Critical loads for Finnish lakes: comparison of three steady-state models

Three simple steady-state water-chemistry models are used to calculate critical loads of sulfur for lakes in Finland. Because of the high concentrations of organic matter in Finnish lakes, the influence of organic anions on the calculation of critical loads has been given special attention. The first two methods are well known ion-balance methods which have been used in many previous lake-acidification studies. The third method, developed for this study, includes the numerical solution of equilibrium equations for organic anions, inorganic carbon species and inorganic monomeric aluminum. The original pH and aluminum concentration of the lakes are estimated with this model, and a method to estimate the original acid neutralizing capacity (ANC) by simulating a Gran-titration is also tested on the lake data. Uncertainty in the predictions is estimated by varying the most critical model parameters.     

Contribution of canopy leaching to sulphate deposition in a Scots pine forest

Radioactive sulphate (35SO4) was applied to the soil below a Scots pine forest on 23 June 1989, and its movement into the canopy and into throughfall and stemflow was measured over 4 months. The specific activity, Bq (mg S)(-1), of the canopy increased monotonically; uptake by current-year (1989) expanding needles was initially twice as fast as by older needles or live twigs. By 10 October the canopy average specific activity was 62 Bq (mg S)(-1). The specific activity of net throughfall (throughfall + stemflow - rain), deduced from measurements from six throughfall collectors, six stemflow collectors and two rain collectors, fell rapidly from 12.6 Bq (mg S)(-1) in late July to <1 Bq (mg S)(-1) in mid-August. The results suggest (assuming rapid equilibration of 35S with sulphate in soil) that root-derived sulphate contributed c. 3% of sulphate in net throughfall and that dry deposition of SO2 and sulphate particles contributed c. 97% of the 0.56 g S m(-2) measured in net throughfall over the period. Simultaneous measurements of SO2 at canopy height and of NH3 above and within the canopy gave mean concentrations of 5.9 and 0.86 microg m(-3), respectively, sufficient to account for the sulphate measured in net throughfall only if codeposition of NH3 and SO2 occurred to canopy surfaces. The large values of specific activity observed in July, however, indicate that throughfall composition may be closely related to recent soil input of sulphate, and that equilibrium cannot be safely assumed. The possibility of a significant contribution of soil-derived sulphate to sulphate deposition in net throughfall cannot be ruled out on the basis of this experiment.     

Deposition of atmospheric ammonia to moorlands

Micrometeorological methods were applied to measure fluxes of atmospheric ammonia (NH3) to moorlands. Measurements were made in a wide variety of surface conditions and included both Calluna vulgaris (L.) Hull and Eriophorum vaginatum L. dominated sites. NH3 was found to deposit rapidly to all the sites investigated, providing large deposition velocities (Vd, typically 10-40 mm s(-1)) and usually minimal surface resistances (rc). A small number of measurements were made in frozen conditions and suggest a possible exception to this pattern with mean rc of 50-200 s m(-1). The effect of vegetation drying was also investigated and a possible increase in rc observed, though this was small (< 10 s m(-1)). The results are interpreted in terms of the processes controlling exchange; it is shown that NH3 deposition is predominantly to the leaf surfaces and that the net NH3 compensation point approaches zero. Annual estimates show that dry deposition of NH3 is a major source of atmospheric nitrogen to moorland ecosystems. For two typical UK sites subject to background air concentrations, NH3 dry deposition is of similar magnitude to equivalent NH4+ inputs in wet deposition. In the vicinity of emission sources, NH3 dry deposition is expected to dominate inputs of atmospheric nitrogen.     

Seasonal trend of fog water chemical composition in the Po Valley

Fog frequency in the Po Valley, Northern Italy, can be as high as 30% of the time in the fall-winter season. High pollutant concentrations have been measured in fog water samples collected in this area over the past few years. The combined effects of high fog occurrence and high pollutant loading of the fog droplets can determine, in this area, appreciable chemical deposition rates. An automated station for fog water collection was developed, and deployed at the field station of S. Pietro Capofiume, in the eastern part of the Po Valley for an extended period: from the beginning of November 1989 to the end of April 1990. Time-resolved sampling of fog droplets was carried out during all fog events occurring in this period, and chemical analyses were performed on the collected samples. Statistical information on fog occurrence and fog water chemical composition is reported in this paper, and a tentative seasonal deposition budget is calculated for H+, NH4+, NO3- and SO4(2-) ions. The problems connected with fog droplet sampling in sub-freezing conditions are also addressed in the paper.     

Impacts of afforestation on water quality trends in two catchments in mid-Wales

The impact of afforestation on stream-water chemistry for two catchments in central Wales is investigated. Trends in water chemistry are evaluated with forest age progressing at 8-15 years and 20-27 years. To assess the possible exacerbating effect of afforestation on surface-water acidification two moorland catchments are used as controls. Absolute differences in inter-catchment streamwater chemistry are evident. Differences in acidity between the moorland and the young forest site reflect site preparation and modifications to water pathways. Differences in the observed present day chemistry between the young and old forest result from past interactions between deposition changes during forest development. An estimate of the future impact of forest growth was attained from model predictions. The model was calibrated to present day stream-water chemistry and incorporates, cation uptake, evapotranspiration/ concentration effect and increased scavenging of occult and dry deposition. Predictions suggest the pH will decline to 5.3 when the young forest progresses to 20 years of age, which is still much higher than the pH recorded at the older forest site at the age of 20 years.     

Death and injury in earthquakes

The assumption that the ratio of mortality to morbidity will approximate 1:3 in earthquake disasters is investigated. When it occurs, a 1:3 ratio is most likely to coincide with a Richter magnitude in the range 6.5–7.4, but many other ratios of death to injuries may instead be probable. For each individual disaster the pattern of casualties is likely to be very heterogeneous, but it would be easier to discover regularities if a more standardized definition of 'injury' could be found.     

Treatability studies of naphthalene in soil,water and air with persulfate activated by iron(Ⅱ)

Chemical oxidation was applied to an artificially contaminated soil with naphthalene (NAP). Evaluation of NAP distribution and mass reduction in soil, water and air phases was carried out through mass balance. Evaluation of NAP distribution and mass reduction in soil, water and air phases was carried out through mass balance. The importance of the air phase analysis was emphasized by demonstrating how NAP behaves in a sealed system over a 4 hr reaction period. Design of Experiments method was applied to the following variables: sodium persulfate concentration [SP], ferrous sulfate concentration [FeSO₄], and pH. The system operated with a prefixed solid to liquid ratio of 1:2. The following conditions resulted in optimum NAP removal [SP] = 18.37 g/L, [FeSO₄] = 4.25 g/L and pH = 3.00. At the end of the 4 hr reaction, 62% of NAP was degraded. In the soil phase, the chemical oxidation reduced the NAP concentration thus achieving levels which comply with Brazilian and USA environmental legislations. Besides the NAP partitioning view, the monitoring of each phase allowed the variabilities assessment over the process, refining the knowledge of mass reduction. Based on NAP distribution in the system, this study demonstrates the importance of evaluating the presence of semi-volatile and volatile organic compounds in the air phase during remediation, so that there is greater control of the system as to the distribution and presence of the contaminant in the environment. The results highlight the importance of treating the contaminant in all its phases at the contaminated site.     

Characterization of atmospheric aerosol (PM10 and PM2.5) from a medium sized city in São Paulo state, Brazil

Air pollution causes deleterious effects on human health with aerosols being among the most polluting agents.The objective of this work is the characterization of the PM_(2.5) and PM_(10) aerosol mass in the atmosphere.The methods of analysis include WD-XRF and EDS.Data were correlated with meteorological information and air mass trajectories(model HYSPLIT)by multivariate analysis.A morphological structural analysis was also carried out to identify the probable sources of atmospheric aerosols in the city of Sao Jose do Rio Preto,Brazil.The mean mass concentration values obtained were 24.54 μg/m~3 for PM_(10),above the WHO annual standard value of 20 μg/m~3 and 10.88 μg/m~3 for PM_(2.5) whose WHO recommended limit is10 μg/m~3.WD-XRF analysis of the samples revealed Si and Al as major components of the coarse fraction.In the fine fraction,the major elements were Al and S.The SEM-FEG characterization allowed identifying the morphology of the particles in agglomerates,ellipsoids and filaments in the PM_(10),besides spherical in the PM_(2.5).The analysis by EDS corroborated WD-XRF results,identifying the crustal elements,aluminosilicates and elements of anthropogenic origin in the coarse fraction.For the fine fraction crustal elements were also identified;aluminosilicates,black carbon and spherical particles(C and O) originating from combustion processes were predominant.The use of multivariate analysis to correlate air mass trajectories with the results of the morpho-structural characterization of the particulate matter allowed confirmation of the complex composition of the particles resulting from the combination of both local and long-distance sources.     

The study of biological activity of transformation products of diclofenac and its interaction with chlorogenic acid

In the present work we compared the biological activity of DCF, 4′-OHDCF and 5-OHDCF as molecules of most biodegradation pathways of DCF and selected transformation products (2-hydroxyphenylacetic acid; 2,5-dihydroxyphenylacetic acid and 2,6-dichloroaniline) which are produced during AOPs, such as ozonation and UV/H₂O₂. We also examined the interaction of DCF with chlorogenic acid (CGA). CGA is commonly used in human diet and entering the environment along with waste mainly from the processing and brewing of coffee and it can be toxic for microorganisms included in activated sludge. In the present experiment the evaluation of following parameters was performed: E. coli K-12 cells viability, growth inhibition of E. coli K-12 culture, LC₅₀ and mortality of Chironomus aprilinus, genotoxicity, sodA promoter induction and ROS generation. In addition the reactivity of E. coli SM recA:luxCDABE biosensor strain in wastewater matrices was measured. The results showed the influence of DCF, 4′-OHDCF and 5-OHDCF on E. coli K-12 cells viability and bacteria growth, comparable to AOPs by-products. The highest toxicity was observed for selected, tested AOPs by-products, in comparison to the DCF, 4′-OHDCF and 5-OHDCF. Genotoxicity assay indicated that 2,6-dichloroaniline (AOPs by-product) had the highest toxic effect. The oxidative stress assays revealed that the highest level of ROS generation and sodA promoter induction were obtained for DCF, 4′-OHDCF and 5-OHDCF, compared to other tested compounds. We have also found that there is an interaction between chlorogenic acid and DCF, which resulted in increased toxicity of the mixture of the both compounds to E. coli K-12, comparable to parent chemicals. The strongest response of E. coli SM biosensor strain with recA:luxCDABE genetic construct in filtered treated wastewaters, comparable to control sample was noticed. It indicates, that E. coli SM recA:luxCDABE biosensor strains is a good tool for bacteria monitoring in wastewater environment. Due to toxicity and biological activity of tested DCF transformation products, there is a need to use additional wastewater treatment systems for wastewater contaminated with pharmaceutical residues.     

Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.