Factors affecting trace-metal bioaccumulation in Finnish headwater lakes

Fourteen unpolluted Finnish headwater lakes with pH values varying from 4.8 to 7.0 were studied for trace-metal concentrations in water, sediment, aquatic plants (Nuphar luteum L., Sparganium sp.), aquatic insect larvae (Limnophilus sp., Phryganea sp.) and fish (Esox lucius L., Perca fluviatilis L., Coregonus sp., Salvelinus fontinalis L., Salmo trutta L.). Trace-metal deposition was estimated by analysing the snowpack. Non-parametric correlation analysis was carried out between trace metal concentrations in biota and pH, ANC, TOC, CA + Mg concentration in water and a given metal concentration in water and sediment. Bioaccumulation of several trace metals increased with increasing acidity and decreasing ANC in water. This was especially true for Pb and Cd. Aquatic plants were, in general, the best indicator group concerning differences in trace-metal bioaccumulation in lakes with different acidity. There was some evidence that a higher concentration of TOC in water may reduce bioaccumulation of Pb, Cd and Zn in aquatic plants and fish. The copper concentration in sediment was the only background variable explaining Cu concentration in aquatic insects. Multivariate analysis of the whole background data gave comparable preliminary results. Over 80% of the trace metal concentrations in biota of different lakes was explained by the background variables. In general, elevated concentrations of most of these trace metals can be expected to occur in the biota of acidified low calcareous lakes.     

Modelling episodic acidification of surface waters: the state of science

Field studies of chemical changes in surface waters associated with rainfall and snowmelt events have provided evidence of episodic acidification of lakes and streams in Europe and North America. Modelling these chemical changes is particularly challenging because of the variability associated with hydrological transport and chemical transformation processes in catchments. This paper provides a review of mathematical models that have been applied to the problem of episodic acidification. Several empirical approaches, including regression models, mixing models and time series models, support a strong hydrological interpretation of episodic acidification. Regional application of several models has suggested that acidic episodes (in which the acid neutralizing capacity becomes negative) are relatively common in surface waters in several regions of the US that receive acid deposition. Results from physically based models have suggested a lack of understanding of hydrological flowpaths, hydraulic residence times and biogeochemical reactions, particularly those involving aluminum. The ability to better predict episodic chemical responses of surface waters is thus dependent upon elucidation of these and other physical and chemical processes.     

Comparison of episodic acidification in Canada, Europe and the United States

Episodic acidification is practically a ubiquitous process in streams and drainage lakes in Canada, Europe and the United States. Depressions of pH are often smaller in systems with low pre-episode pH levels. Studies on European surface waters have reported episodes most frequently with minimum pH levels below 4.5. In Canada and the United States, studies have also reported a number of systems that have had minimum pH levels below 4.5. In all areas, change in water flowpath during hydrological events is a major determinant of episode characteristics. Episodic acidification is also controlled by a combination of other natural and anthropogenic factors. Base cation decreases are an important contributor to episodes in circumneutral streams and lakes. Sulphate pulses are generally important contributors to episodic acidification in Europe and Canada. Nitrate pulses are generally more important to episodic acidification in the Northeast United States. Increases in organic acids contribute to episodes in some streams in all areas. The sea-salt effect is important in near-coastal streams and lakes. In Canada, Europe and the United States, acidic deposition has increased the severity (minimum pH reached) of episodes in some streams and lakes.     

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.     

Cadmium availability to the cyanobacterium Synechocystis aquatilis in solutions containing chloride

Availability of cadmium to Synechocystis aquatilis (estimated by 109Cd sorption and cadmium toxicity-14C method) in solutions containing cadmium and complexing (KCl) or non-complexing (KNO3) salts, in the range of 0-0.5 m was investigated. Both cadmium surface adsorption and transport into the cells were lower in solutions containing cadmium chloride complexes (CdCl+, CdCl2, CdCl3-) than in those containing cadmium in the form of Cd2+. Also, cadmium toxicity in solutions of higher KCl concentrations, in which CdCl+ and CdCl2 forms predominated, was significantly limited.     

Deposition of ozone to a mature spruce forest: measurements and comparison to models

Removal of ozone at terrestrial surfaces provides a major sink for tropospheric ozone and, therefore, a constraint on the peak concentrations achieved during photochemical episodes. This study reports results from 5 years of almost continuous measurements of vertical profiles of ozone and related meteorological variables over a mature spruce forest in Bavaria. Deposition velocities calculated from flux/gradient and eddy correlation flux measurements have been compared with estimates based on a resistance model and yield satisfactory agreement during fine weather conditions. The results also suggest that biogenic emissions of reactive hydrocarbons from the forest influence the vertical profile of ozone.     

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.     

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.     

Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO₂) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NO_x analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO₂, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO₂ varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO₂ degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.