Profile analysis of organic micropollutants in the environment of a coal burning area, NW Greece

The concentrations and profiles of dibenzo-p-dioxins, dibenzofurans, polychlorinated biphenyls and polynuclear aromatic compounds in various environmental matrices are presented in this study. The examined environmental matrices are total suspended particles, fly ash and soil collected in NW Greece, an area characterized by intensive coal burning for electrical power generation. Moreover, the occurrence of organic micropollutants in soot after an accidental fire was examined and the possible impact on the outdoor environment was evaluated. Results were statistically treated to obtain information on representative PCDD/F profiles in each matrix and to compare these profiles with the compositional patterns of possible sources from literature. Coal combustion, fly ash and vehicle exhausts appeared to be the most possible sources in local atmosphere.     

Comparison of different physiological parameter responses in Lemna minor and Scenedesmus obliquus exposed to herbicide flumioxazin

The sensitivity of different physiological parameters in Scenedesmus obliquus and Lemna minor exposed to herbicide (flumioxazin) was investigated to indicate the most convenient and sensitive parameter. To assess toxicity of flumioxazin, we used a panel of biomarkers: pigment contents, chlorophyll fluorescence parameters and antioxidative enzyme activities. Algae and duckweed were exposed to 48-h IC50 for growth rate. In L. minor, the sensitivity of the parameters was as follows: QN > Oxygen emmision > phiS(PSII) > QP > phi(PSII) > CAT, GR > Pigment> APO > Growth. For S. obliquus, this ranking was as follows: CAT > Oxygen emission > QP > APO > GR > Pigment > phiS(PSII) > Growth > phi(PSII) > QN (from the greatest to the least sensitive). The results demonstrated that the observed toxicity is related not only to interspecific variations but also to the selected parameter.     

The effect of ozone on pollen development in Lolium perenne L

Perennial ryegrass plants (Lolium perenne L.) were exposed in "Closed-Top Chambers" to different ozone concentrations and to charcoal filtered ambient air to study the effect of ozone on the development of pollen. Ozone at ambient (65 nl l(-1), 8h) and elevated (110 nl l(-1), 4h) concentrations affected the maturing of pollen by inhibiting starch accumulation in pollen throughout the anther. Affected pollen persisted in the vacuolated state while normal pollen in the same anther were filled with amyloplasts. The percentage of underdeveloped pollen-determined in transversal sections-was significantly higher in exposed plants than in plants grown in filtered air. Results indicate that ozone stress was responsible for the disrupted development of pollen in L. perenne.     

Decolorizing of lignin wastewater using the photochemical UV/TiO2 process

Studies on applying the photochemical UV/TiO2 oxidation process to treat the lignin-containing wastewater for dissolved organic carbon (DOC), color and reducing A254 (the absorption at the wavelength of 254 nm) have been carried out. The data obtained in this study demonstrate that the UV/TiO2 process is effective in oxidizing the lignin thus reducing the color and DOC of the wastewater treated. The combined UV/TiO2 treatment can achieve better removal of DOC and color than the UV treatment alone. Color removal, based on American Dye Manufacture Index (ADMI) measurement, is greater than 99% if the pH is maintained at 3.0 with the addition of 1 g l(-1) TiO2. When 10 g l(-1) TiO2 is applied, the oxidation reduction potential (ORP) value is reached to result in an 88% removal of both DOC and color. A model was developed based on the variation of ORP during the photochemical reaction to simulate the decoloring process. The proposed model can be used to predict the color removal efficiency of the UV/TiO2 process.     

Electrochemical decolourisation of structurally different dyes

The electrochemical decolourisation of structurally different dyes (bromophenol blue, indigo, poly R-478, phenol red, methyl orange, fuchsin, methyl green and crystal violet) by means of the application of DC electric current was assessed. It was found that the electrochemical process allowed a colour removal of all dyes studied, although the decolourisation rate largely depended on the chemical structure of the different dyes. Nearly complete decolourisation was achieved for bromophenol blue followed by methyl orange and methyl green, whereas phenol red was hardly decolourised (30% in 60 min). In mixtures of two dyes, the decolourisation rate became similar for both dyes. However, the addition of a redox mediator, (Co(2+/3+)) clearly enhanced the degradation rate of all tested dyes, but the simplest dye molecules were attacked firstly, followed by dyes with more complex chemical structures. The results revealed the suitability of the process to effectively decolourise wastewaters from dyeing process.     

Sorption and oxic degradation of the explosive CL-20 during transport in subsurface sediments

The abiotic sorption and oxic degradation processes that control the fate of the explosive CL-20, Hexanitrohexaazaisowurtzitane, in the subsurface environment were investigated to determine the potential for vadose and groundwater contamination. Sorption of aqueous CL-20 is relatively small (K(d) = 0.02-3.83 cm3 g(-1) for 7 sediments and 12 minerals), which results in only slight retardation relative to water movement. Thus, CL-20 could move quickly through unsaturated and saturated sediments of comparable composition to groundwater, similar to the subsurface behavior of RDX. CL-20 sorption was mainly to mineral surfaces of the sediments, and the resulting isotherm was nonlinear. CL-20 abiotically degrades in oxic environments at slow rates (i.e., 10s to 100s of hours) with a wide variety of minerals, but at fast rates (i.e., minutes) in the presence of 2:1 phyllosilicate clays (hectorite, montmorillonite, nontronite), micas (biotite, illite), and specific oxides (MnO2 and the ferrous-ferric iron oxide magnetite). High concentrations of surface ferrous iron in a dithionite reduced sediment degraded CL-20 the fastest (half-life < 0.05 h), but 2:1 clays containing no structural or adsorbed ferrous iron (hectorite) could also quickly degrade CL-20 (half-life < 0.2 h). CL-20 degradation rates were slower in natural sediments (half-life 3-800 h) compared to minerals. Sediments with slow degradation rates and small sorption would exhibit the highest potential for deep subsurface migration. Products of CL-20 oxic degradation included three high molecular weight compounds and anions (nitrite and formate). The 2-3.5 moles of nitrite produced suggest CL-20 nitro-groups are degraded, and the amount of formate produced (0.2-1.2 moles) suggests the CL-20 cage structure is broken in some sediments. Identification of further degradation products and CL-20 mineralization rates is needed to fully assess the impact of these CL-20 transformation rates on the risk of CL-20 (and degradation product) subsurface movement.     

Characterisation of the dilute HCl extraction method for the identification of metal contamination in Antarctic marine sediments

A regional survey of potential contaminants in marine or estuarine sediments is often one of the first steps in a post-disturbance environmental impact assessment. Of the many different chemical extraction or digestion procedures that have been proposed to quantify metal contamination, partial acid extractions are probably the best overall compromise between selectivity, sensitivity, precision, cost and expediency. The extent to which measured metal concentrations relate to the anthropogenic fraction that is bioavailable is contentious, but is one of the desired outcomes of an assessment or prediction of biological impact. As part of a regional survey of metal contamination associated with Australia's past waste management activities in Antarctica, we wanted to identify an acid type and extraction protocol that would allow a reasonable definition of the anthropogenic bioavailable fraction for a large number of samples. From a kinetic study of the 1 M HCl extraction of two Certified Reference Materials (MESS-2 and PACS-2) and two Antarctic marine sediments, we concluded that a 4 h extraction time allows the equilibrium dissolution of relatively labile metal contaminants, but does not favour the extraction of natural geogenic metals. In a regional survey of 88 marine samples from the Casey Station area of East Antarctica, the 4 h extraction procedure correlated best with biological data, and most clearly identified those sediments thought to be contaminated by runoff from abandoned waste disposal sites. Most importantly the 4 h extraction provided better definition of the low to moderately contaminated locations by picking up small differences in anthropogenic metal concentrations. For the purposes of inter-regional comparison, we recommend a 4 h 1 M HCl acid extraction as a standard method for assessing metal contamination in Antarctica.     

Analysis of extinction in ultraviolet and visible spectra of water bodies of the Paraguay and Brazil wetlands

The extinction spectra in ultraviolet and visible radiation were analyzed using filtered and unfiltered water samples obtained in 11 open water bodies in the Neembucù (Paraguay) and Pantanal (Brazil) wetlands. The role of dissolved and suspended matter in the total extinction was analyzed between 260 nm and 700 nm. The chromophoric dissolved organic matter (CDOM) was the major component in extinction of considered ultraviolet radiation (260-400 nm). The differences in CDOM concentrations explained the main pattern of extinction of the ultraviolet radiation in the samples. Nevertheless, differences between the studied water bodies were found also to depend on the rate of photodegradation and photobleaching. The methodology developed in the present study was to distinguish "humic optic waters" according to quantity and quality of dissolved and suspended matter present. In the "humic optic water", the penetration of 10% of incident UV radiation and the photoactive layer are estimated. The influence of particulate matter increases in the total extinction of the wavelengths higher than 400 nm. The integral of the extinction curve of suspended matter in the visible wavelengths (400-700 nm) was found to relate with the total suspended solids and chlorophyll concentrations.     

Aerobic sludge digestion under low dissolved oxygen concentrations.

Low dissolved oxygen (DO) concentrations occur commonly in aerobic digesters treating thickened sludge, with benefits of smaller digester size, much reduced aeration cost, and higher digestion temperature (especially important for plants in colder areas). The effects of low DO concentrations on digestion kinetics were studied using the sludge from municipal wastewater treatment plants in Akron, Ohio, and Los Lunas, New Mexico. The experiments were conducted in both batch digestion and a mixed mode of continuous, fed-batch, and batch operations. The low DO condition was clearly advantageous in eliminating the need for pH control because of the simultaneous occurrence of nitrification and denitrification. However, when compared with fully aerobic (high DO) systems under constant pH control (rare in full-scale plants), low DO concentrations and a higher solids loading had a negative effect on the specific volatile solids (VS) digestion kinetics. Nonetheless, the overall (volumetric) digestion performance depends not only on the specific digestion kinetics, but also the solids concentration, pH, and digester temperature. All of the latter factors favor the low DO digestion of thickened sludge. The significant effect of temperature on low DO digestion was confirmed in the mixed-mode study with the Akron sludge. When compared with the well-known empirical correlation between VS reduction and the product (temperature x solids retention time), the experimental data followed the same trend, but were lower than the correlation predictions. The latter was attributed to the lower digestible VS in the Akron sludge, the slower digestion at low DO concentrations, or both. Through model simulation, the first-order decay constant (kd) was estimated as 0.004 h(-1) in the mixed-mode operations, much lower than those (0.011 to 0.029 h(-1)) obtained in batch digestion. The findings suggested that the interactions among sludges with different treatment ages may have a substantially negative effect on digestion kinetics. The use of multistage digesters, especially with small front-end reactors, may be advantageous in both "process" kinetics and "biological reaction" kinetics for sludge digestion.     

Evidence for the "grasshopper" effect and fractionation during long-range atmospheric transport of organic contaminants

Although there is indisputable evidence that long-range atmospheric transport (LRAT) of organic contaminants occurs on a global scale, uncertainties remain about the detailed mechanism and extent of this phenomenon as well as the physical-chemical properties which facilitate LRAT. In this study, we discuss how mass balance models and monitoring data can contribute to a fuller understanding of the mechanism and extent of LRAT. Specifically we address the issues of "grasshopping" or "hopping" (the extent to which molecules are subject to multiple hops as distinct from a single emission-deposition event) and "global fractionation" (the differing behavior of chemicals as they are transported). It is shown that simple mass balance models can be used to assist the interpretation of monitoring data while also providing an instrument that can be used to assess the LRAT potential and the extent of hopping that organic substances may experience. The available evidence supports the notion that many persistent organic pollutants experience varying degrees of "hopping" during their environmental journey and as a consequence become fractionated with distance from source.