Diffusive sampling of methyl isocyanate using 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ) as derivatizing agent

A diffusive sampling method for the determination of methyl isocyanate (MIC) in air is introduced. MIC is collected using a glass fiber filter impregnated with 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ). The urea derivative formed is desorbed from the filter with acetonitrile and analyzed by means of high-performance liquid chromatography (HPLC) using fluorescence detection (FLD) with lambdaex = 471 nm and lambdaex = 540 nm. Additionally, a method was developed using tandem mass spectrometric (MS-MS) detection, which was performed as selected reaction monitoring (SRM) on the transition [MIC-NBDPZ + H]+ (m/z 307) to [NBDPZ + H]+ (m/z 250). The diffusive sampler was tested with MIC concentrations between 1 and 35 microg m(-3). The sampling periods varied from 15 min to 8 h, and the relative humidity (RH) was set from 20% up to 80%. The sampling rate for all 15 min experiments was determined to be 15.0 mL min(-1) (using HPLC-FLD) with a relative standard deviation of 9.9% for 56 experiments. At 80% RH, only 15 min sampling gave acceptable results. Further experiments revealed that humidity did not affect the MIC derivative but the reagent on the filter prior to and during sampling. The sampling rate for all experiments (including long term sampling) performed at 20% RH was found to be 15.0 mL min(-1) with a relative standard deviation of 6.3% (N = 42). The limit of quantification was 3 microg m(-3) (LC-MS-MS: 1.3 microg m(-3)) for 15 min sampling periods and 0.2 microg m(-3) (LC-MS-MS: 0.15 microg m(-3)) for 8 h sampling runs applying fluorescence detection.     

Development of a diffusive sampling method for determination of methyl isocyanate in air

A diffusive sampling method for determination of methyl isocyanate in air has been developed. A glass fibre filter impregnated with 1-(2-methoxyphenyl)piperazine in a commercially available diffusive sampling device was used to collect methyl isocyanate and the derivative formed was analysed with LC-MS/MS. The sampling rate was determined to be 15.6 ml min(-1), with a relative standard deviation of 7.3%. The sampler was validated for sampling periods from 15 min to 8 h, for relative humidities from 20% to 80% and for concentrations from I to 46 microg m(-3). A field validation was also made and the diffusive sampling results showed no difference compared to a pumped reference method. The impregnated filters have to be stored apart from the diffusive sampler housing and loaded into the sampler prior to each sampling.     

A laboratory investigation of the effectiveness of various skin and surface decontaminants for aliphatic polyisocyanates

Isocyanates may cause contact dermatitis and respiratory sensitization leading to asthma. Dermal exposure to aliphatic isocyanates in auto body shops is very common. However, little is known about the effectiveness of available commercial products used for decontaminating aliphatic polyisocyanates. This experimental study evaluated the decontamination effectiveness of aliphatic polyisocyanates for several skin and surface decontaminants available for use in the auto body industry. The efficiency of two major decontamination mechanisms, namely (i) consumption of free isocyanate groups via chemical reactions with active hydrogen components of the decontaminant and (ii) physical removal processes such as dissolution were studied separately for each decontaminant. Considerable differences were observed among surface decontaminants in their rate of isocyanate consumption, of which those containing free amine groups performed the best. Overall, Pine-Sol(R) MEA containing monoethanolamine was the most efficient surface decontaminant, operating primarily via chemical reaction with the isocyanate group. Polypropylene glycol (PPG) had the highest physical removal efficiency and the lowest reaction rate with isocyanates. All tested skin decontaminants performed similarly, accomplishing decontamination primarily via physical processes and removing 70-80% of isocyanates in one wiping. Limitations of these skin decontaminants are discussed and alternatives presented. In vitro testing using animal skins and in vivo testing with field workers are being conducted to further assess the efficiency and identify related determinants.     

Preliminary investigation of submerged aquatic vegetation mapping using hyperspectral remote sensing

The use of airborne hyperspectral remote sensing imagery for automated mapping of submerged aquatic vegetation (SAV) in the tidal Potomac River was investigated for near to real-time resource assessment and monitoring. Airborne hyperspectral imagery and field spectrometer measurements were obtained in October of 2000. A spectral library database containing selected ground-based and airborne sensor spectra was developed for use in image processing. The spectral library is used to automate the processing of hyperspectral imagery for potential real-time material identification and mapping. Field based spectra were compared to the airborne imagery using the database to identify and map two species of SAV (Myriophyllum spicatum and Vallisneria americana). Overall accuracy of the vegetation maps derived from hyperspectral imagery was determined by comparison to a product that combined aerial photography and field based sampling at the end of the SAV growing season. The algorithms and databases developed in this study will be useful with the current and forthcoming space-based hyperspectral remote sensing systems.     

An investigation of arsenic contamination in Peninsular Malaysia based on Centella asiatica and soil samples

The first objective of this study was to provide data of arsenic (As) levels in Peninsular Malaysia based on soil samples and accumulation of As in Centella asiatica collected from 12 sampling sites in Peninsular Malaysia. The second objective was to assess the accumulation of As in transplanted C. asiatica between control and semi-polluted or polluted sites. Four sites were selected which were UPM (clean site), Balakong (semi-polluted site), Seri Kembangan (semi-polluted site) and Juru (polluted site). The As concentrations of plant and soil samples were determined by Instrumental Neutron Activation Analysis. The As levels ranged from 9.38 to 57.05 μg/g dw in soils, 0.21 to 4.33 μg/g dw in leaves, 0.18 to 1.83 μg/g dw in stems and 1.32–20.76 μg/g dw in roots. All sampling sites had As levels exceeding the CCME guideline (12 μg/g dw) except for Kelantan, P. Pauh, and Senawang with P. Klang having the highest As in soil (57.05 μg/g dw). In C. asiatica, As accumulation was highest in roots followed by leaves and stems. When the As level in soils were higher, the uptake of As in plants would also be increased. After the transplantation of plants to semi-polluted and polluted sites for 3 weeks, all concentration factors were greater than 50 % of the initial As level. The elimination factor was around 39 % when the plants were transplanted back to the clean sites for 3 weeks. The findings of the present study indicated that the leaves, stems and roots of C. asiatica are ideal biomonitors of As contamination. The present data results the most comprehensive data obtained on As levels in Malaysia.     

Speciation of organotins in polyvinyl chloride pipe via X-ray absorption spectroscopy and in leachates using GC-PFPD after derivatisation

Three different polyvinyl chloride (PVC) pipe types were subjected to de-ionized water exposures over the course of at least 180 days. Water exposed to the pipe was analyzed for organotin speciation and concentration. Organotin concentrations were the highest during the first 1-5 days. The species and concentrations of organotins leached varied by pipe type. Data were normalized by surface area in order to compare laboratory results with results from a residential pipe system. For one pipe type, the lowest non-zero concentrations from the laboratory tests overestimated organotin concentrations in solution when compared with water samples from the same pipe type in a residence. For organotin exposure estimates, a range of 0.1 ng m(-2) to 10 ng m(-2) could be used for mature pipes (e.g. in use for 1 year). These estimates should be refined with more field study, however, due to the high variation in organotin species and concentrations leached as a function of pipe type, accuracy within an order of magnitude may be optimal as, in many instances, the type of pipe installed or buried may be unknown. X-ray absorption spectroscopy (XAS) was used to identify organic and inorganic tin species in reference materials and the PVC samples. Monobutyl tin was identified as the primary organotin species in the pipes. Results from the XAS analyses also indicate that the technique shows promise for distinguishing between inorganic tin and organotins. Furthermore, organotins may be distinguished between mono-, di-, and tri-ligand species using XAS.     

An indoor test campaign of the tomography long path differential optical absorption spectroscopy technique

In this study we validate the two-dimensional long path DOAS tomography measurement technique by means of an indoor experiment with well-known concentration distributions. The experiment was conducted over an area of 10 m x 15 m using one and two cylindrical polycarbonate containers of diameter 2 m, respectively, filled with NO2. The setup was realized with three of the multibeam instruments recently developed by Pundt and Mettendorf (Appl. Opt., 2005, in press), which allow the simultaneous measurement along at least four light paths each. The configuration consisted of twelve simultaneous light beams, 39 horizontal light paths in total, and 18 different cylinder positions inside the field. It was found that for the discretization and inversion technique shown here reconstructions of the concentration distributions from experimental data agree well with simulated reconstructions. In order to draw conclusions for atmospheric applications, numerical studies including instrumental errors were carried out. It was found that with the presented measurement setup it is possible to measure and reconstruct one or two NO2 plumes of 600 m diameter and average concentrations above 4.2 ppbv each, on a scale of 13.5 km2. Theoretical investigations show that it should be possible to localize and quantify 600 m diameter plumes of SO2 > 1.5 ppbv, H2CO > 6.3 ppbv, HONO > 3.2 ppbv, and ozone > 46.2 ppbv. Larger plumes can be measured with higher precision.     

Sensitive determination of cadmium using solidified floating organic drop microextraction-slotted quartz tube-flame atomic absorption spectroscopy

In this study, solidified floating organic drop microextraction (SFODME) by 1-undecanol was combined with slotted quartz tube flame atomic absorption spectrometry (SQT-FAAS) for the determination of cadmium at trace levels. Formation of a complex with 4,4′-dimethyl-2,2′-bipyridine facilitated the extraction of cadmium from aqueous solutions. Several chemical variables were optimized in order to obtain high extraction outputs. Parameters such as concentration of the ligand, pH, and amount of buffer solution were optimized to enhance the formation of cadmium complex. The SFODME method was assisted by dispersion of extractor solvent into aqueous solutions using 2-propanol. Under the optimum extraction and instrumental conditions, the limit of detection and limit of quantitation values obtained for cadmium using the combined methods (SFODME-SQT-FAAS) were found to be 0.4 and 1.3 μg L^?1, respectively. Matrix effects on the method were also examined for tap water and wastewater, and spiked recovery results were found to be very satisfactory.

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Graphical Abstract SFODME-SQT-FAAS system for sensitive determination of cadmium

     

Determination of some heavy metal levels in soft drinks on the Ghanaian market using atomic absorption spectrometry method

Twenty-three soft drink samples (i.e., four pineapple-based fruit drinks, eight citrus-based fruit juices, one soya-based drink, three cola carbonated drinks, one apple-based fruit drink, and six cocktail fruit drinks) were randomly purchased from retail outlets in an urban market in Accra and analyzed for the concentrations of iron, cobalt, cadmium, zinc, lead, and copper using flame atomic absorption spectrometry. The mean concentration of iron and cadmium were 0.723?±?0.448 mg/L and 0.032?±?0.012 mg/L, respectively. The mean cobalt concentration was 0.071?±?0.049 mg/L, while the mean Zn concentration in the samples was 0.060?±?0.097 mg/L. The mean concentrations of Pb and Cu in the fruit juice samples were 0.178?±?0.091 mg/L and 0.053?±?0.063 mg/L respectively. About 78 % of the samples exceeded the United States Environmental Protection Agency (USEPA) maximum contaminant level of 0.3 mg/L prescribed for iron, whereas all the samples exceeded the USEPA maximum contaminant level of 0.005 mg/L prescribed for cadmium. About 91 % of the samples exceeded the EU maximum contaminant level prescribed for lead insoft drinks.     

Determination of bismuth in environmental samples by slurry sampling graphite furnace atomic absorption spectrometry using combined chemical modifiers

Persistence behavior of insecticides chlorpyriphos, profenofos, triazophos, cypermethrin, and deltamethrin following the use of three combination formulations Action 505 (chlorpyriphos?+?cypermethrin), Roket 44EC (profenofos?+?cypermethrin), and Anaconda Plus (triazophos?+?deltamethrin) was studied in cabbage following the spray application at the recommended and double doses. Bio-efficacy of these formulations was also evaluated against mustard aphids (Lipaphis erysimi Kaltenbach) and diamondback moth (Plutella xylostella L.). The residues of different insecticides persisted for 5–8 days at low dose and 8–12 days at high dose. The residues dissipated with time and 87–100 % dissipation was recorded on the 8th day. The half-life values varied from 0.4 to 1.6 days. Based on the acceptable daily intake (ADI) values, a safe waiting period of 1 day has been suggested for the formulations Action 505 and Roket 44EC and 3 days for Anaconda Plus at the recommended dose of application. Action (1.6 L/ha) treatment was found to be the best as it significantly reduced the diamondback moth (DBM) (~60 %) and aphid population (~70 %) besides giving the highest yield (170 % increase over control).     

An investigation of heavy metal and migration through groundwater from the landfill area of Eskisehir in Turkey

This paper was conducted in order to determine the groundwater and soil pollution within and around the landfill of Eskisehir, Turkey. In this paper, mud, leachate and groundwater samples were collected seasonally a year from near Eskisehir landfill-site to investigate the possible impact of leachate which affects soil and groundwater quality. Concentrations of various heavy metals (Fe, Cu, Zn, Mn, Co, Pb, Cr, Ni and Mo) were determined in mud, leachate and groundwater samples. In addition, the heavy metal transportation infiltrated from landfill through a porous medium into the groundwater was modelled in order to determine the potential groundwater pollution caused by the leachate of the landfill. The modelling of the contaminant transportation was carried out by using a multiflow computer programme which simulates the distribution of heavy metal concentrations. As a result of this study, the distribution of the contaminant concentration was modelled and determined with respect to time and distance. Hence, the contaminant concentrations were determined at any time interval according to distance. The heavy metal contamination in groundwater does not affect the wells found at far points from the source in a short time, e.g. 10, 20 and 30 days according to the obtained experimental results. When the time intervals extended more than 1 year, heavy metal concentrations decrease with distance but the concentration of the contamination increases when it gets closer to the pollution source. In this study, the potential contamination of groundwater was effectively estimated.     

An investigation of the origin and mobility of phosphorus in freshwater sediments from Bort-Les-Orgues Reservoir, France

In order to assess the origin and the potential mobility of phosphorus (P) in the sediment of the Bort-Les-Orgues Reservoir, France, two sequential extraction schemes, i.e., the SMT (modified Williams method) and the Golterman schemes, were compared. Finally, the potential mobility of P in this sediment was estimated from results of sequential extraction. The SMT method appeared to be more satisfactory than the Golterman method, which is in accordance with results from a study currently carried out in the framework of the European programme Standards, Measurements and Testing. Iron-bound P and organic P were the dominant forms of P in the sediment; these forms are likely to be released at the sediment/water interface in case of anoxia and could diffuse into the water column, thus increasing the risk of eutrophication in this sensitive reservoir. The P stock (330 +/- 66 t) is not negligible and should be taken into account in any restoration project of the reservoir. The SMT procedure seems promising and will provide, in the near future, a valuable tool for water managers in the field of lake restoration.     

An assessment of heavy metal contamination in surface sediment using statistical analysis

The distribution and accumulation of heavy metals in the sediments, especially those nearest of wastewater discharges of south of Spain, were investigated. Sediment samples from 14 locations were collected and characterised for metal content (e.g. Ni, Cu, Zn, Cr, Pb, Mn, Cd and Hg), organic carbon, total nitrogen, total phosphorous, n-hexane-extractable material, carbonates and grain size. Concentration data were processed using correlation analysis and factor analysis. The correlation analysis of concentrations data showed important positive correlations among organic carbon, total phosphorus, Cu, Zn, Cd and Hg, otherwise weak correlations among Mn, Cr, Ni and CO₃ ^2???, indicating that these metals have complicated geochemical behaviours. The use of statistical factor analysis also confirmed these results. Sediments pollution assessment was carried out using geoaccumulation and metal pollution indexes (MPI₈). The results revealed that sediments of Cádiz bay and Sancti Petri channel were uncontaminated with the studied metals.     

An investigation of environmental and sustainability discourses associated with the substantive purposes of environmental assessment

This paper investigates the discursive construction of the substantive purposes of environmental assessment (EA). It addresses these purposes by exploring the complex and often multifaceted linkages between political factors and plural views of democracy, public participation, and the role of science that are embedded in environmental and sustainability discourses. The interaction between policy-making and public actors leads to the formulation of divergent and potentially competing rationales for public participation, and for social appraisal more generally. Participatory approaches have also given impetus to the development of several interpretations on the role of science in assessment procedures. Science is important in mediating public participation and the two are therefore reciprocally linked. This leads to discourses that become manifest in the construction of substantive purposes. Discourse analysis in EA is a relevant method for examining trends and patterns in sustainable development. It is argued that public participation is an important, if not decisive, variable in the articulation and civil legitimacy of certain purposes. A general proposition that results from this paper is that EA, although typically presented as an objective scientific tool, is an intrinsically normative process. Enhanced knowledge on the construction, and reconstruction over time, of substantive purposes is required if environmental and sustainability discourses are to be used and understood as meaningful analytical instruments to assess the socio-political implications of EA.     

An investigation on biological stability of product water generated by lab-scale and pilot-scale distillation systems

Material Disposal Area G is the primary low-levelradioactive waste disposal site at Los Alamos NationalLaboratory, New Mexico, and is adjacent to Pueblo of SanIldefonso lands. Pueblo residents and Los Alamos scientists areconcerned about radiological doses resulting from uptake of AreaG radionuclides by mule deer (Odocoileus hemionus) andRocky Mountain elk (Cervus elaphus), then consumption ofdeer and elk meat by humans. Tissue samples were collected fromdeer and elk accidentally killed near Area G and were analyzedfor ³H, ⁹⁰Sr, total U, ²³⁸Pu, ^{239, 240}Pu,²⁴¹Am, and ¹³⁷Cs. These data were used to estimatehuman doses based on meat consumption of 23 kg y^-1. Humandoses were also modeled using RESRAD, and dose rates to deer andelk were estimated with a screening model. Dose estimates tohumans from tissue consumption were 2.9 × 10^-3 mSv y^-1and 1.6 × 10^-3 mSv y^-1 from deer and elk, respectively,and RESRAD dose estimates were of the same order of magnitude. Estimated dose rates to deer and elk were 2.1 × 10^-4 mGyd^-1 and 4.7 × 10^-4 mGy d^-1, respectively. Allestimated doses were significantly less than established exposurelimits or guidelines.     

Air sampling of fungal spores on filters. An investigation on passive sampling and viability

In this study, glycerol was tested as a collection substrate for passive bioaerosol sampling. Filters (mixed cellulose acetate and nitrate) were soaked in glycerol and exposed for an aerosol from three different fungal species: Penicillum commune, Aspergillus versicolor and Paecilomyces variotii. The passive sampling method was compared with a closed-face polycarbonate filter sampling method. Exposure was performed in an exposure chamber. The total number of spores was determined by microscopic techniques, and the cultivable number was determined by cultivation on Malt Extract Agar dishes. The glycerol soaked filter demonstrated a good correlation with the closed-face sampler with regard to the total count. Spores stored in a pumped filter cassette were not affected by storage for up to 7 days. On the other hand, the culturability of the spores was markedly decreased after 1 day when stored on glycerol soaked filters.     

Monitoring of atmospheric nitrogen dioxide by long-path pulsed differential optical absorption spectroscopy using two different light paths

Measurements of the local distribution of atmospheric nitrogen dioxide (NO(2)) by long-path pulsed differential optical absorption spectroscopy (LP-PDOAS) in Tokyo during August 2008 are presented. Two LP-PDOAS systems simultaneously measured average NO(2) temporal mixing ratios along two different paths from a single observation point. Two flashing aviation obstruction lights, located 7.0 km north and 6.3 km east from the observation point, were used as light sources, allowing spatiotemporal variations of NO(2) in Tokyo to be inferred. The LP-PDOAS data were compared with ground-based data measured using chemiluminescence. Surface wind data indicated that large inhomogeneities were present in the spatial NO(2) distributions under southerly wind conditions, while northerly wind conditions displayed greater homogeneity between the two systems. The higher correlation in the NO(2) mixing ratio between the two LP-PDOAS systems was observed under northerly wind conditions with a correlation factor R(2) = 0.88. We demonstrated that the combined deployment of two LP-PDOAS systems oriented in different directions provides detailed information on the spatial distribution of NO(2).