Recycling of petroleum-contaminated sand

The environmental impact of using petroleum-contaminated sand (PCS) as a substitute in asphalt paving mixtures was examined. An appreciable component of PCS is oily sludge, which is found as the dregs in oil storage tanks and is also produced as a result of oil spills on clean sand. The current method for the disposal of oily sludge is land farming. However, this method has not been successful as an oil content of < 1% w/w is required, and difficulty was encountered in reaching this target. The reuse of the sludge in asphalt paving mixtures was therefore considered as an alternative. Standard tests and environmental studies were conducted to establish the integrity of the materials containing the recycled sludge. These included physical and chemical characterization of the sludge itself, and an assessment of the mechanical properties of materials containing 0%, 5%, 22% and 50% oily sludge. The blended mixtures were subjected to special tests, such as Marshall testing and the determination of stability and flow properties. The experimental results indicated that mixtures containing up to 22% oily sludge could meet the necessary criteria for a specific asphalt concrete wearing course or bituminous base course. To maximize the assay from the recycled material, the environmental assessment was restricted to the 50% oily sludge mixture. Leachates associated with this particular mixture were assayed for total organic residue and certain hazardous metal contaminants. The results revealed that the organics were negligible, and the concentrations of the metals were not significant. Thus, no adverse environmental impact should be anticipated from the use of the recycled product. Our research showed that the disposal of oily sludge in asphalt paving mixtures could possibly yield considerable savings per tonne of asphalt concrete, and concurrently minimize any direct impact on the environment.     

The effect of filter material on bioaerosol collection of Bacillus subtilis spores used as a Bacillus anthracis simulant

The objective of this study was to determine filter materials and extraction methods that are appropriate to use for environmental sampling of B. anthracis. Four types of filters were tested: mixed cellulose ester (MCE) with a pore size of 3 microm, polytetrafluoroethylene (PTFE) with pore sizes of 1 and 3 microm, and gelatin with a pore size of 3 microm. Bacillus subtilis var. niger endospores (also known as Bacillus globigii[BG]) were used as a surrogate for B. anthracis. Endospores were collected into Button Inhalable Aerosol Samplers with sampling times of 15 minutes, 1 hour, and 4 hours. Physical collection efficiency was determined by measuring upstream and downstream B. subtilis concentrations with an optical particle counter. Vortexing with ultrasonic agitation and vortexing with shaker agitation extraction methods were evaluated. The MCE, 1 microm PTFE, and gelatin filters provided physical collection efficiencies of 94% or greater. The 3 microm PTFE filter showed inconsistent physical efficiency characteristics between filters. Epifluorescence microscopic analysis of the gelatin filter extraction fluid revealed the presence of contamination by non-culturable bacteria. Mean differences for microbial culturability were not statistically significant for filter materials and extraction methods. However, the vortexing with shaker agitation extraction method resulted in higher total microbial counts in the extraction fluids for MCE and 1 microm PTFE filters when compared to vortexing with ultrasonic agitation. In summary, the MCE and 1 microm PTFE filters in combination with vortexing and shaker extraction demonstrated the best performance for the filter collection and extraction of BG spores.     

Seasonal variations in physico-chemical characteristics of River Yamuna in Haryana and its ecological best-designated use

Various physico-chemical characteristics of the River Yamuna flowing in Haryana through Delhi were studied in the summer (April 1998) and winter (Jan.-Feb. 1999). Ecological parameters like dissolved oxygen (DO), pH, nitrate (NO3-), sulfate (SO4(2-)), and phosphate (PO4(3-)), were analyzed and compared with standard permissible limits to assess the best-designated use of the river water for various purposes. The river in Delhi upstream was of better quality whereas the Delhi downstream stretch was polluted as indicated by very low DO and high total dissolved solids (TDS), electric conductivity (EC), total hardness, Na+, K+, Cl-, F- and SO4(2-). The differences in various parameters were statistically significant (p < 0.01) when compared for the Delhi upstream and downstream stretches of the river, particularly in summer. DO and TDS were found to be two important parameters, which showed strong correlation with several other parameters and hence can serve as good indices of river water quality. The river tended to recover from the pollution stress after flowing through a distance of about 80 km downstream of Delhi.     

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.     

Solid-phase microextraction to monitor the sonochemical degradation of polycyclic aromatic hydrocarbons in water

Solid-phase microextraction (SPME) coupled with GC-MS has been used to monitor the degradation of polycyclic aromatic hydrocarbons (PAHs) by ultrasound treatment. Immersion SPME sampling enabled the fast and solventless extraction of target contaminants at the low microg l(-1) concentration level. The developed protocol was found to be linear in the concentration range from 0.1 to 50 microg l(-1) for most target analytes, with the limits of detection ranging between 0.01 and 0.70 microg l(-1) and the relative standard deviations between 4.31 and 27%. The developed SPME protocol was used to follow concentration profiles of aqueous solutions containing 16 PAHs, which were subject to low frequency ultrasonic irradiation. At the conditions employed in this study (80 kHz of ultrasound frequency, 130 W l(-1) of applied electric power density, 30 microg l(-1) of initial concentration for each of the 16 PAHs), sonochemical treatment was found capable of destroying the lower molecular weight PAHs (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene) within 120-180 min of irradiation. The higher molecular weight PAHs were more recalcitrant to ultrasound treatment.     

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.     

用广义λ—分布拟合空气污染数据

广义λ-分布是一个四参数可变通的概率模型,包括多种单变量分布,这一模型可用于表示空气污染浓度的频率分布。本文采用土耳其安卡拉每日的烟和SO_2监测数据,来证明广义λ-分布具有良好的拟合性质。这里还讨论了与分位数估计和拟合优度有关的一些结果,并与经典对数正态分布进行了比较。     

Quantification of protein adducts of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride in human plasma

Hexahydrophthalic anhydride (HHPA) and methylhexahydrophthalic anhydride (MHHPA) are two highly allergenic compounds used in the chemical industry. A method was developed for quantification of protein adducts of HHPA and MHHPA in human plasma. The plasma was dialysed and the anhydrides were hydrolysed from the proteins at mild acidic conditions. The released hexahydrophthalic acid (HHP acid) and methylhexahydrophthalic acid (MHHP acid) were purified by reversed solid phase extraction followed by derivatisation with pentafluorobenzyl bromide. The derivatives were analysed using GC-MS in negative ion chemical ionisation mode with ammonia as moderating gas. As internal standards, deuterium labelled HHP and MHHP acids were used. The detection limits were 0.06 pmol mL(-1) plasma for HHP acid and 0.03 pmol mL(-1) plasma for MHHP acid. The between-day precisions for HHP acid were 18% at 0.3 pmol mL(-1) and 8% at 4 pmol mL(-1). For MHHP acid, the precisions were 13% at 0.3 pmol mL(-1) and 9% at 4 pmol mL(-1). There were strong correlations (r=0.94 for HHPA and 0.99 for MHHPA) between total plasma protein adduct concentrations and serum albumin adduct levels. Workers exposed to time-weighted average air levels of HHPA between < 1 and 340 microg m(-3) and between 2 and 160 microg m(-3) for MHHPA had plasma adduct levels between the detection limits of the methods and 8.40 and 19.0 pmol mL(-1), respectively.     

Mobilization of aluminium and deposition on fish gills during sea salt episodes--catchment liming as countermeasure

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

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.