Bottom-up approach for the reaction of xenobiotics and their metabolites with model substances for natural organic matter by electrochemistry-mass spectrometry (EC-MS)

Risk assessment of xenobiotics requires a comprehensive understanding of their transformation in the environment. As most of the transformation processes usually involve a redox reaction or a hydrolysis as the first steps of the transformation, we applied an approach that uses an electrochemical cell to investigate model “redox” reactions in aqueous solutions for environmental processes. We investigated the degradation of a variety of xenobiotics from polar to nonpolar and analyzed their degradation products by on-line coupling of electrochemistry with mass spectrometry (EC-MS). Furthermore, we evaluated possible binding reactions with regard to the generation of non-extractable residues with some model substances (catechol, phthalic acid, γ-l-Glutamyl-l-cysteinyl-glycine (GSH) and l-histidine) deduced from a natural organic matter (NOM) structure model and identified possible binding-sites.Whereas typically investigations in soil/water-systems have been applied, we used to our knowledge for the first time a bottom-up approach, starting from the chemicals of interest and different model substances for natural organic matter to evaluate chemical binding mechanisms (or processes) in the EC-MS under redox conditions. Under oxidative conditions, bindings of the xenobiotics with catechol, GSH and histidine were found, but no reactions with the model compound phthalic acid were observed. In general, no chemical binding has yet been found under reductive conditions. In some cases (i.e. benzo[a]anthracene) the oxidation product only underwent a binding reaction, whereas the xenobiotic itself did not undergo any reactions.EC-MS is a promising fast and simple screening method to investigate the environmental behavior of xenobiotics and to evaluate the potential risks of newly synthesized substances.     

Integrated planning and spatial evaluation of megasite remediation and reuse options

Redevelopment of large contaminated brownfields (megasites) is often hampered by a lack of communication and harmonization among diverse stakeholders with potentially conflicting interests. Decision support is required to provide integrative yet transparent evaluation of often complex spatial information to stakeholders with different areas of expertise. It is considered crucial for successful redevelopment to identify a shared vision of how the respective contaminated site could be remediated and redeveloped. We describe a framework of assessment methods and models that analyzes and visualizes site- and land use-specific spatial information at the screening level, with the aim to support the derivation of recommendable land use layouts and to initiate further and more detailed planning. The framework integrates a GIS-based identification of areas to be remediated, an estimation of associated clean-up costs, a spatially explicit market value appraisal, and an assessment of the planned future land use's contribution to sustainable urban and regional development. Case study results show that derived options are potentially favorable in both a sustainability and an economic sense and that iterative re-planning is facilitated by the evaluation and visualization of economic, ecological and socio-economic aspects. The framework supports an efficient early judgment about whether and how abandoned land may be assigned a sustainable and marketable land use.     

Molecular effects and bioaccumulation of levonorgestrel in the non-target organism Dreissena polymorpha

Bioaccumulation and effects of the contraceptive hormone levonorgestrel were examined in the non-target organism Dreissena polymorpha. Molecular biomarkers of biotransformation, elimination, antioxidant defence and protein damage were analyzed after exposure to increasing concentrations of levonorgestrel in a flow-through system. The lowest concentration (0.312 μg L⁻¹) was 100-fold bioconcentrated within four days. A decrease of the bioconcentration factor was observed within one week for the highest test concentrations (3.12 and 6.24 μg L⁻¹) suggesting enhanced excretory processes. The immediate mRNA up-regulation of pi class glutathione S-transferase proved that phase II biotransformation processes were induced. Disturbance of fundamental cell functions was assumed since the aryl hydrocarbon receptor has been permanently down-regulated. mRNA up-regulation of P-glycoprotein, superoxide dismutase and metallothioneine suggested enhanced elimination processes and ongoing oxidative stress. mRNA up-regulation of heat shock protein 70 in mussels exposed to the two highest concentrations clearly indicated impacts on protein damage.     

Evaluation of septum-capped vials for storage of gas samples during air transport

In order to provide information on the suitability of commonly used gas storage vials for air transport, we tested two vial types on their ability to preserve defined nitrous oxide concentrations and excess pressure when exposed to low pressure, low temperature and puncture by needles. Unlike in Crimp Cap vials, in Exetainers no nitrous oxide loss following low pressure storage was detectable. Tightness of Exetainers following multiple puncture was best using a small needle diameter. Pressure loss following 5, 10, or 25 punctures was lowest in the Exetainers. We conclude that Exetainers are suitable for storing gas samples for an extended period of time during aircraft transport.     

Dust exposure in indoor climbing halls

The use of hydrated magnesium carbonate hydroxide (magnesia alba) for drying the hands is a strong source for particulate matter in indoor climbing halls. Particle mass concentrations (PM10, PM2.5 and PM1) were measured with an optical particle counter in 9 indoor climbing halls and in 5 sports halls. Mean values for PM10 in indoor climbing halls are generally on the order of 200-500 microg m(-3). For periods of high activity, which last for several hours, PM10 values between 1000 and 4000 microg m(-3) were observed. PM(2.5) is on the order of 30-100 microg m(-3) and reaches values up to 500 microg m(-3), if many users are present. In sports halls, the mass concentrations are usually much lower (PM10 < 100 microg m(-3), PM2.5 < or = 20 microg m(-3)). However, for apparatus gymnastics (a sport in which magnesia alba is also used) similar dust concentrations as for indoor climbing were observed. The size distribution and the total particle number concentration (3.7 nm-10 microm electrical mobility diameter) were determined in one climbing hall by an electrical aerosol spectrometer. The highest number concentrations were between 8000 and 12 000 cm(-3), indicating that the use of magnesia alba is no strong source for ultrafine particles. Scanning electron microscopy and energy-dispersive X-ray microanalysis revealed that virtually all particles are hydrated magnesium carbonate hydroxide. In-situ experiments in an environmental scanning electron microscope showed that the particles do not dissolve at relative humidities up to 100%. Thus, it is concluded that solid particles of magnesia alba are airborne and have the potential to deposit in the human respiratory tract. The particle mass concentrations in indoor climbing halls are much higher than those reported for schools and reach, in many cases, levels which are observed for industrial occupations. The observed dust concentrations are below the current occupational exposure limits in Germany of 3 and 10 mg m(-3) for respirable and inhalable dust. However, the dust concentrations exceed the German guide lines for work places without use of hazardous substances. In addition, minimizing dust concentrations to technologically feasible values is required by the current German legislation. Therefore, substantial reduction of the dust concentration is required.     

The hygroscopic behaviour of individual aerosol particles in nickel refineries as investigated by environmental scanning electron microscopy

The hygroscopic properties of individual aerosol particles (1-35 microm equivalent projected area diameter) from the Roasting, Anode Casting and Electrorefining Departments of two Ni refineries were studied by environmental scanning electron microscopy (ESEM) and energy-dispersive X-ray microanalysis (EDX) at a relative humidity of 96-98% (at a temperature of 5 degrees C). In the Roasting and Anode Casting Departments, most particles (60-85% by number) showed no visible change in size or surface morphology when exposed to high relative humidity. Approximately 15-30% of the particles developed a thin water film (growth factors between 1.006 and 1.06) indicating the presence of thin surface coatings of sulfates. About 10% of the particles in the Roasting Department formed droplets (growth factors between 1.1 and 2.6) which always contained a large portion of insoluble material. In the Electrorefining Department, most particles (approximately 60%) were residues from the electrolysis bath solution. At a relative humidity of 96-98% these particles formed a solution which contained only small insoluble inclusions. About 30% of the particles in the Electrorefining Department developed thin water films. As only a small fraction of the particles increased substantially in size when exposed to high relative humidity, the deposition pattern of the total aerosol mass fraction will not be changed substantially by hygroscopic growth. The frequent occurrence of thin surface coatings of soluble material on insoluble Ni compounds has to be considered for health assessment purposes.     

Life and Death in the Fast Lane: Demographic Consequences of Road Mortality in the Florida Scrub-Jay

Abstract: We examined the demographic consequences of road mortality in the cooperatively breeding Florida Scrub-Jay (Aphelocoma coerulescens ), a threatened species restricted to the oak scrub of peninsular Florida. Between May 1986 and July 1995 we monitored the survival and reproductive success of a color-banded population of jays along a two-lane highway at Archbold Biological Station. Annual mortality of breeding adults was 0.38 on road territories, significantly higher than the rate of 0.23 for breeders on nonroad territories. High mortality on road territories appeared to be a direct result of automobile traffic per se and not a consequence of road-induced changes in habitat characteristics. Mortality was especially high for immigrants without previous experience living along the road: in their first two years as breeders on road territories, naive immigrants experienced annual mortality of 0.50 and 0.45. From year 3 onward, however, annual mortality dropped to 0.29, not significantly different from the rate for birds on nonroad territories. This experience-dependent decline in road mortality could be caused either by surviving jays learning to avoid automobiles or by selective mortality operating through time (demographic heterogeneity). Proximity to the road had no effect on nesting success beyond its indirect effects on breeder experience and group size. Because the mortality of 30- to 90-day-old fledglings was significantly higher on road territories than on nonroad territories, however, breeder mortality greatly exceeded production of yearlings on road territories. Roadside territories therefore are sinks that can maintain populations of Florida Scrub-Jays only via immigration. Because Florida Scrub-Jays do not avoid roadside habitats and may even be attracted to them, road mortality presents a difficult challenge for the management and conservation of this threatened and declining species.     

Persistence of C-labeled atrazine and its residues in a field lysimeter soil after 22 years

Twenty-two years after the last application of ring-¹⁴C-labeled atrazine at customary rate (1.7 kg ha⁻¹) on an agriculturally used outdoor lysimeter, atrazine is still detectable by means of accelerated solvent extraction and LC-MS/MS analysis. Extractions of the 0-10 cm soil layer yielded 60% of the residual ¹⁴C-activity. The extracts contained atrazine (1.0 μg kg⁻¹) and 2-hydroxy-atrazine (42.5 μg kg⁻¹). Extractions of the material of the lowest layer 55-60 cm consisting of fine gravel yielded 93% of residual ¹⁴C-activity, of which 3.4 μg kg⁻¹ was detected as atrazine and 17.7 μg kg⁻¹ was 2-hydroxy-atrazine. The detection of atrazine in the lowest layer was of almost four times higher mass than in the upper soil layer. These findings highlight the fact that atrazine is unexpectedly persistent in soil. The overall persistence of atrazine in the environment might represent a potential risk for successive groundwater contamination by leaching even after 22 years of environmental exposure.     

Spatio-temporal covariation of urban particle number concentration and ambient noise

Mobile measurements of ambient noise and particle number concentrations were carried out within an urban residential area in Essen, Germany, during summer 2008. A busy major road with a traffic intensity of about 44,000 vehicles per day was situated within the study area. The spatio-temporal distribution of noise and particles was closely coupled to road traffic on the major road. Total particle number concentrations in proximity to the main road were on average between 25,000 cm^?3 and 35,000 cm^?3 while sound levels reached 70–78 dB(A). These estimates were more than double-fold (factor 2.4) in comparison to the urban residential background. At a 50 m distance off the road particle number concentrations were decaying to about 50% of the initial value. The measurements were characterised by close spatial correlation between total particle number concentration and ambient noise with correlation coefficients of up to r = 0.74. However, during one measurement day coupling between both quantities was weak due to higher turbulent mixing within the canopy layer and a change in ambient wind directions. Enhanced dilution of particle emission from road traffic by turbulent mixing and ‘decoupling’ from the influence of road traffic are believed to be responsible.     

Combining functional data with hierarchical Gaussian process models

Gaussian process models have been used in applications ranging from machine learning to fisheries management. In the Bayesian framework, the Gaussian process is used as a prior for unknown functions, allowing the data to drive the relationship between inputs and outputs. In our research, we consider a scenario in which response and input data are available from several similar, but not necessarily identical, sources. When little information is known about one or more of the populations it may be advantageous to model all populations together. We present a hierarchical Gaussian process model with a structure that allows distinct features for each source as well as shared underlying characteristics. Key features and properties of the model are discussed and demonstrated in a number of simulation examples. The model is then applied to a data set consisting of three populations of Rotifer Brachionus calyciflorus Pallas. Specifically, we model the log growth rate of the populations using a combination of lagged population sizes. The various lag combinations are formally compared to obtain the best model inputs. We then formally compare the leading hierarchical Gaussian process model with the inferential results obtained under the independent Gaussian process model.