Treatability studies of naphthalene in soil,water and air with persulfate activated by iron(Ⅱ)

Chemical oxidation was applied to an artificially contaminated soil with naphthalene (NAP). Evaluation of NAP distribution and mass reduction in soil, water and air phases was carried out through mass balance. Evaluation of NAP distribution and mass reduction in soil, water and air phases was carried out through mass balance. The importance of the air phase analysis was emphasized by demonstrating how NAP behaves in a sealed system over a 4 hr reaction period. Design of Experiments method was applied to the following variables: sodium persulfate concentration [SP], ferrous sulfate concentration [FeSO₄], and pH. The system operated with a prefixed solid to liquid ratio of 1:2. The following conditions resulted in optimum NAP removal [SP] = 18.37 g/L, [FeSO₄] = 4.25 g/L and pH = 3.00. At the end of the 4 hr reaction, 62% of NAP was degraded. In the soil phase, the chemical oxidation reduced the NAP concentration thus achieving levels which comply with Brazilian and USA environmental legislations. Besides the NAP partitioning view, the monitoring of each phase allowed the variabilities assessment over the process, refining the knowledge of mass reduction. Based on NAP distribution in the system, this study demonstrates the importance of evaluating the presence of semi-volatile and volatile organic compounds in the air phase during remediation, so that there is greater control of the system as to the distribution and presence of the contaminant in the environment. The results highlight the importance of treating the contaminant in all its phases at the contaminated site.     

Characterization of atmospheric aerosol (PM10 and PM2.5) from a medium sized city in São Paulo state, Brazil

Air pollution causes deleterious effects on human health with aerosols being among the most polluting agents.The objective of this work is the characterization of the PM_(2.5) and PM_(10) aerosol mass in the atmosphere.The methods of analysis include WD-XRF and EDS.Data were correlated with meteorological information and air mass trajectories(model HYSPLIT)by multivariate analysis.A morphological structural analysis was also carried out to identify the probable sources of atmospheric aerosols in the city of Sao Jose do Rio Preto,Brazil.The mean mass concentration values obtained were 24.54 μg/m~3 for PM_(10),above the WHO annual standard value of 20 μg/m~3 and 10.88 μg/m~3 for PM_(2.5) whose WHO recommended limit is10 μg/m~3.WD-XRF analysis of the samples revealed Si and Al as major components of the coarse fraction.In the fine fraction,the major elements were Al and S.The SEM-FEG characterization allowed identifying the morphology of the particles in agglomerates,ellipsoids and filaments in the PM_(10),besides spherical in the PM_(2.5).The analysis by EDS corroborated WD-XRF results,identifying the crustal elements,aluminosilicates and elements of anthropogenic origin in the coarse fraction.For the fine fraction crustal elements were also identified;aluminosilicates,black carbon and spherical particles(C and O) originating from combustion processes were predominant.The use of multivariate analysis to correlate air mass trajectories with the results of the morpho-structural characterization of the particulate matter allowed confirmation of the complex composition of the particles resulting from the combination of both local and long-distance sources.     

The study of biological activity of transformation products of diclofenac and its interaction with chlorogenic acid

In the present work we compared the biological activity of DCF, 4′-OHDCF and 5-OHDCF as molecules of most biodegradation pathways of DCF and selected transformation products (2-hydroxyphenylacetic acid; 2,5-dihydroxyphenylacetic acid and 2,6-dichloroaniline) which are produced during AOPs, such as ozonation and UV/H₂O₂. We also examined the interaction of DCF with chlorogenic acid (CGA). CGA is commonly used in human diet and entering the environment along with waste mainly from the processing and brewing of coffee and it can be toxic for microorganisms included in activated sludge. In the present experiment the evaluation of following parameters was performed: E. coli K-12 cells viability, growth inhibition of E. coli K-12 culture, LC₅₀ and mortality of Chironomus aprilinus, genotoxicity, sodA promoter induction and ROS generation. In addition the reactivity of E. coli SM recA:luxCDABE biosensor strain in wastewater matrices was measured. The results showed the influence of DCF, 4′-OHDCF and 5-OHDCF on E. coli K-12 cells viability and bacteria growth, comparable to AOPs by-products. The highest toxicity was observed for selected, tested AOPs by-products, in comparison to the DCF, 4′-OHDCF and 5-OHDCF. Genotoxicity assay indicated that 2,6-dichloroaniline (AOPs by-product) had the highest toxic effect. The oxidative stress assays revealed that the highest level of ROS generation and sodA promoter induction were obtained for DCF, 4′-OHDCF and 5-OHDCF, compared to other tested compounds. We have also found that there is an interaction between chlorogenic acid and DCF, which resulted in increased toxicity of the mixture of the both compounds to E. coli K-12, comparable to parent chemicals. The strongest response of E. coli SM biosensor strain with recA:luxCDABE genetic construct in filtered treated wastewaters, comparable to control sample was noticed. It indicates, that E. coli SM recA:luxCDABE biosensor strains is a good tool for bacteria monitoring in wastewater environment. Due to toxicity and biological activity of tested DCF transformation products, there is a need to use additional wastewater treatment systems for wastewater contaminated with pharmaceutical residues.     

Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO₂) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NO_x analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO₂, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO₂ varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO₂ degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.     

短期干旱胁迫对马尾松排放挥发性有机物的影响

为探究干旱环境对BVOCs排放的影响,应用动态封闭式采样系统和热脱附-气相色谱-飞行质谱仪,对短期干旱胁迫作用下马尾松的BVOCs排放进行了实验室测量,定量分析BVOCs排放速率和排放组成的变化.结果表明,干旱胁迫时异戊二烯的排放受到抑制,排放速率降低约50%;单萜烯和倍半萜烯的排放水平增强,排放速率分别为137.85和0.98μg/（m²·h）,是未受胁迫时的2.9和2.0倍.除反式-α-香柠檬烯外,干旱胁迫促进各单萜烯和倍半萜烯化合物的排放,是未受胁迫时的1.3~42.4倍,其中3-蒈烯排放的响应最敏感,α-葑烯、α-水芹烯和石竹烯的响应最弱.干旱胁迫时单萜烯和倍半萜烯的排放组成有所变化,但主导的化合物种类不变,单萜烯以α-蒎烯、香桧烯和β-蒎烯为主,占比分别为48%、17%和17%;倍半萜烯以石竹烯和长叶烯为主,占比分别为57%和34%.     

Mercury levels in human population from a mining district in Western Colombia

A biomonitoring study was carried out to examine the adverse impacts of total mercury in the blood(HgB), urine(Hg U) and human scalp hair(HgH) on the residents of a mining district in Colombia. Representative biological samples(scalp hair, urine and blood) were collected from volunteered participants(n = 63) to estimate the exposure levels of THg using a Direct mercury analyzer. The geometric mean of THg concentrations in the hair,urine and blood of males were 15.98 μg/g, 23.89 μg/L and 11.29 μg/L respectively, whereas the females presented values of 8.55 μg/g, 5.37 μg/L and 8.80 μg/L. Chronic urinary Hg(HgU)levels observed in male workers(32.53 μg/L) are attributed to their long termed exposures to inorganic and metallic mercury from gold panning activities. On an average, the levels of THg are increasing from blood(10.05 μg/L) to hair(12.27 μg/g) to urine(14.63 μg/L).Significant positive correlation was found between hair and blood urinary levels in both male and female individuals. Thus the present biomonitoring investigation to evaluate the Hg levels and associated health issues would positively form a framework for further developmental plans and policies in building an ecofriendly ecosystem.     

Yield and grain quality of spring wheat (Triticum aestivum L., cv. Drabant) exposed to different concentrations of ozone in open-top chambers

Spring wheat (Triticum aestivum L., cv. Drabant) was exposed to different concentrations of ozone in open-top chambers for two growing seasons, 1987 and 1988, at a site located in south-west Sweden. The chambers were placed in a field of commercially grown spring wheat. The treatments were charcoal-filtered air (CF), non-filtered air (NF) and non-filtered air plus extra ozone (NF(+)). In 1988, one additional ozone concentration (NF(++)) was used. Grain yield was affected by the ozone concentration of the air. Air filtration resulted in an increase in grain yield of about 7% in both years, compared to NF. The addition of ozone (NF(+), NF(++)) reduced grain yield and increased the content of crude protein of the grain in both years. Filtration of the air had no significant effect on the content of crude protein, compared to NF. The results showed a strong positive chamber effect on grain yield in the cold and wet summer of 1987. In 1988, there was no net chamber effect on grain yield. The relative differences between the CF, NF and NF(+) treatments with respect to grain yield were of the same magnitude in the two years, despite the very different weather conditions.     

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.     

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.