Evidence of the water-cage effect on the photolysis of NO3− and FeOH2+. Implications of this effect and of H2O2 surface accumulation on photochemistry at the air–water interface of atmospheric droplets

Experiments are conducted to determine the effect of a cage of water molecules on the photolysis quantum yields of nitrate, FeOH²⁺, and H₂O₂. Results suggest that the quantum yields of nitrate and FeOH²⁺ are decreased by the recombination of photo-fragments ( OH +  NO₂ and Fe²⁺ +  OH, respectively) before they leave the surrounding cage of water molecules. However, no evidence is found for an enhanced quantum yield for H₂O₂. Therefore, the photolysis of nitrate and FeOH²⁺ could be enhanced if the cage of the solvent molecules is incomplete, as is the case at the air–water interface of atmospheric droplets. The photolysis rate constant distribution within nitrate, FeOH²⁺, and H₂O₂ aerosols is calculated by combining the expected quantum yield data in the bulk and at the interface with Mie theory calculations of light intensity. The photolysis rate constant of nitrate and FeOH²⁺ would be significantly higher at the surface than in the bulk if quantum yields are enhanced at the surface. In the case of H₂O₂, the photolysis rate constant would be enhanced by surface accumulation. The results concerning the expected rates of photolysis of these photoactive species are applied to the assessment of the reaction between benzene and OH in the presence of OH scavengers in an atmospherically relevant scenario. For a droplet of 1 μm radius, a large fraction of the total OH-benzene reaction (15% for H₂O₂, 20% for nitrate, and 35% for FeOH²⁺) would occur in the surface layer, which accounts for just 0.15% of the droplet volume.     

2-D Studies of the kinetic photochemistry of the urban troposphere—II. Normal convective conditions

A two-dimensional model of the photochemistry of the urban troposphere has been applied to the case of normal convective air flow upwind, within and downwind of an urban area representing northern New Jersey. The atmospheric scavenging molecules O₃, HO, and HO₂ are computed to be least abundant at low altitudes near the regions of highest source density. Their concentrations increase downwind and at higher altitudes, leading to maximum production of inorganic acids and other photochemical products in those locations. Cycle analyses for the elements carbon (less CO₂), nitrogen and sulfur are derived from the calculations and indicate that, for the conditions specified in this work, 74% of the carbon, 12% of the nitrogen, and 10 % of the sulfur emitted anthropogenically are not consumed within ~ 100 km of the point of emission but are injected into the free troposphere.     

Assessment of the abiotic transformation of 17β-estradiol in the presence of vegetable matter--II: the role of molecular oxygen

This study characterizes the effect of oxygen in the abiotic transformation of estrogens when they are contacted with a surrogate of the vegetable wastes found in sewage. 17β-Estradiol (E2) and 17β-¹⁴C₄-estradiol (¹⁴C-E2) were utilized as model compounds. Batch experiments were run under both oxic and anoxic conditions. In order to accomplish an accurate mass balance of the target estrogen, two analyses were performed simultaneously: first, radioactivity counting, and second, quantitation of E2 and ¹⁴C-E2, as well as their transformation product estrone and ¹⁴C₄-estrone, by Liquid Chromatography tandem Mass Spectrometry. Under oxic conditions, the total concentration of ¹⁴C-E2 was found to decrease by 78% in 72 h (15% and 7% remained in the liquid and solid phases, respectively). Conversely, when the estrogens were contacted with the synthetic influent under anoxic conditions, E2 was quantitatively recovered after 72 h (70% and 22% in aqueous and solid matrices, correspondingly). These results suggest that when the concentration of dissolved oxygen is null or limited, catalysis through an oxidative coupling mechanism is halted. Moreover, it was confirmed that the catalytic reaction occurred solely in the presence of the solid phase of the model vegetable matter.     

The concentrations of specific C2–C6 hydrocarbons in the air of NW England

Ambient air concentrations of specific C₂–C₆ hydrocarbons (HCs) are reported for various days during the summer months of 1983. The samples are classified as either urban, rural or polluted rural according to the sampling site, meteorological conditions and ozone levels. Generally, both the concentrations and HC/acetylene ratios are similar to those reported by other workers for comparable sites. The alkane/alkene ratio at the rural site exceeded that for the urban site and it is concluded that the major contribution to HCs at the former site is advection from distant sources. It appears that the main source of propane in rural areas is natural gas, with about 4.5–9 ppbC unaccounted for by this source.     

Assessment of the abiotic transformation of 17β-estradiol in the presence of vegetable matter

A study using 17β-¹⁴C₄-estradiol (¹⁴C-E2) was performed to confirm and characterize the catalytic transformation of estrogens in the presence of a model vegetable matter (namely rabbit food) as a surrogate material for vegetable wastes found in sewage. Results corroborated the occurrence of an abiotic transformation. Unknown transformation byproduct(s) accounted, respectively, for 38% and 9% of the initial radioactivity in liquid and extractable solid phases after 72 h; on the other hand, only 15% and 7% of this radioactivity corresponded to ¹⁴C-E2 in those same matrices. Mass balance was closed including the radioactivity irreversibly bounded to the solid phase. Formation of ¹⁴C₄-estrone was monitored by Liquid Chromatography with tandem Mass Spectrometry detection; negative results were found in all sampling events. This process could be harnessed to optimize sustainable technologies for the removal of phenolic microcontaminants from wastewater.     

Revaluation of the “Chattanooga School Children Study” in the Light of Other Contemporary Governmental Studies: The Possible Impact of These Findings On the Present NO2 Air Quality Standard

Data have been collected to indicate the presence of a number of biologically antagonistic air contaminants in ambient air in the immediate vicinity of Chattanooga, Tenn., as a result of the operation of the Volunteer Army Ammunition Plant, Tyner, Tenn. It follows, therefore, from these data that adverse health effects observed in the course of the Chattanooga School Children Study may be accounted for either totally or in part by the presence of epidemiologically interfering compounds such as sulfuric and nitric acid vapors which were not measured in air at the time of the health effects study. It is suggested that the presence of these interferences be considered detrimental to the formulation of a valid air quality standard for nitrogen dioxide.     

Study of turbulent diffusion above and within a forest—application in the case of SO2

Some results concerning characteristics of airflow within and above a forest are presented: horizontal mean windspeed profiles, turbulence intensities, turbulent transfer coefficients, autocorrelation curves, energy spectra, turbulence scales, microscales.To understand the mechanisms of SO₂ diffusion within and above a forest, we have to calculate SO₂ fluxes at the top of the canopy and two methods are used for this: the first one uses speed fluctuations and the second one mean speed values.The aim of that work is to determine the behaviour of the forest towards SO₂ and to develop a diffusion model of SO₂ with associated absorption by the roughness.     

COVID-19: unbalanced management of occupational risks—case of the analysis of the chemical risk related to the use of disinfectants in the dairy industry in Morocco

Environmental Science and Pollution Research - Moroccan employers have a strong responsibility for the safety and health of their employees in the workplace and for protecting them from the risk of...     

Relevance of the Paraná River hydrology on the fluvial water quality of the Delta Biosphere Reserve

The increasing frequency of extreme events in large rivers may affect not only their flow, but also their water quality. In the present study, spatial and temporal changes in fluvial physico-chemical variables were analyzed in a mega-river delta during two extreme hydrological years (La Niña-El Niño) and related to potential explanatory factors. Basic water variables were evaluated in situ at 13 points (distant 2–35 km from each other) in watercourses of the Delta Biosphere Reserve (890 km²) in the Lower Paraná River (Argentina) in nine surveys (October 2008–July 2010) without meteorological tides. Samples for laboratory analyses were collected from each main river. Multivariate tests by permutations were applied. The period studied was influenced by a drought, within a long period dominated by low flows combined with dry weather and wildfires, and a large (10 years of recurrence) and prolonged (7 months) flood. The hydrological phase, followed by the season and the hydrological year (according to the ENSO event) were the principal explanatory factors of the main water quality changes, whereas the drainage sub-basin and the fluvial environment (river or stream) were secondary explanatory factors. During the drought period, conductivity, turbidity, and associated variables (e.g., major ions, silicon, and iron concentrations) were maximal, whereas real color was minimal. In the overbanking flood phase, pH and dissolved oxygen concentration were minimal, whereas real color was maximal. Dissolved oxygen saturation was also low in the receding flood phase and total major ion load doubled after the arrival of the overbanking stage. The water quality of these watercourses may be affected by the combination of several influences, such as the Paraná River flow, the pulses with sediments and solutes from the Bermejo River, the export of the Delta floodplain properties mainly by the flood, the season, and the saline tributaries to the Lower Paraná River. The high influence of the hydrology of this large river on the Delta fluvial water quality emphasizes the relevance of changes in its flow regime in recent decades, such as the seasonality attenuation. Considering that the effects of extreme events differ among and within fluvial systems, specific ecohydrological evaluations and powerful appropriate statistics are key tools to gain knowledge on these systems and to provide bases for suitable management measures in a scenario of climate change and increasing human alterations and demands.     

Antifungal efficiency assessment of the TiO2 coating on façade paints

The work studies the photocatalytic activity and the antifungal efficiency of the TiO₂/Zn-Al coatings placed on the target commercial façade paints. The photocatalytic active nanocomposite based on TiO₂ and Zn-Al-layered double hydroxides (ZnAl-LDHs) was synthesized by a wet impregnation technique with 3 % w/w TiO₂. The freshly prepared suspension was applied by spray technique on the surfaces of the white façade paints. The goal of the work was to develop a method that quickly quantifies the antifungal activity of the commercial façade paints with and without biocidal components covered with a photocatalytic coating. The essence of the proposed method is the monitoring of the fungal growth (artificial ageing conditions) and the quantification of its development (UV-A 0.13 mWcm^?2) on the façade paint surfaces. A special fungus nutrient (potato dextrose agar (PDA)) was inoculated with the spores of the Aspergillus niger ATCC 6275, and the test samples (façade paints with and without photocatalytic coating) were placed on the inoculated nutrient in the petri dishes. The images of the fungal growth on the samples of the facade paints, during a period of 5 days, were imported into Matlab R2012a where they were converted to binary images (BW), based on the adequate threshold. The percentage of the surface coverage was calculated by applying the specifically written program code which determines the ratio of the black and white pixels. The black pixels correspond to the surface covered with hyphae and mycelia of the fungus.     

Kinetics of the gas-phase reactions of alkylnaphthalenes with O3, N2O5 and OH radicals at 298 ± 2 K

Rate constants for the gas-phase reactions of the OH radical with 1-methylnaphthalene and of N₂O₅ with 1- and 2-methylnaphthalene and 2,3-dimethylnaphthalene have been determined at 298 ± 2 K by use of relative rate techniques. The rate constants determined were: for the reaction of OH radicals with 1-methylnaphthalene, (5.30 ± 0.48) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹; for the reaction of N₂O₅ with 1-methylnaphthalene, 2-methylnaphthalene and 2,3-dimethylnaphthalene, (3.3 ± 0.7) × 10⁻¹⁷, (4.2 ± 0.9) × 10⁻¹⁷ and (5.7 ± 1.9) × 10⁻¹⁷ cm³ molecule⁻¹ s⁻¹, respectively. In addition, an upper limit to the rate constant of 1.3 × 10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ was measured for the reaction of O₃ with 1-methylnaphthalene at 298 ± 2 K. These data, when combined with data from previous literature, allow the atmospheric gas-phase removal processes of these alkylnaphthalenes to be quantified.     

The influence of cloud dynamics upon the redistribution and transformation of atmospheric SO2—a numerical simulation

A set of continuity equations describing the evolution of sulphur dioxide, sulphate and ammonia distributions within rain systems is formulated. By means of a simple bulk parameterization of microphysical and chemical processes, several parameters characteristic of acidic precipitation are investigated within the framework of a steady updraft column. The sensitivity of the results to the parameterization is also examined. The techniques described may be readily adapted to more complicated models.     

Estimation of the exchange of sulphur pollution over the Balkan region in 1995–2000

The Bulgarian dispersion model 'Eulerian Model for Air Pollution' (EMAP) is used to estimate the sulphur pollution over the Balkan region for the period 1995–2000. A subdomain of the European Monitoring and Evaluation Programme (EMEP) grid is chosen containing 12 countries. The computational grid in this domain has a space step of 25 km, twice as fine as the EMEP grid. The former operational DWD 'Europa-Model' is used as meteorological driver. The source input is the official EMEP emission data. Monthly calculations are made having the last moment fields from the previous month as initial conditions for the next one. The boundary conditions are set to zero, so the influence of other European sources is not accounted for in this study. According to the EMEP methodology, multiple runs are made setting every time the sources of various countries to zero. The impact of every country in the pollution of all others is estimated.     

Impact of chronic exposure to low doses of chlorpyrifos on the intestinal microbiota in the Simulator of the Human Intestinal Microbial Ecosystem (SHIME®) and in the rat

The impact of the insecticide chlorpyrifos (CPF) on the mammalian digestive system has been poorly described. The present study aimed at evaluating the effect of chronic, low-dose exposure to CPF on the composition of the gut microbiota in a Simulator of the Human Intestinal Microbial Ecosystem: the SHIME® and in rats. The SHIME® comprises six reactor vessels (stomach to colon). The colonic segments were inoculated with feces from healthy humans. Then, the simulator was exposed to a daily dose of 1 mg of CPF for 30 days. The changes over time in the populations of bacteria were examined at different time points: prior to pesticide exposure (as a control) and after exposure. In parallel, pregnant rats were gavaged daily with 1 mg/kg of CPF (or vehicle) until the pups were weaned. Next, the rats were gavaged with same dose of CPF until 60 days of age (adulthood). Then, samples of different parts of the digestive tract were collected under sterile conditions for microbiological assessment. Chronic, low-dose exposure to CPF in the SHIME® and in the rat was found to induce dysbiosis in the microbial community with, in particular, proliferation of subpopulations of some strains and a decrease in the numbers of others bacteria. In compliance with European guidelines, the use of the SHIME® in vitro tool would help to (1) elucidate the final health effect of toxic agents and (2) minimize (though not fully replace) animal testing. Indeed, certain parameters would still have to be studied further in vivo.     

The assessment of the soil–plant-animal transport of the risk elements at the locations affected by brown coal mining

Environmental Science and Pollution Research - The North Bohemian Brown Coal Basin (Czech Republic) is suggested as a source of significant pollution in the surrounding environment with various...     

Hybrid regimes of knowledge? Challenges for constructing scientific evidence in the context of the GMO-debate

Background, aim, and scope

Over the last two decades, there has been a remarkable shift of attention to the scientific and political fundamentals of the precautionary principle. The application of this principle has become a main strategy of coping with the different forms and problems related to non-knowledge. Thus, societies are increasingly confronted with the challenging and hitherto unresolved problem of political and technological decision-making under conditions of diverging framings of non-knowledge. At present, there seems to be no generally accepted scientific or institutional approach. This is why the fundamental question of how different scientific actors define and construct evidence is not answered yet. Hence, this paper is based on the consideration that the conflicts in risk policy concerning genetically modified organisms (GMO) depend on the unresolved conflicts about the diverging scientific strategies and structures of evidence-making between the epistemic cultures involved. Thus, this study investigates two questions: (1) do the epistemic strategies of evidence-making differ systematically with the scientific actors involved in the GMO-debate? (2) What consequences emerge considering institutionalized procedures of decision-making?

Main features

This article is based on a secondary analysis of findings and perspectives reported in the literature and on the methods of qualitative social empirical research, i.e., interviews with experts. A total number of 34 interviews were conducted to explore the different strategies of handling non-knowledge and constructing evidence. Actors from science, administration, business and NGOs were interviewed. In this way, typical epistemic cultures can be described. An epistemic culture is the constellation of methodological strategies, theoretical assumptions and practical-experimental settings which define in every speciality the ways how we know what we know.

Results

There are two main results. Firstly, it was worked out that the epistemic cultures involved in the GMO-debate use rather distinct strategies to define non-knowledge and to classify evidence. There are three types of constructing evidence, which correspond to different types of epistemic cultures. Secondly, the findings imply that the intensity of the conflicts in risk policy fields like the GMO-debate is due to a lack of knowledge politics. Usually, knowledge politics is restricted to the design of institutional procedures to compile knowledge provided by experts. The institutional setting of risk analysis and risk management is based on the premise of strict separation between knowledge and power. However, inadmissible mixing-up of knowledge and power is observable.

Discussion

It seems that non-knowledge leads to an epistemic no man’s land, and, hence, hybrid regimes of knowledge emerge. These regimes are hybrid with respect to the unclear and not explicitly reflected strategies of evidence-making. By lacking of knowledge politics, this situation opens up ‘windows of opportunity’ for actors with special interests in risk policy fields like the GMO-debate. Therefore, there is a difference between the visible institutionalized structures of risk policies and the rather invisible hybrid regimes of knowledge. Structure and scope of expertise have to be reflected and new instruments of knowledge politics have to be designed.

Conclusions

Different epistemic cultures can be qualified by describing their particular strategies of evidence-making. To solve the conflicts between these strategies, a meta-expertise is needed. Besides the institutionalized settings of knowledge politics, the underlying hybrid regimes of knowledge have to be identified.

Recommendations and perspectives

The concept of epistemic cultures and their strategies of evidence-making should be investigated more explicitly with respect to other risk policy fields The analysis of hybrid regimes of knowledge should be deepened by looking at the complex interactions between institutional, discursive and practical rules affecting risk assessment.

     

Mathematical modelling of dispersion and chemical reactions in a plume — oxidation of no to NO2 in the plume of a power plant

A mathematical model is presented for the dispersion and chemical reactions of pollutants in chimney plumes. It assumes that atmospheric dispersion is such that an inert constituent would be distributed in a Gaussian fashion downwind of the chimney, uses a discreet approximation approach to obtain concentrations of reactive pollutants, and can account for reactive species entrained into the plume from the ambient air. The model is used to interpret some data on NO₂ formation in the plume of a power plant chimney.