and for about 2 d at room temperature. The developed methods were applied to the measurement of contamination with CP in a hospital pharmacy. Trace amounts of CP, 1.3 and 1.4 ng, were detected on surfaces in the pharmacy.     

Review of monitoring and assessing ground vegetation biodiversity in national forest inventories

Ground vegetation (GV) is an important component from which many forest biodiversity indicators can be estimated. To formulate policies at European level, taking into account biodiversity, European National Forest Inventories (NFIs) are one of the most important sources of forest information. However, for monitoring GV, there are several definitions, data collection methods, and different possible indicators. Even though it must be considered that natural conditions in different countries form very different understory types, each one has its own cost-efficient monitoring design, and they can hardly be compared. Therefore, the development of general guidelines is a particularly complex issue. This paper is a review of data collection methods and consequently a selection of the best available methods for the set of indicators with an emphasis on GV sampling methodologies in NFIs. As a final result, recommendations on GV definitions and classifications, sampling methodologies, and indicators are formulated for NFIs. Different sampling areas are recommended for each life form (shrubs, herbs, etc.). Inventory cycles and sampling seasons (depending on the phonological stages) should be specially considered and evaluated in the results. The proposed indicators are based on composition at different levels of sampling intensity for each life form and on coverage measurements.     

New approaches for assessment of occupational exposure to metals using on-site measurements

Traditional assessment of occupational exposure to metals typically involves static or personal aerosol sampling on a membrane filter followed by a laboratory determination of the metal content on the filter sample. These techniques give results with high accuracy and low detection limits. However, they all have a drawback in that, since the samples have to be analysed in a laboratory, the results will usually be obtained days or weeks after the sampling took place. Today there is available a new generation of portable electronic micro-balances and instruments for metal analysis based on X-ray fluorescence. These instruments will make on-site measurements of metal exposure possible, which opens the way for new approaches for assessment of occupational exposure to metals. In combination with high-flow pumps, short-term sampling is possible, which allows monitoring of the exposure variation during a work shift as well as the exposure during individual work tasks of short duration. Screening measurements and emission measurements are other examples of monitoring that are facilitated using on-site determinations. Measure control monitoring can effectively be performed using on-site measurements and is an effective tool in the assessment of workplace improvements. On-site determinations can also form an effective and pedagogic tool showing workers how to perform specific tasks and demonstrating the effectiveness of different measures intended to improve their work environment. Other examples are the assessment of skin exposure using aerosol deposition on pads and screening of contamination using bulk samples.     

垃圾渗滤液中微塑料分析的消解方法评价

微塑料(MPs)是近年来国内外关注度极高的新兴污染物,建立实际环境样品中MPs的分析方法是开展相关研究的基础.对于复杂污水样品而言,样品的消解过程至关重要,将极大地影响MPs的准确分析.选择垃圾渗滤液为典型复杂污水样品,采用样品浊度和色度变化、残余悬浮固体量、MPs在颗粒物中的占比为评价指标,对盐酸消解、30％过氧化氢...     

Peak exposures in aluminium potrooms: instrument development and field calibration

Aluminium smelter potrooms are unique in that workplace exposures to hydrogen fluoride (HF), sulfur dioxide (SO2), and particulate matter occur simultaneously for some tasks. The peak exposures to these contaminants are of increasing interest in discovering the etiology of respiratory health effects. While a variety of direct-reading instruments are available for sulfur dioxide and particulate matter, only a few exist for hydrogen fluoride. The sensors in these HF instruments have a cross-sensitivity to sulfur dioxide making it difficult to monitor HF in an environment that also contains SO2. To overcome this problem, we assessed the simultaneous use of two electrochemical instruments: one with a SO2 sensor that does not respond to HF and the second with a hydrogen fluoride sensor that responds to both HF and SO2 in a 1 : 1 ratio, termed 'total acid gas'. The difference in the response between the two instruments should indicate the HF concentration: [HF + SO2] minus SO2 equals HF. The performance characteristics of this sampling train were evaluated in the laboratory through the generation of both HF and SO2 with permeation tubes. The response and recovery times for the SO2 only instrument were acceptable (6 and 15 s, respectively), but the "total acid gas" instrument exhibited both slow response and slow recovery approaching three and six min. The association between the traditional integrated filter sampling method and the direct-reading instrument for SO2 is 0.80 (Spearman's rho). The use of the digital filter strengthens the association between the HF direct-reading instrument and the integrated samples from 0.41 to 0.68.     

Analysis of indoor gaseous formic and acetic acid, using radial diffusive samplers

A diffusive sampling method for the determination of gaseous acetic and formic acids, using a radial symmetry diffusive sampler, has been optimised for a 7-day exposure time in this study. Sampling rate determinations were performed on data obtained from a dynamic exposure chamber, simulating the indoor conditions of an empty, closed, room, at room temperature and minimal wind speed. Analysis has been performed by means of ion chromatography. The sampling rates for formic acid concentrations of 128 microg m(-3) and 1248 microg m(-3) were determined to be 91.2 +/- 3.9 ml min(-1) and 111.6 +/- 2.8 ml min(-1), respectively. The acetic acid sampling rate was independent of the concentration in the range 160 microg m(-3)-1564 microg m(-3), and amounted to 97.3 +/- 3.1 ml min(-1). Experimentally determined sampling rates showed deviations of 3% for acetic acid, and 3-21% for formic acid, in relation to theoretically derived values. The blank values were as low as 1.69 +/- 0.07 microg for formic acid and 1.21 +/- 0.14 microg for acetic acid, and detection limits lower than 0.5 microg m(-3) could be achieved, which is an improvement of 98-99% compared to previously validated diffusive sampling methods. This study describes the first step of an extended validation program in which the applicability of these types of samplers for the measurement of organic acids will be validated and optimised for the environmental conditions typical for museum showcases.     

Suggested protocol for collecting, handling and preparing peat cores and peat samples for physical, chemical, mineralogical and isotopic analyses

For detailed reconstructions of atmospheric metal deposition using peat cores from bogs, a comprehensive protocol for working with peat cores is proposed. The first step is to locate and determine suitable sampling sites in accordance with the principal goal of the study, the period of time of interest and the precision required. Using the state of the art procedures and field equipment, peat cores are collected in such a way as to provide high quality records for paleoenvironmental study. Pertinent field observations gathered during the fieldwork are recorded in a field report. Cores are kept frozen at -18 degree C until they can be prepared in the laboratory. Frozen peat cores are precisely cut into 1 cm slices using a stainless steel band saw with stainless steel blades. The outside edges of each slice are removed using a titanium knife to avoid any possible contamination which might have occurred during the sampling and handling stage. Each slice is split, with one-half kept frozen for future studies (archived), and the other half further subdivided for physical, chemical, and mineralogical analyses. Physical parameters such as ash and water contents, the bulk density and the degree of decomposition of the peat are determined using established methods. A subsample is dried overnight at 105 degree C in a drying oven and milled in a centrifugal mill with titanium sieve. Prior to any expensive and time consuming chemical procedures and analyses, the resulting powdered samples, after manual homogenisation, are measured for more than twenty-two major and trace elements using non-destructive X-Ray fluorescence (XRF) methods. This approach provides lots of valuable geochemical data which documents the natural geochemical processes which occur in the peat profiles and their possible effect on the trace metal profiles. The development, evaluation and use of peat cores from bogs as archives of high-resolution records of atmospheric deposition of mineral dust and trace elements have led to the development of many analytical procedures which now permit the measurement of a wide range of elements in peat samples such as lead and lead isotope ratios, mercury, arsenic, antimony, silver, molybdenum, thorium, uranium, rare earth elements. Radiometric methods (the carbon bomb pulse of (14)C, (210)Pb and conventional (14)C dating) are combined to allow reliable age-depth models to be reconstructed for each peat profile.     

A Passive Sampler for Monitoring Urban Particulate: Preliminary Results

A passive sampling device, developed for personal monitoring of airborne dust levels in industry, has been tested as a site sampler in the urban environment. The device weighs approximately 15g and the essential sampling element is a small disc of electret material (polymer carrying a permanent electric charge). During use it captures particles by electrical attraction, at a rate that depends upon their electrical mobility, but which is independent of the rate at which air flows past the sampler. It collects measurable quantities of particulate, though the sample size tends to be small and correlation with results from conventional samples has not yet been established. Samplers have been exposed to urban particulate for periods of up to seven days, without the electret suffering unacceptable loss of electric charge. It has been shown to be potentially useful for long-term monitoring, a situation in which dispensing with a power source is particularly useful. Being small, the passive sampler is easy to hide or camouflage. It has potential for multiple simultaneous site sampling and for monitoring personal environmental exposure.