Degradation of 17α-ethinylestradiol by ozonation--identification of the by-products and assessment of their estrogenicity and toxicity

The presence of the synthetic estrogen 17α-ethinylestradiol (EE2) in waters at low levels is a concern due to its ability to act as an endocrine disruptor. Ozone (O₃) is commonly used in water treatment and reacts with EE2 to form by-products having characteristics that are mostly unknown. The aim of this study was to identify the by-products of E2 and EE2 ozonation and determine their estrogenicity and toxicity relative to the parent compound. Ozonation by-products were identified via LC-MS analysis. The estrogenicity was measured using the YES assay, and toxicity was determined by monitoring effects on histology of fetal rat testes and testosterone secretion by these tissues. Two EE2 by-products were identified with open phenolic ring structures (masses 302 and 344 u). The Yeast Estrogen Screening (YES) assay showed a decreased but incomplete removal of estrogenicity after ozonation of EE2. Histological analysis of fetal testes revealed that neither E2 nor EE2, with or without ozonation, had any effect on seminiferous cord formation; however, a remarkable negative effect on testosterone secretion was observed, with EE2 by-products after ozonation showing the most rapid and extensive inhibition. These results show that the removal of EE2 via reaction with O₃ resulted in the formation of by-products that are less estrogenic (as demonstrated by the YES assay), but have a greater negative impact on testosterone secretion. Thus, the disappearance of the parent compound is not a sufficient endpoint, as the by-products created may be more toxic. Care should be taken when implementing oxidation applications such as ozone during waste water treatment.     

Response and potential of agroforestry crops under global change

The use of agroforestry crops is a promising tool for reducing atmospheric carbon dioxide concentration through fossil fuel substitution. In particular, plantations characterised by high yields such as short rotation forestry (SRF) are becoming popular worldwide for biomass production and their role acknowledged in the Kyoto Protocol. While their contribution to climate change mitigation is being investigated, the impact of climate change itself on growth and productivity of these plantations needs particular attention, since their management might need to be modified accordingly. Besides the benefits deriving from the establishment of millions of hectares of these plantations, there is a risk of increased release into the atmosphere of volatile organic compounds (VOC) emitted in large amounts by most of the species commonly used. These hydrocarbons are known to play a crucial role in tropospheric ozone formation. This might represent a negative feedback, especially in regions already characterized by elevated ozone level.     

Advances of air pollution science: From forest decline to multiple-stress effects on forest ecosystem services

Over the past 20 years, the focus of forest science on air pollution has moved from forest decline to a holistic framework of forest health, and from the effects on forest production to the ecosystem services provided by forest ecosystems. Hence, future research should focus on the interacting factorial impacts and resulting antagonistic and synergistic responses of forest trees and ecosystems. The synergistic effects of air pollution and climatic changes, in particular elevated ozone, altered nitrogen, carbon and water availability, must be key issues for research. Present evidence suggests air pollution will become increasingly harmful to forests under climate change, which requires integration amongst various stressors (abiotic and biotic factors, including competition, parasites and fire), effects on forest services (production, biodiversity protection, soil protection, sustained water balance, socio-economical relevance) and assessment approaches (research, monitoring, modeling) to be fostered.     

Improved enzymatic hydrolysis of waste paper by ozone pretreatment

Waste paper samples made from newsprint, copier paper, and magazine paper, as well as samples of kraft pulp and thermomechanical pulp, were pretreated with ozone to improve enzymatic hydrolysis. The ozone treatment of pulps of newsprint and of magazine paper increased the specific surface areas and total pore volumes while decreasing the lignin content so that these values became similar to those of thermomechanical pulps. These morphological and chemical changes in the pulps resulted in the increased access of cellulase to the pulp fiber surface and increased enzymatic hydrolysis. For copier paper, in which the lignin content was very low, additives on the pulp fiber surface were oxidized and removed by ozone treatment and extraction, and this allowed improved enzymatic hydrolysis. In contrast, surface areas and total pore volumes of kraft pulp and bleached kraft pulp were decreased by the ozone treatment, resulting in morphological changes in the pulps that decreased enzymatic hydrolysis.     

Ozone and/or Water Stresses Could have Influenced the Betula ermanii Cham. Forest Decline Observed at Oku-Nikko, Japan

A serious forest decline of Betula ermanii Cham. has been observed at Mt. Mae-Shirane, Oku-Nikko, Japan, where high ozone (O₃) concentration and severe water deficiency have been measured. In order to consider the possibility whether O₃ and/or water stresses could have been the causes of the forest decline of B. ermanii, plant growth experiments were conducted in environment-controlled growth cabinets. Two-year-old seedlings of B. ermanii were exposed to either charcoal-filtered air (O₃ concentration <5 ppb) or 50 ppb O₃ (daily average, ranging between 20–100 ppb) for 123 days at 20.0/12.5 ± 1.0°C (day/night) and 70/80 ± 7% relative humidity (day/night). Simultaneously, seedlings were treated with three watering regime: 1.0 < pF < 1.8 (no water stress), 1.8 < pF < 2.5 (mild water stress) or 2.5 < pF < 3.0 (severe water stress). O₃ exposure significantly reduced the dry weights of leaf, root and the whole plant, while water stress significantly reduced the dry weights of each organ and the whole plant. Significant reductions of net photosynthesis, transpiration and stomatal conductance were also observed under O₃ and/or water deficiency treatments, while contents of RuBP carboxylase/oxygenase (Rubisco), chlorophyll _a+b and some essential nutrient elements (N, P, K, Mg and Ca) were not markedly changed. It was suggested that the decrease in net photosynthetic rate induced mainly by stomatal closure was the major cause of the growth reduction under O₃ and/or water stresses. No significant interactions between O₃ and water stresses were observed in terms of the depression of dry matter production, which suggested that simultaneous stress treatments of O₃ exposure and water deficiency could affect the tree growth of B. ermanii additively.     

The use of respirometric measurements to determine the toxicity of textile dyes in aqueous solution and after oxidative decolourisation processes

Selected results from the degradation of reactive-dye hydrolysates after UV irradiation, ozonation and sodium peroxodisulphate (NaPS) treatment are presented. Reactive dyes with representative chromophores and anchor groups were chosen for the research project. Different stages of oxidative decolourisation were examined and determined by water parameters for biological degradation (BOD). The paper focuses on toxicity tests with Pseudomonas putida to consider whether the oxidative treatments result in products with a risk for the environment. Tests were performed with the AQUALYTIC^® Sensomat System, which measures biological oxygen demand (BOD). It was determined that the chosen oxidative treatments had as a rule no bearing on respiration of P. putida. Experiments with hydrolysates after short-term UV irradiation resulted in a slightly increased but not long-lasting toxicity in comparison with treatments with ozone or NaPS. Toxic effects were found in tests with hydrolysates of metalliferous dyes. During oxidative treatment, metals were liberated from the chromophores. This did cause complete inhibition of respiration of P. putida. Dye Blue E, a member of a dye class with chlorotriazine anchor groups, was itself found to be toxic, caused by the reactivity of the anchor group. The hydrolysate is only of minor toxicity.     

Elevated ozone affects the genetic composition of Plantago lanceolata L. populations

The genetic composition and diversity of Plantago lanceolata L. populations were analysed using amplified fragment length polymorphism (AFLP) as well as simple sequence repeat (SSR) markers to test for differences in an old semi-natural grassland after five years of treatment with ambient or elevated ozone (O3) using a free-air fumigation system. Genetic diversity in populations exposed to elevated O3 was slightly higher than in populations sampled from control plots. This effect was significant for AFLP-based measures of diversity and for SSR markers based on observed heterozygosity. Also, a small but significant difference in genetic composition between O3 treatments was detected by analysis of molecular variance and redundancy analysis. The results show that micro-evolutionary processes could take place in response to long-term elevated O3 exposure in highly diverse populations of outbreeding plant species.     

Suitability of Nicotiana tabacum 'Bel W3' for biomonitoring ozone in São Paulo, Brazil

Nicotiana tabacum 'Bel W3' is a widely used sensitive bioindicator for ambient ozone, but it is rarely used in tropical countries. Our goal was to determine the suitability of this plant for biomonitoring ozone in the city of S?o Paulo by evaluating the relationships between leaf necroses and ozone under field conditions and measurements of chlorophyll a fluorescence and antioxidants in plants exposed to different concentrations of ozone in closed chambers. While a weak linear relationship between leaf injury and ozone concentrations (R(2)=0.10) was determined in the field, a strong linear relationship was observed in the chamber experiments. Maximum leaf injury was observed in plants submitted to 40 ppb, which coincided with a significant decrease in fluorescence and total ascorbic acid. The relationship between leaf damage observed in the field and ozone was improved when the concentrations were limited to 40 ppb (R(2)=0.28).     

Seasonal and diurnal gas exchange differences in ozone-sensitive common milkweed (Asclepias syriaca L.) in relation to ozone uptake

Stomatal conductance and net photosynthesis of common milkweed (Asclepias syriaca L.) plants in two different soil moisture regimes were directly quantified and subsequently modeled over an entire growing season. Direct measurements captured the dynamic response of stomatal conductance to changing environmental conditions throughout the day, as well as declining gas exchange and carbon assimilation throughout the growth period beyond an early summer maximum. This phenomenon was observed in plants grown both with and without supplemental soil moisture, the latter of which should theoretically mitigate against harmful physiological effects caused by exposure to ozone. Seasonally declining rates of stomatal conductance were found to be substantial and incorporated into models, making them less susceptible to the overestimations of effective exposure that are an inherent source of error in ozone exposure indices. The species-specific evidence presented here supports the integration of dynamic physiological processes into flux-based modeling approaches for the prediction of ozone injury in vegetation.     

对氯苯甲酸用于测量OH#方法探讨1.机理研究

对氯苯甲酸被用于臭氧氧化过程中羟基自由基的测量,为了检验对氯苯甲酸是否在测量过程中出现误差,进行了臭氧氧化对氯苯甲酸的间歇实验和半连续实验.结果表明,中性条件下间歇试验中,对氯苯甲酸可以强烈促进臭氧分解,它促进臭氧分解的能力比典型的促进剂甲酸和甲醇高10倍.半连续试验的结果进一步表明,臭氧氧化对氯苯甲酸时,可以形成中间产物过氧化氢,过氧化氢能和臭氧反应,形成大量的OH.,从而改变O3/OH.的链式反应,导致采用对氯苯甲酸测量OH.时出现误差.