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Phototoxicology. 1. Light-enhanced toxicity of TNT and some related compounds to Daphnia magna and Lytechinus variagatus embryos.

Many environmental pollutants interact with solar near-ultraviolet (nuv) light in a manner which greatly increases their toxic effects. The phenomenon of light-mediated toxicity (phototoxicity) is only now becoming generally recognized to any significant degree. Manufacture of, and loading munitions with, the explosive 2,4,6-trinitrotoluene (TNT) in past decades caused contamination of soils and sediments at levels exceeding 1000 ppm and of waters at levels near saturation (100 ppm). Manufacture of TNT produces numerous nitrated by-products, and most of these compounds, including TNT, can be metabolized by many species, including bacteria, fungi, plants, and mammals. This study investigated the phototoxicity of TNT, and 2,3-, 2,4-, 2,6-, and 3,4-dinitrotoluene (DNT) and -diaminotoluene (DAT), and the major metabolites 2-amino-4,6-dinitrotoluene (2A) and 4-amino-2,6-dinitrotoluene (4A), to Daphnia magna (acute toxicity) and Lytechinus variagatus (sea urchin) embryos (subacute, developmental toxicity). Most of the compounds were weakly toxic or nontoxic in the dark. All were phototoxic to sea urchins. In D. magna, 2,3- and 3,4-DNT/DAT and 4A were not toxic but were phototoxic, and 2A was toxic and phototoxic; the other isomers were not toxic or phototoxic to this species.

Animals↗

The measurement of soiling.

To show the quantity of soiling due to environmental sources different methods of measuring are applied: two methods pertaining to the mass (classic deposit plates and simple plates) and two optical methods (reflectance and transmission). Deposit plates, anodized aluminium, glazed earthenware plates, and polystyren, glass, "Tergal" cloth plates were used in 8 urban sites and 1 extra-urban site during 1 to 3 months. The simple plate method as well as the measurement of the reflectance and transmission of the light really show the amount of soiling deposit in a town. The simple plates are more suitable for a high particles pollution and the optical methods (especially the light transmission method) are more suitable for a low pollution. The more useful and simple method is the anodized aluminium plates. Also, this study gives evidence of the main responsibility of the motor vehicle in polluting the facades along roads: 70 to 80% of the soiling is due to transportation.

Environmental Pollution↗

Dendroremediation of trinitrotoluene (TNT). Part 1: Literature overview and research concept.

BACKGROUND, AIM AND SCOPE: For decades, very large areas of former military sites have been contaminated diffusely with the persistent nitroaromatic explosive 2,4,6-trinitrotoluene (TNT). The recalcitrance of the environmental hazard TNT is to a great extent due to its particulate soil existence, which leads to slow but continuous leaching processes. Although improper handling during the manufacture of TNT seems to be a problem of the past in developed countries, environmental deposition of TNT and other explosives is still going on unfortunately, resulting from thousands of unexploded ordnance or low order explosions at munitions test areas and at current battlefields. OBJECTIVE: Sustainable phytoremediation strategies for explosives in Germany, which intend to use trees to decontaminate soil and groundwater ('dendroremediation'), have to consider that most of the former German military sites are already covered with woodlands, mainly with conifer stands. Therefore, parallel investigation of the remediation potential is necessary for both of the selected hybrids of fast growing broadleaf trees, which are waiting for planting and forest conifers, which have already proven for decades that they are able to grow on explosive contaminated sites. MAIN FEATURES: A short literature review is given regarding phytoremediation of TNT with herbaceous plants and some general aspects of dendroremediation are discussed. Furthermore, an overview of our TNT-dendroremediation research network is introduced, which has the strategic goal to make dendroremediation more calculable for a series of potent trees for site-adapted in situ application and for the assessment of tree remediation potentials in natural attenuation processes. RESULTS AND DISCUSSION: Some of our methods, results and conclusions yet unpublished are presented. For a preliminary calculation of area-related annual TNT dendroremediation potential of five-year-old trees, the following values were assessed: Salix EW-13 6.0, Salix EW-20 8.5, Populus ZP-007 4.2, Betula pendula 5.2, Picea abies 1.9 and Pinus sylvestris 0.8 g m(-2) a(-1). For a 45-year-old spruce forest, an annual natural attenuation potential of 4.2 g TNT m(-2) a(-1) was found. CONCLUSION, RECOMMENDATIONS AND PERSPECTIVE: Our main results deliver quantitative proposals for dendroremediation strategies in situ and provide decision aids. Also aspects of growth of raw materials for energy production are considered. Our dendroremediation research concept for TNT and its congeners can be easily completed for other trees of interest and it can also be applied to herbaceous plants. Knowing the current bottlenecks of phytoremediation and considering the known environmental behaviour of other contaminants, elements of our methodological approach may be easily adapted to those pollutant groups, e.g. for pesticides, pharmaceuticals, PAHs, chlorinated recalcitrants and, with some restrictions, to inorganics and to multiple contaminations. Our dynamical dendrotolerance test systems will help to predict tree growth on polluted areas. To provide some light into the black box of TNT dendroremediation, experimental data regarding the uptake, distribution and degradation of [14C]-TNT in mature tree tissues will be reported in the second part of this publication.

Biodegradation, Environmental↗

Detection of free radicals and reactive oxygen species.

In plants, reactive oxygen species (ROS), also known as active oxygen species (AOS), are associated with normal, physiological processes as well as with responses to adverse conditions. ROS are associated with stress in many ways; as primary elicitors, as products and propagators of oxidative damage, or as signal molecules initiating defense or adaptation. The photosynthetic electron transport is a major site of oxidative stress by visible or ultraviolet light, high or low temperature, pollutants, or herbicides. ROS production can be presumed from detecting oxidatively damaged lipids, proteins, or pigments as well as from the alleviating effects of added antioxidants. On the other hand, measuring ROS by special sensor molecules provides more direct information. This chapter focuses on the application of spin trapping electron paramagnetic resonance (EPR) spectroscopy for detecting ROS; singlet oxygen and oxygen free radicals in thylakoid membrane preparations.

Electron Spin Resonance Spectroscopy↗

Precipitation in light extinction reconstruction.

The U.S. Environmental Protection Agency (EPA) published the Regional Haze Rule (RHR) in 1999. The RHR default goal is to reduce haze linearly to natural background in 2064 from the baseline period of 2000-2004. The EPA default method for estimating natural and baseline visibility uses the Interagency Monitoring of Protected Visual Environments (IMPROVE) formula. The IMPROVE formula predicts the light extinction coefficient from aerosol chemical concentrations measured by the IMPROVE network. The IMPROVE light scattering coefficient formula using data from 1994-2002 underestimated the measured light scattering coefficient by 700 Mm(-1), on average, on days with precipitation. Also, precipitation occurred as often on the clearest as haziest days. This led to estimating the light extinction coefficient of precipitation, averaged over all days, as the light scattering coefficient on days with precipitation (700 Mm(-1)) multiplied by the percent of precipitation days in a year. This estimate added to the IMPROVE formula light extinction estimate gives a real world estimate of visibility for the 20% clearest, 20% haziest, and all days. For example, in 1993, the EPAs Report to Congress projected visibility in Class I areas would improve by 3 deciviews by 2010 across the haziest portions of the eastern United States because of the 1990 Clean Air Act Amendments. Omitted was the light extinction coefficient of precipitation. Adding in the estimated light extinction coefficient of precipitation, the estimated visibility improvement declines to <1 deciview.

Air Pollutants↗

Photocatalytic degradation of model textile dyes in wastewater using ZnO as semiconductor catalyst.

Semiconductor photocatalysis often leads to partial or complete mineralization of organic pollutants. Upon irradiation with UV/visible light, semiconductors catalyze redox reactions in presence of air/O2 and water. Here, the potential of a common semiconductor, ZnO, has been explored as an effective catalyst for the photodegradation of two model dyes: Methylene Blue and Eosin Y. A 16 W lamp was the source of UV-radiation in a batch reactor. The effects of process parameters like, catalyst loading, initial dye concentration, airflow rate, UV-radiation intensity, and pH on the extent of photo degradation have been investigated. Substantial reduction of COD, besides removal of colour, was also achieved. A rate equation for the degradation based on Langmuir-Hinshelwood model has been proposed.

Catalysis↗

Nitrogen deposition in California forests: a review.

Atmospheric concentrations and deposition of the major nitrogenous (N) compounds and their biological effects in California forests are reviewed. Climatic characteristics of California are summarized in light of their effects on pollutant accumulation and transport. Over large areas of the state dry deposition is of greater magnitude than wet deposition due to the arid climate. However, fog deposition can also be significant in areas where seasonal fogs and N pollution sources coincide. The dominance of dry deposition is magnified in airsheds with frequent temperature inversions such as occur in the Los Angeles Air Basin. Most of the deposition in such areas occurs in summer as a result of surface deposition of nitric acid vapor (HNO3) as well as particulate nitrate (NO3-) and ammonium (NH4+). Internal uptake of gaseous N pollutants such as nitrogen dioxide (NO2), nitric oxide (NO), HNO3, peroxyacetyl nitrate (PAN), ammonia (NH3), and others provides additional N to forests. However, summer drought and subsequent lower stomatal conductance of plants tend to limit plant utilization of gaseous N. Nitrogen deposition is much greater than S deposition in California. In locations close to photochemical smog source areas, concentrations of oxidized forms of N (NO2, HNO3, PAN) dominate, while in areas near agricultural activities the importance of reduced N forms (NH3, NH4+) significantly increases. Little data from California forests are available for most of the gaseous N pollutants. Total inorganic N deposition in the most highly-exposed forests in the Los Angeles Air Basin may be as high as 25-45 kg ha(-1) year(-1). Nitrogen deposition in these highly-exposed areas has led to N saturation of chaparral and mixed conifer stands. In N saturated forests high concentrations of NO3- are found in streamwater, soil solution, and in foliage. Nitric oxide emissions from soil and foliar N:P ratios are also high in N saturated sites. Further research is needed to determine the ecological effects of chronic N deposition, and to develop appropriate management options for protecting water quality and managing plant nutrient resources in ecosystems which no longer retain excess N.

Journal Article↗

The basic helix-loop-helix-PAS protein MOP9 is a brain-specific heterodimeric partner of circadian and hypoxia factors.

PAS (PER, ARNT, SIM) proteins play important roles in adaptation to low atmospheric and cellular oxygen levels, exposure to certain environmental pollutants, and diurnal oscillations in light and temperature. In an attempt to better understand how organisms sense environmental changes, we have characterized a novel member of the PAS superfamily, MOP9 (member of PAS superfamily), that maps to human chromosome 12p11.22-11.23. This protein displays significant homology to the Drosophila circadian factor CYCLE and its putative mammalian ortholog MOP3/bMAL1. Like its homologs, MOP9 forms a transcriptionally active heterodimer with the circadian CLOCK protein, the structurally related MOP4, and hypoxia-inducible factors, such as HIF1alpha. In a manner consistent with its role as a biologically relevant partner of these proteins, MOP9 is coexpressed in regions of the brain such as the thalamus, hypothalamus, and amygdala. Importantly, MOP9 is coexpressed with CLOCK in the suprachiasmatic nucleus, the site of the master circadian oscillator in mammals.

ARNTL Transcription Factors↗

Relating summer ambient particulate sulfur, sulfur dioxide, and light scattering to gaseous tracer emissions from the MOHAVE Power Project.

Project MOHAVE was initiated in 1992 to examine the role of emissions from the 1580 MW coal-fired MOHAVE Power Project (MPP) on haze at the Grand Canyon National Park (GCNP), located about 130 km north-north-east of the power plant. Statistical relationships were analyzed between summertime ambient concentrations of a gaseous perfluorocarbon tracer released from MPP and ambient SO2, particulate sulfur, and light scattering to evaluate whether MPP's emissions could be transported to the GCNP and then impact haze levels there. Spatial analyses indicated that particulate sulfur levels were strongly correlated across the monitoring network, regardless of whether the monitoring stations were upwind or downwind of MPP. This indicates that particulate sulfur levels in this region were influenced by distant regional emission sources. A significant particulate sulfur contribution from a point source such as MPP would result in a non-uniform pattern downwind. There was no suggestion of this in the data. Furthermore, correlations between the MPP tracer and ambient particulate sulfur and light scattering at locations in the park were virtually zero for averaging times ranging from 24 hr to 1 hr. Hour-by-hour MPP tracer levels and light scattering were individually examined, and still no positive correlations were detected. Finally, agreement between tracer and particulate sulfur did not improve as a function of meteorological regime, implying that, even during cloudy monsoon days when more rapid conversion of SO2 to particulate sulfur would be expected, there was no evidence for downwind particulate sulfur impacts. Despite the fact that MPP was a large source of SO2 and tracer, neither time series nor correlation analyses were able to detect any meaningful relationship between MPP's SO2 and tracer emission "signals" to particulate sulfur or light scattering.

Air Pollution↗

Temporal and spatial variations of the Vienna aerosol.

For several intensive sampling periods the mass concentration, light extinction, light scattering and light absorption coefficients, and the mass size distribution of the aerosol have been determined at up to eleven location in the non-industrial town of Vienna. Obviously, large variations of the measured values have been found. The following factors influenced the aerosol markedly: wind speed, wind direction, increased aerosol production such as by space heating or traffic and resuspension. Most of the variations in aerosol were found to be caused by these factors. A comparison of the mass concentration and light absorption of the aerosol upwind and downwind of Vienna permitted the estimation of locally produced aerosols: about 50% of the mass of the aerosol and 75% of the light-absorbing aerosol appears to be produced locally.

Air↗

An objective definition of air mass types affecting Athens, Greece; the corresponding atmospheric pressure patterns and air pollution levels.

This work aims at defining characteristic air mass types that dominate in the region of Athens, Greece during the cold (November-March) and the warm (May-September) period of the year and also at evaluating the corresponding concentration levels of the main air pollutants. For each air mass type, the mean atmospheric pressure distribution (composite maps) over Europe and the Mediterranean is estimated in order to reveal the association of atmospheric circulation with air pollution levels in Athens. The data basis for this work consists of daily values of thirteen meteorological and six pollutant parameters covering the period 1993-97. The definition of the characteristic air mass types is attempted objectively by using the methods of Factor Analysis and Cluster Analysis. The results show that during the cold period of the year there are six prevailing air mass types (at least 3% of the total number of days) and six infrequent ones. The examination of the corresponding air pollution concentration levels shows that the primary air pollutants appear with increased concentrations when light or southerly winds prevail. This is usually the case when a high pressure system is located over the central Mediterranean or a low pressure system lays over south Italy, respectively. Low levels of the primary pollutants are recorded under northeasterly winds, mainly caused by a high pressure system over Ukraine. During the warm period of the year, the southwestern Asia thermal low and the subtropical anticyclone of the Atlantic Ocean affect Greece. Though these synoptic systems cause almost stagnant conditions, four main air mass types are dominant and ten others, associated with extreme weather, are infrequent. Despite the large amounts of total solar radiation characterizing this period, ozone concentrations remain at low levels in central Athens because of its destruction by nitric oxide.

Air Movements↗