Residual dynamics of thiacloprid in medical herbs marjoram, thyme, and camomile and in soil

Thiacloprid is a new insecticide of the chloronicotinyl family. To assess its risk after application, residual characteristics of thiacloprid in marjoram, thyme, and camomile and in soil were studied under field conditions. The active ingredient was extracted from the plant material using a mixture of acetone-water. After filtration, the extract was concentrated to the aqueous phase, diluted with water, and portioned against ethyl acetate on a matrix solid phase dispersion column. Thiacloprid was extracted from soil using a mixture of methanol-water, filtered, and re.extracted （clean up） with dichloromethane. The residues were quantified using HPLC-MS-MS. The methods were validated by recovery experiments. Thiacloprid residues in marjoram, thyme, and camomile and in soil persisted beyond 10, 14, 14, and 21 d but no residues were detected after 14, 21, 21, and 28 d, respectively. The data obtained in this study indicated that the biexponential model is more suitable than the first-order function to describe the decline of thiacloprid in fresh marjoram, fresh thyme, and dried camomile flowers with half-life （t1/2） of 1.1, 0.7, and 1.2 d, respectively. However, both the first-order function and biexponential model were found to be applicable for dissipation of thiacloprid in soil with almost the same t1/2 values of 3.5 and 3.6 d. The results indicated that thiacloprid dissipates rapidly and does not accumulate in the tested herbs and in soil.     

Model-based prediction of long-term leaching of contaminants from secondary materials in road constructions and noise protection dams

In this study, contaminant leaching from three different secondary materials (demolition waste, municipal solid waste incineration ash, and blast furnace slag) to groundwater is assessed by numerical modeling. Reactive transport simulations for a noise protection dam and a road dam (a typical German autobahn), in which secondary materials are reused as base layers, were performed to predict the breakthrough of a conservative tracer (i.e., a salt) and sorbing contaminants (e.g., PAHs like naphthalene and phenanthrene or heavy metals) at the groundwater table. The dam constructions have a composite architecture with soil covers in inclined layers and distinct contrasts in the unsaturated hydraulic properties of the used materials. Capillary barrier effects result in strong spatial variabilities of flow and transport velocities. Contaminant breakthrough curves at the groundwater table show significant tailing due to slow sorption kinetics and a wide distribution of travel times. While conservative tracer breakthrough depends primarily on subsoil hydraulic properties, equilibrium distribution coefficients and sorption kinetics represent additional controlling factors for contaminant spreading. Hence, the three secondary materials show pronounced differences in the temporal development of leached contaminant concentrations with consequences for breakthrough times and peak concentrations at the groundwater table. Significant concentration reductions due to dispersion occur only if the source concentrations decrease significantly prior to the arrival of the contaminant at the groundwater table. Biodegradation causes significant reduction of breakthrough concentrations only if flow velocities are low.     

Overview of surface measurements and spatial characterization of submicrometer particulate matter during the DISCOVER-AQ 2013 campaign in Houston,TX

The sources of submicrometer particulate matter (PM₁) remain poorly characterized in the industrialized city of Houston, TX. A mobile sampling approach was used to characterize PM₁ composition and concentration across Houston based on high-time-resolution measurements of nonrefractory PM₁ and trace gases during the DISCOVER-AQ Texas 2013 campaign. Two pollution zones with marked differences in PM₁ levels, character, and dynamics were established based on cluster analysis of organic aerosol mass loadings sampled at 16 sites. The highest PM₁ mass concentrations (average 11.6 ± 5.7 µg/m³) were observed to the northwest of Houston (zone 1), dominated by secondary organic aerosol (SOA) mass likely driven by nighttime biogenic organonitrate formation. Zone 2, an industrial/urban area south/east of Houston, exhibited lower concentrations of PM₁ (average 4.4 ± 3.3 µg/m³), significant organic aerosol (OA) aging, and evidence of primary sulfate emissions. Diurnal patterns and backward-trajectory analyses enable the classification of airmass clusters characterized by distinct PM sources: biogenic SOA, photochemical aged SOA, and primary sulfate emissions from the Houston Ship Channel. Principal component analysis (PCA) indicates that secondary biogenic organonitrates primarily related with monoterpenes are predominant in zone 1 (accounting for 34% of the variability in the data set). The relevance of photochemical processes and industrial and traffic emission sources in zone 2 also is highlighted by PCA, which identifies three factors related with these processes/sources (~50% of the aerosol/trace gas concentration variability). PCA reveals a relatively minor contribution of isoprene to SOA formation in zone 1 and the absence of isoprene-derived aerosol in zone 2. The relevance of industrial amine emissions and the likely contribution of chloride-displaced sea salt aerosol to the observed variability in pollution levels in zone 2 also are captured by PCA.

Implications: This article describes an urban-scale mobile study to characterize spatial variations in submicrometer particulate matter (PM₁) in greater Houston. The data set indicates substantial spatial variations in PM₁ sources/chemistry and elucidates the importance of photochemistry and nighttime oxidant chemistry in producing secondary PM₁. These results emphasize the potential benefits of effective control strategies throughout the region, not only to reduce primary emissions of PM₁ from automobiles and industry but also to reduce the emissions of important secondary PM₁ precursors, including sulfur oxides, nitrogen oxides, ammonia, and volatile organic compounds. Such efforts also could aid in efforts to reduce mixing ratios of ozone.     

Effect of prochloraz fungicide on biotransformation enzymes and oxidative stress parameters in three-spined stickleback (Gasterosteus aculeatus L.)

The aim of this study was to characterize biomarker responses in three-spined sticklebacks exposed to prochloraz (Pcz). For this purpose, adult sticklebacks were exposed for 2 weeks to prochloraz at 0, 10, 50, 100 and 500 μg/L prior to one week of depuration in clean water. At days 7, 14 and 21, several hepatic biomarkers were measured including 7-ethoxyresorufin-O-deethylase (EROD), glutathione-S-transferase (GST), glutathione peroxidase (GPx), catalase (CAT), total glutathione (GSH) content and thiobarbituric acid reactive substances (TBARS). Pcz induced a transient increase of antioxidant enzymes and a depletion of glutathione content during the first 7 days of exposure. This study showed that EROD activity and antioxidants were disrupted in a transient manner. GST was rapidly induced in a dose-dependent manner and this induction was persistent and observed also after depuration. GST appeared as a valuable biomarker to assess the exposure to Pcz.     

Determination of PM₁₀ deposition based on antimony flux to selected urban surfaces

Deposition of PM(10) particles to several types of urban surfaces was investigated within this study. Antimony was chosen as a tracer element to calculate dry deposition velocities for PM(10), since antimony proved to be present almost exclusively in PM(10) particles in ambient urban air. During 18 months, eight sampling sites in Berlin and Karlsruhe, two cities in Germany, were operated. PM(10) concentrations and dry deposition were routinely sampled as two week averages. Additionally, leaf-samples were collected at three sites with tall vegetation. The obtained deposition velocities ranged from 0.8 to 1.3 cms(-1) at roadside sites and from 0.4 to 0.5 cms(-1) at the other sites. With reference to the whole canopy, additional deposition velocities of about 0.5 cms(-1) were obtained for leaf surfaces. As a consequence, it can be concluded that vegetation-covered areas beside streets show the highest potential to capture particles in urban areas.     

Urban and rural mortality rates during heat waves in Berlin and Brandenburg, Germany

In large cities such as Berlin, human mortality rates increase during intense heat waves. Analysis of relevant data from north-eastern Germany revealed that, during the heat waves that occurred between 1990 and 2006, health risks were higher for older people in both rural and urban areas, but that, during the two main heat waves within that 17-year period of time, the highest mortality rates were from the city of Berlin, and in particular from its most densely built-up districts. Adaptation measures will need to be developed, particularly within urban areas, in order to cope with the expected future intensification of heat waves due to global climate change.     

Adverse effects in wild fish living downstream from pharmaceutical manufacture discharges

A set of biochemical and histological responses was measured in wild gudgeon collected upstream and downstream of urban and pharmaceutical manufacture effluents. These individual end-points were associated to fish assemblage characterisation. Responses of biotransformation enzymes, neurotoxicity and endocrine disruption biomarkers revealed contamination of investigated stream by a mixture of pollutants. Fish from sampled sites downstream of the industrial effluent exhibited also strong signs of endocrine disruption including vitellogenin induction, intersex and male-biased sex-ratio. These individual effects were associated to a decrease of density and a lack of sensitive fish species. This evidence supports the hypothesis that pharmaceutical compounds discharged in stream are involved in recorded endocrine disruption effects and fish population disturbances and threaten disappearance of resident fish species. Overall, this study gives argument for the utilisation of an effect-based monitoring approach to assess impacts of pharmaceutical manufacture discharges on wild fish populations.