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.     

Reduction and avoidance of lubricant mist demands an integrated assessment approach

A case study to identify major factors for lubricant mist exposure covered 15 metal machining sites. The investigation included milling, turning, drilling and grinding applications. Systematic analysis considered all relevant data concerning the machine tool, the lubricant and the suction plant. The efficiency of the implemented maintenance program at the installed filter systems was checked by concentration measurements immediately before and after service. All performed measurements of lubricant aerosol and vapor loads upstream and downstream of the installed filter systems were carried out according to VDI 2066 and BIA 3110, respectively. The selection criteria for the sites to be investigated, the systematic nature of the data acquisition and the procedure of the analysis are demonstrated in detail by performing comparisons between selected applications using emulsions and those employing straight oil for lubrication. The results of the study identify recirculation of ventilated air as the major source of workplace exposure to airborne lubricant emissions. More than 60% of the demisters investigated emit air at total lubricant loads (aerosols and vapor) above the limit of 20 mg m-3 at any time of operation; which also means immediately after service. A common reason for exceeded aerosol loads in recirculated air is e.g. the fact that the type of filter system applied is often not suitable for the separation problem. Loads of lubricant vapor are usually higher at the processes which use water emulsions as lubricant. In a quarter of the cases the limits were exceeded solely due to high vapor loads even immediately after service. The exposure can be reduced by replacing the lubricant, installation of a vapor separation plant or avoiding air recirculation. Maintenance time of the demisting system and aerosol separation efficiency of state-of-the-art demisting systems can be expanded by implementation of enhanced preliminary filter stages. This study confirms that appropriate service measures lower both aerosol emissions and lubricant vapor concentrations due to the reduction of exposed oil-wetted surfaces. The performed measurements show no significant relationship between loads of airborne lubricants and the type of machining process. Therefore, investigations at a much more detailed level have to be performed. However, the individual assessment of any workplace due to the complex situation remains essential.     

Bi-national assessment of the Great Lakes: SOLEC partnerships

Many administrative jurisdictions have authority over parts of the Great Lakes, sometimes with competing purposes as well as governance at differing scales of time and space. As demand increases for high quality information that is relevant to environmental managers, environmental and natural resource agencies with limited budgets must look to interdisciplinary, collaborative approaches for the collection, analysis and reporting of data. The State of the Lakes Ecosystem Conferences (SOLEC) were begun in 1994 in response to reporting requirements of the Great Lakes Water Quality Agreement between Canada and the U.S. The biennial conferences provide independent, science-based reporting on the state of health of the Great Lakes ecosystem components. A suite of indicators necessary and sufficient to assess Great Lakes ecosystem status was introduced in 1998, and assessments based on a subset of the indicators were presented in 2000. Because SOLEC is a multi-agency, multi-jurisdictional reporting venue, the SOLEC indicators require acceptance by a broad spectrum of stakeholders in the Great Lakes basin. The SOLEC indicators list is expected to provide the basis for government agencies and other organizations to collaborate more effectively and to allocate resources to data collection, evaluation and reporting on the state of the Great Lakes basin ecosystem.     

Assessment of uncertainty of NO2 measurements by the chemiluminescence method and discussion of the quality objective of the NO2 European Directive

Hereafter, an assessment of the ability of the chemiluminescence method to measure ambient NO2 with an accuracy within 15%, as requested by the data quality objective of European directive 1999/30/CE, is presented. In general, uncertainty is evaluated using the response to reference materials or by means of inter-comparisons used to determine some statistics like repeatability, reproducibility and calibration bias. These are incomplete approaches and the method of the Guide to the Expression of Uncertainty in Measurement, advised by the Directive, should be preferred. In fact, even if it requires a large data set, it allows the relative influence of all possible sources of uncertainty to be studied. The extent of NO2 uncertainty is mainly dependent on the level of NO. It is decreased by NOx and the correlation between NOx and NO. Furthermore, the uncertainty budget reveals that the contribution of accuracy of calibration standard, linearity, converter efficiency and drift of the analyser between calibration checks to the overall uncertainty is less important than the contribution of interference, mainly humidity and PAN in rural areas. The relative expanded uncertainty of the NO2 hourly average exceeds 30% for NO2 concentrations lower than 40 microg m(-3). Nevertheless, the data quality objective of 15% is reached for 200 microg m(-3), the hourly limit value of the European directive. On the contrary, at the limit value on the annual average, 40 microg m(-3), the data quality objective is not met if NO is higher than 100 microg m(-3). However, the data quality objective could be reached by correcting the measurements with the bias due to interference.     

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.     

Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism

The analysis for arsenic in hair is commonly used in epidemiological studies to assess exposure to this toxic element. However, poor correlation between total arsenic concentration in hair and water sources have been found in previous studies. Exclusive determination of endogenous arsenic in the hair, excluding external contamination has become an analytical challenge. Arsenic speciation in hair appears as a new possibility for analytical assessing in As-exposure studies. This study applied a relative simple method for arsenic speciation in human hair based on water extraction and HPLC-HG-ICP-MS. The concentration of arsenic species in human hair was assessed in chronically As(V)-exposed populations from two villages (Esqui?a and Illapata) of the Atacama Desert, Chile. The arsenic concentrations in drinking water are 0.075 and 1.25 mg L(-1), respectively, where As(V) represented between 92 and 99.5% of the total arsenic of the consumed waters. On average, the total arsenic concentrations in hair from individuals of Esqui?a and Illapata were 0.7 and 6.1 microg g(-1), respectively. Four arsenic species, As(III), DMA(V), MMA(V) and As(V), were detected and quantified in the hair extracts. Assuming the found species in extracts represent the species in hair, more than 98% of the total arsenic in hair corresponded to inorganic As. On average, As(III) concentrations in hair were 0.25 and 3.75 microg g(-1) in Esqui?a and Illapata, respectively; while, the As(V) average concentrations were 0.15 and 0.45 microg g(-1) in Esqui?a and Illapata, respectively. Methylated species represent less than 2% of the extracted As (DMA(V)+ MMA(V)) in both populations. As(III) in hair shows the best correlation with chronic exposure to As(V) in comparison to other species and total arsenic. In fact, concentrations of As(total), As(III) and As(V) in hair samples are correlated with the age of the exposed individuals from Illapata (R= 0.65, 0.69, 0.57, respectively) and with the time of residence in this village (R= 0.54, 0.71 and 0.58, respectively).     

The distribution of molybdenum in the tissues of wild ducks

The Mo contents and the relations between Mo and Cu or Crcontents were investigated in the organs of Japanese wild ducks(spotbill duck, pintail, wigeon, scaup and tufted duck). Thehighest Mo content in kidney and liver of the dabbling duckswere more than 30 g g^-1 dry weight (g g^-1 d.wt.), though that of diving ducks were less than 11 gg^-1 d. wt. The contents were lower in the ducks migratingwithin Japan, Eurasia and North America than those in the birdsmigrating between Japan and Eurasia. The contents of liver inall species were more than 50 and less than 5 g g^-1 d.wt. for Cu and Cr, respectively. Significant correlations werefound between Mo and both elements in pintail and scaup, and Moand Cr in tufted duck. These results suggest that thecontamination of wild ducks reflects the reproductive area, andnot the collected area. Mo contents closely correlated with theCu and/or Cr contaminations.     

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.